15th european student colloid conference · properties of therapeutical muds with nano- and...

ESC 2015 Krakow, June 8-11, 2015

15th European Student Colloid Conference

Krakow • June 8-11, 2015

BOOK OF ABSTRACTS


2

Sponsorship

Gold

Sponsor

Platinium

Sponsor


3

Contents

Organizing Committee 4

Conference Programme 5

List of Posters 7

Abstracts 10

Invited lectures 11

Oral presentations 21

Posters 70

List of Conference Participants 114

Authors’ Index 121


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Organizing Committee

Katarzyna Kilan (chair)

Marek Piotrowski (webmaster)

Karolina Podgórna (event manager)

Magdalena Włodek

Marta Łapczyńska

Anna Pajor-Świerzy

Aneta Kędra

Tomasz Kruk

Grzegorz Potasiewicz

Zofia Krasińska

Krzysztof Szczepanowicz

Marta Kolasińska-Sojka

Magdalena Elżbieciak-Wodka

Ewelina Jarek

Elżbieta Porębska

Supported by:

Prof. dr hab. Piotr Warszyński


Monday, June 8 Tuesday, June 9 Wednesday, June 10 Thursday, June 11

09:00 ENRIQUE LOPEZ-CABARCOS (Spain) Entrapment of Enzymes and Drugs within Colloidal

Particles for their Application in Health Sciences

REINHARD MILLER (Germany) Dynamics of surfactant adsorption layers at

water/oil interfaces

SZCZEPAN ZAPOTOCZNY (Poland) Micellar multilayer films

ZBIGNIEW ADAMCZYK (Poland) Protein Adsorption – a True Story 10.00

10:30 coffee coffee coffee coffee

11:00 MARIA CHATZIDAKI (Greece)

Formulation and in vitro characterization of W/O colloidal nanodispersions for medical applications

JOOYOUNG WON (Germany) β-lactoglobulin adsorption at the water/oil system

at different pH and ionic strength

MOHMED MULLA (United Kingdom) Preparation of Colloidal Inkjet Inks by Emulsion

Polymerisation

ALEKSANDRA KEZWOŃ (Poland) The effect of the protein hydrolysis on surface

activity and surface dilational rheology of type I collagen

11:20 JOANNA SZAFRANIEC (Poland)

Towards Modern Drug Carriers: Nanocapsules Stabilized by Amphiphilic Copolymers

WEI LIN (Germany) A thermodynamic study of ligand adsorption to

colloidal surfaces demonstrated by means of catechols binding to ZnO QDs

MARÍA DEL MAR FERNÁNDEZ MARTÍNEZ-REY (Spain)

Effect of the pore size of activated carbon nanoparticles on CDLE (capacitive energy

extraction based on double layer expansion)

KIRILL EMELYANENKO (Russia) Stability of nanoscale nonionic films atop of

discretely charged electrolyte interface

11:40 ANNALISA SALVATORE (Italy)

Core-Shell Nanoparticles for DNA Delivery Actuated by Magnetic Fields

EMILY JAMES (United Kingdom) Droplet dynamics: Oil droplet attachment and

spreading on solid substrates

PALOMA ARENAS-GUERRERO (Spain) Anomalous birefringence of planar clay particles

GAMON JACINTHE (France) Quantitative determination of anchoring

molecules on the surface of ZnO particules and effects on electronical properties

12:00 ROBERTA LIUZZI (Italy)

Microstructured fluids at skin interface: biomedical applications

TAMAS ONCSIK (Switzerland) Hofmeister Effects in Colloidal Aggregation in

Aqueous Solutions of Ionic Liquids

SŁAWOMIR DROZDEK (Poland) Co-encapsulation of CdSexS1-x/ZnS quantum dots

with photosensitizers- colloidal stability and optical properties

CHRISTIAN REDEKER (United Kingdom) Surface-confined interactions of

lipopolysaccharide layers

12:20

MARTA KUJDA (Poland) Physicochemical characteristics of albumin dimer

and its monolayers on solid surfaces – electrokinetic studies

REKA TOTH (France) Silica-ceria interactions during polishing

KATARZYNA KUBIAK (Poland) In situ QCM-D investigation of silver nanoparticle

monolayer formation on polycation modified surfaces

SEBASTIAN GÖDRICH (Germany) Nanopatterned charge distributions on

polyetherimide electret-films

12:40 KAROLINA PODGÓRNA (Poland)

Synthesis of polyelectrolyte nanocapsules with iron oxide nanoparticles for magnetic targeting

BRETT SYMONDS (United Kingdom) Quantifying the rainfastness of fluorescently

labelled poly(vinyl alcohol) deposits on vicia faba leaf surfaces via fluorescent microscopy

MICHAEL MCNALLY (United Kingdom) Nanoparticle Production by Atomic Vapour

Deposition on a Liquid Jet

MONICA TONELLI (Italy) Investigation of the structural properties of MgO-

based eco-sustainable cements

13:00

BIAO LU (France) Evaluation of Cytotoxicity of Biorefinery-derived

Amphiphilic Molecules on Multi-scale In-vitro Models

IDO COOPERSTEIN (Israel) UV Curable Oil-in-Water Emulsions for 3D

Functional Printing

lunch lunch 13:20

VIKTORIA OLIYNYK/ANDREY PANKO (Ukraine) Modification of colloid-chemical and balneological properties of therapeutical muds with nano- and

microparticles

VAMSEEKRISHNA ULAGANATHAN (Germany) Effect of pH and salt concentration on velocity of

rising bubbles in Beta-Lactoglobulin solution

13:40

MARTA ŁAPCZYŃSKA (Poland) Synthesis of the PCL nanoparticles containing

neuroprotectants from oil-in-water nanoemulsion by phase inversion emulsification method

ANNA NIECIKOWSKA (Poland) Effect of the bubble dimensions and the shape deformation degrees on its coalescence time at

free water surface


6

14:00 lunch lunch WUGE BRISCOE (United Kingdom) Surfactant layers and polymer brushes under

confinement and shear

BRIAN VINCENT (United Kingdom) Aggregation in Dispersions Containing Mixtures of

Particles 15:00 CHRISTIAN SCHULZ (The Netherlands) Author workshop – how to successfully publish

scientific articles

JAN HUPKA (Poland) Filming of bubbles 15.30

Wieliczka Salt Mine Tour + conference dinner

16:30 JIRI SMILEK (Czech Republic)

Diffusion Techniques as Reactivity Mapping Tool of Biocolloids

ANNA LATOWSKA (Poland) Influence of imidazolium ionic liquids structure on

aggregation behavior of triton X-100 nonionic surfactant

16:50

MOHSEN MOAZZAMI GUDARZI (Switzerland) Direct Force Measurements Involving Positively

and Negatively Charged Colloidal Particles in the Presence of Multivalent Cations

SARA SKOGLUND (Sweden) Effect of Laundry Surfactants on Surface Charge

and Colloidal Stability of Silver Nanoparticles

17:10

SAMUEL SKINNER (Australia) Revisiting Kynchian Analysis of Gravitational and

Centrifugal Settling for Strongly Flocculated Suspensions

KIRSTY STARK (United Kingdom) Metallic Nanoparticles and their interfacial

properties

17:30 ANTONIO CARCIATI (Italy)

Linear viscoelasticity of human blood

SAOIRSE DERVIN (Ireland) Sol-Gel derived nanostructured materials for

thermal insulation applications

17:50 coffee coffee

18:10

LIEN VERMEIR (Belgium) Influence of molecular exchange on the enclosed

water volume fraction of W/O/W double emulsions as determined by low-resolution NMR diffusometry

and T2-relaxometry

TRACEY HO (Australia) Adhesion between Surfaces in the Presence of

Polyelectrolyte Multilayers made with Seaweed Polysaccharides

18:30 JOANNA MIODUSKA (Poland)

Impact of WO3 on surface topography of titania photocatalysts

MARTA ORCZYK (Poland) Effect of triterpenoid and steroidal saponins

on DPPC and cholesterol monolayers

18:50

ANNA WAMKE (Poland) Characterization of Langmuir monolayers formed

by derivatives of fluorinated Polyhedral Oligomeric Silsesquioxanes

ŁUKASZ LAMCH (Poland) Zinc phthalocyanines locaton in methoxy

poly(ethylene oxide) and poly(L-lactide) block copolymer micelles – 1H NMR investigation

19:10

MONIKA ĆWIĘKA (Poland) Nondestructive Characterization of Lysozyme

Layers on Silica Surface using MP-Surface Plasmon Resonance and Quartz Crystal Microbalance

FOTEINI DELISAVVA (Czech Republic) Nanoparticle self-assembly in aqueous solutions;

influence of polymer’s molar mass and gemini surfactants’ spacer length

19:30 poster session poster session


List of Posters

1. Adsorption and Interfacial Phenomena

P1_1 Emelyanenko K., Emelyanenko A., L. Boinovich

Many-body Van der Waals interactions in nanoscale wetting and free films

P1_2 Kairaliyeva T.,

Karbaschi M.,

Taeibi-Rahni M.,

Faraji S.,

Schano

K.H., Aidarova

S.B. and Miller R.

Irregularities of Drop Formation at a Circular capillary

P1_3 Księżniak Katarzyna, Pawlos Witold, Hupka Jan

Effect of selected parameters on flotation recovery in KGHM Polska Miedź S.A

P1_4 Maciejewska Julia, Sadowska Marta, Oćwieja Magdalena , Adamczyk Zbigniew

Nanoparticle monolayers on colloid carrier particles

P1_5 Mould Elizabeth, Briscoe Wuge H.

Foam formation and stability as controlled by surfactant adsorption at the air-water interface

P1_6 Radulova Gergana, Danov Krassimir, Kralchevsky Peter, Petkov Jordan and Stoyanov Simeon

Shear rheology of hydrophobin adsorption layers at oil/water interfaces and data interpretation in terms of

a viscoelastic thixotropic model

P1_7 Setiowati Arima Diah, Saeedi Serveh, Van der Meeren Paul

Improved Heat Stability of Whey Protein Isolate Stabilized Emulsions by Conjugation with Low

Methoxyl Pectin using Dry Heat Treatment

P1_8 Slastanova Anna, Chen Meng, Robles Eric, Briscoe Wuge H.

Surfactants and polymers at air-water interface: from molecular interactions and interfacial structures to

foaming properties

P1_9 Ulatowska Justyna

Adsorption of As(III) from aqueous solutions by fly ash agglomerates: Dynamic study

P1_10 Wojewódka Przemysław, Aranowski Robert, Jungnickel Christian

Asphalt binder - interfacial interactions measurements

P1_11 Yamaguchi Atsushi and Kobayashi Motoyoshi

Zeta potential of colloidal particles covered with proteins

2. Polyelectrolytes, Lipids and Self-Assembly

P2_1 Georgieva Gergana, Anachkov Svetoslav, Kralchevsky Peter, Danino Dganit, Abezgauz Ludmila,

Liebewirth Ingo, Koynov Kaloian

Fatty acid induced growth of giant micelles in ternary surfactant solutions

P2_2 Gorczyca Marcelina, Korchowiec Beata, Korchowiec Jacek, Augustyniak Krzysztof,

Regnouf-de-Vains Jean-Bernard, Rogalska Ewa

Investigation of the interaction between phospholipids and tetra-p-guanidinoethylcalix[4]arene having

antibacterial activity

P2_3 Ho Tracey, Krasowska Marta, MacWilliams Stephanie, Bremmell Kristen, Stringer Damien N.,

Beattie David A.

In Situ Spectroscopic Study of Polyelectrolyte Multilayer Formation and Hydration under Confinement

P2_4 Moreno-Cencerrado Alberto,, Tharad

Sudarat, Iturri Jagoba, Mittendorfer Margareta,

Promdonkoy Boonhiang, Krittanai Chartchai and Toca-Herrera Jose L.

Interaction cytolytic protein Cyt2Aa2 / lipid bilayer: binding and structural changes

P2_5 Mzareulishvili N., Kurtanidze

M., and Rukhadze

M.

Study of Microenvironment of Brij30 Reverse Micelles with Optical Probes

P2_6 Sokolan Nina, Voron’ko Nikolay, Derkach Svetlana

Properties of gelatin–chitosan polyelectrolyte complexes

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P2_7 Tokarczyk Karolina, Jachimska Barbara

Investigation of interaction between PAMAM dendrimers and SiO2 surface

P2_8 Tokarczyk Karolina, Jachimska Barbara

Analysis of the PAMAM dendrimers-BSA complexes adsorption using QCM-D and MP-SPR techniques

P2_9 Wlodek Magdalena, Kolasinska-Sojka Marta, Warszynski Piotr

POPC/POPE lipid vesicles deposition on polyelectrolyte films

3. Nanostructured Materials

P3_1 Joanna Starkie, Dr. Alex Routh

The crystallisation of petroleum diesel and wax anti-settling additives

P3_2 Wąsik Patryk, Redeker Christian, Trask Richard, Briscoe Wuge H.

Hierarchical surface patterns from evaporative drying of nanofluids

4. Biomaterials and Medical Aspects of Colloids

P4_1 Bartlomiej Kalaska, Kamil Kaminski, Emilia Sokolowska, Monika Kujdowicz, Iwona Gawlik,

Krzysztof Szczubialka, Dariusz Pawlak, Maria Nowakowska, Andrzej Mogielnicki

Effects of Cationically Modified Polysaccharide Antidotes for Unfractionated Heparin on Blood Pressure

in Rats

P4_2 Jabłczyńska Katarzyna, Sosnowski Tomasz R.

Polysaccharide nanocomposite particles for aerosol therapy

P4_3 Konczak Lukasz, Panczyk Tomasz

Sidewall Functionalization of Magnetically Triggered Nanocontiner by Colloid Nanoparticles and Amide

Groups. A Molecular Dynamics Study

P4_4 Piotr Krzywda, Wiktor Kasprzyk, Szczepan Bednarz

Novel fluorescent silicone materials

P4_5 Manami Nishiya, Takuya Sugimoto, and Motoyoshi Kobayashi

Electrophoretic mobility of latex particles: Effects of divalent counter-ions

P4_6 Piotrowski Marek, Szczepanowicz Krzysztof, Jantas Danuta, Lasoń Władysław, Warszyński Piotr

Evaluation of neuroprotective action of nanoencapsulated model drugs

P4_7 Sun Qian and Routh Alexander F.

Metal coated colloidosomes and potential applications

P4_8 Świątek S, Loch J.I., Lewiński

K., Jachimska B.

Studies of the functional layers of β-lactoglobulin as biomolecules carriers

P4_9 Varga Noémi, Sebők

Dániel, Dékány Imre

Controlled release of encapsulated neurotransmitters from core-shell nanoparticles

P4_10 Wolski Paweł, Pańczyk Tomasz

Molecular dynamics study of Doxorubicin interaction with suspensions of modified carbon nanotubes

5. Thin Films and Functional Coatings

P5_1 Ćwięka Monika, Jachimska Barbara

The effect of the solution pH on the lysozyme immobilization at the gold surface

P5_2 Gaurav Pathak and Dusko Cakara

Spectroscopic Ellipsometry of PEDOT:PSS thin films at solid/liquid and solid/gas interfaces

P5_3 Janikowska Maria, Korchowiec Beata, Gorczyca Marcelina, Wojszko Kamila, Trojan Sonia,

Henry Max, Rogalska Ewa

Action of selected saponins on biological model membranes

P5_4 Kruk Tomasz, Pajor-Świerzy Anna, Szyk-Warszyńska Lilianna, Socha Robert, Warszyński Piotr

Functional ultrathin polyelectrolyte coatings formed with reduced graphene oxide and Prussian Blue

nanoparticles as a sensitive tool for H2O2 detection

P5_5 Kruk Tomasz, Szczepanowicz Krzysztof, Warszyński Piotr

Multifunctional polyelectrolyte ultrathin coatings for biomedicine applications


9

P5_6 Świątek S., Jachimska B.

Bovine β-lactoglobulin layers on gold surface: Role of ionic strength

P5_7 Trojan Sonia, Ustarbowska Małgorzata, Korchowiec Beata, Janikowska Maria, Joly Jean-Pierre,

Rogalska Ewa

The role of chain unsaturation in the formation of organized molecular films of crown ether - modified

phospholipid monolayers

P5_8 Trojan Sonia, Korchowiec Beata, Joly Jean-Pierre, Korchowiec Jacek, Rogalska Ewa

Interactions of amphiphilic crown ether with metal ions in Langmuir films

6. Modeling of Colloid Systems

P6_1 Enev Vojtěch, Klučáková Martina, Smilek Jiří, Doskočil Leoš

Methylation of humic acids – the impact on the reactivity, chemical composition and properties of HAs

studied by spectrometric techniques

P6_2 Krasińska Zofia, Jamróz Dorota

Molecular Dynamics modelling of interaction between heparin and its potential neutralizer P6_3 Mikulcová Veronika, Kašpárková Věra, Pohlodek Jiří

Undecane-in-water Emulsions prepared by the Phase Inversion Temperature Method


10

Abstracts


11

Invited lectures

Enrique Lopez-Cabarcos Entrapment of Enzymes and Drugs within Colloidal Particles for

their Application in Health Sciences

Christian Schulz Author workshop – how to succesfully publish scientific articles

Reinhard Miller Dynamics of surfactant adsorption layers at water/oil interfaces

Jan Hupka Filming of bubbles

Szczepan Zapotoczny Micellar multilayer films

Wuge H. Briscoe Surfactant layers and polymer brushes under confinement and shear

Zbigniew Adamczyk Protein Adsorption – a True Story

Brian Vincent Aggregation in Dispersions Containing Mixtures of Particles


12

Entrapment of Enzymes and Drugs within Colloidal Particles for their

Application in Health Sciences

E. Lopez Cabarcos

Department of Physical Chemistry II, Faculty of Pharmacy, Complutense University of

Madrid, 28040 Madrid, Spain

* - [email protected]

The use of colloidal particles in medical devices and pharmaceutical technology is just

beginning and its development can be spectacular in the coming years. In this contribution I

will present examples of the potential of colloidal systems as matrices for immobilizing

substances such as enzymes and drugs.

First, I will describe the entrapment of redox enzymes within microgels with the aim

to use them as biological component in biosensors. The polymeric microgels supply an

excellent matrix for the immobilization of enzymes since they provide an appropriate

environment for the enzyme and their porosity can be modified through the amount of

crosslinker used in their synthesis, and this fact is very important for entrapment of enzymes

of with different molecular weight. Furthermore, the composition and the surface of the

microgels can be modified to get rid of substances that produce interference in the enzymatic

response and are present in complex samples such as blood and serum. One important

property of these biosensors is their remarkable stability.

Second, the use of colloidal carriers made of biocompatible polymers is an alternative

for improving the transport of hydrophobic drugs across biological surfaces. In this work we

report the synthesis, characterisation, and possible application as drug-delivery system

magnetically triggered, of hybrid microparticles formed by magnetic nanoparticles embedded

within poly(ε-caprolactone). The magnetism of the microparticles permits their localisation

within the body using Magnetic Resonance Imaging and the biodegradable polymer layer

allows entrapping drugs that can be released when temperature increases.

Keywords: microgels, biosensors, hybrid microparticles, biocompatible polymer, drug

delivery system, magnetic resonance imaging, poly(ε-caprolactone).


13

Author workshop – how to successfully publish scientific articles

Christian Schulz (Associate Publisher, Elsevier)

This workshop is for early career scientists looking for assistance in identifying, preparing

and submitting research articles to an academic journal. The workshop will provide advice on

best practices, top tips, ethics, the review process and other important considerations.

Are you:

A PhD student interested in publishing your first scientific or medical article?

A young PostDoc who wants to understand why articles are rejected?

A researcher who wishes to know what goes on behind the scenes in scientific

publishing?

Questions addressed at this workshop will include:

What do I need to consider when preparing my article?

How do I write an article for a specific journal?

What happens after I submit my article to a scientific journal?

How does the peer-review process work?

How do I choose a suitable journal?

Which tools are available during the writing process?

Or any other questions you might have!

Visit www.elsevier.com/authors for more information about publishing your article with

Elsevier.


14

Dynamics of surfactant adsorption layers at water/oil interfaces

J. Won, V. Ulaganathan, T. Kairaliyeva, M. Karbaschi and R. Miller*

Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1,

14424 Potsdam, Germany


The characterization of liquid/liquid interfaces is generally similar to that of liquid surfaces,

with some peculiarities from an experimental as well as theoretical point of view. The work

horse for measuring the interfacial tension and dilational rheology of interfacial layers is the

drop profile analysis tensiometry (Fig. 1). This technique allows studying the formation of

adsorption layers over a rather broad time range and provides also data at very large

adsorption time, which are required for constructing the equilibrium adsorption isotherm.

There are unfortunately some systems which cannot be studies with this profile tensiometry –

systems in which both liquids have the same density. In these cases the only feasible

technique is capillary pressure tensiometry (Fig. 2), which also works under weightlessness

conditions in space.

Using this experimental technique adsorption layers have been studied of various series of

surfactants, of which the cationic surfactants alkyl trimethyl ammonium bromide (CnTAB)

and the sodium alkyl sulphates (SCnS) are in the focus of the presented work here. It will be

shown that at the interface between the aqueous surfactant solution and alkane as the oil phase

the adsorption of the surfactant molecules is in competition to the alkane molecules. For

comparison, also data for the solution/air interface are discussed. It turns out that the interface

between the aqueous solution and an alkane saturated air as the second fluid phase represents

an intermediate situation between the two interfaces water/air and water/alkane (Fig. 3).

Fig. 1 Pendent drop used

for shape analysis

tensiometry

Fig. 2 Spherical drop for

measuring the capillary

pressure

Fig. 3 Interfacial tension isotherms for SDS

measured at the water/air, water/hexane vapor, and

water/hexane interfaces

mailto:[email protected]


15

Filming of bubbles

Jan Hupka

Gdansk University of Technology, Faculty of Chemistry, Department of Chemical

Technology, ul. Gabriela Narutowicza 11/12, 80-233 Gdansk


Key words: oily bubbles, surfactants, flotation, bitumen, precursor film

Fundamental and practical aspects of bubble filming with an oil phase are presented with

respect to flotation of bitumen droplets and the mechanism of bubble generation in porous

media. Positive spreading coefficient is required for bubble filming. It can be easily controlled

by addition of surfactants to the oil phase. The attachment of bitumen to a gas bubble and the

kinetics of bitumen spreading over the bubble surface should be rapid in order to guarantee an

efficient separation process. However, the experimental data have shown that transfer of

viscous bitumen from a quartz surface to an air bubble is relatively slow at room and

moderate temperatures. It was observed, that formation of thin bitumen films (precursor

films) preceded a bulk bitumen layer. The bulk layer spread at the bubble surface with a

velocity of an order of magnitude less than the velocity of the precursor film. Gas bubble

attachment mechanism to bitumen surface, spreading of bitumen on a gas bubble and the

release of bitumen-enveloped bubbles from mineral particles may weigh heavily on process

efficiency in multiple phase systems.



16

Micellar multilayer films

Szczepan Zapotoczny

Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow, Poland


Layer-by-layer (LbL) electrostatic self-assembly deposition method of oppositely charged

polyelectrolytes, is one of the most intensively investigated technique for fabrication of

ultrathin films. Originally introduced by Decher as “fuzzy nanoassemblies” LbL films exhibit

relatively high homogeneity as polymer chains forming adjacent layers highly interpenetrate.

However, for some possible applications (e.g. energy and/or electron transfer), more

stratified, discrete structures are deserved.

Here a novel approach is described to stratify multilayer polymer films by employing

amphiphilic polyelectrolytes as building blocks. These polyelectrolytes form well-define

micellar structures in aqueous solution with alkyl, aryl and/or perfluoroalkyl cores that are

also stable in the films after deposition. Such structured films with hydrophobic nanodomains

served as host matrices for photoactive probes enabling studies of photoinduced

electron transfer (PET) and excitation energy transfer

(EET) (fig. 1). The micellar structures of the films was

confirmed using atomic force microscopy and their

stratification was indicated by following EET between

the energy donors and acceptors embedded within the

micellar layers with varying distance using fluorescence

microscopy. Further characterization of the films was

performed by means of spectroscopic ellipsometry and

contact angle measurements.

Fig. 1 Schematic model of photoinduced electron or

energy transfer between appropriate donor and acceptor

molecules embedded in the neighbouring layers of a

micellar LbL film.

Literature:

1. M. Kopeć, W.Niemiec, A. Laschewsky, M. Nowakowska, S. Zapotoczny, 2014,

„Photoinduced Energy and Electron Transfer in Micellar Multilayer Films", J. Phys.

Chem C, 118, 2215.

2. M. Kopeć, Ł. Łapok, A. Laschewsky, S. Zapotoczny, M. Nowakowska, 2014,

"Polyelectrolyte multilayers with perfluorinated phthalocyanine selectively entrapped

inside the perfluorinated nanocompartments", Soft Matter, 10, 1481.

3. M. Kopeć, T. Kruk, S. Zapotoczny, A. Laschewsky, S. Holdcroft, M. Mac, M.

Nowakowska, 2012, „Photoinduced electron transfer in multilayer films composed of

conjugated polyelectrolyte and amphiphilic copolymer hosting electron acceptor

molecules", J. Mat Chem., 22, 140.

4. W. Niemiec, S. Zapotoczny, K. Szczubiałka, A. Laschewsky, M. Nowakowska, 2010,

"Nanoheterogeneous multilayer films with perfluorinated domains fabricated using layer-

by-layer method", Langmuir, 26, 11915. Acknowledgements:

Polish Ministry of Science and Higher Education „Ideas Plus” program.



17

Surfactant layers and polymer brushes under confinement and

shear

Wuge H. Briscoe

School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS, UK


It is very common in technological applications and biological systems that surfaces come to

close proximity or intimate contact. These surfaces are often decorated with polymers and

surfactants (or lipids), thereby tailoring surface properties and facilitating desired surface

interactions. The efficacy of these processes depends intricately on the structural

characteristics of the polymer and surfactant molecules present on the surface.

Using a version of the surface force apparatus, we have measured normal and, in particular,

shear forces between a pair of surfaces bearing two distinct surface structures in aqueous

media: polymer brushes and surfactant bilayers. Their effectiveness in reducing friction will

be critically compared in this talk, in particular the unifying feature of fluid hydration layers

about charged species in aqueous media. The implications of our results to the lubrication

process in biological living systems will also be discussed.

Literature:

1. Chen, M, Briscoe, WH, Armes, S & Klein, J 2009, ‘Lubrication at physiological pressures by

polyzwitterionic brushes’. Science, vol 323, pp. 1698 – 1701

2. Briscoe, WH, Titmuss, S, Tiberg, F, Thomas, R, McGillivray, D & Klein, J 2006, ‘Boundary

lubrication under water’. Nature, vol 444 (7116), pp. 191 - 194



18

Protein Adsorption – a True Story

Zbigniew Adamczyk

Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences,

ul. Niezapominajek 8, 30-239 Cracow, Poland


Protein adsorption studies are often plagued by many misinterpretations and confusions

stemming from the abandonment of basic physics. Therefore, in this lecture, the thesis of a

dominant role of Coulomb electrostatic interactions in protein adsorption phenomena is

formulated. In order to prove this, a combination of theoretical and direct, in situ experimental

methods are implemented. In theoretical modeling emphasis is focused on coarse-grained

methods, exploiting the efficient bead models of protein molecules. Using this approach basic

hydrodynamic properties of protein molecules, such as the diffusion tensor, hydrodynamic

diameters and intrinsic viscosities are calculated using the linear Stokes equation.

Additionally, the surface blocking functions and jamming coverages for such model shapes

are determined using the random sequential adsorption (RSA) modeling. Knowing the

jamming coverage and blocking functions, boundary conditions for bulk transport equations

are formulated. Solutions of these equations for the convection and diffusion-controlled

transport are discussed. The theoretical results are exploited for the interpretation of protein

adsorption kinetics studied by AFM, QCM and in situ electrokinetic methods (streaming

potential, electrophoresis). Application of such hybrid approaches enabled one to

quantitatively determine protein adsorption mechanisms on various substrates including

polymeric microparticles (polystyrene latexes). It is shown that protein adsorption is mainly

governed by the discrete electrostatic interactions among ion pairs with negligible role of

other interaction types. Anomalous adsorption of proteins at surfaces bearing like surface

charges, where the classical, mean-field theories fail, is explained in terms of heterogeneous

charge distributions on protein molecules. By exploiting these experimental data, the validity

of the coarse grained approaches combined with solutions of the continuity equation for

quantitatively predicting protein adsorption kinetics is confirmed.

Acknowledgements: This work was financially supported by the Research Grants: POIG 01.01.02-

12-028/ 09-00 and the NCN Grant UMO-2012/07/B/ST4/00559.


19

Aggregation in Dispersions Containing Mixtures of Particles

Professor Brian Vincent

University of Bristol, School of Chemistry, Bristol, BS8 1TS, UK


Many colloidal systems industrially consist of mixtures of particles. This introduces new

concepts, and indeed even new types of interparticle forces, compared to dispersions of single

particles. Over the years my group in Bristol has studied different kinds of mixed particle

systems, mainly from the dispersion stability standpoint. This seminar will include a mixture

of earlier and more recent studies in this area, and will attempt to draw together some of the

observations we have made. For binary mixtures of two particle types a recurring theme will

be that the overall stability of the system to aggregation depends on two main factors: the

ratio of the particle sizes, and the ratio of the particle concentrations.

Three types of system will be considered. The first is the classical case of mixtures of

particles of opposite charge. Here the primary driving force for (hetero-) aggregation is long-

range electrostatic attraction (at least at low ionic strengths). Where the particles are of similar

size then fractal hetero-aggregate structures are obtained, with fractal dimensions generally

lower than for homo-aggregates [1]. For systems where the particle size ratio is much greater

than one, then one may consider this as a system where the smaller particles “adsorb” onto the

larger, oppositely-charged particles [2-4]. The particle concentration ratio then controls

whether one obtains particle bridging aggregates or complete coverage of the large particles

by the small ones, preventing further aggregation.

Similar considerations apply when the nature of the attractive force is changed to that between

two sets of particles, each carrying a different adsorbed (or preferably grafted) polymer layer,

but where the equivalent homopolymers (in solution) form coacervate mixtures. A good

example here is mixtures of poly(acrylic acid) [PAA] or poly(methacrylic acid) [PMMA], and

poly(ethylene oxide) [PEO] in water at low pH (below about pH 4.5). These polymers form

coacervates as a result of strong H-boding between the ether oxygen of the PEO chains and



20

the hydrogen of the carboxylic acid groups in the PAA or PMAA chains. At high pH no such

H-bonding can occur, because of ionisation of the carboxylic acid groups; then two polymers

phase separate into two phases, each rich in one of the polymers, rather than coacervate. Here

I will discuss the interactions between two sets of acrylate particles, one having grafted PEO

chains, and the other having grafted PMMA chains [5]. The main technique used in this work

has been controlled stress rheology [6].

The third mixed-particle system, which was more recently explored in my group, is rather

different. Here the main driving force for particle aggregation is the depletion attraction

caused by the addition of non-adsorbing (i.e. free) polymer is solution. Many studies of single

particles plus free polymer systems have been explored, but we were the first (I believe) to

study mixtures of two particles, plus free polymer. The depletion interaction is usually

relatively weak, and leads to reversible aggregation, and colloidal phase separation, rather

than the classical aggregation behaviour observed in systems with stronger interparticle

attraction forces. The phase behaviour in single particle systems is relatively well-understood,

so it was of interest to explore the phase behaviour in mixtures of binary particles, plus free

polymer. Of particular interest was the case where the two particles are of different sizes, one

much larger then the radius of gyration of the free polymer and one where the particle size

was similar to it [7,8].

Literature:

1. Snoswell, Rogers, Howe and Vincent, Langmuir, 2005 21 11439

2. Tadros, Vincent & Young, Faraday Disc. Chem. Soc., 1978 74 337

3. Luckham, Tadros & Vincent, Colloids Surfaces, 1983 6 101

4. Harley, Thompson & Vincent, Colloids & Surfaces, 1992 62 163

5. Cawdery, Milling & Vincent, Colloid Surfaces, 1994 272 1273

6. Starck & Vincent, Langmuir 2006 22 5294

7. Zhou, van Duijneveldt & Vincent, Langmuir 2010 26 9397

8. Zhou, van Duijneveldt & Vincent, Phys. Chem. Chem. Phys, 2011 13 11


21

Oral presentations


22

Formulation and in vitro characterization of W/O colloidal

nanodispersions for medical applications

Chatzidaki D. Maria

1,2*, Damien Amadei

3, Vassiliki Papadimitriou

1, Julien Monteil

3,

Fernando Leal-Calderon3, Frédéric Carrière

4, Xenakis Aristotelis

1,2.

1Institute of Biology Medicinal Chemistry & Biotechnology, National Hellenic Research

Foundation, Athens, Greece 2MTM, Faculty of Science and Engineering, Örebro University, Sweden

3Laboratoire Chimie et Biologie des Membranes et des Nanoobjets, Univ. Bordeaux, France

4Laboratoire d’Enzymology Interfacial and Physiology de la Lipolysis CNRS-Aix-Marseille

Université Marseille, France


For the last decades, there has been a significant increase of interest of medical industries for

W/O nanodispersions. More specifically, their unique ability to form nanostructures and

effectively encapsulate bioactive molecules, make them attractive biomaterials. In this

respect, W/O emulsions and microemulsions were successfully formulated using

biocompatible components and a relatively low percentage of emulsifiers1. Hydrophilic

bioactive molecules such as hydroxytyrosol (HT)2, an antioxidant of Extra Virgin Olive Oil

(EVOO) was effectively encapsulated. Structural characterisation of the systems in terms of

viscosity, Dynamic Light Scattering (DLS) and Electron Paramagnetic Resonance (EPR)

spectroscopy was measured. Moreover, the bioactive molecules’ release was qualitatively

observed by measuring the scavenging activity of HT towards galvinoxyl stable free radical3.

Following, a “two step” in vitro digestion model4 was introduced in order to investigate the

behavior of the systems in the absence and presence of HT under gastrointestinal conditions

and their potential interactions with gastric and pancreatic lipases.

Finally, in order to check the inhibition effect of HT on colon cancer, cell line BRAF V600E

mutant was treated with the proposed microemulsions used as effective vehicles of HT.

Literature:

1. Amadei, D.; Chatzidaki, M. D.; Devienne, J.; Monteil, J.; Cansell, M.; Xenakis, A.; Leal-Calderon,

F. 2014. Low shear-rate process to obtain transparent W/O fine emulsions as functional foods.

Food Res. Int., 62, 533-540.

2. Fernandez-Bolanos, J. G.; Lopez, O.; Fernandez-Bolanos, J.; Rodriguez-Gutierrez, G. 2008.

Hydroxytyrosol and derivatives: isolation, synthesis, and biological properties. Curr. Org. Chem.,

12 (6), 442-463.

3. Papadimitriou, V.; Sotiroudis, T. G.; Xenakis, A.; Sofikiti, N.; Stavyiannoudaki, V.; Chaniotakis,

N. A. 2006. Oxidative stability and radical scavenging activity of extra virgin olive oils: an electron

paramagnetic resonance spectroscopy study. Anal. Chim. Acta, 573-574, 453-8.

4. Fernandez, S.; Chevrier, S.; Ritter, N.; Mahler, B.; Demarne, F.; Carrière, F.; Jannin, V. 2009. In

vitro gastrointestinal lipolysis of four formulations of piroxicam and cinnarizine with the self

emulsifying excipients Labrasol® and Gelucire® 44/14. Pharm. Res., 26 (8), 1901-1910.



23

Towards Modern Drug Carriers: Nanocapsules Stabilized by

Amphiphilic Copolymers

Szafraniec Joanna

1*, Janik Małgorzata

1, Gumieniczek Elżbieta

1, Zapotoczny Szczepan

1

1Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow, Poland


The development of the techniques of preparation of nanocontainers has attracted particular

attention in recent years. Numbers of works have been directed towards controlled release

strategies to achieve high efficiency of encapsulation by minimizing the degradation and

prolonging time of release. This approach is particularly important in pharmaceutical

applications, especially concerning liphophilic active substances. Since the reservoir systems

are expected to have desirable properties it is important to choose appropriate material for

their preparation.

In this work we present studies on surfactant-free technique of preparation of nanocapsules on

liquid cores. Emulsion droplets were stabilized by amphiphilic graft polymers that anchored

the hydrophobic side chains in the oil droplets. Formation of such nanocapsules was

confirmed by dynamic light scattering measurements as well as electron microscopies (SEM

and cryo-TEM). Obtained capsules shown long-term stability which was further improved by

formation of multilayer shells via “layer-by-layer” technique relying on consecutively

alternating adsorption of oppositely charged polyelectrolytes. Moreover, they were able to

effectively encapsulate hydrophobic fluorescence probes which enable application in the field

of nanodelivery systems.1

Literature:

1. Szafraniec Joanna, Janik Małgorzata, Odrobińska Joanna, Zapotoczny Szczepan, 2015.

Nanocapsules Templated on Liquid Cores Stabilized by Graft Amphiphilic Polyelectrolytes.

Nanoscale. DOI: 10.1039/C5NR00064E.

Acknowledgements:

J. S. acknowledges the financial support from the project Interdisciplinary PhD Studies "Molecular

sciences for medicine" (co-financed by the European Social Fund within the Human Capital

Operational Programme).



24

Core-Shell Nanoparticles for DNA Delivery Actuated by Magnetic

Fields

Annalisa Salvatore*, Debora Berti, Massimo Bonini, Piero Baglioni

Department of Chemistry and CSGI, University of Florence, via della Lastruccia 3, 50019

Sesto Fiorentino, Italy


One of the major areas of research in nanomedicine is the design of drug delivery systems

with remotely controllable release of the drug. Despite the enormous progress in the field, this

aspect still poses a challenge, especially in terms of selectivity and possible harmful

interactions with biological components other than the target. We report an innovative

approach for the controlled release of DNA, based on clusters of core–shell magnetic

nanoparticles [1].The coating of magnetic nanoparticles with an external inert shell, such as

gold, has been proposed in order to add further properties (enhance biocompatibility,

protection of the magnetic core against oxidation) to the nanoparticles, without modifying

their superparamagnetic behaviour. Moreover, gold provides an optimized and well-

established platform for chemical functionalization, through the attachment of thiolated

biomolecules, such as DNA. Another possible strategy is to connect DNA by click-chemistry

methods.

The versatility of DNA as a block molecule for nanotechnologies, lies in the unique

recognition selectivity, modularity, molecular recognition properties towards biological

targets, thermal responsitivity, which can be coupled to the optical, thermal, electric

properties of inorganic nanomaterials.

We have accomplished the conjugation of Au@Fe3O4 with a thiolated single-stranded

oligonucleotide, whose pairing with a half-complementary strand in solution induces

clusterization. The application of a low frequency (6 KHz) alternating magnetic field induces

DNA melting with the release of the single strand that induces clusterization. The release and

delivery of the staple is based on the hyperthermic heating of clusters of DNA coated

magnetic NPs [2].

The possibility of steering and localizing the magnetic nanoparticles, and magnetically

actuating the DNA release discloses new perspectives in the field of nucleic-acid based

therapy.

Literature: 1. M. Bonini, D. Berti, P. Baglioni, Nanostructures for magnetically triggered release of drugs and

biomolecules, CURRENT OPINION IN COLLOID & INTERFACE SCIENCE, 2013, 18, 5, 459-

467.

2. M. Banchelli, S. Nappini, C. Montis, M. Bonini, P. Canton, D. Berti and P. Baglioni, Magnetic

nanoparticle clusters as actuators of ssDNA release, Phys. Chem. Chem. Phys., 2014,16, 10023-

10031


25

Microstructured fluids at skin interface: biomedical applications

Liuzzi Roberta

1,2*, Carciati Antonio

1,2, Caserta Sergio

1,2, Guido Stefano

1,2

1Department of Chemical, Materials and Production Engineering, University of Naples

“Federico II”, P.zzle Tecchio 80, 80125 Naples 2CEINGE- Advanced Biotechnologies, Via Sergio Pansini 5, 80131 Naples


In the last years, multiphase fluids, such as emulsions, have been investigated as optimal

dermal or transdermal vehicles for drug permeation into the skin. Several cosmetic and

pharmaceutical products are based on emulsions. Surfactants can be added to reduce

interfacial tension of the droplets and to improve the stability of the final products1. The

morphology of these multiphase fluids can strongly influence the capacity of the dispersed

phases, typically containing the active principles, to penetrate and to interact with skin layers.

Emulsion morphology can be affected by the process flow, or even by the stress induced

during the application of the product. For example the rubbing of a lotion can lead very high

shear stresses on the fluid, causing drop deformation and break-up2. On the other hand, skin is

a very complex structure, that acts as barrier against the penetration of external compounds3

(Fig1). The comprehension of the effective interaction mechanisms between multiphase fluids

and skin by which these formulations work, is today argument of notable interest and not

totally clear. The aim of this work is to propose innovative methodologies to investigate the

penetration of different compounds thorough skin biopsies or model systems by time-lapse

confocal microscopy and images analysis. Confocal laser scanning microscopy can be a

valuable tool for the investigation of the dynamic evolution of the transport process.

Localization of a permeating molecule is possible by using a fluorescent tracers specific of

one of the emulsion components. Our study can provide information useful for a fine tuning

of drug posology and formulation, in order to optimize delivery efficiency for different

applications.

Fig. 1 Autofluorescence of skin samples: arm (a-c), frontal site (b)

Literature:

1. M. J. Lawrence and G. D. Rees. 2000. Microemulsion-based media as novel drug delivery systems.

Advanced drug delivery reviews 45 (1), 89-121.

2. S. Caserta,S. Reynaud,M. Simeone, S. Guido. 2007. Drop deformation in sheared polymer blends.

Journal of Rheology 51. 761-774.

3. K. Moser, K. Kriwet, A. Naik, Y. N. Kalia and R. H. Guy. 2001. Passive skin penetration

enhancement and its quantification in vitro. European journal of pharmaceutics and

Biopharmaceutics 52 (2), 103-112.


26

Physicochemical characteristics of albumin dimer and its

monolayers on solid surfaces – electrokinetic studies

Marta Kujda

1*, Zbigniew Adamczyk

1

1Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences,



Adsorption of globular proteins on solid surfaces has significance in biochemistry,

biotechnology and bioengineering for preparing biosensors, biomaterials and immunological

assays. In these processes, various albumins are often used. Human serum albumin (HSA) is a

monomer protein, which is present at a high concentration in the blood. It plays an important

role as a carrier of fatty acids, hormones, vitamins and drugs. The use of albumin as a carrier

for drugs has been systematically studied. However, the administered HSA is readily

eliminated from blood circulation under pathological conditions. In order to solve this issue it

was suggested to increase a molecular size of HSA and prepare synthetic cross-linked dimeric

form. Therefore, an original objective of this work was the synthesis, thorough

physicochemical characteristics and determination of ligand binding properties of albumin

dimer using electrokinetic methods. The physicochemical characteristics of the monomer and

the synthesized albumin dimer such as diffusion coefficient, hydrodynamic diameter,

electrophoretic mobility and zeta potential have been determined as a function of pH and

ionic strength using the dynamic light scattering (DLS) and laser Doppler velocimetry (LDV)

methods. However, despite essential significance, adsorption of these proteins at solid

surfaces has not been studied in a systematic way. Protein adsorption was carried out for the

range of ionic strength 10-2

to 0.15 M NaCl at pH 3.5. It was determined that maximum

coverage of albumins increases as a function of ionic strength. The study of desorption

process confirmed the stability of monolayers in various conditions of pH. Therefore, in the

next stage, monolayers of albumin dimer on negatively charged mica surface were prepared

and characterized using the in situ streaming potential method. These stable albumin

monolayers were used to perform studies on ligand (such as ions, antioxidants) bindings

properties using the precise electrokinetic method. This technique has great advantages in

comparison to standard binding assays (ex. ELISA test). The obtained results revealed unique

physicochemical properties of HSA dimer and its monolayers and can be used in numerous

practical applications in drug and biomaterials design.

Acknowledgements: This work was supported financially by the Polish National Science Centre,

grant no. PRO-2012/07/N/ST5/02219, Smoluchowski Scholarship from KNOW Leading National

Research Centre and project Doctus.


27

Synthesis of polyelectrolyte nanocapsules with iron oxide

nanoparticles for magnetic targeting

K.Podgórna1

, K.Szczepanowicz1

, A.Karabasz2

, M.Bzowska2, J.Korecki

1

, M.Bielańska1

,

P.Warszyński1


ul. Niezapominajek 8, 30-239 Cracow, Poland 2Faculty of Biochemistry, Biophysics, and Biotechnology of the Jagiellonian Uniwersity,

Gronostajowa 7, 30-387 Krakow, Poland


Magnetic vehicles became highly promising for delivery of therapeutic actives as they

can be targeted to selected pathologically changed tissues/cells through the application of a

magnetic field gradient. That should not only significantly decrease deleterious side effects,

but also may drastically enhance therapy efficiency. Various types of carries were proposed

for targeted drug release. One of them, are polyelectrolyte nanocapsules, prepared by layer by

layer technique. It is a convenient method to form multilayer coatings on colloidal cores by

sequential adsorption of charged species like polyelectrolytes, nanoparticles (e.g. magnetic

nanoparticles), proteins, organic molecules.

The aim of this work was preparation and characterization of magnetically responsive,

loaded nanocapsules based on a liquid core encapsulation by polyelectrolyte (PE) multilayer

adsorption. Nanocapsules were prepared by LBL method using biocompatible

polyelectrolytes (Poly L-lysine and Poly Glutamic acid), with low-energy

microemulsification. Two approaches were proposed for incorporation of magnetic particles

with different sizes within nanocapsules. Iron oxide nanoparticles were encapsulated in the

liquid core or they were embedded into the polyelectrolyte multilayer shell. Moreover, the

model drug (β carotene) was successfully encapsulated in liquid core. Size of obtained

magnetic capsules were investigated using Dynamic Light Scattering and Nanoparticles

Tracking Analysis. Moreover morphology of magnetic carriers were investigated by Cryo-

Scanning Electron Microscopy. Toxicity test of synthesized magnetic nanocapsules were

performed. Additionally, magnetic properties of synthesized nanocapsules were examined

using Mossbauer Spectroscopy. This magnetically responsive drug nano delivery system may

be a promising platform for future targeted therapies or other biomedical applications.

mailto:*[email protected]


28

Evaluation of Cytotoxicity of Biorefinery-derived Amphiphilic

Molecules on Multi-scale In-vitro Models

Lu Biao1*, Miao Yong

2, Chagnault Vincent

2, Grand Eric

2, Wadouachi Anne

2, Postel Denis

2,

Egles Christophe1, Pezron Isabelle

3, Vayssade Muriel

1

1Sorbonne Universités, Université deTechnologie de Compiègne, BMBI UMR CNRS 7388,

France 2Université de Picardie Jules Verne, LG2A CNRS FRE 3517, France

3Sorbonne Universités, Université deTechnologie de Compiègne, EA TIMR 4297, France


Nowadays, a wide variety of new molecules can be synthesized from plants [1,2]. Among

them, the family of glyco-derived molecules, which are considered as alternatives to chemical

surfactants, due to their relatively high biodegradability and biocompatibility, exhibit

interesting properties both in terms of their self-assembly and their ability to induce biological

responses.

In this study, we have screened synthesized glycolipids according to their solubility in

aqueous phase. Four pre-selected molecules, with a C8 chain linked to a glucose or maltose

head through an amide functional group, either under the form of carbamoyl (carbohydrate

scaffold bearing the carbonyl) or alkylcarboxamide (the alkyl chain bearing the carbonyl),

were then dissolved in water for surface tension measurements. To evaluate the cytotoxicity

of these molecules on cells and tissues, 3 in-vitro models were established: i) Monolayer

model, L929 cells were seeded in a culture plate to form a single cell layer; ii) 3D cell culture

model, L929 cells were embedded into collagen gel; iii) Commercialized HSE (Human Skin

Equivalent), differentiated human keratinocytes were cultured at air-liquid interface.

Results show that the synthesized glycolipids, Glu1amideC8, Glu6amideC8, Glu6amideC8’

and Mal1amideC8 can reduce the surface tension of water solution to the same level as

Tween 20 and Hecameg do. In the meantime, Glu1amideC8, Glu6amideC8’ and

Mal1amideC8 present less cytotoxicity effects on L929 cells both in the monolayer model and

the 3D model than Tween 20 and Hecameg. All synthesized molecules have no obvious

influence on cell metabolic activity in HSE. It indicates their potential of being used for

biological related products.

This work was performed, in partnership with the SAS PIVERT, within the frame of the

French Institute for the Energy Transition (Institut pour la Transition Energétique (ITE)

P.I.V.E.R.T. (www.institut-pivert.com) selected as an Investment for the Future

(“Investissements d’Avenir”). This work was supported, as part of the Investments for the

Future, by the French Government under the reference ANR-001.

Literature:

1. Krister Holmberg, Natural surfactants, Current Opinion in Colloid & Interface Science, 2001, 6(2),

p. 148-159.

2. Valery M. Dembitsky, Astonishing diversity of natural surfactants: 1. Glycosides of fatty acids and

alcohols, Lipids, 2004, 39(10), p. 933-953.

Acknowledgements:

Acknowledgements to the Chinese Scholarship Council for the financial support of Biao Lu PhD

grant.


29

Modification of colloid-chemical and balneological properties of

therapeutical muds with nano- and microparticles

V.O. Oliynyk

1*, A.V. Panko

1, O.M. Nikipelova

2

1F.D.Ovcharenko Institute of biocolloid chemistry

2Ukrainian Research Institute of Medical Rehabilitation and Balneology


An influence of modification additives on the basis of montmorillonite and calcium carbonate

[1, 2] containing nano- and microparticles on colloid-chemical and balneological properties of

peloids (therapeutical muds) was investigated with rheological, SEM, XRD, chemical and

medico-biological methods. It was showed that such additives allow increasing therapeutical

mud medicobiological activity in 2-3 times in established conditions of their modification

influence on peloids. It was established that besides of modificators’ adsorption, ion-

exchanging characteristics and ability to isothermal or nanochemical recondensation in

laminar or convective mixing mode, their positive influence on therapeutical mud properties

is specified with processes of their interaction with peloid microorganisms. They promote

slow-down of nanoparticle growth process caused by isothermal Van der Waals

recondensation.

Literature:

1. Panko A.V., Ablets E.V., Kovzun I.G., Protsenko I.T., Ulberg Z.R., Nikipelova E.M. 2014.

Biocolloid nanoparticle influence of CaCO3 on medicoendoecological peloid properties. CERECO-

2014: Proceedings of the Conference: P.152-158

2. Olejnik V.A., Panko A.V., Nikipelova E.M., Alekseenko N.A., Kovzun I.G. 2012. Influence of

nanomaterials on biological activity of marine pelagic sediments (peloids). Proc. of the

International Conference Nanomaterials: Applications and Properties. Vol. 1, № 2: 02NNBM16

(3pp).


30

Synthesis of the PCL nanoparticles containing neuroprotectants

from oil-in-water nanoemulsion by phase inversion emulsification

method

Łapczyńska M.

1*, Piotrowski M.

1, Jantas D.

2, Szczepanowicz K.

1, Warszyński P.

1


ul. Niezapominajek 8, 30-239 Cracow, Poland 2Department of Experimental Neuroendocrinology Polish Academy of Sciences,

Smętna 12, 31-343 Cracow, Poland


Alzheimer’s and Parkinson’s are called diseases of civilization and are strongly related

with rapidly ageing of population. Prevention and treatment of stroke and neurodegenerative

diseases are major and unresolved problems of contemporary medicine. Despite of the

progress in understanding of molecular mechanisms of neuronal injury and preventing them,

only few neuroprotective substances are used in the clinic. However, their efficiency in the

treatment is not satisfactory. One of the major limitations is an inefficient delivery of

neuroprotective drugs by the blood-brain barrier (BBB) to the affected part of the brain.

Therefore, the main aim of the research is to develop a new strategy of delivery of

neuroprotectants by the nanocarriers, which are able to cross BBB without imposing side

effect on its normal function.

In the present work we were focused on synthesis of PCL (polycaprolactone)

nanoparticles containing active neuroprotectants (Polydatin and/or Resveratrol) as well as

model drugs (Cumarin-6 and/or Clozapine). This neuroprotectant loaded PCL nanocarriers

were prepared from oil-in-water nanoemulsion by phase inversion emulsification method. All

nanocarriers were characterized by size, size distribution, zeta potential and imaged by SEM.

Biotest of the synthsized nanosystems and their stability in the simulated body fluid (SBF)

was also determined.

Acknowledgements: This study was supported by the Norwegian Financial Mechanism grant Pol-

Nor/199523/64/2013 NanoNeucar and M. Smoluchowski scholarship, KNOW.


31

Diffusion Techniques as Reactivity Mapping Tool of Biocolloids

Smilek Jiří

1*, Sedláček Petr

1, Klučáková Martina

1

1Brno University of Technology, Faculty of Chemistry, Materials Research Centre, Purkyňova

464/118, 61200 Brno, Czech Republic


One of the most important gaps in the knowledge of biocolloids or biopolymers is the study

on their reactivity. Simple universal reactivity mapping tool for these compounds is needed.

Major gaps in knowledge of biocolloids are still found in their reactivity and barrier properties

in natural dynamic systems. To overcome the problem with study on reactivity, new universal

reactivity-mapping tool is required.

The original combination of simple diffusion experiments of suitable diffusion probe with the

advantages of hydrogel porous media (simple preparation of hydrogels, the diffusion is

undisturbed by convection, etc.) provides very valuable information about the reactivity of

biocolloids. The transport and barrier properties of these compounds are studied by diffusion

of simple organic dyes through hydrogel material where different biocolloids are

homogenously distributed. The reactivity and barrier properties of biocolloids are compared

by determination of fundamental diffusion parameters such as effective diffusion coefficient,

sorption capacity, lag time (the time needed for penetration of chosen organic dye through

hydrogel porous barrier) or concentration of organic dye on the interface hydrogel-solution.

The barrier and transport properties were studied by both non-stationary and stationary

diffusion experiments in the diffusion cell. The linear polysaccharide agarose was used for

preparation of porous hydrogel media in both cases. The influence of changes in physical-

chemical properties of the system can be studied very easily (pH, ionic strength, temperature,

concentration of active substances, modification of humic acids, etc.). Hydrogels contain the

majority of water and the system used for study on reactivity of biocolloids is dynamic,

because of mentioned facts, conditions of studied biocolloids in laboratory are closed to real

biocolloids environment. Developed methods together with classical sorption experiments

could be the universal tool for study on reactivity of various natural compounds. The

universality of developed methods was tested also on systems with natural biopolymers

(chitosan, sodium alginate, hyaluronic acid), supramolecular compounds (humic acids)1,2

. The

influence of basic physical-chemical conditions of the systems containing natural substances

can be studied easily at laboratory conditions and this is one of the greatest advantages of

developed methods.

Literature:

1. Sedláček Petr, Smilek Jiří, Klučáková Martina. 2013. How the interactions with humic acids affect

the mobility of ionic dyes in hydrogels – Results from diffusion cells. Reactive and Functional

Polymers: 1500-1509.

2. Sedláček Petr, Smilek Jiří, Klučáková Martina. 2014. How the interactions with humic acids affect

the mobility of ionic dyes in hydrogels – 2. Non-stationary diffusion experiments. Reactive and

Functional Polymers: 41-50.

Acknowledgements:

This work was supported by the project “Materials Research Centre at FCH BUT - Sustainability and

Development” No. LO1211 of the Ministry of Education, Youth and Sports of the Czech Republic.

http://www.sciencedirect.com/science/article/pii/S1381514813001612





32

Direct Force Measurements Involving Positively and Negatively

Charged Colloidal Particles in the Presence of Multivalent

Cations

Moazzami Gudarzi Mohsen

1*, Maroni Plinio

1, Borkovec Michal

1

1Department of Inorganic and Analytical Chemistry, University of Geneva, Geneva,

Switzerland


Classical theory of DLVO is able to present an accurate prediction of the interactions among

colloidal particles in simple monovalent salts, especially at low ionic strength. However, it

fails to capture the forces involve at short distances. The presence of these short range non-

DLVO interactions becomes more pronounce in the presence of multivalent ions. These

forces could have different origin, magnitude and range depending on the surface properties

and interacting medium.

Interactions between positively and negatively charged latex particles in the aqueous solution

of rod-like oligoamine were investigated using colloidal probe technique. Our technique

allows us to attach individual particles to the cantilever in situ in fluid cell and measure the

colloidal forces between two particles in both symmetric and asymmetric fashions (Fig. 1).

Oligoamine cations strongly adsorb to negative interface, even overcharge the interface

whereas they repel from the positively charged interface. DLVO theory can quantitatively

predict the interaction between the surfaces, but at large distances (>6nm). Additional

attractive forces exist at short distances among both positive and negative interfaces. These

non-DLVO forces decay exponentially with average decay length of 1nm and 0.3nm for

negatively and positively charged particles, respectively. Analysing the interactions in

asymmetric system showed that the non-DLVO forces can be modelled with decay length of

0.5nm. The magnitude of these forces is between the non-DLVO forces in symmetric cases.

Apart from the origin of these forces, these results fairly indicate there is not a noticeable

synergistic or antagonistic effect as dissimilar interfaces interact together compare to when

they interact in symmetric mode.

Fig. 1 Surface forces can be measured among the dissimilar particles in symmetric (A-A, B-B) and asymmetric

(A-B) fashions using multi-particle colloidal probe technique.


33

Revisiting Kynchian Analysis of Gravitational and Centrifugal

Settling for Strongly Flocculated Suspensions

Skinner Samuel

1*, Stickland Anthony

1, Usher Shane

1, Scales Peter

1

1Particulate Fluids Processing Centre, The University of Melbourne


Solid-liquid separation involving strongly flocculated suspensions is important in a large

range of industrial applications, including mineral processing and wastewater treatment and

disposal. Development of theoretical descriptions of solid-liquid separation, or dewatering,

has allowed modelling of different dewatering behaviour and optimisation of dewatering

device design. Kynch (1952) developed a dewatering theory for interpreting experimental

gravitational settling results at high particle concentrations but it failed to account for

compression of the settled material1. Buscall and White (1987) introduced a fundamentally

rigorous dewatering theory for colloidal suspensions able to account for this material

compressibility2. The theory uses two key parameters; the extent of dewatering or

compressive yield stress, Py(ɸ), and the rate of dewatering or hindered settling function, R(ɸ).

R(ɸ) is a material property dependent on the solids volume fraction, ɸ, that quantifies the

interphase drag or hydrodynamic force on colloidal suspensions. This can be applied to a

solid moving through liquid during settling or liquid moving through solids in the case of

cake consolidation. There are existing methods for determining R(ɸ) from gravitational

settling tests3 and centrifugal settling tests

4 that have been shown to accurately model

dewatering behaviour. The work of Usher et al. (2013) assumes certain aspects of centrifugal

sedimentation behaviour that only approximate model predictions. A more rigorous analysis

using the method of characteristics is conducted in this analysis. This study extends the work

of Lester et al. (2005) by applying the same methodology to settling under a centrifugal force.

The model suspensions used in this study were wastewater treatment sludges, which are

dewatered industrially using a wide variety of operations from basic sedimentation to high-

speed centrifugation. R(ɸ) values were extracted for these materials over a large range of

volume fractions. These results enable more rigorously valid characterisation of material

dewaterability from batch gravitational and centrifugal settling tests, thus providing useful

information for suspension processing.

Literature:

1. Kynch, George1, 1952. A theory of sedimentation. Transactions of the Faraday Society 48: 166-

176.

2. Buscall, Richard1, White, Lee

2. 1987. The consolidation of concentrated suspensions. Part 1. The

theory of sedimentation. Journal of the Chemical Society. Faraday Transactions 1: Physical

Chemistry in Condensed Phases 83(3): 873-891

3. Lester, Daniel1, Usher, Shane

2, Scales, Peter

3. 2005. Estimation of the hindered settling function

R(ɸ) from batch-settling tests. AIChE Journal 51(4): 1158-1168.

4. Usher, Shane1, Studer, Lindsay

2, Wall, Rachael

3, Scales, Peter

4. 2013. Characterisation of

dewaterability from equilibrium and transient cenrifugation test data. Chemical Engineering

Science 93: 277-291


34

Linear viscoelasticity of human blood

Carciati Antonio

1, 2*, Tomaiuolo Giovanna

1, 2, Caserta Sergio

1, 2, Guido Stefano

1, 2

1Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale,

Università di Napoli Federico II 2CEINGE Biotecnologie avanzate, Napoli


Rheology of soft-colloid suspensions such as human blood are extremely relevant from both a

scientific point of view and for clinic. Human blood can be seen as a colloidal system, in

which red blood cells (RBCs) are the suspended particles and plasma is the liquid. From the

rheological pint of view, in fact, blood is a complex fluid with non-Newtonian characteristics.

It consists primarily of deformable red blood cells2 which tend to aggregate reversibly in

microstructures, called “rouleaux”, which resemble stacks of coins (Fig 1); this tendency is a

major contributor to the viscoelastic flow behavior of blood. An increasing amount of clinical

and experimental data underlines the importance of the flow behavior of blood, the latter

being a major determinant of proper tissue perfusion1.

Fig. 1 Typical rouleaux structures at volume fraction of 8% (A) and 16% (B).

In order to provide valuable information about blood microstructure, linear viscoelastic tests are

necessary. Currently few results are available in the literature and only a recent investigation by

passive microrheology3 has measured blood viscoelastic moduli, but the application of this

technique to a heterogeneous material such as blood is questionable.

Here, we report on an extensive rheological characterization of human blood both under steady

and oscillatory state. In particular, we present the first systematic set of oscillatory shear

measurements by conventional bulk rheology in order to evaluate storage and loss moduli of

whole human blood. The rheological behavior of human blood was characterized both in

physiological conditions and in RBC aggregating media. The latter ones were obtained by the

addition of a polymer and by increasing the hematocrit above the normal physiological levels.

Literature:

1. Baskurt OK, Meiselman HJ. 2003. Blood rheology and hemodynamics. In: Seminars in thrombosis

and hemostasis. New York: Stratton Intercontinental Medical Book orporation, c1974-. 435-450.

2. Tomaiuolo G, Simeone M, Martinelli V, Rotoli B, Guido S. 2009. Red blood cell deformation in

microconfined flow. Soft Matter. 5(19): 3736-3740.

3. Campo-Deaño L, Dullens RP, Aarts DG, Pinho FT, Oliveira MS. 2013. Viscoelasticity of blood

and viscoelastic blood analogues for use in polydymethylsiloxane in vitro models of the circulatory

system. Biomicrofluidics. 7(3): 034102.

A B

10 µm


35

Influence of molecular exchange on the enclosed water volume

fraction of W/O/W double emulsions as determined by

low-resolution NMR diffusometry and T2-relaxometry

Vermeir Lien

1*, Balcaen Mathieu

1, Sabatino Paolo

2, Dewettinck Koen

3, Van der Meeren Paul

1Particle and Interfacial Technology Group

2NMR and Structure Analysis Unit

3Laboratory of Food Technology and Engineering

123Ghent University, Belgium


Oil in water (O/W) emulsions are widely used in various fields, ranging from foods to

pharmaceuticals. During the last years, the incorporation of water within the emulsified oil

phase has received an ever increasing interest. First of all, these so-called water in oil in water

(W1/O/W2) emulsions enable the formulation of light foods as part of the oily dispersed phase

is replaced by water. In addition, this technology enables to separate an internal water phase

(Water1) from an external water phase (Water2) by the oily phase, which opens perspectives

for encapsulation of otherwise incompatible water-soluble components.

Low-resolution T2-relaxometry and pfg-NMR diffusometry can be applied for determination

of the enclosed water volume fraction of W/O/W emulsions. Whereas pfg-NMR diffusometry

enables the discrimination between internal and external water based on differences in

diffusion behavior, the T2-relaxometry method is based on the relaxation behavior differences

of the internal and external water upon addition of an external water-soluble paramagnetic

probe, such as manganese dichloride. As compared to most alternative techniques, low

resolution NMR does not require the physical separation of both water phases. In addition,

both low resolution NMR techniques do not require any tracer addition during multiple

emulsion preparation, and hence can also be applied on existing formulations. Whereas T2

relaxation is faster and less affected by NMR parameters, pfg-NMR has the advantage that it

does not require any sample pretreatment.

The exchange kinetics seemed to play a crucial role in both NMR methods. More specifically,

water exchange effects on the enclosed water volume fraction as estimated by pfg-NMR

diffusometry became more noticeable with increasing NMR diffusion delay (in the seconds

range), whereas Mn2+

exchange mediated effects on the estimated enclosed water volume

fraction obtained by T2-relaxometry became more pronounced with increasing storage time

(in the days range). In terms of Mn2+

repartitioning kinetics (Mn2+

-doped), double emulsions

with different fat phases behaved differently, as could be observed from the behavior of the

slow mode relaxation time as a function of storage time. However, an increased solid fat

content did not guarantee slower exchange kinetics. These experiments also demonstrate the

applicability of both methods to investigate exchange kinetics in emulsion systems [1].

Literature:

1. Vermeir Lien, Balcaen Mathieu, Sabatino Paolo, Dewettinck K. and Van der Meeren Paul (2014).

Influence of molecular exchange on the enclosed water volume fraction of W/O/W double

emulsions as determined by low-resolution NMR diffusometry and T2-relaxometry. Colloids and

Surfaces A, 456, 129-138.


36

Impact of WO3 on surface topography of titania photocatalysts

Mioduska Joanna*, Anna Zielińska-Jurek, Hupka Jan

Gdansk University of Technology, Faculty of Chemistry,

Department of Chemical Technology


Titanium dioxide is promising photocatalyst for purification of water and air.

The most significant limitations in its use result from wide band gap (around 3.2 eV

for anatase), making it active in UV light. In order to extend light absorption to the visible

range of solar radiation, titanium dioxide has to be modified and/or doped.

In the presented work, titania was modified with tungsten trioxide (WO3). WO3 has its

valence and conduction bands correspondingly lower than those of titanium dioxide.

The combination of these two semiconductors results in obtaining a composite with lower

energy gap, hence with the activity shifted toward visible region. Absorbance spectrum versus

wavelength of modified and pure titania is presented in Fig. 1.

The surface morphology plays an important role in the photocatalytic activity

of semiconductor nanoparticles. The use of scanning electron microscope was the preliminary

examination of the photocatalyst topography, in order to evaluate, changes of modified

or catalyst doped samples. Besides SEM images, the samples were subsequently characterized

using XRD, which allowed to determine the dominated crystal phase.

Fig. 1 Absorbance spectrum versus wavelength of modified and pure titania


37

Characterization of Langmuir monolayers formed by derivatives

of fluorinated Polyhedral Oligomeric Silsesquioxanes

Anna Wamke1*, Marta Piechocka1, Katarzyna Dopierała1, Krystyna Prochaska1,

Hieronim F. Maciejewski2, Aneta D. Petelska3

1Institute of Chemical Technology and Engineering, Poznan University of Technology,

Berdychowo 4, 60-965 Poznań, Poland 2Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznań, Poland

3Institute of Chemistry, University of Bialystok, Ciolkowskiego 1K, 15-245 Bialystok, Poland


Previous studies have shown that fully condensed polyhedral oligomeric silsesquioxanes

(POSS) were able to form stable insoluble monolayers at the A/W interface [1]. The chemistry of

this class of amphiphilic materials has emerged as a new field of modern nanotechnology. POSS

derivatives consisting of a thermally robust inorganic SiO core with flexible organic functional

corona, represent hybrid organic-inorganic materials with unique physico-chemical properties.

Interfacial properties of POSS play a key role in future applications. However, there are very few

reports which describe the Langmuir monolayers form by POSS at the interface. Some derivatives

of fully condensed fluorinated POSS have been used in the development of high performance

materials as well as in medical applications [2].

In this study, the monolayer behavior at the A/W interface for six derivatives of fully

condensed fluorinated POSS were presented. The differences between chemical structure of

POSS compounds analysed results from various ratio of unreactive (fluorinated, F) and reactive

(trimethoxysilane, TMS) substituents added to the inorganic core of their molecules. One of the

goal of this study was observing the hydrolysis and condensation processes of TMS substituents

in POSS molecules forming a monolayer at the A/W interface.

The interfacial properties were analysed by using computer–controlled KSV NIMA

Langmuir film balance system (KN 0033) with KSV NIMA Surface Potential Sensor (SPOT) and

a Brewster Angle Microscopy (BAM) (KSV NIMA MicroBAM). The Polarization modulation

Infrared Reflection Absorption Spectrometer (KSV NIMA PM-IRRAS) was used to study the

effectivity of the hydrolysis and condensation reactions of TMS groups present in POSS

molecules.

The results obtained showed that derivatives of fully condensed fluorinated POSS

compounds formed liquid stable monolayers at the A/W interface which compressibility strongly

depends on the type of substituents present in POSS molecules. Moreover it was found that the

effectivity of hydrolysis and condensation reactions of TMS groups is strongly affected by the pH

values of subphase.

Literature:

1. K. Dopierała, A. Wamke, M. Dudkiewicz, H.F. Maciejewski, K. Prochaska, 2014. Interfacial

Properties of fully condensed functional POSS. A Langmuir Monolayer Study. J PHYS CHEM C

118: 24548-24555.

2. S.T. Iacono, A.J. Peloquin, D.W. Smith, J.M. Mabry Chapter 6 in Applications of Polyhedral

Oligomeric Silsesquioxanes, Volumen 3 J. G. Matisons, C. Hartmann-Thompson, Dordrecht,

Heidelberg, London, New York: Springer Science+Business Media B.V., 2011.

Acknowledgements:

This work was financially supported by Polish National Science Center, Grand No. UMO-

2012/05/B/ST02200. The authors are grateful for the opportunity to perform research on KSV NIMA

PM-IRRAS purchased within EU Project number POPW.01.03.00-20-004/1.

http://www.scopus.com.scopus.han3.library.put.poznan.pl/record/display.url?eid=2-s2.0-84855582447&origin=resultslist&sort=plf-f&src=s&st1=Kraus-Ophir&st2=&nlo=1&nlr=20&nls=count-f&sid=1CAC4A632CF796C461246057C44B112B.fM4vPBipdL1BpirDq5Cw%3a733&sot=anl&sdt=aut&sl=41&s=AU-ID%28%22Kraus-Ophir%2c+Shlomit%22+42262037200%29&relpos=1&relpos=1&citeCnt=5&searchTerm=AU-ID%28%5C%26quot%3BKraus-Ophir%2C+Shlomit%5C%26quot%3B+42262037200%29#corrAuthorFooter


38

Nondestructive Characterization of Lysozyme Layers on Silica

Surface using MP-Surface Plasmon Resonance and Quartz

Crystal Microbalance

Ćwięka Monika*, Jachimska Barbara




Lysozyme has a very important function in the immune system, as it exhibits strong

antibacterial activity against gram-positive bacteria. This phenomenon has found practical

applications in medicine, the pharmaceutical industry and the food processing industry. For

this reason, the understanding of how the protein interacts with inorganic material surfaces is

of major interest in both fundamental research and applications such as biotechnology.

However, despite intense studies, the mechanism and the structural determinants of the

protein/surface interactions are still not fully understood.

The development of new research techniques makes it possible to study adsorption

with increasing accuracy: from simple measurements of adsorption kinetics at high protein

concentrations to detecting even a single protein molecule adsorbed on a surface. The

adsorption of lysozyme (LSZ) at a silica surface has been chosen as a model system. We have

analysed the LYZ adsorption using Quartz Crystal Microbalance with Dissipation (QCM-D)

and Multi-Parametric Surface Plasmon Resonance (MP-SPR) methods. A combination of

these complementary techniques has provided crucial information on the mechanisms behind

the protein-material interactions, LSZ structural changes and biomolecular rearrangements.

We have found that the pH strongly affects the effectiveness of LSZ adsorption onto the

surface and leads to orientation changes of protein on the surface. The highest adsorption

value was attained near the protein’s Iso-electric Point. The data clearly indicates that

electrostatic interactions are a driving force for LSZ adsorption.

Furthermore, from the combination of the QCM-D and MP-SPR data with the

assumption that the excess sensed mass measured in QCM-D compared to the MP-SPR mass

is due to trapped water, we have estimated the hydration of LSZ layer on the surface of silica.

Acknowledgements:

This work was supported by Grant NCN OPUS4 2012/07/B/ST5/00767.


39

β-lactoglobulin adsorption at the water/oil system

at different pH and ionic strength

Jooyoung Won

1,*, Jürgen Krägel

1, Georgi Gochev

1,2 and Reinhard Miller

1

1Max Planck Institute of Colloids and Interfaces, D-14424 Potsdam/Golm, Germany

2Institute of Physical Chemistry, Bulgarian Academy of Sciences, 1113, Sofia, Bulgaria


Proteins, in general, adsorb at liquid interfaces and are well-known as efficient stabilizers of

foams and emulsions [1,2]. β-lactoglobulin (BLG) is one of the most widely studied ones due

to its major industrial applications particularly in food processing.

Oscillating drop tensiometry was applied to study adsorbed protein interfacial layers at

water/oil interfaces. In this work, the influence of different pH and ionic strength on the

dynamics of BLG water/tetradecane interface has been investigated. Dynamic interfacial

tension () and interfacial dilational elastic modulus (E’) of BLG solutions at three different

pH values of 3, 5 and 7 and at three different ionic strength are measured by Profile Analysis

Tensiometer (PAT-1, SINTERFACE Technologies, Berlin). Furthermore, interfacial tension

and dilational rheology of mixed solutions of BLG and with the anionic surfactant SDS

(sodium dodecyl sulphate) of varying protein/surfactant concentrations have been also

studied.

The presented results of the adsorption isotherm and the dilational visco-elasticity under

equilibrium and dynamic conditions is based on measurements of the dynamic interfacial

pressure and its response to sinusoidal drop area variations.

Literature:

1. Eric Dickinson and Yanda B.Galazka. 1991. Emulsion stabilization by ionic and covalent

complexes of β-lactoglobulin with polysaccharides. Food Hydrocolloids,5,281-296.

2. Georgi Gochev, Inga Retzlaff, Dotchi R. Exerowa and Reinhard Miller. 2014. Electrostatic

stabilization of foam films from β-lactoglobulin solutions. Colloids and Surfaces A, 460, 272–279.


40

A thermodynamic study of ligand adsorption to colloidal surfaces

demonstrated by means of catechols binding to ZnO QDs

Wei Lin,

1* Johannes Walter,

1 Alexandra Burger,

2 Harald Maid,

2 Andreas Hirsch,

2

Wolfgang Peukert,1 Doris Segets

1

1Institute of Particle Technology, 2Institute of Organic Chemistry,

Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen, Germany


Although being of major importance for various particle-based applications, the characterization

of liquid-borne colloidal surfaces in solution especially with respect to functionalization and

ligand exchange reaction is still an open and highly challenging question. Therefore, a general

strategy to study the thermodynamics of ligand adsorption to colloidal surfaces was established by

means of catechol (Ethyl 3,4-dihydroxybenzoate, CAT) binding to ZnO quantum dots (QDs).1

First, isothermal titration calorimetry (ITC) was used to extract all relevant thermodynamic

parameters, namely association constant, enthalpy, entropy and free energy of the ligand binding.

To confirm the characterization of ligand binding by measuring the heat of adsorption, the free

energy was cross-validated by mass-based adsorption isotherms. To close the mass balance,

analytical ultracentrifugation (AUC) was applied to detect the amount of free, unbound catechol

in solution. Then, Raman spectroscopy and nuclear magnetic resonance spectroscopy (NMR)

were performed to quantify the replaced amount of acetate with CAT (65%) and to distinguish

bound (chemisorbed) and unbound (physisorbed) CAT. Finally, based on a collection of all our

results, the full picture of ligand binding to the ZnO colloid is obtained as illustrated in Fig. 1.

ZnO in EtOH

0.25

ML

0.5

ML

0.75

ML

1.0

ML

free acetate bound acetate free CAT physisorbed CAT chemisorbed CAT

CH3

O

O

CH3O

O

CH3O

O

CH3O

O

CH3

O OH3C

O

O

H3C

O

O

H3CO

O

H3C O

O

H3CO

O

CH3

OO CH3

O

O

O

-O CH3

O

O

O

-O

O

-O

O

-O

O

-O

O

-O

O

-O

O

-O

O

-O

O

-O

O

-O

O

-O

O

-O

R

HO

HO R

O

O

O

O

HO

HO

O

O

HO

HO

R

HO

HO

O

-OO

-O

O

-O

O

-O

R

O

O

RO

O

R

O OR

O

O

R

O

OR

O

O

R

O

O

RO

O

R

OO

R

O

O

CH3O

O

H3C

O

O

R

OH

OH

RHO

HO

R

HO

HO R

HO

HO

R

HO

HOR

HO

HO

ROH

OH

R

OH

OH

R

OHHO

Fig. 1 Full picture of ligand exchange reaction and particle-ligand structure for ZnO quantum dots and CAT.

As all our results are in good agreement with each other and highly complementary, it is sufficient

to get the full picture of ligand binding in various particle-ligand interfacial systems even if only

parts of our approach can be applied. We believe that the general applicability of our

methodologies will provide strong encouragement for similar studies in the field of colloids and

thus paves the way to a knowledge-based interface design.

Literature: 1. Lin W., Walter J., Burger A. Maid H., Hirsch A., Peukert W., Segets D., 2015. A thermodynamic

study of ligand adsorption to colloidal surfaces demonstrated by means of catechols binding to

ZnO quantum dots. Chem. Mater., 27: 358−369.


41

Droplet dynamics: Oil droplet attachment and spreading on solid

substrates

James Emily,

1* Vaccaro Mauro

2, Graydon Andrew

2, Brooker Anju

2, Jamadagni Sumanth

3,

Biggs Simon

4, Cayre Olivier

1, Hunter Timothy

1, and Harbottle David

1

1Institute of Particle Science and Engineering, University of Leeds, Leeds, UK

2Procter & Gamble Ltd, Whitley Road, Newcastle, Tyne and Wear, UK 3Procter & Gamble, Corporate R&D, Modeling and Simulation, West Chester, USA

4Faculty of Engineering, Architecture and Information Technology, The University of

Queensland, Brisbane, Australia


The interaction between liquid droplets and solid substrates is ubiquitous in many commercial and

industrial applications. Often the application governs the nature of the liquid-solid interaction with

the droplet adhesion and ability to coat a substrate controlled by physical, chemical and

environmental conditions.

In the current research, short-time droplet spreading dynamics have been studied by measuring

the droplet contact diameter as a function of spreading time on a solid substrate in air. The droplet

spreading dynamics are shown to confirm two spreading regimes; i) inertial regime (r ∝ t0.5)

immediately after droplet-solid contact; and ii) viscous regime confirming Tanners law (r ∝ t0.1).

A series of silicone-based oils (poly (dimethyl siloxane) or PDMS) all bearing a methyl terminal

group but of different viscosities (10 – 10000 cSt) were initially studied. Normalization of the

spreading time by the oil viscosity resulted in a master curve that represents the viscous spreading

dynamics of these PDMS oils, see Figure 1. The effect of droplet impact velocity was also

assessed by varying the release height (6 cm and 3 cm) of the PDMS oil droplet. While both

heights result in a single master curve as a function of PDMS oil viscosity, there are differences

between the two master curves in the inertial regime and the long-time viscous regime. Reasoning

for the long-time deviation is currently being investigated.

Finally, the study considered the effect of PDMS oil terminal group by comparing the methyl-

terminated oils against amino-terminated counterparts of similar viscosities and droplet spreading

dynamics in water. Multiple master curves for the different terminal groups and the varying

droplet height enable greater understanding of the droplet spreading dynamics and the governing

parameters which promote rapid droplet spreading.

0.01 0.1 1 10

1

2

3

4

5

6

10 cSt

50 cSt

500 cSt

1000 cSt

10000 cSt

Dia

me

ter

(mm

)

Time (s)

1E-3 0.01 0.1 1 10 100

1

2

3

4

5

6

10 cSt

50 cSt

500 cSt

1000 cSt

10000 cSt

Dia

me

ter

(mm

)

Time/Viscosity (Pa)

Fig. 1 a) Time dependent droplet spreading as a function of oil viscosity, b) normalization by the oil viscosity.

a) b)


42

Hofmeister Effects in Colloidal Aggregation in Aqueous Solutions

of Ionic Liquids

Oncsik Tamas*, Szilagyi Istvan, Trefalt Gregor, Borkovec Michal

Department of Inorganic and Analytical Chemistry, University of Geneva, Geneva,

Switzerland


Specific ion effects are important for many scientific phenomena such as properties of

electrolyte solutions (e.g. viscosity, surface tension), protein behavior, colloid aggregation,

etc. There is an extensive literature about ion-specific aggregation of different type of

particles according to the Hofmeister series. However, most of them have dealt with simple

electrolytes. In this project we used ionic liquids (ILs) as coagulating agents, systematically

varying their constituents. The colloidal particles used were polystyrene latex particles

functionalized with charge-determining sulfate and amidine groups. The diameters of the

particles were 530 nm and 220 nm, respectively. Time-resolved dynamic light scattering

(DLS) and electrophoresis were used for the characterization. While with DLS we determined

the absolute aggregation rates and the corresponding critical coagulation concentrations

(CCC) which separates the slow and fast aggregation regimes, electrophoresis was used to

determine the charge state of the particles in different conditions. We tried to correlate the

suspension stability to the Hofmeister effect. We have also investigated the effect of increased

cation hydrophobicity. Depending on the type of salt, screening, neutralization, overcharging

can be observed at the concentration range investigated which is in good agreement with

previous results1. In some systems even restabilization can be seen. Based on our

measurements we placed the IL cations and anions into the well-known Hofmeister series.

Fig. 1 Aggregation and charging behavior of SL530 particles in the presence of ILs containing cations of

different hydrophobicity

Literature:

1. Szilagyi Istvan, Szabo Tamas, Desert Anthony, Trefalt Gregor, Oncsik Tamas, Borkovec Michal

2014. Particle aggregation mechanisms in ionic liquids, Phys. Chem. Chem. Phys. 16, 9515-9524


43

Silica-ceria interactions during polishing

Réka Toth

1,2 *, Grégory Lefèvre

1, Philippe Barboux

1, David Carrière

3, Lauriane D'Alençon

2,

Thierry Le Mercier2, Valérie Buissette

2

1RMD, Institut de Recherche de Chimie Paris, CNRS - France

2Solvay, Centre de Recherche et Innovation de Paris Aubervilliers – France

3Laboratoire LIONS, CEA Saclay - France


Chemical mechanical polishing is widely used in microelectronics industry. Polishing

consists in applying a slurry of colloidal particles onto a solid surface called substrate,

through a pressure applied with a rotating polymeric pad. Polishing is not simply a grinding

or abrasion problem, since in some case a substrate may be polished by softer powders. The

understanding of particle-substrate interactions is important to improve industrial polishing

performances in the future. For example, we have studied the interaction between the

substrate and the particles during a polishing experiment of SiO2 with CeO2.

Mechanical contact, hydrodynamic behaviour of the colloidal suspension, interaction

between particles and substrate, or adsorption effects between particle and dissolved species

are all important parameters to consider for polishing. Indeed, studies show the importance of

surface charge on polishing rate [1], and a proposed mechanism is that silica is torn away

from the substrate by the ceria particles sticking onto it [2].

To verify this hypothesis we followed the properties of the colloidal ceria particles

during a model polishing experiment. The evolution of the zeta potential of the particles

indicates that silica progressively covers their surface. This is in agreement with Energy

Dispersive X-ray analysis, which shows the presence of a silica layer deposited onto the

particles after polishing. These samples have been compared with model mixtures of ceria and

silica by small angle X-ray scattering (SAXS) that follows the ceria-silica interaction. Finally,

Infrared spectroscopy performed on the particles has shown that this silica layer results of the

peeling of the substrate, also confirmed by an AFM study on the substrate after polishing.

Literature:

1. Lee M. Cook, 1990, Chemical processes in glass polishing, J. Non-Crystalline Solids 120:152-171

2. Tetsuya Hoshino, Yasushi Kurata, Yuuki Terasaki, Kenzo Susa, 2001, J. Non-Crystalline Solids

283:129-136

Fig. 1: Schematic illustration of a typical polishing tool.


44

Quantifying the rainfastness of fluorescently labelled

poly(vinyl alcohol) deposits on vicia faba leaf surfaces via

fluorescent microscopy

Brett Symonds

1*, Niall Thomson

2, Chris Lindsay

2, Vitaliy Khutoryanskiy

1

1Reading School of Pharmacy, University of Reading, Whiteknights, PO Box 224, Reading,

RG6 6AD 2Formulation Technology Group, Jealott’s Hill International Research Centre, Bracknell,

RG42 6EY


The world faces the significant challenge of securing a sustainable supply of food for a

growing population. This challenge must be met with less arable land per person and with

fewer resources. It is estimated that by 2050 the world’s population will reach 9 billion and

the United Nations Food and Agricultural Organisation estimates that the 2006-7 world

agricultural output must increase by 60% in order to meet projected demand.1 In some

situations up to 90% of the sprayed product may not reach the target site.2 This reduced

efficiency has been accredited to poor penetration through the plant cuticle, photolytic,

hydrolytic, microbial degradation and wash-off due to rain.3 There is evidence that, among

other substances, polymers are useful rainfastness agents.4

A laboratory scale method for characterising rainfastness is reported, as well as a larger scale

experiment using artificial rain to validate the method. A series of poly(vinyl alcohol) (PVA)

samples were fluorescently labelled with 5-(4,6-dichlorotriazinyl) aminofluorescein (5-

DTAF). Using fluorescent microscopy and ImageJ image analysis a method was developed to

follow how deposits of these polymer samples washed off of vicia faba (field/broad bean)

leaves (Fig. 1). This quantification of rainfastness is of great interest in the area of

agrochemical formulation. Characterising molecular weight of the polymers proved that those

PVA deposits of higher molecular weight were more rainfast than those of lower molecular

weight.

Fig. 1 An exemplary wash-off profile of a labelled deposit of PVA with corresponding pictures where the area of

coverage in the pictures is quantified with ImageJ and plotted.


45

Literature:

1. FAO Statistical Yearbook 2013. (United Nations, 2013). At

<http://www.fao.org/docrep/018/i3107e/i3107e00.htm>

2. Pimentel, D. Amounts of pesticides reaching target pests: Environmental impacts and ethics. J.

Agric. Environ. Ethics 8, 17–29 (1995).

3. Wang, C. J. & Liu, Z. Q. Foliar uptake of pesticides—Present status and future challenge. Pestic.

Biochem. Physiol. 87, 1–8 (2007).

4. Gaskin, R. E. & Steele, K. D. A comparison of sticker adjuvants for their effects on retention and

rainfastening of fungicide sprays. New Zeal. Plant Prot. Soc. 342, 339–342 (2009).

Acknowledgements:

We acknowledge the BBSRC (CASE Studentship: BB/J0124401/1) and Syngenta for funding the

doctorate project. We also acknowledge the Chemical Analysis Facility (CAF) at the University of

Reading for use of NMR, WAXS and DSC equipment. Finally, we acknowledge our colleagues at the

University of Reading and Syngenta for their useful input, in particular Anne Stalker for providing

plants as well as Jill Foundling for help with microscopy, both of Syngenta.


46

UV Curable Oil-in-Water Emulsions for 3D Functional Printing

Cooperstein Ido, Prof Magdassi Shlomo

Casali Center for Applied Chemistry, Institute of Chemistry and Center for Nanoscience

and Nanothechnology, The Hebrew University of Jerusalem, Jerusalem, Israel


In recent years the technology and materials for 3D printing was highly advanced and enable

printing of high resolution 3D structures. Additive manufacturing, or three dimensional

printing, is implemented in a variety of fields such as rapid prototyping and scaffolds for

medical applications. The 3D structures are formed with various monomers or polymeric

precursors and additives, while currently the main function of the printed object is the

structure itself. The goal of our research is to fabricate 3D porous structures containing

continuous functional matrix within the pores. These structures are fabricated by printing a

newly developed oil-in-water emulsion ink composed of curable acrylic monomers mixture as

the "oil" droplets, dispersed in water phase. The printing is performed by the digital light

process (DLP) method, in which the structure is formed by localized polymerization of

monomers. At the first stage, the UV light initiates curing of the monomer droplets, while at

the second stage, the continuous water phase evaporates and interconnected voids are formed.

Currently we focus on impregnating these voids within the printed structures with silver

nanoparticles that after a simple room temperature sintering process forms a conductive,

continues silver matrix within a solid polymer.

Fig. 1: Images of electric circuit printed from the curable emulsion (A) Image of the clean porous 3D

structure (B) Image of the porous structure after inserting Ag in DB dispersion, sintering and connecting

to 1.5V and LED, (C) UHR-SEM cross-section image of the printed structure with embedded Ag NPs.

Literature:

1. Cooperstein, I., M. Layani, and S. Magdassi. 2015. 3D printing of porous structures by UV-curable

O/W emulsion for fabrication of conductive objects. J. Mater. Chem. C, 3, 2040-2044.

A B C


47

Effect of pH and salt concentration on velocity of rising bubbles

in Beta-Lactoglobulin solution

V.Ulaganathan1,*

, G.Gochev1, M.Krzan

2, S.S.Dukhin

3, C.Gehin-Delval

4 and R.Miller

1

1Max-Planck-Institut für Kolloid- und Grenzflächenforschung, 14424 Potsdam, Germany

2Jerzy Haber Institute of Catalysis and Surface Chemistry, PAN, 30-239 Cracow, Poland

3New Jersey Institute of Technology, University Heights, Newark, NJ 07102, USA 4Nestlé Research Centre, Vers-Chez-Les-Blanc, 1000 Lausanne 26, Switzerland


The rising velocity profile of air bubbles in surfactant solutions is a sensitive measure for the

formation of a dynamic adsorption layer (DAL) at the bubble surface. Due to a certain surface

coverage by adsorbed surfactants the bubble surface becomes partly or completely immobilized

depending on the bulk concentration which retards the bubble’s rising velocity [1]. The adsorption

of ionic surfactants is affected by salt concentration due to presence of counter ions [2], which

eventually affects the rising bubble velocity [3]. In case of proteins the presence of salt and pH in

the solution would influence its molecular conformation and its adsorption properties [4].

Therefore, the present study gives an insight into the effect of solution conditions on the

f -lactoglobulin.

Fig.1 Local velocity profiles of bubbles of 1.5 mm diameter (approx.) rising in 5x10

-7 mol/l -lactoglobulin

solution in 10mM of citric phosphate buffer at different pH.

Literature:

1. S.S. Dukhin, R. Miller, G. Loglio, Physico-chemical hydrodynamics of rising bubble, in: D.

Möbius, R. Miller (Eds). 1998. Drops and Bubbles in Interfacial Research, New York, Elsevier,

367-432.

2. P. Warszyński, W. Barzyk, K. Lunkenheimer, H. Fruhner. 1998. Surface Tension and Surface

Potential of Na n-Dodecyl Sulfate at the Air−Solution Interface: Model and Experiment, J. Phys.

Chem. B. 102, 10948–10957.

3. M. Krzan, K. Malysa. 2012. Influence of electrolyte presence on bubble motion in solutions of

sodium n-alkylsulphates, (C8, C10, C12), 48, 49–62.

4. K. Engelhardt, M. Lexis, G. Gochev, C. Konnerth, R. Miller, N. Willenbacher, et al. 2013. pH

Effects on the Molecular Structure of β-Lactoglobulin Modified Air–Water Interfaces and Its

Impact on Foam Rheology, Langmuir. 29, 11646–11655.

Acknowledgement:

Nestle Research Centre, Lausanne, Switzerland for PhD grant (VU).


48

Effect of the bubble dimensions and the shape deformation

degrees on its coalescence time at free water surface

Niecikowska Anna

1*, Wiertel Agata

1, Zawała Jan

1, Małysa Kazimierz

1




Degree of the bubble shape deformations during collisions with liquid/air interfaces

affects dimensions of the thin liquid films formed at free liquid surface and therefore plays an

important role in kinetics of the bubble coalescence. Depending on the bubble size and actual

deformation degree, the kinetics of drainage and stability of the intervening liquid film, separating

the interacting surfaces, can be quite different. When the bubble collides with free water surface

the outcome of collision depends on mutual rates of the competitive processes: (i) transfer of the

kinetic energy, associated with the bubble motion, into the surface energy, and (ii) drainage of the

separating liquid film to so-called critical thickness of rupture (hcr). The differences in kinetics of

these two simultaneous processes determine if bubble bursts or bounces prior to its rupture.

This paper presents the results of investigations on effect of the air bubble size and the

shape deformation degree on its coalescence time at free surface of distilled water. The

phenomena occurring during collisions and bouncing of the bubbles of radii 0.50 - 0.88 mm were

monitored using high-speed video recordings. The movies recorded were analysed frame-by-

frame to determine the bubble shape deformations and its local velocity variations during the

consecutive collisions. The bubble coalescence time (tc) was determined as the time interval from

the moment of the bubble 1st collision till its rupture. It was found that the tc values varied from ca.

25 to ca. 80 ms, when the bubble diameter was changed from 0.50 to 0.88 mm, respectively.

Prolongation of the tc was a consequence of larger number of the bubble bouncing from the water

surface prior to the rupture. Results of the experiments showed that the degree of bubble shape

deformation decreases with the subsequent collision number, due to dissipation of the kinetic

energy associated with the bubble motion and lower impact velocity of each consecutive strike

(see Fig. 1). The same effect was observed for all ranges of the bubble sizes studied. Kinetics of

the bubble coalescence is therefore determined by variations in radius of the intervening liquid

film (Rf), which is lower for smaller bubble deformation degrees.

Fig. 1 Photos and simulations of the bubble deformations at the consecutive collisions

Acknowledgements:

Financial support from National Research Center (NCN grant No. 2013/09/D/ST4/03785) is

acknowledged with gratitude.


49

Influence of imidazolium ionic liquids structure on aggregation

behavior of triton X-100 nonionic surfactant

Anna Latowska*, Justyna Łuczak, Jan Hupka

Department of Chemical Technology, Chemical Faculty, Gdańsk University of Technology,

ul. Narutowicza 11/12, 80-952 Gdańsk, Poland


Physical and chemical properties of ionic liquids (ILs) have attracted much attention

in respect to their applications in organic synthesis, separation processes, electrochemistry, as well

as nanomaterials preparation. Particularly important is ILs negligible volatility, which prevents air

pollution, thereby makes them an alternative to volatile organic solvents. Moreover,

by modification of the cation structure and selection of the anion type, the properties of ILs may

be controlled and designed for selective applications [1, 2].

ILs have also gained an interest in colloid and surface chemistry due to their surface and

interface properties which enable to promote self-assembly of amphiphiles. Up to date only few

ILs were confirmed to support micellization of amphiphiles, however data on examined systems

are scarce and not classified yet. Moreover it was found that aggregation in ILs occurs less readily

than in water, due to solute-solvent interactions, different from those in aqueous systems [3].

Here we demonstrate an influence of ILs structure on micelle formation of Triton X-100

nonionic surtactant at 25oC. A group of imidazolium ionic liquids containing from two to eight

carbon atoms in the alkyl chain of the imidazolium cation and four different anions, namely

tetrafluoroborate, [BF4], hexafluorophosphate, [PF6], bis(trifluoromethanesulfonyl)imide, [Tf2N]

and trifluoromethanesulfonate, [TfO] anions were investigated for supporting surfactant

aggregation. The presence of aggregates in IL/Triton X-100 solutions was examined by means of

surface tension measurements as well as dynamic light scattering. It was observed that shortening

of the hydrocarbon substituent in the imidazolium cation as well as selection of the anion with

smaller size and less diffuse nature, strongly facilitates micelle formation. Therefore, aggregation

behavior was confirmed in ionic liquids composed of two to six carbon atoms in IL imidazolium

cation and with [BF4] and [PF6] anions. In given experimental conditions solvents composed of

eight carbon atoms in cation alkyl substituents, [Tf2N] and [TfO] anions did not support surfactant

aggregation. The presence of micelles in ionic liquids was confirmed by dynamic light scattering

measurements. The results revealed that the micellar diameter strictly depends on surfactant

concentration and increases significantly with increase of the surfactant content.

1. Greaves, T.L. and C.J. Drummond, Solvent nanostructure, the solvophobic effect and amphiphile

self-assembly in ionic liquids. Chemical Society Reviews, 2013. 42(3): p. 1096-1120.

2. Łuczak, J., A. Latowska, and J. Hupka, Micelle formation of Tween 20 nonionic surfactant in

imidazolium ionic liquids. Colloids and Surfaces A: Physicochemical and Engineering Aspects,

2015. 471(0): p. 26-37.

3. Inoue, T. and H. Yamakawa, Micelle formation of nonionic surfactants in a room temperature

ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate: Surfactant chain length dependence of

the critical micelle concentration. Journal of Colloid and Interface Science, 2011. 356(2): p. 798-

802.


50

Effect of Laundry Surfactants on Surface Charge and Colloidal

Stability of Silver Nanoparticles

Sara Skoglund

1*, Troy Lowe

1, Jonas Hedberg

1, Eva Blomberg

1, Inger Odnevall Wallinder

1,

Susanna Wold2 and Maria Lundin

3

1KTH Royal Institute of Technology, School of Chemical Science and Engineering, Surface

and Corrosion Science, SE-100 44 Stockholm, Sweden 2KTH Royal Institute of Technology, School of Chemical Science and Engineering, Applied

Physical Chemistry, SE-100 44 Stockholm, Sweden 3§Chemistry, Materials and Surfaces, SP Technical Research Institute of Sweden, Box 5607,

SE-114 86 Stockholm, Sweden


The stability of silver nanoparticles (Ag NPs) potentially released from clothing during a

laundry cycle and their interactions with laundry-relevant surfactants [anionic (LAS), cationic

(DTAC), and nonionic (Berol)] have been investigated. Surface interactions between Ag NPs

and surfactants influence their speciation and stability. In the absence of surfactants as well as

in the presence of LAS, the negatively charged Ag NPs were stable in solution for more than

1 day. At low DTAC concentrations (≤1 mM), DTAC−Ag NP interactions resulted in charge

neutralization and formation of agglomerates. The surface charge of the particles became

positive at higher concentrations due to a bilayer type formation of DTAC that prevents from

agglomeration due to repulsive electrostatic forces between the positively charged colloids.

The adsorption of Berol was enhanced when above its critical micelle concentration (cmc).

This resulted in a zeta potential close to zero and subsequent agglomeration. Extended DLVO

theory calculations were in compliance with observed findings. The stability of the Ag NPs

was shown to depend on the charge and concentration of the adsorbed surfactants. Such

knowledge is important as it may influence the subsequent transport of Ag NPs through

different chemical transients and thus their potential bioavailability and toxicity.

Fig 1: Particle size distribution measurements based on volume density of Ag NPs in aqueous solutions of pH

10 with different concentrations of DTAC, showing larger agglomerates in 1 mM DTAC than in the other

DTAC concentrations (left). This correlates well with zeta potential measurements, showing a charge

neutralization at 1 mM DTAC (right), making it more prone to agglomerate


51

Metallic Nanoparticles and their interfacial properties

Stark Kirsty

1*, Cayre Olivier

1, Biggs Simon

2

1Institute of Particle Science Engineering, School of Chemical and Process Engineering,

University of Leeds 2Faculty of Engineering, Architecture & Information Technology,

The University of Queensland


Particle stabilised emulsion systems have received a renewed interest over the past few years

due to their differing properties compared to conventional surfactant stabilised emulsions.

Nanometer sized particles are able to stabilise emulsion droplets as small as a few

micrometers in diameter. Nanoparticles have been shown to adsorb strongly to oil-water

interfaces.

In this work we describe a nanoparticle system, where the polymeric stabilisers for the

particle themselves facilitates the particle adsorption at liquid-liquid and liquid-air interfaces.

In particular, we will show the use of metallic nanoparticles to stabilise hexadecane in water

emulsions.

Polymer-stabilised nanoparticles were synthesised via a one-pot method, whereby metal ions

are reduced in the presence of the polymer. Studies have been conducted which demonstrate

the drastic influence of the ratio between polymer and metal particles on the interfacial

tension measurements. Additionally metallic nanoparticles provide functionality, such as the

potential for acting as catalysts and therefore efforts to maximise the emulsion droplet surface

loading of nanoparticles have been made. We present here some initial studies to show the

effect of oil to water volume ratio and particle concentration on both the characteristics of the

emulsions produced and the interfacial rheology of corresponding 2D interfaces. Comparisons

are also drawn between the adsorption on corresponding 2D polymer surfaces.

Figure 1: a) TEM micrograph of polymer stabilised metal nanoparticles, b) cryoTEM micrograph of nanoparticle

stabilised oil droplet


52

Figure 1 Aerogel formation via sol-gel technology

Sol-Gel derived nanostructured materials for thermal insulation

applications

Dervin Saoirse*, Pillai Suresh

Institute of Technology Sligo, Nanotechnology research group, Department of Environmental

Science, Ash lane, Sligo, Ireland


Sol gel technology facilitates effortless control of the composition, properties, and nano-

architecture of nanosystems, depicting this process as an advantageous approach for the

synthesis of nanostructures, such as aerogels. Aerogels are highly porous nanostructured solid

frameworks of gel, isolated in tact from the gels liquid component, formed as a result of the

agglomeration of solid nano-sized particles dispersed within a homogenous precursor.

At present, buildings account for approximately 40% of Europe’s energy consumption, with

almost half of this energy required for heating and cooling purposes alone. Such poor energy

ratings advocate a demand for novel, effective thermal insulation materials. The current

research therefore proposes to employ aerogel powders as an insulation material, in the form

of a paint additive. Aerogels express remarkable features including ultralow density and

thermal conductivity, yielding an ideal material for thermal insulation applications. Added to

a paint, the aerogel powders will act as an additional layer of insulation, creating an energy

efficient building. Thus this study aims to optimise the sol-gel process in order to produce an

aerogel with abundant, nanometre scale pores (≥90% air), high surface area (>600m2/g) and

ultra-low thermal conductivity and further enhance the mechanical strength, of the

occasionally brittle, nanostructured aerogels via the incorporation of graphene into the aerogel

sol. The synthesis of graphene reinforced aerogels, and the characterisation of the

nanostructures using XRD, Raman and FESEM will be discussed.

Literature:

1. EU Directive 2010/31/EU of the European Parliament and of the Council of 19 May 2010, Energy

performance of buildings

2. Xie, T ; He, Y.L. Hu, Z.J. (2013), Theoretical study on thermal conductivities of silica aerogel

composite insulating material, International Journal of Heat Transfer, 58, 540-542.

3. Baetens, Ruben, Bjørn Petter Jelle, and Arild Gustavsen. Aerogel insulation for building

applications: a state-of-the-art review. Energy and Buildings 43.4 (2011): 761-769

Acknowledgements:

The authors would like to acknowledge Science Foundation Ireland (SFI) for financial support to carry

out the research.


53

Adhesion between Surfaces in the Presence of Polyelectrolyte

Multilayers made with Seaweed Polysaccharides

Tracey Ho

1*, Marta Krasowska

1, Kristen Bremmell

2, Damien N. Stringer

3,

David A. Beattie 1

1Ian Wark Research Institute, University of South Australia, Mawson Lakes, Adelaide, SA

5095, Australia 2School of Pharmacy and Medical Science, University of South Australia, City East Campus,

North Terrace, Adelaide, SA 5000 3

Marinova Pty Ltd, 249 Kennedy Drive, Cambridge, TAS 7170, Australia


A drive towards creating biologically relevant functional surface coatings has led to the

emergence of polysaccharide-based polyelectrolyte multilayers (PEM) for applications in

biomimetic lubrication. These polysaccharide-based PEM surface coatings are formed easily

through the Layer-by-Layer (LbL) assembly technique. In this study, we focus on the

formation and properties of polysaccharide-based PEM consisting of alternating layers of

polyanionic fucoidan and polycationic chitosan. Whereas chitosan is a well-studied

component of polysaccharide PEMs, fucoidan, a sulfated polysaccharide extracted from

seaweed, is relatively little studied in PEM formation. Two pharmaceutical-grade fucoidan

samples, extracted from two different species of seaweed, were studied in this work. The two

fucoidans exhibit variation in sugar monomer composition and in molecular weight.

The formation of the fucoidan/chitosan PEM was investigated by zeta potential

measurements, quartz crystal microbalance with dissipation monitoring (QCM-D), and

spectroscopic ellipsometry. Their behaviour in controlling surface forces and adhesion

between two silica surfaces was investigated using colloid probe atomic force microscopy

(CP AFM). Surface forces upon approach of surfaces, and magnitude of adhesion upon

retraction of surfaces, were determined layer-by-layer, as the multilayer built up. Differences

were observed dependent upon the identity of the outer layer (chitosan or fucoidan), and also

dependent on the identity of the fucoidan polymer. The implications of these observations on

the use of such PEM coatings as adhesion modifiers will be discussed.


54

Effect of triterpenoid and steroidal saponinson DPPC and

cholesterol monolayers

Orczyk Marta

1*, Kamil Wojciechowski

1

1Warsaw University of Technology, Faculty of Chemistry

* [email protected]

Saponins are a family of glycoside type biosurfactants, produced by plants, microorganisms

as well as some marine organisms. These natural biologically active substances present a

number of interesting properties. In spite of numerous potential applications of saponins there

is still lack of viable and detailed information confirming the effectiveness and mechanism of

their interaction with biological membranes. The most probable hypothesis explaining the

effect of saponins on biological membranes is based on formation of complexes with

membrane lipids, especially cholesterol. Nevertheless, the exact mechanism of action of

saponins on biological membranes has not yet been fully elucidated. Hence the necessity for

carrying out such research.

Fig. Possible application of saponins

In this study, we compare the activity of four different saponins, i.e., glycyrrhizic acid, α-

hederin, hederacoside C and digitonin on model Langmuir monolayers. The study was

conducted on monolayers composed of a single lipid (DPPC) and of its mixtures with

cholesterol. In order to study the resistance of the monolayers against saponins, a combination

of surface pressure relaxation and surface dilational rheology were employed. In an attempt to

observe the morphology changes and phase transitions of the single and mixed monolayers

exposed to different saponins, fluorescence microscopy was additionally employed. All

studied saponins are capable of penetrating the DPPC and DPPC/cholesterol monolayers.

However, clearly the most pronounced increase in surface preasure in Gibbs layers as well as

in the saponin-penetrated monolayers were observed for α-hederin and digitonin.

Acknowledgements:

This work was financially supported by the Polish National Science Centre, grant no. DEC-

2011/03/B/ST4/00780.


55

Zinc phthalocyanines locaton in methoxy poly(ethylene oxide) and

poly(L-lactide) block copolymer micelles – 1H NMR investigation

Łukasz Lamch

1*, Rafał Latajka

1, Kazimiera A. Wilk

1

1Department of Organic and Pharmaceutical Technology, Faculty of Chemistry, Wroclaw

University of Technology, WybrzezeWyspianskiego 27, 50-370 Wroclaw, Poland


Polymeric nanostructures, including polymeric micelles, have attracted much attention as

delivery vehicles in photodynamic therapy (PDT), owing to their abiliy to selectively

accumulate the desired photosensitizers molecules within the tumor tissue with vestigial or no

uptake by nontarget cells and necessarily without the loss of their activity. Phthalocyanines

are important group of photosensitizers for PDT, due to excellent photochemical properties,

i.e. exceptional stability and high light absorption coefficient with maximum in the red/near

IR region. The location of the solubilizate, depending upon the chemical structure of block

copolymer and cargo, is fundamental for improving photosensitizers’ properties after

encapsulation and interiactions with biological systems [1].

In our study we report preparation and characterization of polymeric micelles of methoxy

poly(ethylene oxide)-b-poly(L-lactide) loaded with three different zinc phthalocyanines (zinc

phthalocyanine (ZnPc) as well as its tetrasulfonic acid (ZnPc-sulfo4) and perfluorinated

(ZnPcF16) derivatives). The size distribution (i.e. the hydrodynamic diameter), the

morphology of the polymeric micelles and the concentration of the entrapped photosensitizer

was determined by DLS, AFM and UV–Vis spectroscopy, respectively. The studied

nanocarriers exibited good physical stability, high drug loading efficiency and appropiate size

(less than about 150 nm). The structure of polymeric micelles and the location of cargo were

analyzed utilizing nuclear magnetic resonance of protons (1H NMR). Spectra, performed in

different solvents, showed that poly(L-lactide) chains formed polymeric micelles solidelike

core in water. We proved that ZnPc-sulfo4 and ZnPcF16 interacts with poly(ethylene oxide)

chains of block copolymer and water molecules, despite their different hydrophobicity.

Polymeric micelles, loaded with ZnPc, were confirmed not to exhibit any interactions

between cargo and miclles corona. According to our results ZnPc was found to locate in the

polymeric micelles core, while both ZnPcF16 and ZnPc-sulfo4 – in polymeric micelles corona.

Literature:

1. Łukasz Lamch, Urszula Bazylińska, Julita Kulbacka, Jadwiga Pietkiewicz, Katarzyna Bieżuńska-

Kusiak, Kazimiera A. Wilk. Polymeric micelles for enhanced Photofrin® delivery, cytotoxicity and

pro-apoptotic activity in human breast and ovarian cancer cells. Photodiagn Photodyn Therapy 11

(2014) 570—585

Acknowledgements:

This work was supported by Wroclaw Research Center EIT+ under the project ‘Biotechnologies and

advanced medical technologies’ – BioMed (POIG 01.01.02-02-003/08-00) financed from the

European Regional Development Fund Operational Programme Innovative Economy 1.1.2, and was

also financed by a statutory activity subsidy from the Polish Ministry of Science and Higher Education

for the Faculty of Chemistry of Wrocław University of Technology.


56

Nanoparticle self-assembly in aqueous solutions; influence of

polymer’s molar mass and gemini surfactants’ spacer length.

Fotini Delisavva

*, Karel Prochazka, Mariusz Uchman

Department of Physical and Macromolecular Chemistry; Faculty of Science, Charles

University in Prague, Hlavova 8, 12840 Prague 2, Czech Republic


Nanoparticle self-assemly has been under thorough investigation for decades due to numerous

potential applications in cosmetics, detergent products and medicine1. In this study, we focus

on the coassembly of a series of gemini surfactants2, of the type alkendiyl-α,ω-

bis(dimethylalkylammonium bromide) with varying length of the spacer group3 (12-s-12, s=

2, 3, 4, 6, 8, 10, 12), mixed with block copolymer polyelectrolyte poly(ethylene oxide)-b-

poly(methacrylic acid)4 of different unit lengths, PEO705-PMAA476 and PEO681-PMAA188 in

aqueous solutions. The complex nanoparticles were characterized using dynamic, static and

electrophoretic light scattering, small angle x-ray scattering, atomic force microscopy and

cryo-transmision electron microscopy. Thermodynamic and kinetic aspect of the systems was

investigated using isothermal titration calorimetry. It was found that the properties of the

particles can be tailored by changing the spacer group of gemini surfactants, as well as the

length of polyelectrolyte block.

Literature: 1. Yuchun Han, Yilin Wang. 2010. Aggregation behavior of gemini surfactants and their interactions

with macromolecules in aqueous solution. Physical Chemistry Chemical Physics 13: 1939-1956.

2. Roul Zana. 2002. Dimeric (gemini) surfactants: effect of the spacer group on the association

behavior in aqueous solution. Journal of Colloid and Interface Science 248: 203-220.

3. Yuchun Han, Wentao Wang, Yongqiang Tang, Shusheng Zhang, Zhibo Li, Yilin Wang. 2013.

Coassembly of poly(ethylene glycol)-block-poly(glutamate sodium) and gemini surfactants with

different spacer lengths. Langmuir 29: 9316-9323.

4. Mariusz Uchman, Miroslav Stepanek, Sylvain Prevost, Borislav Angelov, Jan Bednar, Marie-

Sousai Appavou, Michael Gradzielski, Karel Prochazka. 2012. Coassembly of poly(ethylene

oxide)-block-poly(methacrylic acid) and N-dodecylpyridinium chloride in aqueous solutions

leading to ordered micellar assemblies within copolymer aggregates. Macromolecules 45: 6471-

6480.

Acknowledgements: The authors acknowledge the financial support from the Ministry of Education of the Czech Republic

(long-term Research Project No. MSM0021620857) and the Grant Agency of the Czech Republic

(Grants No. P208/12/P236, P106/12/0143 and P106/13-02938S).


57

Preparation of Colloidal Inkjet Inks by Emulsion Polymerisation

Mohmed Mulla*, Huai Nyin Yow, Olivier Cayre, and Simon Biggs

University of Leeds


Nanoparticles are widely used in ink formulations as they offer some very desirable

advantages, including a long shelf life due to the high stability of the dispersions, and

controllable jetting behaviour. The aim of this project is to produce high solids content, sub

100 nm monodisperse latex particles to be used as model inkjet inks. Highly concentrated (up

to 45 wt% solids content) stable PMMA latex particle dispersions have been prepared via

emulsion polymerisation. More specifically a chain transfer agent has been utilised to enhance

particle nucleation efficiency, aiding the preparation of polymer particles with a narrow

weight distribution and increased monodispersity. Our initial work has found that high

nanolatex concentration can be achieved with a relatively low emulsifier concentration,

without sacrificing the colloidal stability of the dispersions. Waterborne nanoparticles around

50 nm have been obtained with a 45 wt % solids content. These dispersions do not require any

lengthy processing to perform rheological experiments in regions where the particle

suspensions show clear shear thinning behaviour.

In this study, we systematically study the effect of the emulsifier, initiator and chain transfer

agent concentration on final particle size and polydispersity of the synthesised particles. We

also determine the depletion flocculation behavior, upon addition of free polymer to these

systems. In addition we also study the stability, deposition and jetting behavior of the

prepared dispersions at various particle concentrations, in ethylene glycol as a co-solvent and

at various concentrations of non-adsorbing polymer (to induce depletion flocculation).


58

Effect of the pore size of activated carbon nanoparticles on CDLE

(capacitive energy extraction based on double layer expansion)

M.M. Fernández*, G.R. Iglesias, S. Ahualli , M.L. Jiménez, A.V. Delgado

1

1Department of Applied Physics, School of Science, University of Granada, 18071 Granada,

Spain


The Capacitive energy extraction based on Double Layer Expansion (CDLE) is the name of a new

method devised for extracting energy from the exchange of fresh and salty water in porous

electrodes (1, 2). It is based on the change of the capacitance of electrical double layers at the

electrode/solution interface when the concentration of the bulk electrolyte solution is modified.

Fig. 1 shows the typical evolution of the cell voltage when 20 and 500 mM NaCl solutions are

exchanged.

0 100 200 300 400

300

350

400

450

FRESH WATER

Po

ten

tia

l (m

V)

Time (s)

SALT

WATER

Fig. 1 Cell voltage evolution when salt and fresh water solutions are exchanged through activated carbon

electrodes.

In this contribution we test different pore size carbons electrodes as supporting surfaces for the

exchange and energy harvesting process (3). We found that, despite of the huge accumulated

charge in small pore size electrodes, larger pore electrodes determines the ease with which the

ions can diffuse inside and therefore, improve the performing of CDLE cycles. Moreover, we

could optimise the extracted power of larger pore size electrodes by some parameters as charging

voltage, cycle time, charging and discharging resistance and distance between electrodes. All this

improvements have lead to a power of 6 mW/m2. This can be considered a promising result for

Capmix techniques

Literature:

1. R. E. Pattle. Production Of Electric Power By Mixing Fresh And Salt Water In The Hydroelectric

Pile. Nature, 174(4431):660–660, 1954.

2. D. Brogioli. Extracting renewable energy from a salinity difference using a capacitor. Phys. Rev.

Lett., 103(5):058501, July 2009.

3. Guillermo R. Iglesias, María M. Fernández, Silvia Ahualli, María L. Jiménez, Oleksander P.

Kozynchenko, and Ángel V. Delgado. Materials selection for optimum energy production by

double layer expansion methods. Journal of Power Sources, 261:371-377, 2014.

Acknowledgements:

This work was partially supported by PE2012-0694 (Junta de Andalucía, Spain) and FIS2013-47666-

63-1-R (MINECO, Spain) .


59

Anomalous birefringence of planar clay particles

Paloma Arenas-Guerrero

1*, Guillermo Iglesias

1, Ángel V. Delgado

1, María L. Jiménez

1

1Department of Applied Physics, University of Granada, Spain


Upon application of an external electric field, non-spherical nanoparticles in suspension can

orient giving rise to a macroscopic optical anisotropy known as electric birefringence. Although

the foundations of this phenomenon have been long-established [1], the process is hitherto not

fully understood and many materials with interesting properties have been reported to exhibit

anomalous birefringent behaviours that are still under discussion [2,3,4].

One of these materials is sodium montmorillonite (NaMt) [4,5], a plate-like clay which shows a

sign reversal of the birefringence, i.e., a shift in the axis of alignment of the particles. This

suggests that NaMt particles possess at least 2 different dipole moments, one along the symmetry

axis and one along the surface. However, the mechanism of formation and physical properties of

such dipoles are still to be satisfactorily elucidated.

Fig. 1 Field-dependence of the birefringence of a sample of NaMt (0.01 g/l, 0.3 mM NaCl) for several values of

the frequency of the applied field. The response goes from negative to positive when the frequency is raised.

With this motivation we have carried out a thorough analysis of the electric birefringence of

NaMt particles in aqueous suspension. Thus, the dynamic response of the system, the field

strength dependence and the spectral behaviour of this material have been studied under different

experimental conditions of pH and ionic strength in order to further understand the anomalous

birefringent phenomenology of the clay. Literature:

1. E. Frederiq, C. Houssier. Electric Dichroism and Electric Birefringence. Clarendon: Oxford

(1973).

2. H. Hoffmann, D. Gräbner. Adv. in Colloid and Interface Science 216, 20–35 (2015).

3. F. Mantegazza, M. Caggioni, M. L. Jiménez, T. Bellini. Nature Physics 1, 103-106 (2005).

4. D. Shah, C. Thompson. Hart. J. Phys. Chem., 67 (6), 1170-1178 (1963).

5. K. Yamaoka, R. Sasai. J. Colloidal and Interface Sci., 209 (2), 408-420 (1999).

Acknowledgements: This work was partially supported by PE2012-0694 (Junta de Andalucía, Spain),

FIS2013-47666-C3-1-R (MINECO, Spain) and the FPU 2014 Program (MEC, Spain).



60

Co-encapsulation of CdSexS1-x/ZnS quantum dots with

photosensitizers- colloidal stability and optical properties

Drozdek Sławomir

1*, Janusz Szeremeta

2, Marcin Nyk

2,

Marek Samoć2, Kazimiera A. Wilk

1

1Department of Organic and Pharmaceutical Technology, Faculty of Chemistry, Wroclaw

University of Technology, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland 2Advanced Materials Engineering and Modelling Group, Faculty of Chemistry, Wroclaw

University of Technology, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland


Polymeric nanoparticles are promising nanocarriers which have attracted much attention as a

delivery system in many biomedical applications due to improved permeation, specific cell

targeting and long circulation in blood. Co-encapsulated therapeutic and diagnostic

compounds in polymeric nanoparticles can be protected from the biological environment also

their bioavailability and biodistribution can be enhanced [1].

In our studies we report a new approach to fabricate theranostic nanocapsules prepared via

solvent/emulsification method. The hydrophobic quantum dots CdSexS1-x/ZnS (QDs) with

photosensitizer (zinc phthalocyanine ZnPc or aluminum phthalocyanine AlPc) were

encapsulated in biocompatible polymeric nanocapsules intended for energy transfer between

QDs as donors and photosensitizer molecules as acceptors. Pluronic P123 was applied as the

polymer component; Cremophor EL®

as the nonionic surfactant and silicone oil as the oil

phase. Dynamic light scattering (DLS), transmission electron microscopy (TEM) and atomic

force microscopy (AFM) investigations confirmed the particle diameter below 250 nm and

polydispersity of ca. 0.1-0.3. UV-vis spectroscopy was applied to determine encapsulation

efficiencies of ZnPc and AlPc (which were about 60% and 50%, respectively). The studied

nanocarriers demonstrated good kinetic stability, which was verified by backscattered profiles

obtained by the turbidimetric technique. The presence of energy transfer was proved by

evaluation of fluorescence lifetimes of QDs/ZnPc and QDs/AlPc-loaded nanocapsules using

time-correlated single-photon counting (TCSPC). The nanocarriers showed strong one- and

two-photon-induced luminescence, the latter upon excitation in the NIR biological optical

transmission window spectral range. Furthermore, we confirmed that the co-encapsulation of

QDs with ZnPc or AlPc in physically stable polymeric nanocapsules increases their solubility

in aqueous solution and moderates their chemical and physical status in the nanocarriers oil

microenvironment e.g., enhanced photostability. Our results suggest that this simple hybrid

system possesses the essential features required for both energy transfer and potential

application in PDT.

Literature:

1. Bazylińska Urszula, Drozdek Sławomir, Nyk Marcin, Kulbacka Julita, Samoć Marek, Wilk

Kazimiera. 2014. Core/Shell quantum dots encapsulated in biocompatible oil-core nanocarriers as

two-photon fluorescent markers for bioimaging. Langmuir 30: 14931−14943

Acknowledgements:

Support for this work by the National Science Center (Poland) under Grant No. 2012/05/B/ST4/00095

is gratefully acknowledged.


61

In situ QCM-D investigation of silver nanoparticle monolayer

formation on polycation modified surfaces

Katarzyna Kubiak*, Zbigniew Adamczyk, Magdalena Oćwieja



* [email protected]

Silver nanoparticles and their monolayers deposited on solid surfaces find

a wide spectrum of applications as antibacterial coatings, catalysis materials, antireflection

coatings or filters and conductive inks [1]. Because of that, silver particles play an important

role in nanoscience and nanomedicine.

The Quartz Crystal Microbalance (QCM) offer an exceptional opportunity to

investigate in situ kinetics of silver nanoparticles deposition by controlling a mass of particles

adsorbed on a surface of a sensor.

In this work silver particle monolayers at polyelectrolyte modified surfaces were

investigated. The deposition kinetics of silver nanoparticles on Au/SiO2/PAH substrate was

studied under in situ conditions by using the QCM method and the ex situ SEM imaging.

Because of low dissipation, the Sauerbrey’s equation was used for calculating the mass per

unit area (coverage). Measurements were done for various bulk suspension concentrations,

flow rates and ionic strengths. It was shown that particle deposition for the low coverage

regime is governed by the bulk mass transfer step that results in a linear increase of the

coverage with the time. A comparison of QCM and SEM results showed that the hydration of

the silver monolayers was negligible. This allowed one to derive a universal kinetic equation

that describes the mass transfer rates in the cell as a function of the bulk concentration, flow

rate and diffusion coefficient. Measurements were also performed for longer times and for

various ionic strengths where the deposition kinetics and the maximum coverage of particles

were determined. The experimental data confirmed a significant increase in the maximum

coverage with ionic strength, This was interpreted as due to the decreasing range of the

electrostatic interactions among deposited particles. These results were adequately interpreted

in terms of the extended random sequential adsorption (eRSA) model. Additionally, it was

shown that the QCM data matched the ex situ SEM results indicating that the monolayer

hydration was also negligible for higher coverage range. These results derived for the model

silver nanoparticle system can be exploited as reference data for the interpretation of protein

adsorption kinetics where the dry mass is needed in order to assess the extent of hydration.

Literature: 1. M. Oćwieja, Z. Adamczyk, K. Kubiak, J. Colloid Interface Sci. 2012, 376, 1.

Acknowledgment: This work has been supported by the EU Human Capital Operation Program,

Polish Project No. POKL.04.0101-00-434/08-00 and Malopolskie Centrum Przedsiebiorczosci

“Doctus” project.

http://vls1.icm.edu.pl/cgi-bin/search.pl/GetSearchResults?Any=&Title=&Abstract=&Author=Ocwieja%2C%20Magdalena&JournalTitle=&Past=No+Restriction...&Since=&Start=1&Max=10


62

Nanoparticle Production by Atomic Vapour Deposition on a

Liquid Jet

Michael J. McNally

1*, Gediminas Galinis

1, Hanieh Yazdanfar

1, Mumin M. Koc

1,

Oliver Youle1, Ruth L. Chantry

2, Klaus von Haeften

1

1University of Leicester, UK

2SuperSTEM, STFC Daresbury Campus


Synthesis of metal nanoparticles in liquids encompasses powerful empirical methods for

production of a variety of shapes, structures and compounds relevant to emerging applications

in medicine, sensing, catalysis and energy harvesting [1]. Chemical synthesis techniques

generate individual metal atoms or ions well dispersed in a solvent by chemical reduction. In

order to realise this reaction step, certain boundary conditions must be met, such as reagent

solubility and the presence of additives or impurities. These requirements complicate

synthesis and, in effect, mean that individual synthesis protocols are unique and specific to a

particular metal and shape [2]. Here we demonstrate an intuitively simpler route, the

introduction of metal atoms directly into a liquid solvent, in a procedure suitable for almost

any combination of metals and liquids.

A straightforward method for generating atomic metal vapours is evaporation in vacuum.

Subsequent deposition into solution has, to date, been limited to deposition into solvents with

low vapour pressure such as ionic liquids [3] and dense organic oils [4]. Using a liquid micro-

jet to inject solvent into vacuum, we have been able to deposit silver atoms directly into liquid

ethanol, producing stable nanoparticles (Fig. 1). An immediate advantage of this method is

that all particles produced are ligand free, with active surfaces accessible for enhanced

catalytic performance [5]. By depositing metal atoms into a solution of pre-existing

nanoparticles, or by simultaneous deposition of multiple materials, hybrid particles could be

produced in one step, and continuously, enabling the large-scale synthesis of nanomaterials

such as TiO2 decorated with gold for the photocatalytic splitting of water [6].

Fig. 1 Schematic of liquid jet production process: Metal atoms are evaporated from a target material, arriving as

individual, well dispersed atoms in the liquid jet (a), where they nucleate (b), and then grow into larger

nanoparticles (c).


63

Literature:

1. Lohse, S. E. & Murphy, C. J., 2012, Applications of colloidal inorganic nanoparticles: From

medicine to energy. J. Am. Chem. Soc. 134: 15607-15620

2. Xia, Y., Xiong, Y., Lim, B. & Skrabalak, S. E., 2009, Shape-controlled synthesis of metal

nanocrystals: Simple chemistry meets complex physics? Angew. Chemie - Int. Ed. 48: 60-103

3. Torimoto, T. et al., 2006, Sputter deposition onto ionic liquids: Simple and clean synthesis of

highly dispersed ultra-fine metal nanoparticles. Appl. Phys. Lett. 89: 243117

4. Wender, H. & Gonçalves, R. V., 2011, Sputtering onto liquids: from thin films to nanoparticles. J.

Phys. Chem. C. 115: 16362-16367

5. Li, D. et al., 2011, Surfactant removal for colloidal nanoparticles from solution synthesis: The

effect on catalytic performance. ACS Catal. 2: 1358-1362

6. Linic, S., Christopher, P. & Ingram, D. B., 2011, Plasmonic-metal nanostructures for efficient

conversion of solar to chemical energy. Nat. Mater. 10: 911-921


64

The effect of the protein hydrolysis on surface activity and surface

dilational rheology of type I collagen

Kezwoń Aleksandra

1*, Frączyk Tomasz

2, Chromińska Ilona

1, Wojciechowski Kamil

1

1Department of Microbioanalytics, Warsaw University of Technology, Warsaw, Poland.

2Department of Biophysics, The Institute of Biochemistry and Biophysics

Polish Academy of Sciences, Warsaw, Poland.


Collagen is the most abundant protein in vertebrates, constituting about 30% of all proteins in

tissues of a human body [1]. It can be found in skin, tendons, cartilages, bones, teeth and even

blood vessel walls [2]. There are currently about 28 known types of collagen differing in

amino acid composition, structure, length, biological role and abundance [1]. For the purpose

of the present research, the surface tension and surface dilational rheology for the native,

temperature- and pH-modified, as well as enzymatically hydrolyzed collagen (type I) were

measured using Axisymmetric Drop Shape Analysis method. Both the enzyme concentration

and incubation time were optimized for enzymatic hydrolysis using a collagen-specific

collagenase from Clostridium histolyticum, CHC, at 37°C.

Unmodified collagen is weakly surface active, but its layers formed by spontaneous

adsorption at the water/air surface display exceptional dilational rheology parameters. At high

oscillation frequency limit (0.1 Hz) the layers are predominantly elastic, with the storage

modulus, E’ = 36 mN/m for collagen concentration of 5 · 10−6

M [3]. Our results suggest that

even simple modifications (temperature, pH, enzymatic hydrolysis) of collagen can enhance

the collagen’s surface properties, especially in terms of the surface dilational elasticity

modulus, E’, which can reach values as high as 69 mN/m. The best results were achieved for

collagen only slightly hydrolysed, which encourages us to further extend our research in this

direction.

Literature:

1. Karl E. Kadler, Clair Baldock, Jordi Bella, Raymond P. Boot-Handford. 2007. Collagens at a

glance. J Cell Sci 120: 1955-1958.

2. Joseph M. Wallace, Qishui Chen, Ming Fang, Blake Erickson, Bradford G. Orr, Mark M. Banaszak

Holl. 2010. Type I collagen exists as a distribution of nanoscale morphologies in teeth, bones, and

tendons. Langmuir 26: 7349–7354.

3. Aleksandra Kezwoń, Kamil Wojciechowski. 2014. Effect of temperature on surface tension and

surface dilational rheology of type I collagen. Colloids and Surfaces A: Physicochem Eng Aspects

460: 168-175.

http://jcs.biologists.org/search?author1=Karl+E.+Kadler&sortspec=date&submit=Submit

http://jcs.biologists.org/search?author1=Clair+Baldock&sortspec=date&submit=Submit

http://jcs.biologists.org/search?author1=Jordi+Bella&sortspec=date&submit=Submit

http://jcs.biologists.org/search?author1=Raymond+P.+Boot-Handford&sortspec=date&submit=Submit

http://pubs.acs.org/action/doSearch?ContribStored=Wallace%2C+J+M

http://pubs.acs.org/action/doSearch?ContribStored=Chen%2C+Q

http://pubs.acs.org/action/doSearch?ContribStored=Fang%2C+M

http://pubs.acs.org/action/doSearch?ContribStored=Erickson%2C+B

http://pubs.acs.org/action/doSearch?ContribStored=Orr%2C+B+G

http://pubs.acs.org/action/doSearch?ContribStored=Banaszak+Holl%2C+M+M

http://pubs.acs.org/action/doSearch?ContribStored=Banaszak+Holl%2C+M+M


65

Stability of nanoscale nonionic films atop of discretely charged

electrolyte interface

Emelyanenko K.

1*, Emelyanenko A.

1, Boinovich L.

1

1A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of

Sciences, Moscow, Russia


Understanding the polarization effects and the electrostatic forces arising due to the presence

of ionized molecules or charged nanoparticles in the vicinity of interfaces is of considerable

interest both in science and technology. During last decades the theoretical analysis of this

problem was given in numerous papers, taking into account uniform and nonuniform smeared

charge distribution as well as discrete charges. The case of charges located inside ionic liquid

or aqueous electrolyte solution with nonpolar wetting film on the top may be of great interest,

on one hand, for studying the stability of such films. On the other hand, the interface charging

can be effectively used in nanotechnological applications, for example in controlling the

thickness of nonpolar and nonionic coatings. Note that for such systems the real charges are

dressed by a cloud of counterions and coions, that is, the polarization effects and the

electrostatic forces are significantly screened in all contacting media.

In this presentation we consider the surface forces arising in thin wetting film of nonpolar

liquid due to discrete charges embedded inside the aqueous solution at its interface with

nonionic wetting film. The polarization of contacting media by the discrete charges will be

treated by the image charge method. It will be shown that the arising polarization effects lead

to the appearance of additional contribution to the disjoining pressure in the film associated

with image charge forces. The analytical solution for disordered ensemble of charges at

water/oil interface will be presented for the cases of diluted and concentrated solutions [1]. It

will be shown that for particular systems the image-charge component of the disjoining

pressure can dominate over the other types of surface forces.

Literature 1. Emelyanenko K.A. Emelyanenko A.M., Boinovich L.B. (2015) Image-charge forces in thin

interlayers due to surface charges in electrolyte. Physical Review E 91, 032402 (8 pages). DOI:

10.1103/PhysRevE.91.032402.

Acknowledgements This study was financially supported by the Program for fundamental studies of Presidium of the

Russian Academy of Sciences, and by the President of the Russian Federation (grant for the support

of leading scientific schools of the Russian Federation, project no. NSh-2181.2014.3).


66

Quantitative determination of anchoring molecules on the surface

of ZnO particules and effects on electronical properties

J. Gamon

1,2,*, P. Barboux

1, D. Giaume

1, T. Le Mercier

2

1Institut de Recherche de Chimie Paris (IRCP), CNRS 11 rue Pierre et Marie Curie, 75005

Paris, France 2Solvay, Research and Innovation Center of Paris (RIC Paris) 52 rue de la Haie-Coq, 93306

Aubervilliers, France

* [email protected]

Improving electrical conductivity in thin film semiconductor devices such as solar cells,

thermoelectric modules, or in display applications for instance, remains a key point for better

performances. As polycrystalline films have the favor of the industry for their lower

fabrication cost, the limitation of the current is most of the time attributed to charge scattering

at the grain boundaries due to high energy barriers at the interface between grains.(1)

This work focuses on the understanding of intergranular electrical conductivity in the view of

improving thin film semiconductor performances deposited via a soft chemistry deposition

routes. In this goal, ZnO:Al was chosen as a model for our investigations as it is a reference

material in many semiconductor applications (sensors, solar cells, Transparent Conducting

Oxides)(2).

Many studies have already demonstrated the role of adsorbed species onto ZnO thin films and

nanostructures surfaces to improve sensor selectivity or charge transfer in dye sensitized solar

cells for instance (3).

With this in mind, we have performed liquid phase adsorption studies of organic molecules

onto ZnO particles through conductimetry and IR. Intergap molecular surface states were

identified thanks to electrochemical impedance spectroscopy (Mott Schottky measurements).

Conductivity on pressed powders was studied as a function of the applied pressure to show

the effect of the grain boundaries and of the powder compaction.

This study allows a quantitative determination of molecules at the surface of particles.

Literature:

1. Greuter F, Blatter G. Electrical properties of grain boundaries in polycrystalline compound

semiconductors. Semicond Sci Technol. 1990;5(2):111.

2. Klaus Ellmer, Andreas Klein, Bernd Rech. Transparent Conductive Zinc Oxide. Springer Series in

Material Science. 2008.

3. Galoppini E. Linkers for anchoring sensitizers to semiconductor nanoparticles. Coord Chem Rev.

2004 juillet;248(13–14):1283–97.


67

Surface-confined interactions of lipopolysaccharide layers

Christian Redeker

1*, Richard Stevenson

1, M. Carmen Galan

1, Wuge H. Briscoe

1

1School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS, UK


Gram-negative bacteria are widespread microbes and examples include key pathogenic

species such as Escherichia coli and Salmonella. They are characterised by the distinct

structure of their outer membrane, which is mainly comprised of bacterica-specific

lipopolysaccharides (LPS). In contrast to zwitterionic human lipids, LPS is negatively

charged. Hence, the membrane can act as a bacteria-specific target for cationic antibacterial

agents. Electrostatic and hydrophobic

interactions between the peptides and membrane

components can lead to disturbance of the

membrane order, weakening the protective and

regulatory functions of the bacterial membrane.

LPS and mixed phospholipid-LPS layers have

been used as model membranes to study the

interactions between peptides and bacterial

membranes [1]. However, the effect of the LPS

polysaccharide chain length, its composition in

the mixed model membrane, and presence of

divalent cations on the membrane structure and

interactions have not been systematically

studied. This study investigates the influence on

the structure and interactions of surface-confined

LPS layers as a function of LPS carbohydrate

chain length, calcium cation concentration and

surface properties using X-ray reflectometry

(XRR) [2] and the surface force apparatus (SFA)

[3]. Preliminary XRR results show the formation

of LPS (Rd mutant) bilayers on three surfaces of

different physicochemical properties (bare mica,

STAI-coated mica, polyethyleneimine (PEI)

coated mica) (Fig. 1) in the presence of calcium cations and elevated temperatures (45 °C).

We will further investigage the effect of a number antimicriobial peptides on the membrane

structure.

Literature:

1. Wasim Abuillan et al. 2013. Physical interactions of fish protamine and antisepsis peptide drugs

with bacterial membrane revealed by combiantion of specular x-ray reflectivity and grazing-

incidence x-ray fluorescence. Physical Review E. 88:012705.

2. Wuge H. Briscoe et al. 2012. Synchrotron XRR study of soft nanofilms at the mica-water

interface. Soft Mater. 8:5055

3. Wuge H. Briscoe et al. 2006. Boundary lubrication under water. Nature. 444:191

Acknowledgements: C.R. is supported by Douglas Everett fund.

10-7

10-6

10-5

10-4

10-3

10-2

10-1

100

Reflectivity

0.60.50.40.30.20.1

Q (Å-1

)

1

2

3

4

5

++

Fig.1 BM28 XRR curves from LPS liposomes adsorption with ~10 mM Ca++: 1) On negatively charged bare mica; RT; 2) On bare mica at 52 °C; 3) On positively charged PEI-coated mica; 52 °C; 4) Rinsed with 20 mM Ca++ subsequent to 3); 5) On hydrophobic STAI coated mica, 52 °C.


68

Nanopatterned charge distributions on polyetherimide electret-

films

Gödrich Sebastian

1*, Bartz Christian

2, Schmidt Hans-Werner

2, Papastavrou Georg

1

1Physical Chemistry II, University of Bayreuth, 95447 Bayreuth, Germany

2Macromolecular Chemistry I, University of Bayreuth, 95447 Bayreuth, Germany


Electrets are dielectric materials with quasi-permanent polarization due to external charging.

In particular, polymer electrets are widely used in various applications such as microphones,

electret-filters, and xerography. A promising class of such polymer electret materials are

polyetherimides (PEI). This class of aromatic polymers shows a good thermal stability and

has been characterized extensively in the recent years, in particular with respect to its

macroscopic charge storage properties [1, 2]. For applications, the charge stability with

respect to environmental influences, such as temperature and humidity is essential.

Here, we investigate by in-situ techniques the surface-potential decay of Ultem® 1000 PEI-

films with defined charge distribution in the nm-range at elevated temperatures and ambient

conditions. Charge is injected into the polymer films by an atomic force microscopy (AFM)

contact-charging approach (Fig. 1, a). Afterwards, the generated charge pattern is read-out by

Kelvin probe force microscopy (KPFM)-imaging (Fig. 1, b) during in-situ tempering of the

sample. Thereby, the temperature-induced surface-potential decay can be analyzed as a

function of time. Comparable in-situ studies have been carried out so far primarily with

respect to the influence of humidity.[3] Here, we compare the results obtained by scanning

probe techniques for local charge distributions with those by macroscopic techniques for

homogeneously charged Ultem® 1000 PEI-films and find good agreement. Electret films

with nano-structured charge distributions are predestined for applications in electret field-

effect transistors, energy harvesting MEMS, or high-density data storage.

Fig. 1 a) Charge patterns are generated in an Ultem® 1000 PEI film by applying voltage pulses between a

conductive AFM-tip and a conductive substrate serving as a counter-electrode. b) Surface-potential

measurement by KPFM-imaging showing a charge pattern (3 lines) prepared with the aforementioned charging

technique.

Literature: 1. Erhard D. P., Giesa R., Altstädt V., Schmidt H.-W., 2010, J. Appl. Polym. Sci., 115, 1247.

2. Erhard D. P., Lovera D., Giesa R., Altstädt V., Schmidt H. W., 2010, J. Polym. Sci. B: Polym.

Phys., 48, 990.

3. Knorr N., Rosselli S., Nelles G., 2010, J. Appl. Phys., 107, 054106.


69

Investigation of the structural properties of MgO-based

eco-sustainable cements

Tonelli Monica1*, Francesca Ridi1, Emiliano Fratini1, Piero Baglioni1, Silvia Borsacchi2,

Francesca Martini2, Marco Geppi2,3

1Department of Chemistry “Ugo Schiff” & CSGI, University of Florence, Sesto F.no (FI) 50019,

Italy 2Istituto di Chimica dei Composti Organo Metallici del Consiglio Nazionale delle Ricerche CNR,

U.O.S di Pisa, Pisa 56124, Italy 3Department of Chemistry and Industrial Chemistry, University of Pisa, Pisa 56124, Italy


Cement is the binder at the base of one of the most important building materials, the concrete.

Because of the large amounts involved in the global consumption, its production process is responsible

for ingent quantities of CO2 emitted [1]. Nowadays, worldwide interest is becoming more and more

focused in developing an eco-compatible cement and formulations based on reactive periclase (MgO)

constitute one of the most promising emerging technologies [2]. In the presence of water,

MgO/silicate mixtures hydrate and form a binder phase, M-S-H (magnesium silicate hydrate), a

colloidal gel analogue to calcium silicate hydrate, C-S-H, present in traditional cements. A systematic

study defining the relationship among composition, structure and properties of these binders is still

lacking, but this knowledge is essential to optimize the properties of building materials and to

modulate their perfomances to specific applications [3]. In this regard, the effect of mixing traditional

cement and MgO-based eco-sustainable cement was evaluated. In this work, we considered the effect

of changing percentages of Portland cement. The kinetics of hydration of the pastes prepared were

monitored, as they give access to crucial informations for practical applications. Concurrently, pastes

were characterized starting from molecular level up to the micro/macroscopic scale. The results show

that both C-S-H and M-S-H gel phases have been obtained and the identification of the two binders

confirm the idea that it could be possible to combine the ecological features of MgO-based cement

with traditional cements.

Fig. 1 Schematic illustration of the eco-sustainability of the MgO-based cement.

Literature:

1. Ellis M. Gartner and Donald E. Macphee. 2011. A physico-chemical basis for novel cementitious

binders. Cement and Concrete Research 41: 736-749.

2. Stuart M Evans and Nikolas Vlasopoulos. 2010. Novacem: Carbon Negative Cement and the

Green Cement Bond.

3. Francesca Ridi, Emiliano Fratini, Piero Baglioni. 2011. Cement: a two thousand year old nano-

colloid. Journal of Colloid and Interface Science 357: 255-264.

Acknowledgements: CSGI and FIR2013 (Project RBFR132WSM) for financial support.


70

Posters


71

P1_1

Many-body Van der Waals interactions in nanoscale wetting and

free films

Emelyanenko K.

1*, Emelyanenko A.

1, Boinovich L.

1

1A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of

Sciences, Moscow, Russia


Van der Waals forces result from electrodynamic interactions between the bodies separated

by a thin interlayer. They bear a universal character, acting between the bodies with any

chemical nature and represent one of the strongest type of interactions at small separations.

Two main distinct approaches are used for the calculation of these forces. The microscopic

approach was developed by Hamaker on the basis of London theory for interactions between

separate atoms. In the macroscopic theory, formulated by Dzyaloshinsky, Lifshitz and

Pitaevsky, the interaction between two bodies is considered as a result of interaction between

fluctuating electromagnetic fields.

Both abovementioned approaches are valid within definite restrictions, which do not allow

their application for calculation of forces between nanosize particles or for the analysis of

surface forces in very thin, a few molecular diameter films. However the accounting for the

many-body interactions in the frame of microscopic approach allows one to treat the van der

Waals interactions in abovementioned systems adequately. To realize this approach we have

adopted the coupled oscillating dipoles method. In this method the van der Waals interactions

between two bodies or in thin films are calculated by direct summation of two-atom, three-

atom, four-atom, etc. interactions. In our work we applied this approach to compute the van

der Waals forces in free [1] and wetting films. We have analyzed the peculiarities of surface

forces in very thin films and incomplete monolayers, where the macroscopic theory is not

applicable. Other problem addressed in our study was related to the influence of finite size of

substrate on the stability of wetting films.

Literature 1. Emelyanenko K.A. Emelyanenko A.M., Boinovich L.B. (2012) Calculation of van der Waals

Interaction Energy in Free Liquid Films Accounting for Many-body Contributions. Chemistry

Letters, 41, 1253-1255.

Acknowledgements This study was financially supported by the Program for fundamental studies of Presidium of the

Russian Academy of Sciences, and by the President of the Russian Federation (grant for the support

of leading scientific schools of the Russian Federation, project no. NSh-2181.2014.3).


72

P1_2

Irregularities of Drop Formation at a Circular capillary

T. Kairaliyeva

1,2*, M. Karbaschi

1, M. Taeibi-Rahni

1,3, S. Faraji

1, K.H. Schano

4,

S.B. Aidarova2 and R. Miller

1

1Max Planck Institute of Colloids and Interfaces, 14424 Potsdam/Golm, Germany 2Kazakh National Technical University after K.I.Satpayev, Almaty, Kazakhstan

3Sharif University of Technology, Teheran, Iran

4 Gamma-Service, Berlin, Germany


A wide range of important phenomena in fluid dynamics contains multiphase flows and thus

such flows are of great importance to many scientists and engineers. Even though there has

been a great deal of research conducted in this area of fluid mechanics, the complete

dynamics of such flows are not yet fully understood due to their complex interphase coupling,

whereby different phases may strongly affect one another. Fluid interfaces are omnipresent in

most modern technologies and their quantitative characterization is essential for the optimum

use of such technologies. It turned out over the recent years that non-equilibrium properties

are very essential and the interactions between physico-chemical interfacial properties and

hydrodynamics make interfacial dynamics considerably complicated. In particular, processes

like emulsification, foaming, or coating require the understanding of very dynamic properties.

The quantitative understanding of the mutual dynamical bulk-interface interactions is the

main challenge in studying the stability of many systems (like foams and emulsions). Thus,

the properties of the adsorbed layers depend on rather complex mutual bulk-interface

interrelations [1].

The drop volume method is a frequently used technique to measure the surface tension of

liquids and the interfacial tension between two immiscible liquids. Its application is limited to

a certain interval of drop formation time. At smaller drop formation times, less than say 20 s

for capillaries of about 1 mm in diameter, a remarkable hydrodynamic effect on the drop

formation can be observed. At still smaller drop times, irregularities can be observed which

appear to be of chaotic nature. More careful studies showed that these chaotic irregularities

are regular in nature and are highly reproducible. The aim of the present studies is to

investigate the nature of these irregularities, under certain conditions showing bifurcation [2].

In our work we used a specially designed instrument - Drop Detachment Analyzer (DDA).

This instrument can show us how the formation time of single drops at a circular tip of a

capillary tube are measured with high precision. During the work we expect that drop

formation time (DFT) to be linear with time, but in experiments non-linear effects have been

observed. The first objective was to find out what causes these non-linearities and second one

to check the effects of surface tension and viscosity on these phenomena. We used pure water,

different water-ethanol and water-glycerol mixtures.

Literature:

1. M. Taeibi Rahni, M. Karbaschi, and R. Miller, “Computational Methods for Complex Liquid-Fluid

Interfaces”, To be soon published in the series “Progress in Colloid and Interface Science”, CRC

Press, Taylor & Francis Group, in press

2. V.B. Fainerman, R. Miller, “Hydrodynamic effects in measurements with the drop volume

technique at small drop times. 2. Drop time and drop volume bifurcations”, Colloids and Surfaces, A:

Physicochemical and Engineering Aspects 97 (1995) 255-262.


73

P1_3 Effect of selected parameters on flotation recovery

in KGHM Polska Miedź S.A.

Księżniak Katarzyna

1*, Pawlos Witold

2, Hupka Jan

1

1Gdansk University of Technology, Faculty of Chemistry, Department of Chemical

Technology 2KGHM Polska Miedź S.A. - Divisions of Concentrators (O/ZWR)


The operations of Division of Concentrators KGHM Polska Miedź S.A. are comprised

of three ore enrichment plants, located in the vicinity of mines but having separate

organization structures. Ore processing facilities play special role in the production of copper

concentrate.

Our laboratory research data pertain to flotation efficiency of feeds with different

densities and at varying rotor speeds. The material used in the experiments originated from

preliminary flotation feed from the second technological line of ZWR Polkowice Region.

Froth flotation is one of the most important process in the field of mineral processing. The

success of flotation widely depends on proper selection of flotation reagents: collector and

frother. The mixture of ethyl and isobutyl sodium xanthates was used as collector. Flotation

was carried out in single fractional operations. The feed was add before process, reagents

were added in one portion and subsequently started flotation. The concentrate was collected in

each experiment at intervals of 7 minutes. The concentrate and tailings were dried, weighed

and then analysed for the content of copper.

In the investigation feed and remaining products were subjected to Cu content [%]

analysis, grain composition and Cu content determination in given grain classes. The flotation

efficiency measured as shows a linear increase of the recovery with an increase of feed

density and rotor speed.

Fig. 1 Flotation recovery (%) as a function of flotation pulp density for three different impeller rotational speed

Fig. 2 Cu concentration (%) (copper content in concentarte) as a function of impeller rotational speed for three different flotation pulp denisty


74

P1_4

Nanoparticle monolayers on colloid carrier particles

Maciejewska Julia*, Sadowska Marta, Oćwieja Magdalena

, Adamczyk Zbigniew




Adsorption of colloid particles and proteins on larger micro-particles is an interesting

phenomenon from the basic science point of view. Elucidation of the adsorption mechanisms

is important for many practical processes, e.g., microcapsule formulations used for controlled

drug delivery. However, despite a vital significance, there are few systematic works in the

literature devoted to this subject. Therefore, the aim of this work was to quantitatively

evaluate nanoparticle deposition mechanisms on spherically shaped interfaces under diffusion

controlled transport conditions. Our system consisted of negative charged polystyrene latex

particles (820 nm in diameter) used as colloid carriers and positively charged amidine latex

nanoparticles (98 nm in diameter) or hematite nanoparticles (90 nm in diameter). Adsorption

of nanoparticles was studied by using the in situ LDV and the concentration depletion

methods involving AFM and SEM imaging (see Fig.1). This allowed one to determine the

electrophoretic mobility of larger negative latex particles as a function of the nanoparticle

coverage. Also the influence of ionic strength on the maximum coverage of particles was

systematically studied. These dependencies were quantitatively interpreted in terms of the 3D

electrokinetic model previously used for planar interfaces. In this way a robust method was

developed enabling one to determine the coverage of nanoparticles and protein on latex

carriers under in situ conditions. These calibration experiments obtained for monodisperse

amidine latex particles were also exploited for the interpretation of hematite nanoparticle

deposition from polydisperse suspensions.

Fig. 1 SEM micrograph: a) positively charged amidine latex nanoparticles b) positively charged hematite

nanoparticles, both adsorbed on negatively sulfonate polystyrene latex particles

Acknowledgements: This work is financially supported by the PRELUDIUM 2013/11/N/ST4/00981

and OPUS 2012/07/B/ST4/00559.

a) b)


75

P1_5

Foam formation and stability as controlled by surfactant

adsorption at the air-water interface

Mould Elizabeth

1*, Briscoe Wuge H.

1

1University of Bristol


Foams are ubiquitous in our everyday lives, widespread in cosmetics, detergency and food

products. An aqueous foam can be defined as a dispersion of gas in a liquid phase, generally

stabilized by the adsorption of surfactants at the air-water interface.1 This project aims to

examine thin-film stability as controlled by surfactant adsorption,2 studying the relationship

between surfactant structure and the properties of the resulting foam following gas dispersion,

with the synergistic effects of surfactant mixtures also considered. Different analytical

techniques have been used including tensiometry, foam analysis, and conductivity to measure

various physical parameters such as surface tension, the critical micelle concentration, and

foamability and decay parameters. Following the quantification of various physical

parameters these were linked to the macroscopic structure of the foam.

Literature: 1. Prud’homme Robert, Khan Saad. 1996, Foams: Theory, Measurements and Applications, Marcel

Dekker, Volume 57: 1-285.

2. Karakashev Stoyan, Manev Emil. 2014. Hydrodynamics of thin liquid films: Retrospective and

perspectives, Advances in Colloid and Interface Science.

Acknowledgements:

The project is supported by an EPSRC Impact Acceleration grant. E.M. would like to thank the

Briscoe research group for their guidance and support.

Water

Air

Surfactant

Air


76

P1_6

Shear rheology of hydrophobin adsorption layers at oil/water

interfaces and data interpretation in terms of a viscoelastic

thixotropic model

Radulova Gergana*

1, Danov Krassimir

1, Kralchevsky Peter

1,

Petkov Jordan2 and Stoyanov Simeon

3,4

1Department of Chemical Engineering, Faculty of Chemistry & Pharmacy, Sofia University,

1164 Sofia, Bulgaria 2Unilever Research & Development, Port Sunlight, Wirral, Merseyside CH63 3JW, U.K.

3Unilever Research & Development, 3133AT Vlaardingen, The Netherlands

4Laboratory of Physical Chemistry & Colloid Science, Wageningen University, 6703 HB

Wageningen, Netherlands


We investigated the surface shear rheology of class II HFBII hydrophobin layers at the

oil/water interface. Experiments in two different dynamic regimes, fixed rate of strain and

oscillations, have been carried out with a rotational rheometer. The rheological data obtained

in both regimes comply with the same viscoelastic thixotropic model, which is used to

determine the surface shear elasticity and viscosity, Esh and sh. Their values for HFBII at

oil/water interfaces are somewhat lower than those at the air/water interface. Moreover, Esh

and sh depend on the nature of oil, being smaller for hexadecane in comparison with

soybean-oil. It is remarkable that Esh is independent of the rate of strain in the whole

investigated range of shear rates. For oil/water interfaces, Esh and sh determined for HFBII

layers are considerably greater than for other proteins, like lysozyme and -casein. It is

confirmed that the hydrophobin forms the most rigid surface layers among all investigated

proteins not only for the air/water, but also for the oil/water interface. The wide applicability

of the used viscoelastic thixotropic model is confirmed by analyzing data for adsorption

layers at oil/water interfaces from lysozyme and -casein – both native and cross-linked by

enzyme, as well as for films from asphaltene. This model turns out to be a versatile tool for

determining the surface shear elasticity and viscosity, Esh and sh, from experimental data for

the surface storage and loss moduli, G' and G".

Fig. 1. (left) Plots of the shear stress sh vs. time t – data obtained in fixed-rate-of-strain regime. (right) Mean

shear elasticity Esh vs. the rate-of-strain amplitude a, calculated from the experimental G' and G".


77

P1_7

Improved Heat Stability of Whey Protein Isolate Stabilized

Emulsions by Conjugation with Low Methoxyl Pectin using

Dry Heat Treatment

Setiowati Arima Diah*, Saeedi Serveh, Van der Meeren Paul

Particle and Interfacial Technology Group, Ghent University


Whey Protein Isolate (WPI) is known to have excellent emulsifying properties. However,

WPI is also known to be very susceptible to heat denaturation. On the other hand, heat

processing is commonly encountered in industry for improving the safety and shelf life of

foods. As heat induced denaturation of whey proteins will lead to the alteration of their

functional properties, heating of whey protein stabilized emulsions can alter

theircharacteristics, such as the consistency, which may betransformed from liquid to highly

viscous fluid and, in the worst case, to a gel.Previous research has shown that combining the

hydrophobic properties of proteins and the hydrophilic properties of polysaccharides can help

improving the functional properties and heat stability of whey proteins. This can be achieved

through conjugation of protein and polysaccharide. In this research,the heat stability of oil in

water emulsions(10% w/w) stabilized by 0.5 % conjugates of WPI-Low Methoxyl (LM)

Pectin with ratio of 2:1(WPI:LM Pectin) was compared to the stability of emulsions stabilized

by 0.5% WPI and by 0.5% mixture of WPI and LM Pectin. The emulsions were prepared by

microfluidisation at a driving air pressure of 4 bars, at a pH value of 6.5 and 5, and with a

NaCl concentration of 30 mM.

WPI tended to have lower emulsifying properties at pH 5, i.e. around its isoelectric point,

which is thought to be due to a lack of electrostatic repulsion. On the other hand,

electrophoretic mobility measurements indicated that conjugation shifted the isoelectric point

to a lower pH value, which caused the conjugates to be able to maintain their functionality at

the native protein’s isoelectric point. Particle size distribution results indeed showed that the

conjugates displayed much better emulsifying properties at pH 5.

WPI stabilized emulsions displayeda poor stability towards heat irrespective of pH and ionic

strength at temperatures above 80°C. On the other hand, emulsions stabilized by conjugates of

WPI and LM Pectin exhibited excellent heat stability. Upon heating at 80oC up to 20 minutes,

oil droplet size measurement showed that there was almost no change in the particle size

distribution of the conjugate-stabilized emulsions after heating. Viscosity measurements

showeda similar trend: whereas the consistency of emulsions stabilized by WPI ranged from a

highly viscous to a gel-like structure after heating, heat treated emulsions stabilized by

conjugates did not show any change in consistency and had flow behavior indexvalues close

to Newtonian fluid (n=1). This pronounced heat stabilizingeffect of LM Pectin,however, was

not observed in emulsions stabilized by a mixture of WPI and LM Pectin. Therefore, the

conjugation between WPI and LM Pectin seems to play an important role for the improved

emulsifying and heat stabilizing propertiesof the emulsion.

Overall, our experiments indicated that conjugation of WPI and LM Pectin by dry heat

treatment could largely improve the functional properties of the protein, whereby not only the

pH sensitivity, but also the heat-sensitivity of WPI-stabilized emulsions could be significantly

improved.


78

P1_8

Surfactants and polymers at air-water interface: from molecular

interactions and interfacial structures to foaming properties

Slastanova Anna

1*, Chen Meng

2, Robles Eric

3, Briscoe Wuge H.

1

1University of Bristol

2Procter & Gamble Beijing Innovation Centre

3Procter & Gamble Newcastle Innovation Centre


Liquid foams are a class of soft matter defined as a dispersion of gas bubbles in a surfactant

solution. The stability of a foam is influenced by the layer of surfactant/polymer complexes at the

air-water interface. Understanding the structure and properties of this interfacial layer is therefore

of fundamental importance and relevance to a variety of practical applications, e.g. consumer

products and oil industries. In recent years, studies using surface-sensitive experimental

techniques such as X-ray and neutron reflectivity have considerably advanced our understanding

on interfacial behaviours of these mixtures1. However, the correlation is yet to be fully established

between polymer structural parameters (e.g. polymer architecture, charge density, molecular

weight and hydrophobicity) and the complex polymer/surfactant interfacial behaviour. Two

neutral comb co-polymers (arbitralily named Polymers A & B) with a hydrophilic PEG backbone

and differing lengths and densities of hydrophobic PVAc grafts were studied using surface

tensiometry, foam analysis, and X-ray reflectivity. Such comb co-polymers can be thought of as a

very sparsely grafted polymer brush, with interesting interfacial properties and effective roles in

stabilising foams and removing grease. Our initial XRR results (Fig. 1) at the solid-liquid

interface of Polymers A & B indicate their strong interactions with lipid multilayers, and suggest

promising detergency properties.

Fig. 1 a) X-ray reflectivity results of Polymers A and B with a DOPC lipid multilayer obtained at ESRF BM28;

b) Proposed mechanism of detergency mediated by the polymer, whereby lipid multilayers are disrupted and

removed in larger blocks of lipids rather than layer by layer.

Literature:

1. Taylor DJ., Thomas RK., Penfold J. 2007. Polymer/surfactant interactions at the air/water interface.

Advances in Colloid Interface Science 132: 69-110.

Acknowledgements: The project is jointly funded by EPSRC Case Award and Procter & Gamble (P&G). The polymers are

kindly donated by P&G. Advice and support from Dr Meng Chen and Dr Eric Robles at P&G Beijing

and Newcastle Innovation Centres, repectively, are gratefully acknowledged.

a)

b)


79

P1_9

Adsorption of As(III) from aqueous solutions by fly ash

agglomerates: Dynamic study

Justyna Ulatowska*

Wroclaw University of Technology, Faculty of Chemistry, Division of Chemical Engineering,

Norwida 4/6, 50-373 Wrocław, Poland


Many efforts have been made to remove As(III) from water and wastewater using various

adsorbents [1]. Fly ash is a powdery material generated from the combustion of coal in power

plants and has a pozzolanic property and therefore it is valuable and desirable material. In

many different branches of industry, fly ash is converted into more convenient compressed

form of granules, pellets or briquettes [2]. Granulated fly ash has been used as a sorbent for

heavy metal ions such as As(III), Cu(II) or Cd(II) [2,3].

The purpose of this study was to investigate the possibility of the utilization of fly ash as

a low cost adsorbent. Dynamic tests were carried out in terms of breakthrough curves of

lab-scale fixed bed column at different parameters: flow rate, size of fly ash agglomerates and

the amount of sorbent. Adsorption dynamic of As(III) was studied in a 0.025 m length and

0.015 m ID glass column, bed with fly ash agglomerates of size from 2.5 to 5.0 mm (20 g).

The liquid flow rate was 1.66 mL/min, initial As(III) concentration was 1000 mg/L and

experiments were performed at room temperature (about 25±1 oC).

The adsorption dynamic was described by Thomas and Yoon-Nelson models, and the

experimental data fitted well with Yoon-Nelson model. The external mass transfer and the

pore diffusion coefficient could be estimated using theoretical correlations [4]. It was shown

that the mass transfer process is controlled by the film mass transport in liquid.

The test results indicated that fly ash agglomerates could be used as a cheap adsorbent for the

removal of As(III) from aqueous solutions.

Literature:

1. Mohan Dinesh i Pittman Charles. 2007. Arsenic removal from water/wastewater using adsorbents –

A critical review. Journal of Hazardous Materials 142: 1-53.

2. Polowczyk Izabela, Bastrzyk Anna, Koźlecki Tomasz, Sawiński Wojciech, Rudnicki Piotr,

Sokołowski Adam i Sadowski Zygmunt. 2010. Use of fly ash agglomerates for removal of arsenic.

Environmental Geochemistry and Health 32: 361-366.

3. Aguilar-Carrillo Javier, Garrido Fernando, Barrios Laura i Garcia-Gonzalez Maria Teresa. 2006.

Sorption of As, Cd and Tl as influenced by industrial by–products applied to an acidic soil:

Equilibrium and kinetics experiments. Chemosphere 65: 2377–2387.

4. Karau Andreas, Benken C., Thömmes Jörg i Kula Maria Regina. 1997. The influence of particle

size distribution and operating conditions on the adsorption performance in fluidized bed.

Biotechnology and Bioengineering 55: 54-64.

Acknowledgements: The work was financed by a statutory activity subsidy from the Polish Ministry

of Science and Higher Education for the Faculty of Chemistry of Wrocław University of Technology.


80

P1_10

Asphalt binder – aggregate interfacial interactions measurements

Przemysław Wojewódka*, Robert Aranowski, Christian Jungnickel




Adhesion between asphalt and aggregates is the most crucial parameter for pavement

durability. Insufficient adhesion results in stripping process of asphalt binder from the surface

of the aggregate, what can lead to damage of the pavement. In this regards, estimation of the

adhesion forces in the simple and quick way is very important.

In this paper, we present method developed for asphalt-aggregate contact angle direct

measurements in a wide range of temperature. Contact angles at the mineral-binder-air

interface were measured using a high temperature contact angle goniometer by a sessile drop

technique, which allows quick estimation of adhesion agent and aggregate type impact on

asphalt mixes durability. Developed method was verified by two other techniques – EU

Standard Test Method 12697 and by calculation contact angles with Young-Dupré equation.

The surface tensions values were obtained by the contact angle measurements between

samples and probe liquids with well-known surface tension. Research was performed with

granite and limestone aggregates and with the road binder paving grade 35/50 (range of

needle penetration @25°C).


81

P1_11

Zeta potential of colloidal particles covered with proteins

Atsushi YAMAGUCHI

1 and Motoyoshi KOBAYASHI

2*

1Graduate School of Life and Environmental Sciences, University of Tsukuba, Japan

2Faculty of Life and Environmental Sciences, University of Tsukuba, Japan


Colloidal particles covered with proteins are found in many applications in pharmacy,

cosmetic, food, and so on. In these applications, predicting and controlling the interfacial

properties of protein-covered particles are important. In the present study, we measured

adsorption mass of lysozymes on silica particles (diameter 302 nm) and zeta potentials of

silica particles covered with lysozymes. Moreover, zeta potentials of silica particles with

lysozymes were analyzed by using 3D model with zeta potentials of lysozymes and silica

particles experimentally determined.

In 10 mM KCl, zeta potentials of lysozymes are 31 mV at pH 5 and 16 mV at pH 7, and

those of silica particles are -10 mV at pH 5 and -41 mV at pH 7. Adsorption mass at pH 7 is

larger than that at pH 5 (Fig.1). This is because, at pH 7, the electric repulsive force between

lysozymes is weak and the electric attractive force between a lysozyme and a silica particle is

strong. All the lysozymes are adsorbed on silica particles till the adsorption mass reaches near

the maximum value.

Zeta potentials of bare silica particles are negative (Fig.2). Then they gradually get close to

0 mV by adsorption of lysozymes. Further adsorption of lysozymes causes charge reversal of

silica particles. Calculated zeta potentials by 3D model are in good agreement with

experimental ones at low adsorption mass. Especially 3D model successfully describes the

isoelectric point at both pH. When the adsorption amount of lysozymes is high, on the other

hand, calculated values underestimate experimental ones. We suppose this discrepancy is

caused by the change of deprotonation amount of lysozymes and silica particles upon

adsorption.

-50

-40

-30

-20

-10

0

10

20

30

0 0.005 0.01 0.015 0.02 0.025

Zet

a p

ote

nti

al (

mV

)

Added lysozyme /mass of silica (g/g)

pH 5, Experiment

pH 7, Experiment

pH 5, 3D model

pH 7, 3D model

Fig.1 Adsorption mass of lysozymes on silica particles at 10 mM KCl. Symobols are experimental values (○: pH 5, □: pH 7). The full line represents the adsorption mass if all the added lysozymes are completely adsorbed on silica particles.

Fig.2 Zeta potentials of silica particles covered with lysozymes at 10 mM KCl. Symobols are experimental values (○: pH 5, □: pH 7). Lines represent the culculated values with 3D model from zeta potentials of lysozymes and silica particles.

0

0.005

0.01

0.015

0.02

0.025

0 0.005 0.01 0.015 0.02 0.025

Ad

sorp

tion

mas

s (g

/g)

Added lysozyme /mass of silica (g/g)

completely adsorb

10 mM KCl, pH 7

10 mM KCl, pH 5


82

P2_1

Fatty acid induced growth of giant micelles in ternary surfactant

solutions

Georgieva Gergana

1*, Anachkov Svetoslav


1,

Danino Dganit2, Abezgauz Ludmila

2, Liebewirth Ingo

3, Koynov Kaloian

3

1Dpt. Chemical and Pharmaceutical Engineering, Sofia University, Sofia, Bulgaria

2Dpt. Biotechnology and Food Engineering, Technion - IIT, Haifa, Israel

3Max Planck Institute for Polymer Research, Mainz, Germany


Synergistic growth of rodlike micelles was recently reported in binary mixed solutions of

anionic (SLES, sodium laurylethersulfate) and zwitterionic (CAPB, cocamidopropyl betaine)

surfactants at relatively low concentrations1. In our study, the composition in terms of SLES and

CAPB was selected to be near the maximal micelle size of the binary system and we added a third

component – fatty acid: caprylic (HC8) and lauric (HC12). For a given fatty acid concentration,

the viscosity of the micellar solution exhibits a sharp and high maximum, which is higher for the

short-chain fatty acid. Experiments with polarized light and NMR revealed that these viscous

solutions are isotropic, rather than liquid-crystalline. Cryo-TEM experiments of the ternary

micellar solution with lauric acid demonstrated a complex phase behavior: wormlike micelles to

the left of the peak; giant interweaved wormlike micelles at the peak, and wormlike micelles

transforming into disclike aggregates to the right of the peak. Such coexistence of worm-like and

disclike aggregates is possible in view of the theory on micellar growth2. In the case of HC8,

cryo-TEM imaging revealed that giant interweaved wormlike micelles form in the vicinity of the

peak in viscosity. The observed resonance growth of giant micelles could be explained by a fine

balance of packing constraints, which significantly depend on fatty acid concentration.

Fig. 1 Dependence of viscosity on fatty acid concentration (left) and a cryo-TEM image at the peak (right).

Literature:

1. Christov Nikolay1, Denkov Nikolai


3, Ananthapadmanabhan Kavssery

4, Lips

Alex5. 2004. Synergistic sphere-to-rod micelle transition in mixed solutions of sodium dodecyl

sulfate and cocoamidopropyl betaine. Langmuir 20: 565-571.

2. Anachkov Svetoslav1, Kralchevsky Peter

2, Danov Krassimir

3, Georgieva Gergana

4,

Ananthapadmanabhan Kavssery5. 2014. Disclike vs. cylindrical micelles: Generalized model of

micelle growth and data interpretation. J. Colloid Interface Sci. 416: 258-273.

HC8 in 70 mM CAPB + 30 mM SLES-1EO

25 oC

HC8 concentration (mM)

0 10 20 30

Vis

co

sit

y (

mP

a.s

)

0

10000

20000

30000

27900


83

P2_2

Investigation of the interaction between phospholipids and tetra-

p-guanidinoethylcalix[4]arene having antibacterial activity

Gorczyca Marcelina

1*, Korchowiec Beata

1, Korchowiec Jacek

1, Augustyniak Krzysztof

1,

Regnouf-de-Vains Jean-Bernard2, Rogalska Ewa

2

1Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060 Krakow, Poland

2Structure et Réactivité des Systèmes Moléculaires Complexes, BP 239, CNRS/Université de

Lorraine, 54506 Vandoeuvre-lès-Nancy cedex, France

* – [email protected]

Calixarenes, a class of macrocyclic oligomers, have shown antibacterial activity. In this

regard, we demonstrated recently that different calixarene derivatives modify the properties

of model membranes [1-2]. In the present work the behavior of tetra-p-

guanidinoethylcalix[4]arene (CX) and its monomer p-guanidinoethylphenol (mCX) in

a membrane environment was studied. CX was synthesized as an antibacterial agent. Indeed,

this derivative is active against different Gram-positive and Gram-negative bacteria and does

not show cell toxicity [3]. Interestingly, the antibacterial activity of mCX is much weaker

compared to CX. Here, all atom molecular dynamics simulations (MD) and surface pressure

measurments were employed to better understand the mechanism of the the interaction of CX

and mCX with lipid membranes. A zwitterionic 1,2-dimyristoyl-sn-glycero-3-phosphocholine

(DMPC) and a negatively charged 1,2-dimyristoyl-sn-glycero-3-phospho-L-serine (DMPS)

were used as models of eukaryotic and bacterial cell membranes, respectively. All MD

simulations were performed using NAMD2 package and CHARMM27 force field.

The simulations were carried out under a constant number of particles (N), constant

temperature (T), constant normal pressure (pN), and constant surface tens N

ensemble. The results obtained show that the two guanidinoethyl derivatives have different

impact on model lipid membranes. It was demonstrated that CX and mCX concentrate near

the anionic DMPS monolayer. Moreover, in contrast to the p-guanidinoethylphenol,

calixarene penetrates the hydrophobic part of the phospholipid film. In the case of the

zwitterionic DMPC, no significant effect of CX and mCX on the properties of phospholipd

film was observed. The overall results indicate that charge-charge and apolar interactions

between CX and lipids are responsible for the reorganization of model membranes.

Literature:

1. Korchowiec B., Gorczyca M., Ben Salem A., Regnouf de Vains J.-B., Rogalska E., Colloids Surf.

B 2013, 103, 217-222.

2. Korchowiec B., Korchowiec J., Gorczyca M., Regnouf de Vains J.-B., Rogalska E.,

J. Phys. Chem. B 2015, 119(7), 2990-3000.

3. Mourer M., Duval R. E., Finance C., Regnouf de Vains J.-B., Bioorg. Med. Chem. Lett. 2006, 16,

2960-2963.

Acknowledgements: This work was supported by the Polish National Science Centre, project No.

2012/07/B/ST5/00890. M. G. acknowledges the financial support from the project Interdisciplinary

PhD Studies “Molecular sciences for medicine” (co-financed by the European Social Fund within the

Human Capital Operational Programme).


84

P2_3

In Situ Spectroscopic Study of Polyelectrolyte Multilayer

Formation and Hydration under Confinement

Tracey Ho

1*, Marta Krasowska

1, Stephanie MacWilliams

1, Kristen Bremmell

2,

Damien N. Stringer3, David A. Beattie

1

1Ian Wark Research Institute, University of South Australia, Mawson Lakes, Adelaide, SA

5095, Australia 2School of Pharmacy and Medical Science, University of South Australia, City East Campus,

North Terrace, Adelaide, SA 5000 3

Marinova Pty Ltd, 249 Kennedy Drive, Cambridge, TAS 7170, Australia


The formation of fucoidan/chitosan-based polyelectrolyte multilayers (PEMs) has been

studied with in situ FTIR spectroscopy. Attenuated total reflectance (ATR) FTIR

spectroscopy has been used to follow the sequential build-up of the multilayer, with peaks

characteristic of each polymer being seen to increase in intensity with each additional

adsorption stage. In addition, spectral processing allowed for the extraction of spectra from

individual adsorbed layers of the build-up, and these were then used to provide unambiguous

determination of the adsorbed mass of the PEM at each stage of formation.

The nature of the hydration water within the polyelectrolyte multilayer has also been studied

with FTIR spectroscopy, specifically in situ synchrotron FTIR microscopy. Measurements

were made with the polymer film confined between two solid surfaces, to remove bulk water

from the area probed by the infrared evanescent wave. The acquired spectra have enabled the

hydrogen bonding environment of the polymer film hydration water to be determined. The

implications of the altered water environment in the multilayer are discussed within the

context of potential application of the multilayer film as a lubricant.


85

P2_4

Interaction cytolytic protein Cyt2Aa2 / lipid bilayer:

binding and structural changes

Alberto Moreno-Cencerrado

1 Sudarat Tharad

2, Jagoba Iturri

1, Margareta Mittendorfer

3,

Boonhiang Promdonkoy3, Chartchai Krittanai

2 and Jose L. Toca-Herrera

1

1Institute for Biophysics, Department of Nanobiotechnology, University of Natural Resources

and Life Sciences Vienna (BOKU), Vienna 1190, Austria 2Institute of Molecular Biosciences, Mahidol University, Salaya Campus, Nakhonpathom

73170, Thailand 3National Center for Genetic Engineering and Biotechnology, National Science and

Technology Development Agency, Pathumthani 12120, Thailand.


Cyt2Aa2, a cytolytic protein produced by the Bacillus Thuringiensis Gram-positive soil

bacterium known by its insecticide and antimicrobial properties,[1]

shows capability to bind

and form a protein complex with a synthetic lipid membrane without the requirement of a

receptor.[2]

However, the binding mechanism by which the interaction of Cyt2Aa2 to lipid

bilayers occurs is still unclear.

In this work, quartz crystal microbalance with dissipation (QCM-D) and atomic force

microscopy (AFM) techniques were employed for real time characterization of the interaction

of Cyt2Aa2 onto hybrid cholesterol/lipid surface-supported bilayers. This allowed not only

for a qualitative (i.e. binding kinetics, mechanical properties) but also for a quantitative

characterization (Cyt2Aa2 deposited mass) of the process, which turned to be critically

dependent on the protein concentration employed. Thus, at low concentrations (10 μg/ml)

Cyt2Aa2 binds slowly on the lipid bilayer forming a compliance protein/lipid layer with

aggregates. On the contrary, at higher protein concentrations (100 μg/ml) the binding is much

faster, and the complex formed is more rigid. Such a structure is also featured by the

appearance of randomly distributed holes. These results suggests that the protein/lipid bilayer

binding mechanism seems to be carpet-like at low protein concentrations and pore forming-

like at high protein concentrations.

Keywords: cytolytic protein, (cholesterol-)lipid bilayer, binding mechanism, atomic force

microscopy, quartz crystal microbalance with dissipation

Literature: 1. Hofte, H. et al. Microbiol. Rev. 1989, 53, 242-255.

2. Suktham, K. et al. Toxicon 2013, 74, 130-137


86

P2_5

Study of Microenvironment of Brij30 Reverse Micelles

with Optical Probes

N.Mzareulishvili

1, M.Kurtanidze

2 and M.Rukhadze

3

1Iv.Javakhishvili Tbilisi State University, I.Chavchavadze ave 3, 0179, Tbilisi


Reverse micelles became very popular in different areas of life sciences [1]. Reverse

micelles are used as artificial model of biomembranes due to resemblance of their

structure. Nonionic surfactants provide milder environment for encapsulation of enzymes

and proteins inside the water nanocages of reverse micelles. Investigation of reverse

micelles through the UV-visible absorption spectra of optical probes provides important

information about nature of water in water droplets of reverse micelles [2].

The microenvironment of reverse micelles of polyoxyethylene(4)lauryl ether(Brij 30) was

investigated by UV-visible spectroscopy on the basis of methyl orange(MO) and o-

nitroaniline as molecular probes.

The influence of both additives of water and water solutions of some kosmotropic and

chaotropic salts on the association degree of methyl orange with reverse micelles was

studied. Association degrees of MO with Brij30 reverse micelles were calculated by

absorption data of MO at wavelengths of 408 and 416 nm in 0.13 M Brij30 solution in

hexane at different water/surfactant ratio (W). The existence of three types of water is

revealed by dependence of methyl orange absorption maxima versus water content in the

nanocages of reverse micelles. Different influence of kosmotropic and chaotropic anions

on the formation of free water in water core of reverse micelle was observed, viz. the

formation of free water in water core of reverse micelle begins at different W in the

presence of perchlorate and iodide as compared with acetate and fluoride ions.

The influence of both additives of water and water solutions of some salts on the binding

of o-nitroaniline (o-NA) to the reverse micelles of Brij-30 was determined by UV-visible

spectroscopy. Binding constants of o-NA with Brij30 reverse micelles were calculated by

absorption data of o-NA at wavelengths of 376 and 400 nm in hexane (0.0 M and 0.23 M

Brij30). Concentrations of free and bound o-NA were determined by solution of equation

systems at intermediate concentrations of Brij30 [3]. Different influence of kosmotropic

and chaotropic anions on binding constant Kb was revealed, viz. the values of binding

constants in the presence of chaotropic anions are higher than those in the presence of

kosmotropic ions.

Literature:

1. P.M. Wiggins, Water in Complex environments such as living systems, Physica A. 314(2002)

485-491.

2. Qi L. and Ma J. Investigation of the Microenvironment in Nonionic Reverse Micelles Using

Methyl Orange and Methylene Blue as Absorption Probes. Journal of colloid and interface

science. 197 (1998) , 36 - 42.

3. R.D. Falcone, J.J. Silber, M.A. Biasutti, N.M. Correa, Binding of o-Nitroaniline to Nonaqueous

AOT Reverse Micelles, Organic Chemistry in Argentina, ARKIVOC, vii, (2011) 369-379.


87

P2_6

Properties of gelatin–chitosan polyelectrolyte complexes

Nina Sokolan

1*, Nikolay Voron’ko

1, Svetlana Derkach

1

1Murmansk State Technical University


The most frequently used stabilizers in the food industry are proteins and gelatin is the most

popular among them. This compound is the product of the hydrolytic degradation of fibrillar

collagen proteins and retains many important properties of collagen. However, the

composition of proteins (which provide the high rate of adsorption) with polysaccharides

(which are responsible for the steric factor of stabilization and increase in the viscosity of a

continuous phase) are currently considered as the most perspective stabilizers.

The protein/polysaccharide interaction can be realized by two modes: the formation of

covalent bonds between functional groups of macromolecules or electrostatic (non-covalent)

interactions. Electrostatic interactions lead to the formation of polyelectrolyte complexes. It is

worth mentioning that the complexes have a unique ability for reversible changes in their

phase state according to variations in ambient factors (pH, ionic strength, temperature etc.).

Therefore, they are treated as so-called smart or intelligent polymer systems.

In the presented work the interaction of gelatin and cationic polysaccharide chitosan with

stoichiometric (bio)polyelectrolyte complexes formation inside of the aqueous phase which

has pH less than isoelectric point of gelatin has been studied by capillary viscosimetry, UV

spectroscopy (Fig. 1) and dispersion of light scattering methods. The aqueous dispersions of

complexes show increase in the particle size of dispersed phase and accordingly the relative

viscosity compared with sols of the individual components – gelatin and polysaccharide.

Fig. 1 UV-spectra for gelatin (1) gelatin-chitosan (2 - 5) and chitosan (6) sols

at different concentration of chitosan and pH 3.7

The models and mechanism of (bio)polyelectrolyte complexes formation are discussed to be

due to the electrostatic interactions between the positive charged amino groups of chitosan

and negative charged amino acids residues (glutamic Glu and aspartic Asp acids) of gelatin.

The properties of gelatin–chitosan complexes as food emulsion stabilizers have been

investigated.

Acknowledgements:

This work was supported by the Russian Foundation for Basic Research (project № 14-08-98811

r_Sever_a).

0.0

0.5

1.0

1.5

2.0

2.5

3.0

180 200 220 240 260 280 300 320 340 360

A

l, nm

224

234 237

2

5 3 4

1 6


88

P2_7

Investigation of interaction between PAMAM dendrimers and

SiO2 surface

Tokarczyk Karolina*, Jachimska Barbara




Dendrimers are a new class of macromolecules increasingly used in a wide range of

scientific research. Over the past decade, much research has been focused on the application

of dendrimers both in biomedical fields (drug delivery, gene delivery, cancer-targeting

therapy, diagnosis) and catalytic research (solar energy conversion, artificial photosynthesis

and hydrogenation of olefins and aromatic compounds). There is particular interest with

properties such as globular shape and defined size resulting from low dispersities of these

macromolecules with regular and highly branched three-dimensional architectures.

The experimental studies of 6th

-generation poly (amidoamine) G6 PAMAM

dendrimers have been carried out using various techniques such as quartz crystal

microbalance (QCM-D) and surface plasmon resonance (MP-SPR). QCM-D and MP-SPR are

powerful methods that enable highly sensitive, qualitative, real-time, label-free, and

noninvasive detection of adsorbed macromolecules. These measurements allowed the

determination of the kinetics of adsorption of PAMAM from aqueous solution on a SiO2-

coated surface. We found that the thickness of the PAMAM films depends strongly on the pH

of the solution which influences swelling of the PAMAM films. These results supply

compelling experimental evidence for significant swelling of G6 PAMAM dendrimer upon its

protonation at the solid/solution interface. This phenomenon is a consequence of spatial

relocation of the dendrimer amide groups due to the interactions of the positively charged

amines with the oppositely charged condensed counter-ions and the penetrating water

molecules.

Literature: 1. Jachimska Barbara, Łapczyńska Marta, Zapotoczny Szczepan. 2013. Reversible Swelling Process

of Sixth-Generation Poly(amido amine) Dendrimers Molecule As Determined by Quartz Crystal

Microbalance Technique. J. Phys. Chem. C 117: 1136

Acknowledgements:



89

P2_8

Analysis of the PAMAM dendrimers-BSA complexes adsorption

using QCM-D and MP-SPR techniques

Tokarczyk Karolina*, Jachimska Barbara




Dendrimers are fascinating hyperbranched polymers, which are multifunctional, well-

defined and nano-sized compounds. Due to their unique properties and specific structure they

have been considered to be one of the most promising groups which could revolutionise

medicine. At present, dendrimers are very popular in many areas of research: drug delivery,

gene delivery, cancer-targeting therapy and diagnosis. Thus, control over the interactions

between these macromolecules and blood plasma media is a key parameter in the design of

advanced materials.

In our present work we analyse interactions between 6th-generation polyamidoamine,

PAMAM, dendrimers and bovine serum albumin (BSA). BSA albumin has been selected as it

belongs to the dominant group of mammalian blood plasma proteins, namely albumin. BSA is

characterised by: a relatively high molecular weight, three-domain structure and an

asymmetric charge distribution. BSA is able to adopt different conformations, which are

modified by changes in pH or ionic strength. The physicochemical properties of G6

PAMAM-BSA complexes have been investigated using different techniques such as surface

plasmon resonance (MP-SPR) and quartz crystal microbalance (QCM-D). These are powerful

methods that enable highly sensitive, qualitative, real-time, label-free and noninvasive

detection of macromolecular interactions. These measurements allow the determination of the

kinetics of adsorption of PAMAM-BSA from aqueous solution on a SiO2-coated surface. It

was found that the thickness of the PAMAM-BSA films depends strongly on the pH of the

solution. Comparison of the results obtained from MP-SPR and QCM-D makes it possible to

estimate the water content of the film. These results are essential for designing an alternative

scheme for drug and gene delivery.

Literature: 1. Jachimska Barbara, Łapczyńska Marta, Zapotoczny Szczepan. 2013. Reversible Swelling Process

of Sixth-Generation Poly(amido amine) Dendrimers Molecule As Determined by Quartz Crystal

Microbalance Technique. J. Phys. Chem. C 117: 1136

Acknowledgements:

This work was supported by Grant NCN OPUS4 2012/07/B/ST5/00767


90

P2_9

POPC/POPE lipid vesicles deposition on polyelectrolyte films

Wlodek Magdalena

1*, Kolasinska-Sojka Marta

1, Warszynski Piotr

1




Polyelectrolyte – supported lipid bilayers (SLB) are interesting systems for various

biomimetic applications such as cell-membrane models, biosensors and drug delivery carriers.

Understanding of the mechanism of supported lipid bilayers formation after exposure of small

lipid vesicles to a soft support is still a scientific challenge.

In this work, by combining the quartz crystal microbalance with dissipation (QCM-D) and

atomic force microscopy (AFM), we have investigated the formation of SLB on

polyelectrolyte multilayers as a function of buffer’s pH and an addition of NaCl as well as the

type of the underlying cushion.

The vesicles used were mixtures of zwitterionic 1-palmitoyl-2-oleoyl-sn-glycero-3-

phosphocholine (POPC) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine

(POPE) in phosphate buffer with or without NaCl addition. Three various pH values of buffer

were also investigated. Polyelectrolyte cushions applied as a support for lipid bilayer were

constructed by the layer by layer deposition of pairs of polycations (PEI, PDADMAC, PLL)

and polyanions (PSS, PGA) on quartz or silicon surface, with different number of layers.

Surface structure and properties of the solid substrates were characterized with ellipsometry to

find thickness and swelling properties and their roughness was determined using AFM.

We found that pathway of adsorption and deposition of lipid vesicles depended on pH and

addition of NaCl in buffer solution. The kinetics of SLB formation and the quality of already

formed lipid bilayer depended on the type of support used, i.e., type of cushion, the amount of

water entrapped within polyelectrolyte multilayer.

Acknowledgements:

The work presented was financed by the National Science Centre, Contract No. DEC-

2011/01/DST5/04913 and COST Action CM1101.


91

P3_1

The crystallisation of petroleum diesel and wax anti-settling

additives

Joanna Starkie

1*, Dr. Alex Routh

1

1University of Cambridge


Crystallisation of long chain n-alkanes from petroleum diesel causes engine problems at low

temperatures. Cold flow additives have been developed to counteract these problems. One

example are wax anti-setting additives (WASAs), which are used to limit the sedimentation of

wax crystals by reducing the crystal size and improving the stability of the wax crystals

suspensions. In comparison with other additives, the mechanism of WASAs action has

received very little attention in the scientific literature and current knowledge is mainly

sourced from industry and reported in patents.1

Initial work has been conducted to produce a model diesel system using long chain n-alkanes

that crystalise at room temperature to study the effect of cold flow additives and WASAs.

Figure 1 showes the effect of cold flow additives and WASAs on this model diesel system.

Fig. 2: a) shows large wax crystal plates formed without the presence of cold flow additives. b) shows smaller

needle-like wax crystals formed in the presence of cold flow additives and WASAs.

Literature:

1. Marie Emmanuelle, Chevalier Yves, Brunel Sylvain, Eydoux Franck, Germanaud Laurent and

Flores Philippe 2004, Journal of Colloid and Interface Science, 269: 117-125.

Acknowledgements: We thank Prof. Pete Dowding, Prof. Ken Lewtas for their help with this project. This work was

supported by Infineum Ltd. and the Cambridge Trusts.


92

P3_2

Hierarchical surface patterns from evaporative drying of

nanofluids

Wąsik Patryk

1,2,*, Redeker Christian

2, Trask Richard

3, Briscoe Wuge H.

2

1Bristol Centre for Functional Nanomaterials, University of Bristol, Bristol, BS8 1FD, UK

2School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS, UK 3Advanced Composites Centre for Innovation and Science, Bristol, BS8 1TR, UK


Nature articulates language of shapes fluently and delivers complex structures on all length

scales with ease via self-assembly. A simple, yet versatile method used in nanotechnology to

obtain surface patterns of hierarchical nanostructures is Evaporation Controlled Self-

Assembly (ECSA). During the ECSA process, particles inside a droplet are organized into a

variety of structures guided by the inter-particle forces and evaporation-induced flows of the

solvent. It can be harnessed to produce a plethora of surface patterns by manipulating

parameters such as particle concentration, size and shape, evaporation rate, addition of

polymers, and surface chemistry of the substrate.

Recently, the possibility of creating sophisticated residual patterns using a novel ECSA

process has been demonstrated [1]. In this process, upon evaporation, ZnO nanorods in a

droplet undergo chemical and morphological transformations via a dissolution and non-

equilibrium recrystallization process (Fig. 1a), producing a self-assembled 3D network

structures made of ultra-long (up to 1.5 cm) Zn(OH)2 fibres (Figs. 1 b-c). It has been shown

that, by further annealing, the 3D networks undergo further transformation to porous

structures made of ZnO nanocrystals (Fig. 1d).

In nanotechnology, we aspire to study and understand the mechanisms that control the

formation of surface patterns with intriguing geometry to create sophisticated hierarchical

nanostructures with tailored functionalities. Here we would like to present results on how size

and shape of ZnO nanoparticles, types of solvent mixtures, incorporation of other

nanoparticles and active compounds, as well as different substrates govern the structure and

composition of residual surface patterns created by the use of this novel ECSA process.

Fig. 1 a) ZnO nanorods in a nanofluid droplet undergo transformation into Zn(OH)2 residual surface patterns

during the evaporation, b)-c); d) porous network of ZnO, produced by annealing Zn(OH)2 network at 550 °C [1].

Literature:

1. Wu Hua et al. 2014. Self-assembly in an evaporating nanofluid droplet: rapid transformation of

nanorods into 3D fibre network structures. Soft Matter 10: 5243-5248.

Acknowledgements:

This project is funded by The Engineering and Physical Sciences Research Council (EPSRC) through

the Bristol Centre for Functional Nanomaterials (BCFN).


93

P4_1

Effects of Cationically Modified Polysaccharide Antidotes for

Unfractionated Heparin on Blood Pressure in Rats

Bartlomiej Kalaska

1, Kamil Kaminski

2, Emilia Sokolowska

1, Monika Kujdowicz

2,

Iwona Gawlik2* Krzysztof Szczubialka

2, Dariusz Pawlak

1, Maria Nowakowska

2,

Andrzej Mogielnicki1

1Department of Pharmacodynamics, Medical University of Bialystok, Mickiewicza 2C,

Bialystok, Poland 2Faculty of Chemistry, Jagiellonian University, Ingardena 3, Krakow, Poland


Introduction: Unfractionated heparin (UFH) as one of the most popular anticoagulants requires

safer antidote than currently used protamine. Derivatives of polysaccharides are proven to be

effective antidotes for UFH. They could replace protamine because of their better

biocompatibility and lower immunogenicity. One of protamine adverse effects that is particularly

dangerous is blood pressure decrease

Methods: Polymers were synthesized by substitution of Dextran (Dex) and γ-cyclodextrin (GCD)

with glycidyltrimethylammonium chloride (GTMAC) or N-acrylamidopropyl-N,N,N-

trimethylammonium chloride (APTMAC). Dex was cationically modified also by grafting

poly(allylamine hydrochloride) (PAH) using the radical polymerization process. The amino

groups in the resulting graft polymer (Dex40-PAH) were then substituted with arginine to obtain

Dex40-PAH-Arg polymer possessing two types of cationic groups. The structure of the polymers

was confirmed using 1H NMR, FT-IR and the elemental analysis, and proper compounds were

chosen for animal testing. MBP course was measured in rats over one hour after administration of

chosen GTMAC derivatives of sugar polymers. Maximum doses: Dex40-GTMAC2 (12.5 mg·kg-

1), Dex40-GTMAC3 (22.5 mg·kg1), Dex6-GTMAC (28.8 mg·kg-1), GCD-GTMAC2 (32.4

mg·kg-1) and protamine as reference agent (3 and 9 mg·kg-1). Course of mean blood pressure

(MBP) was also registered for 60 min after iv administration of UFH (300 U∙kg-1 followed by the

administration of the investigated polymer or protamine. The statistical analysis was performed

using the U Mann Whitney test.

Results: The obtained polymers were animal tested for UHF reversal effect, early toxicity and

effects on mean blood pressure. Studied agents reversed antithrombotic effect of UFH. Majority

of polysaccharides derivatives we obtained have no statistically significant effect on blood

pressure compared to vehicle. Some of the polymers caused severe hypotonia and animal studies

were interrupted.

Conclusion: The novel polymers have very promising properties and can potentially substitute

protamine as the UFH antidote.

Literature:

1. Kaminski K, Plonka M, Ciejka J, Szczubialka K, Nowakowska M, Lorkowska B, Korbut R, Lach

R (2011) Cationic derivatives of dextran and hydroxypropylcellulose as novel potential heparin

antagonists. J Med Chem 54: 6586-6596.

Acknowledgement: The study was supported by National Science Centre Grant No. DEC-

2011/03/B/NZ7/00755. BK was supported by funds from Leading National Research Center in

Bialystok (31/KNOW/2013). KK and IG was supported by National Science Centre Grant No. UMO-

2013/09/D/ST5/03864. KK, KS, and MN acknowledge the financial support of the

Foundation for Polish Science Team Programme co-financed by the EU European Regional

Development Fund, PolyMed, TEAM/2008-2/6.


94

P4_2

Polysaccharide nanocomposite particles for aerosol therapy

Jabłczyńska Katarzyna*, Sosnowski Tomasz R.

Faculty of Chemical and Process Engineering, Warsaw University of Technology


The work is focused on analysis of particles produced by spray drying from a precursor

containing biocompatible and biodegradable polysaccharide nanoparticles, which can be

carriers for active substances used in inhalation therapy. Suspensions of nanoparticles which

had been synthesized from dextran and carboxymethylcellulose were dried in Büchi B-290

spray dryer. The effect of process variables and type of precursor on the morphology and

powder characteristic was determined. Powder particles size and morphology examination

was carried out by means of scanning electron microscopy. Polisaccharide powders were

aerolized with commercially available dry powder inhaler and the size distributions of

resulting aerosol particles were measured using a diffraction spectrometer (Malvern).

The obtained results indicate that adjustment of the drying conditions allow the preparation

of the nanostructured modified polysaccharide powder particles with the characteristics

making them suitable for inhalation as drug carriers.

Fig. 1 a) Drying of nanosuspension droplet in different process conditions; b) SEM micrograph of powder

obtained by spray drying of suspension of nanoparticles from modified dextran.

Literature:

1. Jabłczyńska Katarzyna, Janczewska Magdalena, Kulikowska Aleksandra, Sosnowski Tomasz R.

2015. Preparation and Characterization of Biocompatible Polymer Particles as Potential

Nanocarriers for Inhalation Therapy. Int. J. Polymer Sci., 2015:1-8.

Acknowledgements:

The work is financed by National Science Centre, Poland, Project No. 2014/13/N/ST8/01667. The

study is related to the activity of the European network action COST MP1106 “Smart and green

interfaces - from single bubbles and drops to industrial, environmental and biomedical applications”

a b


95

P4_3

Sidewall Functionalization of Magnetically Triggered

Nanocontiner by Colloid Nanoparticles and Amide Groups.

A Molecular Dynamics Study

Konczak Lukasz1*, Panczyk Tomasz

1

1 Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences,



This work discusses two approaches for controlling of capping and uncapping the inner cavity

of the magnetically triggered nanocontiner1,2

, that is magnetic nanoparticles covalently linked

to carbon nanotube tips (Figure 1). The first approach is the noncovalent functionalization of

nanotube sidewalls based on adsorption of charged fine colloid nanoparticles. The second

approach is covalent functionalization of the nanotubes sidewalls by incorporation of polar

amide groups. Single and triple walled carbon nanotubes were analysed as well as the

presence of cisplatin molecules encapsulated in the nanotubes inner cavities. Both approaches

might result in obtaining the preferred energetic balance that is less stable uncapped state and

relatively low activation barrier for spontaneous transition from the uncapped to the capped

state. However, adsorption of fine colloids turned out to be too weak to make the whole

system stable for a long time. On the other hand, covalent attachment of polar amide

functional group leads to the required energetic balance of the nanocontiner.

Fig. 1 Covalent and noncovalent functionalization of carbon nanotube.

Literature:

1. Panczyk T., Jagusiak A., Pastorin G., Ang W. H., Narkiewicz-Michalek J., 2013. Molecular

Dynamics Study of Cisplatin Release from Carbon Nanotubes Capped by Magnetic Nanoparticles.

J. Phys. Chem. C: 117, 17327–17336.

2. Panczyk T., Da Ros T., Pastorin G., Jagusiak A., Narkiewicz-Michalek J., 2014. Role of

Intermolecular Interactions in Assemblies of Nanocontainers Composed of Carbon Nanotubes and

Magnetic Nanoparticles: A Molecular Dynamics Study. J. Phys. Chem. C: 118, 1353–1363.

Acknowledgements:

This work was supported by Polish National Science Center grant UMO-2012/07/E/ST4/00763.


96

P4_4

Novel fluorescent silicone materials

Krzywda Piotr

1*, Kasprzyk Wiktor

1, Bednarz Szczepan

1

1Cracow University of Technology, Faculty of Chemical Engineering and Technology,

Department of Biotechnology and Physical Chemistry,

Warszawska 24 St. 31-155 Krakow, Poland


Fluorescence is one of the most frequently used phenomena in many fields of science.

Nowadays, we are looking for original dyes that may contribute to the development of various

fluorescence techniques and expand the area of their applications. Novel group of fluorescent

dyes are the compounds obtained through low-temperature pyrolysis of citric acid in the

presence of α,β-diamines, α,β-aminoalcohols or α,β-aminothiols. These compounds are very

promising because of their non-toxic and biocompatible nature, relatively high fluorescence

quantum yields and chemical inertness. It is also possible to apply them in the synthesis of

fluorescent polymeric materials [1].

The main aim of this research was to develop a methodology for the synthesis of

transparent and flexible silicone materials with fluorescent properties. The first step was the

incorporation of α,β-diamine moieties into chemical structure of silicone polymer. Thus, N-

[3-(Trimethoxysilyl)propyl]ethylenediamine was used as a source of α,β-diamine groups. The

next step involved surface condensation of these groups with citric. Latter step produced

fluorescent derivative of 2-pyridone (i.e. 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-7-

carboxylic acid) chemically bonded to the silicone chain.

The obtained fluorescent flexible silicon materials were characterized according to

their FT-IR spectra, wetting and hydrolytic properties. Their possible application as silicone

material’s markers was confirmed by the fluorescence stability tests under various

environmental conditions. Furthermore, it was found, that obtained fluorescent polymers can

be used for the detection of iron ions, chromates and vitamin C.

Fig. 1. Transparent silicone material with fluorescent properties;

A- under daylight, B- under UV light 365 nm.

Literature:

1. Kasprzyk Wiktor, Bednarz Szczepan, Bogdał Dariusz. 2013. Luminescence phenomena of

biodegradable photoluminescent poly(diol citrates). ChemComm 49, 57, p. 6445-6447

Acknowledgements:

The authors gratefully acknowledge the support for this work from the European Union through the

European Social Funds (contract no. UDA-POKL.04.01.01-00-029/10-00) and (contract no.

UDAPOKL. 04.01.02-00-217/11-00).

A B


97

-10

-9

-8

-7

-6

-5

-4

-3

-2

-1

0

2 4 6 8 10 12

Elec

tro

ph

ore

tic

mo

bili

ty (

10

-8 m

2 V

-1 s

-1)

pH

(a) 10 mM without Ca2+ association

○ X=0.5

● X=0.1

△ X=0.01

■ X=0

-10

-9

-8

-7

-6

-5

-4

-3

-2

-1

0

2 4 6 8 10 12

Elec

tro

ph

ore

tic

mo

bili

ty (

10

-8 m

2 V

-1 s

-1)

pH

(b) 10 mM with Ca2+ association

○ X=0.5

● X=0.1

△ X=0.01

■ X=0

P4_5

Electrophoretic mobility of latex particles:

Effects of divalent counter-ions

Manami Nishiya

1, Takuya Sugimoto

1, and Motoyoshi Kobayashi

2*

1Graduate School of Life and Environmental Sciences, University of Tsukuba, Japan

2Faculty of Life and Environmental Sciences, University of Tsukuba, Japan


We measured electrophoretic mobility (EPM) of carboxyl latex particles in mixed

solutions of KCl and CaCl2. Experiments were carried out as functions of the solution pH, the

mixed molar ratio of Ca2+

to K+ (X= [Ca

2+] / [K

+]), and the ionic strength. Experimental EPM

was analyzed by using 1-pKH with or without Ca2+

association model, diffuse double layer

model, and the Ohshima equation including the relaxation effect or the Smoluchowski

equation neglecting the relaxation effect for calculating theoretical EPM value. Figure 1

shows the EPM of carboxyl latex particles at the ionic strength I=10 mM as a function of the

solution pH. In Fig. 1, symbols are experimental values, lines are theoretically calculated.

While the lines in Fig. 1 (a) are drawn by neglecting Ca2+

association, lines in Fig. 1 (b) are

obtained taking account of Ca2+

association. The magnitude of the EPM is large at high pH

due to deprotonation of carboxyl groups on the particle. At high pH, as the ratio X increases,

the absolute value of the experimental EPM decreases. In contrast, at low pH, EPMs are on a

single curve irrespective of the ratio X; the charging behavior is controlled by ionic strength at

low pH even in the presence of Ca2+

. The theoretical EPMs calculated by using 1-pKH without

Ca2+

association model demonstrated the same tendency of the experimental ones (Fig. 1 (a)).

Thus, effects of double layer are significant in mixed solutions containing Ca2+. At high pH,

however, the magnitude of the theoretical EPMs without Ca2+

association is larger than the

experimental ones. On the other hand, the theoretical EPMs calculated by using 1-pKH model

with Ca2+

association quantitatively agree with the experimental ones (Fig. 1 (b)). Therefore,

the modeling of the binding of Ca2+

with deprotonated carboxyl groups is crucial for the

evaluation of charging behavior of the particle. That is, the binding of Ca2+

reduces the net

surface charge.

Fig.1 The relationship between electrophoretic mobility of carboxyl latex particles and pH at ionic strength I =10 mM. Symbols are experimental values. Solid and dashed lines are theoretical values calculated by the Ohshima equation and the Smoluchowski equation, respectively. Mixed molar ratios X= [Ca2+] / [K+] are 0, 0.01, 0.1, and 0.5 from lower to upper lines. Calculated values are obtained (a) without Ca2+ association and (b) with Ca2+ association.


98

P4_6

Evaluation of neuroprotective action of nanoencapsulated

model drugs

Piotrowski Marek

1,*, Szczepanowicz Krzysztof

1, Jantas Danuta

2,

Lasoń Władysław2, Warszyński Piotr

1


ul. Niezapominajek 8, 30-239 Cracow, Poland 2Institute of Pharmacology, PAS, Krakow, Poland


The purpose of the present study was to evaluate the neuroprotective action of

nanoencapsulated inhibitors of intracellular biochemical cascades leading to neuronal cell

death. Core-shell nanocapsules were synthesized using nanoemulsification and the layer-by-

layer technique. The average size of synthesized nanocapsules was around 80 – 100 nm and

the concentration was in the rage of 1010

- 1011

particles/ml. Their zeta potential values ranged

from less than -30 mV for the ones with external polyanion layers through -4 mV for the

PEG-ylated layers to more than 30 mV for the polycation layers. Nanocapsules were

colloidally stable for the period not shorter than 30 days. Biocompatibility of synthesized

nanocarriers was evaluated in the SH-SY5Y human neuroblastoma cell line using

biochemical cell viability/toxicity assays (MTT, LDH). The results obtained showed that

synthesized nanocapsules coated with poly-aminoacids (PLL, PGA) were non-toxic to SH-

SY5Y human neuroblastoma cells, therefore they were used as nanocarriers for selected

neuroprotective substances (MDL 28170, undecylenic acid, cyclosporine A and curcumin).

Moreover, studies with fluorescently labeled polyelectrolytes demonstrated approximately

20% cellular uptake of synthetized nanocapsules. Further studies showed that

nanoencapsulated forms of neuroprotectants were biocompatible and protected SH-SY5Y

cells in a model of cell death induced by cell-damaging agents (H2O2, staurosporine,

doxorubicin) in lower concentrations than those of the same drug added directly to the culture

medium. These data suggest that designed nanocapsules might serve as a novel solution for

the delivery of hydrophobic neuroprotective agents.

Acknowledgements: This PhD thesis was completed thanks to the financial support from the project Interdisciplinary PhD

Studies "Molecular sciences for medicine" (co-financed by the European Social Fund within the

Human Capital Operational Programme). The research leading to these results has also received

funding from the Polish-Norwegian Research Programme operated by the National Centre for

Research and Development under the Norwegian Financial Mechanism 2009-2014 in the frame of

Project Contract Pol-Nor/199523/64/2013 NanoNeucar.


99

P4_7

Metal coated colloidosomes and potential applications

Qian Sun

1,2*and Alexander F. Routh

1,2

1Department of Chemical Engineering and Biotechnology, Pembroke Street, Cambridge CB2

3RA, United Kingdom 2BP Institute, University of Cambridge, Madingley Road, Cambridge CB3 0EZ,

United Kingdom


Polymer shell colloidosomes can be used in a wide variety of industries, such as food,

bioreactors and medicine. In our group we make them by emulsifying an aqueous latex

dispersion in sunflower oil. The latex particles migrate to the oil-water interface and are

locked in place, typically by heating. Fig 1 shows a SEM image of a colloidosome where the

surface is quite smooth.

Fig. 1 SEM image of a colloidosome

To expand applications of the colloidosomes, we aim to place on metal shell around the

outside. Recently, we used sodium citrate (Na3Citrate) in the core and gold chloride (HAuCl4)

in the wash solution, to successfully make gold coated colloidosomes. Fig 2 shows SEM

images of the capsules. The colloidosomes are fully covered with gold particles. The next step

is to explore applications. For example targeted cell delivery will necessitate binding a guide

protein to the colloidosome shell.

Fig. 2 SEM image colloidosomes coated with gold particles

Acknowledgements:

The authors thank Richard Langford (Department of Physics, University of Cambridge) for his

assistance with use of the scanning electron microscope.


100

P4_8

Studies of the functional layers of β-lactoglobulin as biomolecules carriers

S. Świątek1*, J.I. Loch2, K. Lewiński2, B. Jachimska1

1J. Haber Institute of Catalysis and Surface Chemistry, PAS, Niezapominajek 8,

30-239 Cracow, Poland, 2Jagiellonian University, Faculty of Chemistry, Ingardena 3, 30-060 Cracow, Poland

*[email protected]

Bovine β-lactoglobulin (LGB) is a globular protein with weakly understood physiological function, however it has been proven that LGB can transport hydrophobic compounds: retinol, vitamin D3 or fatty acids, therefore this protein can be potentially used as a carrier of biomolecules [1]. Previous studies showed that interactions of LGB with ligands strongly depends on pH of the solution and is related to the Tanford transition [2]. The main binding site of LGB is located inside the β-barrel and the second one on the protein surface [3].

Studies of the effectiveness of forming LGB complex with one of the anasthetic drug - tetracaine (TCA) was undertaken. Both the natural ligands of LGB like fatty acids and TCA are linear molecules of similar size, therefore this ligand with biomedical properties was chosen to perform preliminary studies of its interaction with LGB. Physicochemical properties of LGB and LGB-TCA complex were characterized. The zeta potential and isoelectric point (i.e.p) of the protein were determined by utilizing electrophoretic mobility with capillary electrophoresis technique. UV-vis spectra for LGB, TCA and its complex were recorded. The adsorption capacity of LGB was studied using quartz crystal microbalance with dissipation energy monitoring technique (QCM-D).

Correlation between the adsorption capacity (mass and thickness of layers) of LGB and pH or ionic strength of the solution was evaluated and the optimized conditions for ligand-LGB binding were investigated. Performed experiments revealed that characterization of the layers formed on the QCM sensor may play an important role in studies of future protein-hydrophobic ligand interactions.

Literature: 5. Kontopidis George, Holt Carl, Sawyer Lindsay, 2004. Invited Review: β-Lactoglobulin:

Binding Properties, Structure and Function. Journal of Dairy Science 87: 785-796. 6. Bin Y. Qin, Maria C. Bewley, Lawrence K. Creamer, Heather M. Baker, Edward N.

Baker, Geoffrey B. Jameson, 1998. Structural Basis of the Tanford Transition of Bovine β-Lactoglobulin. Biochemistry 37: 14014-4023.

7. Ming-Chi Yang, Hong-Hsiang Guan, Ming-Yih Liu, Yih-Hung Lin, Jinn-Moon Yang, Wen-Liang Chen, Chun-Jung Chen, Simon J. T. Mao, 2008. Crystal structure of a secondary vitamin D3 binding site of milk β-lactoglobulin. Proteins 71: 1197-1210.

Acknowledgements: This work was supported by Grant NCN OPUS4 2012/07/B/ST5/00767.


101

P4_9

Controlled release of encapsulated neurotransmitters from core-

shell nanoparticles

Noémi Varga

1*, Dániel Sebők

1, Imre Dékány

1

1Institution MTA-SZTE Supramolecular and Nanostructured Materials Research Group,

University of Szeged, Department of Medical Chemistry, Faculty of Medicine, H-6720,

Dóm tér 8, Szeged, Hungary


Novel, carrier-systems with the desired properties in nanoscale may promote the drug

delivery into the brain which give possibility to treat the neurological disorders (Alzheimer,

Parkinson disease). For this purpose we have synthetized one-layered core-shell

nanocomposites for delivery of neurotransmitters, like the kynurenic acid (KYNA) and the

dopamine hydrochloride (DOPA). Bovine serum albumin (BSA) and poly-L-lactide-co-

glycolic acid (PLGA) were used as carrier systems. A polyelectrolyte layer was formed on the

core/dopant surfaces. The composites were characterized by dynamic light scattering (DLS),

fluorescence measurements and transmission electron microscopy (TEM). The changes in the

structure during the formation of the core-shell nanocomposites were investigated by infrared-

, CD spectroscopy and small angle X-ray scattering (SAXS). The in vitro release properties of

drug molecules were investigated by a vertical diffusion cell (Franz cell) at 25 and 37.5°C.

The interaction between the carrier and the drug are reversible based on the release studies.

The application of kinetic models suggest possibility to describe the release kinetic. The

properties of the core-shell nanocomposites (size, zeta potential, structural parameters, etc.)

suggest that these core-shell nanoparticles are applicable in future in the controlled delivery of

therapeutic agents [1,2].

Fig. 1 Schematic picture of the formation of the core-shell nanoparticles (not to scale)

Literature:

1. Noémi Varga, Mária Benkő, Dániel Sebők, Imre Dékány, 2014. BSA/polyelectrolyte core–shell

nanoparticles for controlled release of encapsulated ibuprofen. Colloids and Surfaces B:

Biointerfaces 123: 616–622.

2. Noémi Varga, Mária Benkő, Dániel Sebők, Gabriella Bohus, László Janovák and Imre Dékány,

2015. Mesoporous silica core-shell composite functionalized with polyelectrolytes for drug

delivery. http://dx.doi.org/10.1016/j.micromeso.2015.02.008

Acknowledgements: We thank the ECIS and COST for their financial support.



102

P4_10

Molecular dynamics study of Doxorubicin interaction with

suspensions of modified carbon nanotubes

Paweł Wolski

1*, Tomasz Pańczyk

1




Doxorubicin (DOX) is a member of anthractcline class of chemotherapeutic agents used for

the treatment of many common human cancers1. Congo red (CR) is a diazo dye revealing the

ability of formnig ordered amyloid-like organization of protein aggregates and is used in

testing amyloid proteins2. We performed extensive molecular dynamics simulation of DOX

interaction with CNT covered by CR molecules. We studied serveral combinations of systems

parameters in order to assess how the density of CR and DOX affects the structure and

stability of DOX-CR-CNT conjugates at various pH and ionic strength conditions. We found

that in case of CNT with chirality (10,0) the CR molecules tend to form ribbon-like micellar

structures attached to the nanotubes surfaces. At pH>5 DOX molecules incorporate into the

micelar structure of CR and avoid adsorption on the CNT surfaces. At more acidic pH, when

the CR switches into its protonated form, the DOX molecules are removed from the CR

micele due to enhanced intermolecular interactions between CR molecules and locate in the

bulk. Fig. 1 shows the radial distribution functions for distances between carbon nanotubes

and DOX molecules as well as CR -DOX. It is clearly seen that upon lowering pH the release

of DOX from the CNT-CR conjugates ocurrs. That phenomenon can be utilized in realisation

of pH controlled drug release process.

a

b

Fig. 1 Radial distribution functions (rdf) a - between carbon nanotubes and DOX, b – between CR and DOX. Literature:

1. R.B. Weiss;1992; The anthracyclines: will we ever find a better doxorubicin?; Semin.

Oncol;19(6):670-86.

2. M. Skowronek et all;Self-assembly of Congo Red-A theoretical and experimental approach to

identify its supramolecular organization in water and salt solutions; Biopolymers;46:267-81.

Acknowledgement

This work was supported by Polish National Science Center (NCN) grant UMO-2012/07/E/ST4/00763



103

P5_1

The effect of the solution pH on the lysozyme immobilization

at the gold surface

Ćwięka Monika*, Jachimska Barbara




Lysozyme is a small enzyme that exhibits strong antibacterial activity against gram-

positive micro-organisms. This phenomenon has found practical applications in medicine, the

pharmaceutical industry and the food processing industry. For this reason, the understanding

of how the protein interacts with inorganic surfaces, and how its orientation is governed by

the properties of the surface, is of major interest in both fundamental research and in

biomedical applications.

The development of new research techniques makes it possible to study adsorption

with increasing accuracy: from simple measurements of adsorption kinetics at high protein

concentrations to detecting even a single protein molecule adsorbed on a surface. Quartz

Crystal Microbalance with Dissipation of Energy (QCM-D) and Multi-Parametric Surface

Plasmon Resonance (MP-SPR) are powerful techniques that enable highly sensitive,

qualitative, real-time, label-free, and non-invasive detection of adsorbed proteins.

A combination of these methods has provided significant information on the mechanisms

responsible for the protein surface interactions, structural changes and biomolecular

rearrangements. Using MP-SPR measurements one can determine mechanisms of LSZ

adsorption, e.g., the reversibility and orientation of molecules at interfaces. Furthermore, from

the combination of the QCM-D and MP-SPR data with the assumption that the excess sensed

mass measured in QCM-D compared to the MP-SPR mass is due to trapped water, we have

estimated the hydration of LSZ layer on the surface of gold.

Acknowledgements:



104

P5_2

Spectroscopic Ellipsometry of PEDOT:PSS thin films at

solid/liquid and solid/gas interfaces

Gaurav Pathak* and Dusko Cakara

Centre for Micro and Nano Sciences and Technology,

University of Rijeka, 51000, Rijeka, Croatia.


We report the results of the in-situ spectroscopic ellipsometry study of poly (3,4-

ethylenediosythiophene): poly(styrene sulfonate) (PEDOT:PSS) films spin-coated on silicon,

in the visible range of spectrum. When in contact with different ambient media, these films

undergo swelling which is clearly evidenced in the spectroscopic ellipsometric data. The

Lorentz-Drude model of the dielectric function, in combination with the stratified layer

optical model, can be well fitted to the measured ellipsometric data, whereby a very good

agreement is found between the fitted film thickness and the value directly measured by

means of the atomic force microscopy. On the other hand, once the film thickness is

independently determined from the AFM measurement, the real and imaginary parts of the

complex refractive index as function of wavelength (i.e. the dielectric function), can be

obtained from the ellipsometric data by mathematical inversion. The dielectric functions

obtained in that manner are found to be comparable with the dielectric functions obtained by

fitting the Lorentz-Drude model, which leads to the conclusion that this model is indeed

applicable for the description of the dielectric behavior of PEDOT:PSS films.


105

P5_3

Action of selected saponins on biological model membranes

Janikowska Maria

1,2*, Korchowiec Beata

1, Gorczyca Marcelina

1, Wojszko Kamila

1,

Trojan Sonia1, Henry Max

3, Rogalska Ewa

3

1Faculty of Chemistry, Jagiellonian University, ul. R. Ingardena 3, 30-060 Krakow, Poland

2Faculty of Physics, Astronomy, and Applied Computer Science, Jagiellonian University, ul.

S. Lojasiewicza 11, 30-348 Krakow, Poland

3CNRS, University of Lorraine, BP 239, 54506 Nancy-Vandoeuvre, France


Saponins, naturally occurring plant secondary metabolites are known for their biological

and pharmacological activity [1]. This activity is strongly related to the amphiphilic character

of saponins that allows them to aggregate in aqueous solution and interact with membrane

components [2]. In our work, Langmuir monolayer techniques combined with polarization

modulation infrared reflection-absorption spectroscopy (PM-IRRAS) and Brewster angle

microscopy were used to study the interaction of selected saponins with lipid model

membranes. Two structurally different saponins were used: digitonin and commercial Merck

Saponin. The membranes of different composition, to be precise, cholesterol, 1,2-dipalmitoyl-

sn-glycero-3-phosphocholine and 1,2-dipalmitoyl-sn-glycero-3-phospho-rac-(1-glycerol)

were formed at the air/water and air/saponin solution interfaces. Saponin-lipid interaction was

characterized by changes in surface pressure, surface potential, surface morphology and PM-

IRRAS signal. Both saponins interact with model membranes and change the physical state of

membranes by perturbing the lipid acyl chain orientation. The changes in membrane fluidity

were more significant upon the interaction with Saponin. A higher affinity of saponins for

cholesterol than phosphatidylglycerols was observed. Moreover, our results indicate that

digitonin interacts strongly with cholesterol and solubilize the cholesterol monolayer at higher

surface pressures. It was shown, that digitonin easily penetrate to the cholesterol monolayer

and forms a hydrogen bond with the hydroxyl groups. These findings might be very useful in

further understanding of the saponin action at the membrane interface, and the mechanism of

membrane lysis.

Literature: 1. Böttger S., Hofmann K., Melzig M. F., 2012. Saponins can perturb biologic membranes and reduce

the surface tension of aqueous solutions. A correlation? Bioorganic & Medicinal Chemistry (2012)

20, 2822-2828.

2. Podolak I., Galanty A., Sobolewska D., 2010. Saponins as cytotoxic agents: a review.

Phytochemistry Reviews (2010) 9, 425-474.

Acknowledgements: Marcelina Gorczyca acknowledges the financial support from an Interdisciplinary PhD Studies project

entitled “Molecular Sciences for Medicine” co-financed by the European Social Fund within the

Human Capital Operational Programme.


106

P5_4

Functional ultrathin polyelectrolyte coatings formed with reduced

graphene oxide and Prussian Blue nanoparticles as a sensitive tool

for H2O2 detection

Kruk Tomasz*, Pajor-Świerzy Anna, Szyk-Warszyńska Lilianna, Socha Robert,

Warszyński Piotr




Graphene - a new material consisting of single layer of sp2 – bonded carbon atoms with

unique two-dimensional (2D) nanostructure of a honeycomb lattice attracts attention of many

specialists from various branches of science. Since its discovery in 2004 [1], graphene has

emerged as the “material of the future” due to its unique nanostructure, electrical, thermal and

mechanical properties.

Sequential adsorption of charged nanoobjects, as polyelectrolytes, nanoparticles (known

also as the “Layer by layer” (LbL) deposition method) [2] is considered as one of the most

promising techniques of surface modification and formation of highly tailored functional thin

films for the wide range of possible applications. As graphene is a hydrophobic material, it can

not be directly used for construction of multilayer films with the LbL method. Therefore, we have

proposed to use suspension of graphene oxide ((GO) – negatively charge – anionic layer) for

formation of such films and its subsequent reduction to the reduced graphene oxide (rGO). For

formation of thin, multilayer graphene films using the Layer-by-Layer (LbL) method we

deposited polyelectrolytes, Prussian Blue (PB) nanoparticles and graphene oxide (GO) from their

solutions. We compared several reduction methods to turn GO into reduced graphene oxide. We

noticed that the thermal reduction of GO above the temperature 1800C is the most effective

process leading to formation of sp2-bonded carbon atoms.The examination of XPS spectra

indicated that after the reduction the ratio of the sp2 carbon increased to c.a. 80 at.%. The structure

and properties of the films before and after reduction were investigated using Ellipsometry

Spectroscopy, ATR-FTIR Spectroscopy, AFM and SEM. The electric conductivity of films after

the reduction was analyzed by the four point surface conductivity measurements, whereas cyclic

voltamperometry was used to determine the electroactive properties of multilayer films.

We showed that using the proposed method it is possible to obtain ultrathin conductive

films on quartz and polyimide (PI) plates. In addition the modified GO – positively charge were

used as polycation to improve surface conductivity. We noticed that in the presence of rGO sheets

the intensity of the redox current of PB embedded in the multilayer films markedly increased due

to enhancement of electron transport to the polyimide electrode surface. In the presence of

hydrogen peroxide characteristic peaks from reduction of H2O2 to OH- ions and oxidation to O2

molecules appeared. Formation of such thin films on PI allows creating flexible electrodes, which

can find applications in biomedicine as disposable, electroactive sensors.

Literature:

1. Novoselov K.S., Geim A.K., Morozov S.V., Jiang D., Zhang Y., Dubonos S.V., Grigorieva I.V.,

Firsov A.A., 2004, Science, 306 666-669.

2. Decher G., Schlenoff J., 2011, Multilayer Thin Films Sequential Assembly of Nanocomposite

Materials, , ISBN 978-3-527-31648-9 - Wiley-VCH, Weinheim.



107

P5_5

Multifunctional polyelectrolyte ultrathin coatings for biomedicine

applications

Kruk Tomasz*, Szczepanowicz Krzysztof, Warszyński Piotr




The formation of bacterial slime or of biofilms at the surface of biomaterials e.g.

diagnostic devices and a variety of biomedical implants, represents a major medical problems

leading, if untreated to chronic microbial infection. One of the most significant problem is the

process of biofouling, i.e. the unwanted adsorption of proteins, occurring on the surfaces

exposed to solutions containing biological material. Therefore, the development of the

“antifouling” coatings protecting against non-specific protein adsorption, bacteria and fungi

colonization are an important area of research within a broader field of biointerface science.

Immobilization of neutral hydrophilic polymers (e.g. poly(ethylene glycol)) (PEG) at surfaces

is one of the accepted methods to reduce non-specific adsorption of proteins. On the other

hand, silver or copper nanoparticles containing materials and coatings with antimicrobial

activity find applications: in medicine to reduce infections.

The Layer-by-Layer technique of electrostatic self-assembly of charged nanoobjects

has been demonstrated to be a versatile technique for the formation of multilayer thin films.

The method is based on the sequential adsorption of the oppositely charged species on solid

surfaces [1]. „LbL” method, which is considered as one of the most promising techniques of

surface modification can be used for formation of those coatings

The goal of this work was to build up anti adhesive films able to cover any type of

surface and containing PEG. This type of films is expected to reduce/eliminate the non-

specific adsorption of proteins at surface as well as the bacterial colonization of implanted

materials. Synthesized copolymers of poly(glutamic acid) or poly(L-lysine) with grafted PEG

chains with various grafting ratio and various chain lengths, were used for that modification

by formation of the external layer of films. The biofouling process was investigated by

studying the adsorption of different proteins: HSA, fibrinogen as well as proteins from

Human serum using QCM. Apart from polyelectrolytes, negatively charged silver or copper

nanoparticles were used for the multilayers construction that led to the formation of

nanocomposite films. It was found that nanocomposite films have antimicrobial properties.

Literature:

1. Decher G., Schlenoff J., 2011, Multilayer Thin Films Sequential Assembly of Nanocomposite

Materials, ISBN 978-3-527-31648-9 - Wiley-VCH, Weinheim.

Acknowledgements: The work was financed by NCN project UMO 2012/07/N/ST5/00173.



108

P5_6

Bovine β-lactoglobulin layers on gold surface: Role of ionic strength

S. Świątek*, B. Jachimska

J. Haber Institute of Catalysis and Surface Chemistry, PAS, Niezapominajek 8,

30-239 Cracow, Poland,

*[email protected]

Bovine β-lacoglobulin (LGB) is a protein with unknown physiological function belonging to lipocalin family. LGB is probably involved in transport of hydrophobic compounds and can be potentially used as a carrier protein for biomolecules [1].

The main goal of presented research was to evaluate effectiveness adsorption of the β-lactoglobulin on the gold surface at different conditions concerning changes in pH and ionic strength of the solution. Dynamic Light Scattering (DLS) Malvern Nano ZS method was used to analyze physicochemical properties of LGB and to determine the size of the particles. The zeta potential and isoelectric point (pI) of the protein were determined by utilizing electrophoretic mobility with capillary electrophoresis technique. The adsorption of protein onto gold surface was studied with quartz crystal microbalance (QCM-D).

Obtained results revealed that electrophoretic mobility strongly depends on both pH and ionic strengths of the protein solution. The value of pI was determined to 4.8. The electophoretic mobility measurements allowed to calculate the zeta potential. For all LGB isoforms zeta potential was negative in pH>5 and positive at acidic pH. Experiments performed using QCM-D method showed that adsorption capacity of LGB on the gold surface highly correlates to pH and ionic strength of the solution. All LGB layers were identified as molecular layers with low viscoelasticity, as indicated by a low value of dissipation energy (D<1·10-6). The adsorption data could be well described by the Sauerbrey model that correlates observed changes in resonance frequency with mass and thickness of adsorbed LGB layers.

Understanding the mechanism of LGB adsorption process has an important issues for establishing the optimal conditions for immobilization of this protein on adsorption surface, for designing bioconjugates for in vivo and in vitro applications and to examine LGB molecular affinity to soluble ligands.

Literature: 8. Kontopidis George, Holt Carl, Sawyer Lindsay, 2004. Invited Review: β-Lactoglobulin:

Binding Properties, Structure and Function. Journal of Dairy Science 87: 785-796. Acknowledgements: This work was supported by Grant NCN OPUS4 2012/07/B/ST5/00767.


109

P5_7

The role of chain unsaturation in the formation of organized

molecular films of crown ether - modified phospholipid

monolayers

Trojan Sonia

1*, Ustarbowska Małgorzata

2, Korchowiec Beata

2, Janikowska Maria

1,

Joly Jean-Pierre3, Rogalska Ewa

3

1Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University,

ul. R. Ingardena 3, 30-060 Cracow, Poland 2Department of Physical Chemistry, Faculty of Chemistry, Jagiellonian University,

ul. R. Ingardena 3, 30-060 Cracow, Poland 3Structure et Réactivité des Systémes Moléculaires Complex, BP 239, CNRS/Université

de Lorraine, 54506 Vandoeuvre-lés-Nancy cedex, France


The nature of phospholipids, their structural diversity, and content in the bilayer

determine the properties of biological membrane [1]. Crown ethers are used as well as

membrane forming amphiphiles and due to their ionophoretic properties, as model ion

channels [2].

In this work, the interaction between the synthetic crown ether and

phosphatidylcholines (PCs) having different number of unsaturated chains were studied.

Three phosphatidylcholines were chosen, namely 1,2-dipalmitoyl-sn-glycero-3-

phosphocholine (DPPC), 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), and

1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). PCs monolayers formed at the air/water

interface were used as simple models of biological membranes allowing to investigate the

effect of hydrocarbon chain unsaturation on the membrane activity of crown ether. To this

aim, the properties of mixed monolayers were studied using the Langmuir film technique, as

well as Brewster angle microscopy. The miscibility of phosphatidylcholines and crown ether

was studied using surface pressure and surface potential measurements. The polarization-

modulation infrared reflection-absorption spectroscopy (PM-IRRAS) was used to gain more

information on the intra- and intermolecular interactions in the mixed PCs/crown ether films.

The obtained results indicate that both the degree of hydrocarbon chain unsaturation of PCs

and the amount of crown ether influence the interfacial properties of the mixed monolayers. It

was showed, that the crown ether derivative is miscible with PCs and can be easily

incorporated into lipid membranes.

Literature:

1. Karp, G.. 2004. Cell and Molecular Biology: Concepts and Experiments, 4th ed.. Wiley & Sons:

New York. Chapter 4.

2. Cazacu A., Tong C., Van der Lee A., Fyles T. M., Barboiu M.. 2006. J. Am. Chem. Soc., 128.

p.9541-9548.

Acknowledgements: This work was supported by the Polish National Science Centre, project No.

2014/13/B/ST4/04995.


110

P5_8

Interactions of amphiphilic crown ether with metal ions

in Langmuir films

Trojan Sonia

1*, Korchowiec Beata

2, Joly Jean-Pierre

3, Korchowiec Jacek

1, Rogalska Ewa

3

1Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University,

ul. R. Ingardena 3, 30-060 Cracow, Poland 2Department of Physical Chemistry, Faculty of Chemistry, Jagiellonian University,

ul. R. Ingardena 3, 30-060 Cracow, Poland 3Structure et Réactivité des Systémes Moléculaires Complex, BP 239, CNRS/Université

de Lorraine, 54506 Vandoeuvre-lés-Nancy cedex, France


Crown ethers are macrocyclic organic compounds which can be easily modified. Lariat

ethers are a class of membrane-active crown ethers containing hydrocarbon chains attached to

the ether crown. Crown ethers are intensively studied due to their complexation

[1, 2], ionophoretic and channel forming properties [3].

The aim of this work was to investigate the ability of newly synthesized lariat crown ethers

to selective complexation of metal cations. The properties of monomolecular films formed by

crown ether were investigated using Langmuir film techniques. In our research the model

amphiphilic monolayer, corresponding to the single layer of cell membrane was prepared.

Monolayers were formed on the water subphase and on salt solutions containing Cu2+

, Zn2+

and Ni2+

cations. In the case of salt solutions, the compression isotherms were recorded in

order to investigate the influence of cation concentration on the complex formation. Moreover

the studies using polarization modulation infrared reflection-absorption spectroscopy were

carried out. The morphology of monolayers was investigated using Brewster angle

microscopy. The interaction between cation and crown ether compounds were analysed using

the DFT method. Molecular modeling was performed to obtain the conformational details of

the formed complexes.

Literature:

1. Plehnert R., Schrӧter J. A., Tschierske C.. 1998. Langmuir, 14. p.5245-5249.

2. Corvis Y., Korchowiec B., Korchowiec J., Badis M., Mironiuk-Puchalska E., Fokt I., Priebe W.,

Rogalska E.. 2008. J. Phys. Chem. B, 112. p.10953-10963.

3. Cazacu A., Tong C., Van der Lee A., Fyles T. M., Barboiu M.. 2006. J. Am. Chem. Soc., 128.

p.9541-9548.

Acknowledgements:

The research was partially financed by the European Commission within Erasmus program.

This research was supported in part by PL-Grid Infrastructure.


111

P6_1

Methylation of humic acids – the impact on the reactivity,

chemical composition and properties of HAs studied by

spectrometric techniques

Enev Vojtěch

1, 2*, Klučáková Martina

1, 2, Smilek Jiří

1, 2, Doskočil Leoš

1, 2

1Institute of Physical and Applied Chemistry

2Materials Research Centre, Faculty of Chemistry, Brno University of Technology, Purkyňova 118,

Brno, 612 00, Czech Republic


The aim of this work was study chemical composition, chemical properties and reactivity of

methylated standard humic acid (mHA) and its native form. Humic acid (standard sample of

humic acid – International Humic Substances Society – Leonardite HA 1S104H) was

modified by methylation. All samples of Leonardite HAs were characterized by elemental

analysis (EA), total organic carbon analysis (TOC), ultraviolet-visible spectroscopy (UV/Vis),

Fourier transform infrared spectroscopy (FTIR), steady-state fluorescence spectroscopy and

nuclear magnetic resonance (13C NMR). The elemental composition was determined by

a CHNS/O Microanalyser Flash 1112 Carlo Erba. Oxygen content was calculated by

difference: O % = 100 – (C + H + N + S) %, and data obtained were corrected for moisture

and ash content. Absorption coefficients (EET/EBz, E250/E365 and E465/E665) of Leonardite HAs

were calculated from the absorbance values. Infrared spectroscopy is a useful technique in

characterization of structure, functional groups and formation modes of HAs. For the

fluorescence experiments the final concentration of the HAs was adjusted to 10 mg∙L–1

. The

pH-value of the samples was adjusted to seven using a standard phosphate buffer.

Fluorescence mono-dimensional spectra and total luminescence spectra (TLS) of HAs were

obtained using steady-state fluorescence spectroscopy. All fluorescence spectra were

performed on a Horiba Scientific Fluorolog. Total luminescence spectra (TLS) were obtained

in the form of excitation/emission matrix (EEM) by scanning the wavelength emission over

the range of 300–600 nm, also the excitation wavelength was in 5 nm steps from 240 to

550 nm. The EEM spectrum of ultrapure water (Mili-Q) was obtained, and it was subtracted

from the EEMs of all samples examined to decrease the influence from the 1st- and 2

nd-order

Raman scattering. Fluorescence index (Milori index and HIX) of HAs was calculated from

the area of the emission spectra. The fluorescence intensity (IF) values (in CPS) of samples

were corrected using method of Lakowicz1. 13C NMR spectra of Leonardite HAs were

obtained with a Bruker Avance III NMR spectrometer at an observation frequency of 125.8

MHz for 13C. The approximate number of scans was 25.000. Aromaticity (fa), hydrophilicity

and hydrophobicity ratio (Hfi/Hfo) and biological activity (BiA) of HAs were calculated from

the area of the NMR spectra.

Literature:

1. Lakowicz, J. R., 2006. Principles of Fluorescence Spectroscopy, 3rd edition, Springer, Baltimore,

Maryland.

Acknowledgements: This work has been supported by Ministry of Education, Youth and Sports,

Project LO1211.


112

P6_2

Molecular Dynamics modelling of interaction between heparin

and its potential neutralizer

Krasińska Zofia

1*, Jamróz Dorota

2


ul. Niezapominajek 8, 30-239 Cracow, Poland 2Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland


Heparin belongs to the group of glycosaminoglycans. Molecules of this biopolymer are

characterized by high density of negative charge. That property determines anticoagulant

activity of heparin and in consequence its application in medicine. However, long presence of

its molecules in cardiovascular system, leads to many side effects, such as dangerous

haemorrhages. In order to avoid that, neutralization of heparin is needed. Currently,

protamine, which is polypeptide with high content of arginine, is used for this purpose.

Unfortunately, application of this substance carries the risk of life-threatening complications

like those connected with anaphylaxis. Therefore, search for a new antidote for heparin,

effective and safe at the same time, are conducted.

This work presents study of a new potential heparin neutralizer, which is based on

a polyallylamine hydrochloride (PAH) polymer, modified by grafting arginine. Molecular

dynamics simulations of interaction between those polymers were performed in both aqueous

and physiological solution. It has been proved that the new compound has ability to

effectively bind heparin due to its strong interaction with the positively charged arginine

chain. Dihedrals distribution analysis of different parts of both molecules allowed to obtain

information about conformational changes of both polymers, resulting from their association.

This information, together with radial distribution function analysis, brings insight into

interaction between both polymers at the molecular level. That determines their binding ratio

in physiological solution.

Literature:

1. Kamiński, K., Kałaska, B., Koczurkiewicz, P., Michalik, M., Szczubiałka, K., Mogielnicki, A.,

Buczko, W., Nowakowska, M., 2014, New arginine substituted derivative of poly(allylamine

hydrochloride) for heparin reversal., Med. Chem. Commun., 5:489-495


113

P6_3

Undecane-in-water Emulsions prepared by the Phase Inversion

Temperature Method

Mikulcová Veronika

1*, Kašpárková Věra

1,2, Pohlodek Jiří

1

1Department of Fat, Surfactant and Cosmetics Technology, Faculty of Technology, Tomas

Bata University in Zlín, nám. T. G. Masaryka 5555, 760 01 Zlín, Czech Republic 2Centre of Polymer Systems, Tomas Bata University in Zlin, T.G.M. Sq. 5555, 760 01 Zlin,

Czech Republic


There has been a growing interest in the development and preparation of emulsions by using

low energy methods. In the current study, the phase inversion temperature (PIT) method was

used to prepare n-undecane/water nanoemulsions in the presence of two pairs of non-ionic

surfactants (Brij 30/Brij 56 and Brij 30/Brij 98). The PIT values were determined by

conductivity measurements and photon correlation spectroscopy (PCS) temperature trend and

applied for the preparation of the nanoemulsions. The influences of HLB value, surfactant

type and concentration on the PIT values were investigated. The effect of oil-to-water ratio

and HLB value on the size and distribution of emulsion droplets was also studied. The

stability of emulsions at different storage temperatures (4 °C, 25 °C and 35 °C) was evaluated

by visual observation and from the changes of particle size measured during the storage by

PCS. The phase inversion temperature method was also compared to another low energy

approach, emulsion phase inversion (EIP) method. The results show that the PIT value

changes with the all above mentioned operational parameters. Conductivity measurements

reveal linear correlation between PIT and HLB. PIT value is also influenced by surfactant

concentration – lower surfactant concentration leads to the higher values of PIT. Therefore, it

is evident that during emulsification using PIT, the samples with the lower surfactant

concentrations need larger energy input to be heated near the PIT and subsequently to be

rapidly cooled down to produce small particles. Regarding size of the emulsion droplets,

prepared samples can be classified as the nanoemulsions, as their particles were smaller than

200 nm. The best stability was obsered for emulsions stored at the temperature of 4 °C.

Acknowledgements:

This work was performed with support of internal grant of TBU in Zlin IGA/FT/2015/002 financed

from funds of specific academic research.


114

List of Conference Participants

Adamczyk Zbigniew

Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, ul. Niezapominajek 8, 30-239

Cracow, Poland

[email protected]

Arenas-Guerrero Paloma

Department of Applied Physics, University of Granada, Spain.

[email protected]

Augustyniak Krzysztof

Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060 Krakow, Poland

[email protected]

Briscoe Wuge


[email protected]

Carciati Antonio

Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale, Università di Napoli Federico II

CEINGE Biotecnologie avanzate, Napoli

[email protected]

Chatzidaki Maria

Institute of Biology Medicinal Chemistry & Biotechnology, National Hellenic Research Foundation, Athens, Greece

MTM,

Faculty of Science and Engineering, Örebro University, Sweden

[email protected]

Cooperstein Ido

Casali Center for Applied Chemistry, Institute of Chemistry and Center for Nanoscience and Nanothechnology, The

Hebrew University of Jerusalem, Jerusalem, Israel

[email protected]

Ćwięka Monika


Cracow, Poland

[email protected]

Delisavva Fotini

Department of Physical and Macromolecular Chemistry; Faculty of Science, Charles University in Prague, Hlavova

8, 12840 Prague 2, Czech Republic

[email protected]

Saoirse Dervin

Institute of Technology Sligo, Nanotechnology research group, Department of Environmental Science, Ash lane,

Sligo, Ireland

[email protected]

Drozdek Sławomir

Department of Organic and Pharmaceutical Technology, Faculty of Chemistry, Wroclaw University of Technology,

Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland

[email protected]

Emelyanenko Kirill

A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russia

[email protected]




115

Enev Vojtěch

Institute of Physical and Applied Chemistry

Materials Research Centre, Faculty of Chemistry, Brno University of Technology, Purkyňova 118, Brno, 612 00,

Czech Republic

[email protected]

Fernández Maria del Mar

Department of Applied Physics, School of Science, University of Granada, 18071 Granada, Spain

[email protected]

Gamon Jacinthe

Institut de Recherche de Chimie Paris (IRCP), CNRS 11 rue Pierre et Marie Curie, 75005 Paris, France

Solvay Research and Innovation Center of Paris (RIC Paris) 52 rue de la Haie-Coq, 93306 Aubervilliers, France

[email protected]

Gawlik Iwona

Faculty of Chemistry, Jagiellonian University, Ingardena 3, Krakow, Poland

[email protected]

Gergana Georgieva

Dpt. Chemical and Pharmaceutical Engineering, Sofia University, Sofia, Bulgaria

[email protected]

Gödrich Sebastian

Physical Chemistry II, University of Bayreuth, 95447 Bayreuth, Germany

[email protected]

Gorczyca Marcelina

Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060 Krakow, Poland

[email protected]

Ho Tracey

Ian Wark Research Institute, University of South Australia, Mawson Lakes, Adelaide, SA 5095, Australia

[email protected]

Hupka Jan

Gdansk University of Technology, Faculty of Chemistry, Department of Chemical Technology, ul. Gabriela

Narutowicza 11/12, 80-233 Gdansk

[email protected]

Jabłczyńska Katarzyna

Faculty of Chemical and Process Engineering, Warsaw University of Technology

[email protected]

James Emily

Institute of Particle Science and Engineering, University of Leeds, Leeds, UK

[email protected]

Janikowska Maria

Faculty of Chemistry, Jagiellonian University, ul. R. Ingardena 3, 30-060 Krakow, Poland

Faculty of Physics, Astronomy, and Applied Computer Science, Jagiellonian University, ul. S. Lojasiewicza 11, 30-

348 Krakow, Poland

[email protected]

Kairaliyeva Talmira

Max Planck Institute of Colloids and Interfaces, 14424 Potsdam/Golm, Germany

Kazakh National Technical University after K.I.Satpayev, Almaty, Kazakhstan

[email protected]

Kezwoń Aleksandra

Department of Microbioanalytics, Warsaw University of Technology, Warsaw, Poland.

[email protected]

Konczak Łukasz

Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences ul. Niezapominajek 8, 30-239

Cracow, Poland

[email protected]



116

Krasińska Zofia

Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences ul. Niezapominajek 8, 30-239

Cracow, Poland

[email protected]

Kruk Tomasz


Cracow, Poland

[email protected]

Krzywda Piotr

Cracow University of Technology, Faculty of Chemical Engineering and Technology, Department of Biotechnology

and Physical Chemistry, Warszawska 24 St. 31-155 Krakow, Poland

[email protected]

Księżniak Katarzyna

Gdansk University of Technology, Faculty of Chemistry, Department of Chemical Technology

[email protected]

Kubiak Katarzyna


Cracow, Poland

[email protected]

Kujda Marta


Cracow, Poland

[email protected]

Lamch Łukasz

Department of Organic and Pharmaceutical Technology, Faculty of Chemistry, Wroclaw University of Technology,

WybrzezeWyspianskiego 27, 50-370 Wroclaw, Poland

[email protected]

Latowska Anna



[email protected]

Lin Wei

Institute of Particle Technology,

Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen, Germany

[email protected]

Liuzzi Roberta

Department of Chemical, Materials and Production Engineering, University of Naples “Federico II”, P.zzle Tecchio

80, 80125 Naples

CEINGE- Advanced Biotechnologies, Via Sergio Pansini 5, 80131 Naples.

[email protected]

Lopez Cabarcos

Enrique Department of Physical Chemistry II, Faculty of Pharmacy, Complutense University of Madrid, 28040

Madrid, Spain

[email protected]

Lu Biao

Sorbonne Universités, Université deTechnologie de Compiègne, BMBI UMR CNRS 7388, France

[email protected]

Łapczyńska Marta

Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, ul. Niezpaminajek 8, 30-239

Cracow, Poland

[email protected]



117

Maciejewska Julia


Cracow, Poland

[email protected]

McNally Michael

University of Leicester, UK

[email protected]

Mikulcova Veronika

Department of Fat, Surfactant and Cosmetics Technology, Faculty of Technology, Tomas Bata University in Zlín,

nám. T. G. Masaryka 5555, 760 01 Zlín, Czech Republic

[email protected]

Miller Reinhard



[email protected]

Mioduska Joanna

Gdansk University of Technology, Faculty of Chemistry, Department of Chemical Technology

[email protected]

Moazzami Gudarzi Mohsen

Department of Inorganic and Analytical Chemistry, University of Geneva, Geneva, Switzerland

[email protected]

Moreno-Cencerrado Alberto

Institute for Biophysics, Department of Nanobiotechnology, University of Natural Resources and Life Sciences

Vienna (BOKU), Vienna 1190, Austria.

[email protected]

Mould Elizabeth

University of Bristol

[email protected]

Mulla Mohmed

University of Leeds

[email protected]

Mzareulishvili Natia

Iv.Javakhishvili Tbilisi State University, I.Chavchavadze ave 3, 0179, Tbilisi

[email protected]

Niecikowska Anna


Cracow, Poland

[email protected]

Nishiya Manami

Graduate School of Life and Environmental Sciences, University of Tsukuba, Japan

[email protected]

Oliynyk Viktoria

F.D.Ovcharenko Institute of biocolloid chemistry

[email protected]

Oncsik Tamas

Department of Inorganic and Analytical Chemistry, University of Geneva, Geneva, Switzerland

[email protected]

Orczyk Marta

Warsaw University of Technology, Faculty of Chemistry

[email protected]

Ottoboni Sara

Strathclyde University, Glasgow, United Kingdom

[email protected]


118

Pathak Gaurav

Centre for Micro and Nano Sciences and Technology, University of Rijeka, 51000, Rijeka, Croatia.

[email protected]

Piotrowski Marek


Cracow, Poland

[email protected]

Podgórna Karolina


Cracow, Poland [email protected]

Radulova Gergana

Department of Chemical Engineering, Faculty of Chemistry & Pharmacy, Sofia University, 1164 Sofia, Bulgaria

[email protected]

Redeker Christian


[email protected]

Salvatore Annalisa

Department of Chemistry and CSGI, University of Florence, via della Lastruccia 3, 50019 Sesto Fiorentino, Italy

[email protected]

Schulz Christian

Associate Publisher, Elsevier, Amsterdam, The Netherlands

Setiowati Arima Diah

Particle and Interfacial Technology Group, Ghent University

[email protected]

Skinner Samuel

Particulate Fluids Processing Centre, The University of Melbourne

[email protected]

Skoglund Sara

KTH Royal Institute of Technology, School of Chemical Science and Engineering, Surface and Corrosion Science,

SE-100 44 Stockholm, Sweden

[email protected]

Slastanova Anna

University of Bristol

[email protected]

Smilek Jiri

Brno University of Technology, Faculty of Chemistry, Materials Research Centre, Purkyňova 464/118, 61200 Brno,

Czech Republic

[email protected]

Sokolan Nina

Murmansk State Technical University

[email protected]

Stark Kirsty

Institute of Particle Science Engineering, School of Chemical and Process Engineering, University of Leeds

[email protected]

Starkie Joanna

University of Cambridge

[email protected]

Sun Qian

Department of Chemical Engineering and Biotechnology, Pembroke Street, Cambridge CB2 3RA, United Kingdom

BP Institute, University of Cambridge, Madingley Road, Cambridge CB3 0EZ, United Kingdom

[email protected]


119

Symonds Brett

Reading School of Pharmacy, University of Reading, Whiteknights, PO Box 224, Reading, RG6 6AD

[email protected]

Szafraniec Joanna


[email protected]

Świątek Sylwia


Cracow, Poland,

Jagiellonian University, Faculty of Chemistry, Ingardena 3, 30-060 Cracow, Poland

[email protected]

Tokarczyk Karolina


Cracow, Poland

[email protected]

Tonelli Monica

Department of Chemistry “Ugo Schiff” & CSGI, University of Florence, Sesto F.no (FI) 50019, Italy

[email protected]

Toth Reka

RMD, Institut de Recherche de Chimie Paris, CNRS - France

Solvay, Centre de Recherche et Innovation de Paris Aubervilliers – France

[email protected]

Trojan Sonia

Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, ul. R. Ingardena 3, 30-060

Cracow, Poland

[email protected]

Ulaganathan Vamseekrishna



[email protected]

Ulatowska Justyna

Wroclaw University of Technology, Faculty of Chemistry, Division of Chemical Engineering, Norwida 4/6, 50-373

Wrocław, Poland

[email protected]

Varga Noémi

Institution MTA-SZTE Supramolecular and Nanostructured Materials Research Group, University of Szeged,

Department of Medical Chemistry, Faculty of Medicine, H-6720, Dóm tér 8, Szeged, Hungary

[email protected]

Vermeir Lien

Particle and Interfacial Technology Group Ghent University, Belgium

[email protected]

Vincent Brian

University of Bristol, School of Chemistry, Bristol, BS8 1TS, UK

[email protected]

Wamke Anna

Institute of Chemical Technology and Engineering, Poznan University of Technology, Berdychowo 4, 60-965

Poznań, Poland

[email protected]

Warszyński Piotr


Cracow, Poland

[email protected]



120

Włodek Magdalena


Cracow, Poland

[email protected]

Wojewódka Przemysław

Department of Chemical Technology, Chemical Faculty, Gdańsk University of Technology, ul. Narutowicza 11/12,

80-952 Gdańsk, Poland

[email protected]

Wolski Paweł

Jerzy Haber Institute of Catalysis and Surface Chemistry Polish Academy of Sciences, ul. Niezapominajek 8, 30-239

Cracow, Poland

[email protected]

Won Jooyoung

Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1, 14424 Potsdam, Germany

[email protected]

Yamaguchi Atsushi Graduate School of Life and Environmental Sciences, University of Tsukuba, Japan

[email protected]

Zapotoczny Szczepan


[email protected]



121

Authors’ Index

Abazović N., 36

Abezgauz L., 82

Adamczyk Z., 18, 26, 61, 74

Ahualli S., 58

Aidarova S.B., 72

Amadei D., 22

Anachkov S., 82

Aranowski R., 80

Arenas-Guerrero P., 59

Aristotelis X., 22

Augustyniak K., 83

Baglioni P., 24, 69

Balcaen M., 35

Barboux P., 43, 66

Bartz C., 68

Beattie D.A., 53, 84

Bednarz S., 96

Berti D., 24

Bielańska M., 27

Biggs S., 41, 51, 57

Blomberg E., 50

Boinovich L., 65, 71

Bonini M., 24

Borkovec M., 32, 42

Borsacchi S., 69

Bremmell K., 53, 84

Briscoe W., 17, 67, 75, 78, 92

Brooker A., 41

Buissette V., 43

Burger A., 40

Bzowska M., 27

Cakara D., 104

Carciati A. 25, 34

Carević M., 36

Carmen Galan M., 67

Carrière D., 43

Carrière F., 22

Caserta S., 25, 34

Cayre O., 41, 51, 57

Chagnault V., 28

Chantry R.L., 62

Chatzidaki M., 22

Chen M., 78

Chromińska I., 64

Čomor M., 36

Cooperstein I., 46

Ćwięka M., 38, 103

D'Alençon L., 43

Danino D., 82

Danov K., 76

Dékány I., 101

Delgado A.V., 58, 59

Delisavva F., 56

Derkach S., 87

Dervin S., 52

Dewettinck K., 35

Dopierała K., 37

Doskočil L., 111

Drozdek S., 60

Dukhin S.S., 47

Egles C., 28

Emelyanenko A., 65, 71

Emelyanenko K., 65, 71

Enev V., 111

Faraji S., 72

Fernández M.M., 58

Fratini E., 69

Frączyk T., 64

Galinis G., 62

Gamon J., 66

Gawlik I., 93

Gehin-Delval C., 47

Geppi M., 69

Gergana G., 82

Giaume D., 66

Gochev G., 39, 47

Gödrich S., 68

Gorczyca M., 83, 105

Grand E., 28

Graydon A., 41

Guido S., 25, 34

Gumieniczek E., 23

Haeften K.von, 62

Harbottle D., 41

Hedberg J., 50

Hirsch A., 40

Ho T., 53, 84

Hunter T., 41

Hupka J., 15, 36, 49, 73

Iglesias G.R., 58, 59

Iturri J., 85

Jabłczyńska K., 94

Jachimska B., 38, 88, 89, 100, 103, 108

Jamadagni S., 41

James E., 41

Jamróz D., 112

Janik M., 23

Janikowska M., 105, 109

Jantas D., 30, 98

Jiménez M.L., 58, 59

Joly J.-P., 109, 110

Jungnickel C., 80

Kairaliyeva T., 14, 72

Kalaska B., 93

Kaminski K., 93

Karabasz A., 27

Karbaschi M., 14, 72

Kašpárková V., 113

Kasprzyk W., 96

Kezwoń A., 64

Khutoryanskiy V., 44

Klučáková M. 31, 111


122

Kobayashi M., 81, 97

Koc M.M., 62

Kolasińska-Sojka M., 90

Konczak Ł., 95

Korchowiec B., 83, 105 109, 110

Korchowiec J., 83, 110

Korecki J., 27

Koynov K., 82

Krägel J., 39

Kralchevsky P., 76, 82

Krasińska Z., 112

Krasowska M., 53, 84

Krittanai C., 85

Kruk T., 106, 107

Krzan M., 47

Krzywda P., 96

Księżniak K., 73

Kubiak K., 61

Kujda M., 26

Kujdowicz M., 93

Kuljanin-Jakovljević J., 36

Kurtanidze M., 86

Lamch Ł., 55

Lasoń W., 98

Latajka R., 55

Latowska A., 49

Leal-Calderon F., 22

Lefèvre G., 43

Lewiński K., 100

Liebewirth I., 82

Lin W., 40

Lindsay C., 44

Liuzzi R., 25

Loch J.I., 100

Lopez-Cabarcos E., 12

Lowe T., 50

Lu B., 28

Lundin M., 50

Łapczyńska M., 30

Łuczak J., 49

Maciejewska J., 74

Maciejewski H.F., 37

MacWilliams S., 84

Magdassi S., 46

Maid H., 40

Małysa K., 48

Maroni P., 32

Martini F., 69

Max H., 105

McNally M.J., 62

Mercier T., 43, 66

Miao Y., 28

Mikulcová V., 113

Miller R., 14, 39, 47, 72

Mioduska J., 36

Mittendorfer M., 85

Moazzami G.M., 32

Mogielnicki A., 93

Monteil J., 22

Moreno-Cencerrado A., 85

Mould E., 75

Mulla M., 57

Mzareulishvili N., 86

Niecikowska A., 48

Nikipelova O.M., 29

Nishiya M., 97

Nowakowska M., 93

Nyk M., 60

Oćwieja M., 61, 74

Oliynyk V.O., 29

Oncsik T., 42

Orczyk M., 54

Pajor-Świerzy A., 106

Panczyk T., 95, 102

Panko A.V., 29

Papadimitriou V., 22

Papastavrou G., 68

Pathak G., 104

Pawlak D., 93

Pawlos W., 73

Petelska A.D., 37

Petkov J., 76

Peukert W., 40

Pezron I., 28

Piechocka M., 37

Pillai S., 52

Piotrowski M., 30, 98

Podgórna K., 27

Pohlodek J., 113

Postel D., 28

Prochaska K., 37

Prochazka K., 56

Promdonkoy B., 85

Radoičić M., 36

Radulova G., 76

Redeker C., 67, 92

Regnouf-de-Vains J.-B., 83

Ridi F., 69

Robles E., 78

Rogalska E., 83, 105, 109, 110

Routh A., 91, 99

Rukhadze M., 86

Sabatino P., 35

Sadowska M., 74

Saeedi S., 77

Salvatore A., 24

Samoć M., 60

Scales P., 33

Schano K.H., 72

Schmidt H.W., 68

Schulz C. 13

Sebők D., 101

Sedláček P., 31

Segets D., 40

Setiowati A.D., 77

Skinner S., 33

Skoglund S., 50

Slastanova A., 78

Smilek J., 31, 111

Socha R., 106


123

Sokolan N., 87

Sokolowska E., 93

Sosnowski T.R., 94

Stark K., 51

Starkie J., 91

Stevenson R., 67

Stickland, A., 33

Stoyanov S., 76

Stringer D.N., 53, 84

Sugimoto T., 97

Sun Q., 99

Symonds B., 44

Szafraniec J., 23

Szczepanowicz K., 27, 30, 98, 107

Szczubialka K., 93

Szeremeta J., 60

Szilagyi I., 42

Szyk-Warszyńska L., 106

Świątek S., 100, 108

Taeibi-Rahni M., 72

Tharad S., 85

Thomson N., 44

Toca-Herrera J.L., 85

Tokarczyk K., 88, 89

Tomaiuolo G., 34

Tonelli M., 69

Toth R., 43

Trask R., 92

Trefalt G., 42

Trojan S., 105, 109, 110

Uchman M., 56

Ulaganathan V., 14, 47

Ulatowska J., 79

Usher S., 33

Ustarbowska M., 109

Vaccaro M., 41

Van der Meeren P., 35, 77

Varga N., 101

Vayssade M., 28

Vermeir L., 35

Vincent B., 19

Voron’ko N., 87

Vranješ M., 36

Wadouachi A., 28

Wallinder I.O., 50

Walter J., 40

Wamke A., 37

Warszyński P., 27, 30, 90, 98, 106, 107

Wąsik P., 92

Wiertel A., 48

Wilk K.A., 55, 60

Włodek M., 90

Wojciechowski K., 54, 64

Wojewódka P., 80

Wojszko K., 105

Wold S., 50

Wolski P., 102

Won J., 14, 39

Yamaguchi A., 81

Yazdanfar H., 62

Youle O., 62

Yow H.N., 57

Zapotoczny S., 16, 23

Zawała J., 48

Zielińska-Jurek A., 36

15th european student colloid conference · properties of therapeutical muds with nano- and...

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