steering committee meeting / 26.11 - nc state universityojrojas/lignocell/report nov 2013.pdf ·...

LIGNOCELLVALUE-ADDED MATERIALS AND FUNCTIONAL STRUCTURES FROM LIGNOCELLULOSICS

Steering Committee Meeting / 26.11.2013

Scientific Report

(see also budget info at the end)

http://www4.ncsu.edu/~ojrojas/Lignocell.htm

Time Tuesday 26.11.2013, 12.00-17.00

Place Aalto-Forest Products

Technology/Espoo, Finland

Vuorimiehentie 1, room 220

http://www4.ncsu.edu/~ojrojas/Lignocell.htm

Agenda

Opening of the meeting Appointment of chairman and secretaryApproval of the agendaMinutes of the previous meetingStatus of the projectIntroduction and general report work performed last semester (Orlando Rojas, Aalto-NCSU)

Update on current work:llari FilpponenLuis MoralesEster RojoArcot LokanathanKaroliina Junka

Other issuesPlans for next period (Orlando Rojas, Aalto-NCSU) Status of costs (Janne Laine, Aalto) Next meeting (date and place)

End of meeting

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Opening of the meetingOrlando Rojas opened the meeting at 10.15. Jonni Ahlgren was selected as a chairman and Ilari Filpponen as a secretary. A short introduction round was conducted.3 Approval of the Agenda and the Minutes of the previous meetingThe agenda of the meeting and minutes of the previous meeting were approved. 4 Next meetingThe next meeting was discussed while all the participants were present. It is to be held on November 2013 and the final date will be based on the results of Doodle poll.5 Status of the Project & PresentationsOrlando Rojas gave a general report and introduction of the LignoCell project. He reminded that all the presentations will be posted on the project website: http://www4.ncsu.edu/~ojrojas/Lignocell.htm. Jonni Ahlgren pointed out that the project website has been out of date. Orlando Rojas mentioned that he updated the website before the meeting and now all the material can be found from there.

Highlights of the results from the project include active exchange of ideas and students and publications at international conferences and peer-reviewed, high-impact journals.

MINUTES OF THE LIGNOCELL STEERING COMMITTEE MEETING (7)Time Friday 24.05.2013 at 10 amPlace Aalto University/Espoo, FinlandPresent Janne Laine (Aalto), Orlando Rojas (NCSU/Aalto), Ilari Filpponen (Aalto), Luis Morales (Aalto), Ester

Rojo (Aalto), Arcot Lokanathan (Aalto) / Kemira: Jonni Ahlgren / Stora Enso: Kalle Ekman / Tekes: Inkeri HuttuNOTE: The UPM representative was not present.

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Orlando also presented on behalf of Raquel Martin (UNIA, Spain), Carlos Carrillo (NCSU), Julio Arboleda (NCSU), Mariko Ago (Tokushima Bunri University, Japan), OriolCusola (UPC, Spain), Karoliina Junka (Aalto/NCSU) and Henry Bock (Heriot-Watt University, United Kingdom). They are/were LignoCell exchange students and visitors at Aalto and NCSU in spring/fall 2012 and spring 2013.

Raquel Martin (OR): The effect of lignin in enzymatic hydrolysis of cellulose. Raquel prepared bicomponent films from cellulose triacetate and acetylated lignin and studied enzyme adsorption and enzymatic degradation with quartz-crystal microbalance in deacetylated films (Cellulose/lignin films). CBH has higher affinity to cellulose and EG to lignin. EGs more sensitive to lignin amount than CBH:ses. In addition, faster enzymatic hydrolysis rate was observed for NFC in comparison to other substrates. The feasibility to apply hydrolysis in the presence of lignin was discussed. Possible solutions are to use enzymes that do not have affinity towards lignin and blocking of lignin by using surfactants. Overall, it was discussed that the interest towards lignin is increasing, e.g. fibers, films, particles etc.

Luis Morales: Effects of lignin and hemicelluloses on the enzymatic hydrolysis of nanofibrillated softwood lignocellulose after SO2-ethanol-water (SEW) fractionation. SEW pulps exist with variety of chemical compositions (cellulose, hemicelluloses and lignin) which allows to investigate the effects of each component to the enzymatic hydrolysis. SEW pulps were provided by Dr. Mikhail Yakovlev (Aalto).

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It was observed that the hemicelluloses enhance the enzymatic hydrolysis of small particle size nanofibrillated lignocellulose (NFLC) and that the lignin has a negative effect on the enzymatic hydrolysis of NFLC. The importance of identifying the location and structure of lignin after fluidization was addressed. Luis Morales also presented the recent results of the bacterial cellulose (BC) research. He has been working in this topic in collaboration with Dr. Hannes Orelma (Aalto). BC study was initiated in Aalto when Dr. Cristina Castro visited (October 2012) the group and gave training on the preparation of BC. Composites of BC and CMC have been prepared and their properties are under investigation.

Carlos Carrillo (OR): Novel methods in NFC production. The results of an oil in water microemulsion as a pulp pretreatment for NFC manufacture showed that the defibrillation is improved and energy consumption is reduced by using microemulsions. Moreover, the unbleached fibers produced stiffer and denser nanopaper. In addition, the microemulsification of NFC in a reverse microemulsion and ASA emulsification using cationic NFC as emulsifier were presented. In both cases stable emulsions were formed. The possibility to use microemulsions in wood preservation was discussed.

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Oriol Cusola (OR): Laccase-mediated coupling. The enzymatic treatments of paper surface using hydrophobic compounds. The results of using dodecyl 3,4,5-trihydroxybenzoate (HB-C12) and laccase were presented. QCM-D results showed successful coupling of HB-C12 on the cellulose model surface. In addition, the contact angle was increased up to 80 degrees.

Karoliina Junka (OR): Carbon nanodots (CNDs). Carboxymethylated NFC model surfaces were modified with amine-containing CNDs via EDC/NHS coupling chemistry. CNDs are easy to prepare, non-toxic and they have potential in biosensing applications utilizing their photoluminescence properties. QCM-D and AFM results showed successful covalent coupling of CNDs to the carboxymethylated NFC. Next, the experiments will be upscaled to the NFC suspensions.

Henry Bock (OR): CNC modeling. The computer modeling of interactions between polymer grafted CNC aggregates.

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Ilari Filpponen: The efforts in modification of lignin and reducing end groups of cellulose nanocrystals (CNC). CDI coupling chemistry (reaction between hydroxyls and amine groups) was used to install alkyne and azide groups on organosolv lignin thus activating the substrate for the subsequent click chemistry reaction. The clickable functionalities are yet to be decided. This work was conducted in close collaboration with Dr. Ago who applied the same chemistry to prepare aerogels from lignin and amylopectin. These experiments are in progress. The modification of reducing end groups of CNCs was conducted via sodium chlorite oxidation and EDC/NHS coupling chemistry, i.e., aldehyde groups were first selectively oxidized to carboxylic acids in which the alkyne and azide containing molecules were installed using EDC/NHS chemistry. Click chemistry was employed to attach fluorescent probe and PEG polymer on the activated CNCs. This work will be extended to regenerated cellulose nanocrystals so that the both ends of the crystal can be modified. Overall, the aim is to create reaction toolbox that allows systematic tuning of the supramolecular properties of CNCs. One possible application is affinity filtration where the analyte can be concentrated using magnetic fields.This work is continous collaboration with Dr. ArcotLokanathan.

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Arcot Lokanathan: Asymmetric CNC modification. The modification was conducted via reductive amination of reducing end aldehydes of CNCs. Molecules containing thiolgroups were installed and the affinity of thiol to gold surface was exploited to construct a “nanoforest” where CNCs are pointing outwards from the gold surface. In addition, the grafted thiols were tagged with Ag nanoparticles which showed regiospesificity only in the one end of the CNCs (cellulose I). The alignment of chemisorbed CNC-SH was achieved by drop casting technique. The inter CNC distance between the individual CNCs was controlled by attaching amine-PEG polymers on the surface of CNCs.

6 Other issuesStatus of costs: The budget was checked and the possibility to extend the project ending day from 31.12.2013 to March/April 2014 was discussed. The industry partners and the representative of the funding agency (TEKES) agreed that the project can be extended as long as the remaining funds are sufficient.

7. The meeting was closed at 14.55.

Lignocell: Instrument to develop knowledge in lignocellulose science and engineering

Students: • Temporal: Learn from core competences and apply

their skills in proposed Lignocell subjects• Permanent: Long-term learning to become top-notch

scientists

Mentors:To provide ideas, guidance and to connect people

Industry: Opportunity to “steer” work in strategic areas in an open, scientifically-driven effort

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Laura TaajamaaAalto, FIN

Dr. Arcot LokanathanAalto, FIN

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Dr. Cristina CastroUPB, Colombia

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Angelica GrandonU. Concepcion, Chile

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Dr. Mariko AgoTokushima Bunri, Japan

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Prof. O. Rojas

Dr. Raquel MartinINIA, Spain

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2013

Lignin &

Biopolymer StructuresCellulose

nanocrystals

Cellulose nanofibrils

Composites, Fibers, Additives , Hydro- and Aero-gels

Plant and microorganism Biopolymers

João V. WirbitzkiUNICAMP, Brazil

NC State University

Aalto University

Depts. Forest Biomaterials &

Chemical & Biomolecular

Engineering

Fatima Vargas

www4.ncsu.edu/~ojrojas

Bicomponentfilms

Electro-SpinningPorous

structures

NFCQCM

degradationEnzymes

SPRChitosan

FilmsBiomolecule

binding

NFCLignin

Mechanicalproperties

Soy proteinsCMC

Nano-particles

Click chem.Click chem.Conductive

fibers

Lignin-cellulose blendsEnzyme activity

ElisabetQuintana

UPC

Laura Taajamaa

Aalto

HannesOrelmaAalto

Dr. Maria S. Peresin

VTT

XiaomengLiu

Singenta

Ingrid Hoeger

NCSU/FPL

Dr. IlariFilponnen

Aalto

Raquel Martin

Complutense

Justin ZoppeAalto

Stimuli-responsive

CNCs

Ana FerrerUniv.

Cordoba

NFC from EFB

Raquel Martin

INIA

Enzyme inhibition

TiinaNypeloNCSU

Magnetic CNCs

Cristina Castro

Univ. Pontificia

Julio Arboleda

NCSU

Bacterial cellulose

Soy proteins aerogels

Bio coupling

OriolCusola

UPC

LignoCell

2010to

2012

http://www.facebook.com/photo.php?pid=3023429&id=666131894&op=1&view=global&subj=1354236973

http://www.facebook.com/photo.php?pid=3023429&id=666131894&op=1&view=global&subj=1354236973

http://www.flags.net/ARGE.htm

http://www.flags.net/ARGE.htm

http://www.flags.net/CHIN.htm

http://www.flags.net/CHIN.htm

http://www.flags.net/VENZ.htm

http://www.flags.net/VENZ.htm

LignoCell

2012to

2013Dr. Arcot

LokanathanAalto, FIN

Nan

o-

tech

no

logy

Laura TaajamaaAalto

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Nov 2013 Meeting -Subjects1. Introduction and general report

(Orlando Rojas)2. Functionalization of NFC with

metal nanoparticles (IlariFilpponen)

3. Bacterial cellulose as biomolecule carrier (Luis Morales)

4. SEW fibers, NFC and nanopaper(Ester Rojo)

5. Cellulose Nanocrystal Nano-Forest: A Cilia Mimic (Arcot Lokanathan)

6. Modification of NFC using luminescent carbon dots (KaoliinaJunka)

1. Park, J., Hung, I., Gan, Z., Rojas, O.J., Lim, K-H, Park, S. Activated carbon from biochar: Influence of its physicochemical properties on the sorption characteristics of phenanthrene, Bioresoruce Technology, accepted x.doi.org/10.1016/j.biortech.2013.09.085

2. Carrillo, C., Saloni, D., Rojas, O.J. Evaluation of O/W microemulsions to penetrate the capillary structure of woody biomass: interplay between composition and formulation in green processing, Green Chemistry, Accepted, DOI: 10.1039/C3GC41325J

3. Rojas, O.J., Lokanathan, A.R., Kontturi, E., Laine, J., Bock, H. The unusual interactions between polymer grafted cellulose nanocrystal aggregates, Soft Matter, 9, 8965-8973 (2013)

4. Salas, C., Genzer, J., Lucia, L.A., Hubbe, M.A., Rojas, O.J., Water-wettablepolypropylene fibers by facile surface treatment based on soy proteins, ACS Applied Materials & Interfaces, 5, 6541–6548 (2013)

5. Zhang, Y., Islam, N., Carbonell, R., Rojas, O.J. Specificity and Regenerability of Short Peptide Ligands Supported on Polymer Layers for Immunoglobulin G Binding and Detection, ACS Applied Materials and Interfaces, 5, 8030–8037, 2013.

6. Arboleda, J.C., Hughes, M., Lucia, L.A., Laine, J., Ekman, K., Rojas, O.J., Composite aerogels of soy proteins and cellulose nanofibrils, Cellulose, 20, 2417–2426 (2013)

7. Lokanathan, A.R., Seitsonen, J., Nykänen, A., Johansson, L-S., Campbell, J., Rojas, O.J., Ikkala, O., Laine, J. Cilia-Like Hairy Surfaces Based on End-Immobilized Nanocellulose Colloidal Rods, Biomacromolecules, 14, 2807–2813 (2013)

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8. Zhang, Y., Carbonell, R.G., Rojas, O.J. Bioactive Cellulose Nanofibrils for Specific Human IgG Binding, Biomacromolecules, dx.doi.org/10.1021/bm4007979

9. Hoeger, I.C., Gleisner, R., Negron, J., Rojas, O.J., Zhu, J.Y., Bark Beetle-killed LodgepolePine for the Production of Submicron Lignocellulose Fibrils, Journal Forest Science, doi.org/10.5849/forsci.13-012

10. Ago, M., Jakes, J, Rojas, O.J. Thermal-Mechanical Properties of Lignin-based Electrospun Nanofibers and Films Reinforced with Cellulose Nanocrystals: A Dynamic Mechanical and Nanoindentation Study, ACS Applied Materials & Interfaces, DOI: 10.1021/am403451w

11. Zhang, Y., Nypelö, T., Salas, C., Arboleda, J., Hoeger, I., Rojas, O. J. Cellulose Nanofibrils: From Strong Materials to Bioactive Surfaces, Journal of Renewable Resources, 1, 195-211 (2013).

12. Goli, K., Gera, N. Liu, X., Rao, B., Rojas, O.J., Genzer, J., Generation and properties of antibacterial coatings based on electrostatic attachment of silver nanoparticles to protein-coated polypropylene fiber, ACS Applied Materials & Interfaces, 5, 5298-5306 (2013).

13. Garcia-Ubasart, J., Vidal, T., Torres, A.L., Rojas, O.J. Laccase-mediated coupling of nonpolar chains for the hydrophobization of lignocellulose, Biomacromolecules, 14: 1637–1644 (2013).

14. Song, J., Rojas, O.J., Approaching Superhydrophobicity Based on cellulosic materials: A Review, Nordic P&P Research Journal, 28: 216-238 (2013).

15. Martín-Sampedro, R., Rahikainen, J.L., Johansson, L-S., Marjamaa, K., Laine, J., Kruus, K., Rojas, O.J., Preferential adsorption and activity of monocomponent cellulases on lignocellulose thin films …, Biomacromolecules, 14: 1231 (2013) 16

16. Taajamaa, L., Rojas, O.J., Laine, J., Yliniemi, K., Kontturi, E. Protein-assisted 2D assembly of gold nanoparticles on a polysaccharide surface, Chemical Communications, 59: 1318-1320 (2013).

17. Ago, M., Jakes, J., Rojas, O.J. Thermo-Mechanical Properties of Lignin-based Electrospun Nanofibers and Films Reinforced with Cellulose Nanocrystals, Biomacromolecules, accepted

18. Zhang, Y., Islam, N., Carbonell, R.G., Rojas, O.J. Specific binding and detection of IgGby bioactive short peptides immobilized on supported copolymer layers, Analytical Chemistry, 2013, 85 (2): 1106–1113 (2013).

19. Salas, C.; Rojas, O.J.; Lucia, L.A.; Hubbe, M.A., Genzer, J., On the surface interactions of proteins with lignin, ACS Applied Materials & Interfaces, 5: 199-206 (2013)

20. Rahikainena, J., Martin-Sampedro, R., Heikkinena, H., Rovioa, S., Marjamaaa, K., Tamminena, T., Rojas, O.J., Kruus, K., Inhibitory effect of lignin during cellulose bioconversion: the effect of lignin chemistry on non-productive enzyme adsorption, Bioresource Technology, 133, 270–278 (2013)

21. Hoeger, I.C., Nair, S.S., Ragauskas, A.J., Yulin Deng, Y., Rojas,O.J., Zhu, J.Y., Mechanical Deconstruction of Lignocellulose Cell Walls and their Enzymatic Saccharification, Cellulose, 20: 807-818 (2013).

22. Junka, K., Filpponen, I., Johansson, L-S., Kontturi, E., Rojas, O.J., Laine, J., A method for the heterogeneous modification of nanofibrillar cellulose in aqueous media, Carbohydrate Polymers, Accepted doi:10.1016/j.carbpol.2012.11.063.

23. Park, J., Meng, J., Lim, K.H., Rojas, O.J., Park, S. Transformation of lignocellulosic biomass during torrefaction, Journal of Analytical and Applied Pyrolysis, 100: 199–206(2013). 17

24. Abdelgawad, A.M., Hudson, S.M., Rojas, O.J. Antimicrobial wound dressing microfiber mats from multicomponent (chitosan/silver-NPs/polyvinyl alcohol) systems, Carbohydrate Polymers, Accepted CARBPOL-D-12-01631R1

25. Martin-Sampedro, R., Filpponen, I.; Hoeger, I.C., Zhu, J.Y., Laine, J., Rojas, O.J., Rapid and Complete Enzyme Hydrolysis of Lignocellulosic Nanofibrils, ACS Macro Letters, 1, 1321-1325 (2012)

26. Goli, K, Rojas, O.J., Genzer, J. Formation and antifouling properties of amphiphiliccoatings on polypropylene fibers, Biomacromolecules, 13, 3769-3779 (2012).

27. Orelma, H., Filpponen, I., Johansson, L-S., Österberg, M., Rojas, O.J., Laine, J. Surface functionalized nanofibrillar cellulose (NFC) film as a platform for rapid immunoassays and diagnostics, Biointerphases, 7, 61 (2012).

28. Hoeger, I.C., Filpponen, I., Martin-Sampedro, R., Johansson, L-S., Österberg, M., Laine, J., Kelley, S., Rojas, O.J. Bi-component lignocellulose thin films to study the role of surface lignin in cellulolytic reactions, Biomacromolecules, 13, 3228–3240 (2012).

29. Ago, M., Jakes, J.E., Johansson, L-S., Park, S., Rojas, O.J. Interfacial Properties of Lignin-based Electrospun Nanofibers and Films Reinforced with Cellulose Nanocrystals, ACS Applied Materials and Interfaces, 4(12): 6849-6856 (2012).

30. Hao-yu, J., Lucia, L.A., Rojas, O.J., Hubbe, M.A., Pawlak, J.J., A Survey of Soy Protein Flour as a Novel Dry Strength Additive for Papermaking Furnishes, Journal of Agricultural and Food Chemistry, 60, 9828-33

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31. Ferrer, A., Filpponen, I., Rodríguez, A., Laine, J., Rojas, O.J. Valorization of Residual Empty Palm Fruit Bunch Fibers (EPFBF) by Microfluidization: Production of Nanofibrillated Cellulose and EPFBF Nanopaper, Bioresource Technology, 125, 249-255 (2012).

32. Ferrer, A., Quintana, E., Filpponen, I., Solala, I., Vidal, V., Rodríguez, R., Laine, J., Rojas, O.J. Effect of Residual Lignin and Heteropolysaccharides in Nanofibrillar Cellulose and Nanopaper, Cellulose, 19, 2179–2193 (2012)

33. Orelma, H., Johansson, L-S., Filpponen, I., Rojas, O.J., Laine, J. Generic Method for Attaching Biomolecules via Avidin-Biotin Complexes Immobilized on Films of Regenerated and Nanofibrillar Cellulose, Biomacromolecules, 13, 2802−2810 (2012)

34. Carrillo,C.A., Saloni, D., Lucia, L.A., Hubbe, M.A., Rojas, O.J. Capillary flooding of wood with microemulsions from Winsor I systems, Journal of Colloids and Interface Science, 381, 171–179 (2012).

35. Csoka, L., Hoeger, I.C., Peralta, P., Peszlen , I., Rojas, O.J. Piezoelectric Effect of Cellulose Nanocrystals Thin Films, ACS Macro Letters, 1, 867–870 (2012)

36. Payne, K., Jackson, C., Aizpurua Gonzalez, C., Rojas, O.J., Hubbe, M., Oil Spills Abatement: Factors Affecting Oil Uptake by Cellulosic Fibers, Environmental Science & Technology, 46:7725-7730 (2012)

37. Vallejos, M.E., Peresin, M.S., Rojas, O.J. All-Cellulose Composite Fibers Obtained by Electrospinning Dispersions of Cellulose Acetate and Cellulose Nanocrystals, Journal of Polymers and the Environment, 20:1075–1083 (2012).

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1. Taajamaa, L., Laine, J., Kontturi. E., Rojas, O.J., Bicomponent fibre mats with adhesive ultra-hydrophobicity tailored with cellulose derivatives J. Mater. Chem., DOI:10.1039/C2JM30572K.

2. Zoppe, J.O., Venditti, R.A., Rojas, O.J. Pickering emulsions stabilized by cellulose nanocrystals grafted with thermo-responsive polymer brushes. Journal of Colloid and Interface Science, 369 202–209 (2012)

3. Goli, K., Rojas, O. J., Ozcam, A., Genzer, J. Generation of functional coatings on hydrophobic surfaces through deposition of denatured proteins followed by grafting from polymerization, Biomacromolecules, In press, DOI: 10.1021/bm300075u

4. Castro, C., Zuluaga, R., Álvarez, C., Putaux, J-L., Caro, G., Rojas, O.J. Mondragon, I., Gañán, P. Bacterial cellulose produced by a novel acid-resistant strain Gluconacetobacter medellensis, Carbohydrate Polymers, In press, DOI: 10.1016/j.carbpol.2012.03.045

5. Ago, M., Okajima, K., Jakes, J.E., Park, S., Rojas, O.J., Lignin-based biomimetic electrospun nanofibers reinforced with cellulose nanocrystals, Biomacromolecules, 13: 918–926 (2012)

6. Salas, Carlos, Rojas, O. J., Lucia, L. Hubbe, M.A., Genzer, J. Adsorption of glycinin and ß-conglycinin on silica and cellulose:surface interactions as a function of denaturation, pH, and electrolytes, Biomacromolecules, 13: 387-396 (2012)

7. Li, Y., Rojas, O.J., Hinestroza, J.P., Boundary Lubrication of PEO-PPO-PEO Triblock Copolymer Physisorbed on Polypropylene, Polyethylene, and Cellulose Surfaces, Ind. Eng. Chem. Res. , 51: 2931-2940 (2012)

8. Liu, X., He, F., Salas, C., Pasquinelli, M., Genzer, J., Rojas, O.J. Experimental and Computational Study of the Effect of Alcohols on the Solution and Adsorption Properties of a Nonionic Symmetric Triblock Copolymer, Journal of Physical Chemistry B, 116: 1289–1298 (2012).

9. Liu, H., Li, Y., Krause, W., Rojas, O.J., Pasquinelli, M. The Soft-Confined Method for Creating Molecular Models Amorphous Polymer Surfaces, The Journal of Physical Chemistry B, 116: 1570–1578 (2012)

10. Li, Y., Rojas, O.J., Hinestroza, J.P., Boundary Lubrication of PEO-PPO-PEO Tri-block Copolymer Physisorbed on Polypropylene, Polyethylene and Cellulose surfaces, Industrial & Engineering Chemistry Research

11. Liu, H., Li, Y., Krause, W., Pasquinelli, M., Rojas, O.J. Mesoscopic Simulations of the Phase Behavior of Aqueous EO19PO29EO19 Solutions Confined and Sheared by Hydrophobic and Hydrophilic Surfaces, ACS Applied Materials & Interfaces, 4: 87-95(2012)

12. Orelma, O., Filpponen, I., Johansson, L-S, Laine, J., Rojas, O.J. Modification of Cellulose Films by Adsorption of CMC and Chitosan for Controlled Attachment of Biomolecules Biomacromolecules, 12(12): 4311–4318(2011).

13. Taajamaa, L., Rojas, O.J., Laine, J, Kontturi. E. Phase-specific pore growth in ultrathin bicomponent films from cellulose-based polysaccharides, Soft Matter, 7: 10386-10394 (2011)

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14. Hoeger, I., Rojas, O.J., Efimenko, K., Velev, O.D., Kelley, S.S. Ultrathin film coatings of aligned cellulose nanocrystals from a convective-shear assembly system and their surface mechanical properties Soft Matter, 7 (5), 1957-1967 (2011)

15. Csoka, L., Hoeger, I., Peralta, P., Peszlen, I., Rojas, O.J. Dielectrophoresis of cellulose nanocrystals and their alignment in ultrathin films by electric field-assisted shear assembly, Journal of Colloid and Interface Science, 363(1):206-12 (2011).

16. Spence, K.L., Venditti, R.A., Rojas, O.J., Pawlak, J.J., Hubbe, M.A., Water Vapor Barrier Properties of Microfibrillated Cellulose Films, Bioresources, 6(4):4370-4388 (2011).

17. Zoppe, J.O., Österberg, M., Venditti, R.A., Laine, J., Rojas, O.J. Surface Interaction Forces of Cellulose Nanocrystals Grafted with Thermo-responsive Polymer Brushes, Biomacromolecules, 12 (7): 2788–2796 (2011).

18. Liu, X., Vesterinen A-H., Genzer, J., Seppälä, J.V., Rojas, O.J. Adsorption of PEO−PPO−PEO Triblock Copolymers with End-Capped Cationic Chains of Poly(2-dimethylaminoethyl methacrylate), Langmuir, 27 (16), 9769–9780 (2011).

19. Martin-Sampedro, R., Capanema, E.A., Hoeger, I., Villar, J.C., Rojas, O.J. Lignin Changes after Steam Explosion and Laccase-Mediator Treatment of Eucalyptus Wood Chips, Journal of Agricultural and Food Chemistry, 59 (16): 8761–8769 (2011).

20. Li, Y., Liu, H., Song, J., Rojas, O.J., Hinestroza, J.P., Adsorption and Association of a Symmetric PEO-PPO-PEO Triblock Copolymer on Polypropylene, Polyethylene, and Cellulose Surfaces, ACS Applied Materials and Interfaces, 3 (7): 2349–2357 (2011)

21. Wu, N., Hubbe, M.A., Rojas, O.J., Park, S., Permeation of a Cationic Polyelectrolyte into Meso-porous Silica. Part 3, Colloids and Surfaces A, 381, 1-6 (2011).

22. Liu, X., Kiran, K., Genzer, J., Rojas, O.J. Multilayers of Weak Polyelectrolytes of Low and High Molecular Mass Assembled on Polypropylene and Self-assembled Hydrophobic Surfaces, Langmuir 27 (8), 4541–4550 (2011)

23. Spence, K.L., Venditti, R.A., Rojas, O.J., Habibi, Y., Pawlak, J.P. A comparative study of energy consumption and physical properties of microfibrillated cellulose produced by different processing methods, Cellulose, 18:1097–1111 (2011).

24. Wang, Z., Hauser, P., Rojas, O.J., Multilayers of low-charge-density polyelectrolytes on thin films of carboxymethylated and cationic cellulose, Journal of Adhesion Science and Technology, 25 (6-7), 643-660 (2011)

25. Álvarez, C., Rojano, B., Almaza, O.,Rojas, O.J., Gañán, P., Self-bonding boards from plantain fiber bundles after enzymatic treatment, Journal of Polymers and the Environment, 19(1), 182-188 (2011).

26. Silva, D.J., Rojas, O.J., Hubbe, M.A., Park, S.W. Enzymatic treatment as a pre-step to remove cellulose films in from sensors, Macromolecular Symposia, 299/300, 107–112 (2011). 21

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1. Fibras Bioactivas, XXI LatinAmerican Congress on Textile Chemistry, Medellin, Colombia, September 3, 2013

2. Integration of Lignocellulose and Soy Proteins: Adhesion Modification, Papermaking and Fibers, Simposio Internacional sobre MaterialesLignocelulosicos, Iguazu, Argentina August 20-21, 2013

3. Cellulose synthesis, structure, matrix interactions and technology”InternationalMeeting organized by the Center for Lignocellulose Structure and Formation at Penn State University, University Park, PA, May 16-18 May, 2013

4. “Frontiers in nanocellulose research and utilization”, Nordic Polymer Days 2013, University of Helsinki, May 29-31, 2013

Workshop:http://www4.ncsu.edu/~ojrojas/PASI/index.htmlPolymer and Composite Materials from Renewable Resources and Biorefinery: from Chemistry to Applications /COSTA RICA, August 5-16, 2013

http://www4.ncsu.edu/~ojrojas/PASI/index.html

Orals:1. Nanoparticles and Nanostructures from Direct- and Self- Assembly of Components Cleaved from

Fiber Cell Walls, Orlando Rojas, North Carolina State & Aalto University2. 2-Dimensional Nanoscale Structures from Cellulosic Materials, Eero Kontturi, Aalto University3. Super-Strong Soy Protein/Nanocellulose Composite Aerogels, Julio Arboleda, North Carolina State

University4. Surface Assembly of Chemically Reactive Polysaccharides on Nanocellulose, Janne Laine, Aalto

University5. Magnetic Cellulose Nanocrystal Hybrid, Tiina Nypelö, North Carolina State University6. ZnO-Bacterial Cellulose Nanocrystal Composite and its Potential as Energy Harvesting Material,

Levente Csoka, University of West Hungary7. Surface Functionalized Nanofibrillar Cellulose (NFC) Film as a Platform for Immunoassays and

Diagnostics, Ilari Filpponen, Aalto University8. Nanofibrillated Cellulose as Carrier for Short Peptides Assemblies for Human IgG Detection and

Affinity Separation, Yanxia zhang, North Carolina State University9. Self-Assembly of Cellulose Fibrils/SiO2 Nanoparticles During Synthesis by Gluconacetobacter

Bacteria- Robin Zuluaga Gallego, Pontificia Bolivariana University

Posters:1. Reinforcing Nanocellulose Isolated from Banana Rachis and Corn Husk-Robin Zuluaga Gallego,

Pontificia Bolivariana University2. Hydrophobization of Cellulosic Substrates by Creating Surface Nanostructures Using Enzymatic

Methods-Oriol Cusola, Universitat Politècnica de Catalunya UPC-BarcelonaTech 24

245th ACS Meeting, April 7-11, 2013 | New Orleans, Louisiana

1. In situ self-assembly and hydrophobization of Gluconacetobacter bacterial cellulose,Cristina Castro, Robin Zuluaga,

Jean-Luc Putaux, Marlon Osorio, Gloria Caro, Orlando Rojas, Piedad Gañán

2. Short peptide-conjugated copolymer based biosensor for specific binding of immunoglobulin G, Yanxia Zhang, Orlando

Rojas, Nafisa Islam, Ruben Carbonell

3. Lignin nano- and microparticles for coating and interfacial stabilization, Tiina Nypelo, Mariko Ago, Shuai Li, Orlando

Rojas

4. Effect of composition and formulation variables in biomass flooding capacity by o/w microemulsions, Carlos A Carrillo,

Daniel Saloni, Orlando J Rojas

5. Phase behavior and properties of the oil-in-water emulsions stabilized by carboxymethylated and acetylated lignins,

Shuai Li, Maryam Mazloumpour, Professor Julie Willoughby, Professor Orlando J Rojas

6. Magnetic cellulose nanocrystals: Demonstration and properties of organic-inorganic hybrid system, Tiina Nypelo, Carlos

Rodriguez-Abreu, José Rivas, Michael Dickey, Orlando Rojas

7. Surface modification of hydrophobic substrates by soy protein adsorption, Carlos L. Salas, Orlando J. Rojas, Jan

Genzer, Martin A. Hubbe, Lucian Lucia

8. Cellulose acetate/lignin-based electrospun fibers, Joao V. W. Silveira, Ana L. G. Millas, Mariko Ago, Orlando J. Rojas,

Edison Bittencourt

9. Mechanical deconstruction of lignocellulose cell walls and production of nanopaper, Ingrid C Hoeger, Orlando J Rojas,

Junyong-FS Zhu

10.Effects of lignin and hemicelluloses on the enzymatic hydrolysis of nanofibrillated softwood lignocellulose after SO2-

ethanol-water (SEW) fractionation, Luis O Morales, Mikhail Iakovlev, Jenni Rahikainen, Leena-Sisko Johansson, Raquel

Martin, Janne Laine, Adriaan van Heiningen, Orlando Rojas

25

245th ACS Meeting, April 7-11, 2013 | New Orleans, Louisiana

12. Influence of the deconstruction of the cell wall in the enzymatic saccharification of softwoods, Ingrid C Hoeger, Sandeep

S Nair, Professor Arthur J Ragauskas, Professor Yulin Deng, Professor Orlando J Rojas, Junyong-FS Zhu

13.Asymmetric thiolation of cellulose nanocrystals using reductive amination of reducing ends, Lokanathan R Arcot, Jani

Seitsonen, Antti Nykänen, Leena S Johansson, Joseph Campbell, Janne Ruokolainen, Olli Ikkala, Orlando Rojas, Janne

Laine

14.Protein-assisted 2D assembly of gold nanoparticles on an ultrathin cellulose film, Laura Taajamaa, Orlando J Rojas,

Janne Laine, Eero Kontturi

15.Synthesis and characterization of soy protein-nanocellulose composite aerogels, Julio C Arboleda, Orlando J Rojas,

Lucian A Lucia, Janne Laine

16. Surface functionalized nanofibrillar cellulose (NFC) film as a platform for immunoassays and diagnostics, Ilari

Filpponen, Hannes Orelma, Leena-Sisko Johansson, Monika Österberg, Orlando Rojas, Janne Laine

17.Novel Pretreatment in the Manufacture of Nanofibrillated Cellulose via Microfluidization , Carlos A Carrillo, Janne Laine,

Orlando J Rojas

26

23-26 June 2014 Vancouver, Canada

Preparation & Characterization

Renewable nanomaterial isolation & separation

•Cellulose nanocrystals and nanofibrils

•Plant, algal, bacterial and other sources

•Lignin, heteropolysaccharides, chitosan, etc.

Lab & Pilot-Scale Production

•Process Optimization

•New isolation & extraction methods

•Drying processes

•Separation processes for renewable nanomaterials

Metrology

•Sizing, mechanical, chemical, optical and surface properties

•Purity, molecular weight, crystallinity, etc.

•Thermal, electrical and other properties

•Toxicity & Biodegradability

Self- and direct- assembly & Functionalities

Nanostructured materials by self-assembly

•Nano manufacture & self-assembly

•Photonic bandgap pigments for special optical effects

•Controlled delivery, immobilization, etc.

Novel Nano-enabled Functionalities

•Surface modification and responsive materials

•Novel optical effects

•Novel electric, magnetic and piezoelectric effects

Carbon Fibers from Biomass

•Production, characterization & uses

Membranes & Filters

•New Membrane technologies

•Air, water and bio filtration

Biomedical Applications

•Ligament replacements, scaffolds, advanced wound technology

•Bioactive materials

Immunoassays

Rheology and dispersion phenomena

•Rheology behavior in aqueous and non-aqueous systems

•Viscoelastic properties, etc

Computer modeling and simulation

•Multiscale Modeling

•Solvation structure and hydrodynamics

Composites, Liquid Gels, and Aerogels

Nanocomposites and renewable nanomaterials

•Nano-reinforced films and fibers.

•Biomimetic nanocomposites

•Porous materials, gels and aerogels, foams, etc.

•Bio-derived matrix polymers

•Processing

Organic/Inorganic Hybrids

•Catalysts

•Flexible electronics, etc.

•Metal functionalization, ALD, etc,

Manufacturing Applications

•Industrial processing applications

•Dispersion and flocculation

Additive Manufacturing

•Raw nanomaterials

•Medical applications

•3D printing

Paper, Board & Packaging

•Coatings & Fillers

•High modulus paper coatings

•Wear and scratch resistant coatings

•Flexible Packaging

•Barriers

Printing Technologies

•Printing inks

•Smart materials

•Sensing technologies

Environmental, Health and Safety Issues

•Workplace Safety & Standards

•Current understanding and critical gaps

•Consumer perception and regulations

•Management of risks and perceptions

•Sustainability assessment, LCA

Info / Conference Chairs:

Orlando Rojas, NCState (USA)

Wadood Hamad, UBC (Canada)

Akira Isogai, Univ. of Tokyo (Japan)

STUDENT OPPORTUNITIESStudent Travel AwardAbstracts submitted by students for oral presentations and posters will be reviewed and evaluated by a group appointed by the Technical Program Committee. Discounts on conference registration and other fees and partial expenses will be covered to the selected submissions.

Student Poster CompetitionVerso Paper Corp. will sponsor the Student Poster Competition. All accepted posters will be evaluated at the conference by a team of judges. The three poster winners will be recognized at the conference, and the top two poster presenters awarded a prize.

1. Rojas, O.J., Nanoparticles and Nanostructures from Direct- and Self- Assembly of Components Cleaved from Fiber Cell

Walls, XXI International Materials Research Congress (MRS), Cancun, Mexico, August 12-16, 2012

2. Rojas, O.J., Nypelo, T., Ago, M., Zhang, Y., Taajamaa, L., Orelma, H., Filpponen, I. Laine, J. Cellulose as Tunable

Material in Nanotechnologies: Thin Films of Cellulose and Cellulose Derivatives with Designed Properties by Surface

Modification, 3rd International Cellulose Conference, Sapporo, Japan, October 10-12, 2012.

3. Filpponen, I., Lokanathan, A., Rojas, O.J., Laine, J. Click chemistry reactions on the reducing end groups of cellulose

nanocrystals, 3rd International Cellulose Conference, Sapporo, Japan, October 10-12, 2012.

4. Martín-Sampedro, R., Rahikainen, J., Hoeger, I., Marjamaa, K., Kruus, K., Filponnen, I., Laine, J., Rojas, O.J., 4th Effects

of Lignin on the Hydrolysis of Cellulose by Pure and Multicomponent Enzymes, International Conference on Pulping,

Papermaking and Biotechnology (ICPPB’12), Nanjing, China, November 7-9, 2012

5. Ago, M., Silveira, J., Taajamaa, L., Jakes, J.E., Kontturi, K., Bittencourt, E., Laine, J., Rojas, O.J., Electrospun Micro-

and Nano- Fibers from Multicomponent Lignocellulose Systems: Functional Materials with Special Surface, Mechanical

and Thermal Properties, International Conference on Pulping, Papermaking and Biotechnology (ICPPB’12), Nanjing,

China, November 7-9, 2012

6. Hubbe, M.A., Payne, K.C., Jackson, C.D., Aizpurua, C.E., Rojas, O.J. Application of Cellulosic Fiber Materials for The

Remediation of Petroleum Spills in Water, International Conference on Pulping, Papermaking and Biotechnology

(ICPPB’12), Nanjing, China, November 7-9, 2012.

7. Filpponen, I., Laine, J., Rojas, O.J. Click chemistry for producing lignin-based novel materials, International Conference

on Pulping, Papermaking and Biotechnology (ICPPB’12), Nanjing, China, November 7-9, 2012.

8. Carrillo, C., Rojas, O.J. High water content microemulsions as a novel method for wood pretreatment and extraction,

12th European Workshop on Lignocellulosics and Pulp, Espoo, Finland, August 27-30, 2012.

9. Silveira, J.V.W., Millas, A.L.G., Tessarolli, L.F., Ago, M., Rojas, O.J., Bittencourt, E., Produção de Fibras Eletrofiadas a

Partir de Acetato de Celulose e Lignina, XIX Brazilian Congress in Chemical Engineering (COBEQ 2012), Búzios, RJ,

Brazil, September 9-12, 2012

28


Functionalization of NFC with metal

nanoparticles

Steering group meeting 26.11.2013

Background

Cationization of NFC:

+ Immobilization of nanoparticles ( Ag, Au…)

+ Interaction with anionic compounds (anionic dyes, anionic polymers,

layer-by-layer etc.)

+ Antibacterial properties (Ag, quatenary ammonium salts)

Incorporation of noble metal nanoparticles:

Data storage

Biomedicine

MRI

Nanofluids

Catalysis

Procedure:

Synthesis of azide- and alkyne-modified NFCs

Preparation of tosylcellulose:

Chemicals: 12 equiv. TsCl, 12

equiv. Et3N

Reaction: RT, 24hrs

Preparation of alkyne-modified NFC:

Chemicals: 10 equiv. propargyl bromide

Reaction: RT, 20hrs

Preparation of azide-modified NFC

Chemicals: DMF, 10 equiv. NaN3

Reaction: 100ºC, 20hrs

Dissolution of NFC in aqueous NaOH:

8.5% NaOH

Cool to -18ºC

5.0% NaOH

Elchinger et. Green Chemistry, 2012, 3126-3131.

Faugeras et. Green Chemistry, 2012,598-600.

Copper(I)-catalyzed Azide-Alkyne Cycloaddition (CuAAC)

Widely applied for the generation of carbohydrate mimetics and derivatives

1,3-dipoledipolarophile triazole ring

Huisgen, R. Proc. Chem. Soc. 1960, 357–369.

Lewis, W. G.; Green, L. G.; Grynszpan, F.; Radic, Z.; Carlier, P. R.; Taylor, P.; Green, M. G.; Fokin, V. V.;

Sharpless. K. B. Angew. Chem., Int. Ed. 2002, 41, 1053-1057.

Liebert, T.; Hänsch, C.; Heinze, T. Macromol. Rapid Commun. 2006, 27, 208-213.

Hafrén, J.; Zou, W.; Córdova, A. Macromol. Rapid Commun. 2006, 27, 1362–1366.

FTIR spectra of azide- and alkyne-modified NFCs

4000 3500 3000 2500 2000 1500 1000 500

Tra

nsm

itta

nce (

%)

wavelength (cm-1)

NFC

Tosyl-terminated NFC

Azide-terminated NFC

4000 3500 3000 2500 2000 1500 1000 500

Tra

nsm

itta

nce (

%)

wavelength (cm-1)

NFC

Propargyl-NFC

2116 cm-1

2110 cm-1

Characteristic bands for azide and alkyne moieties observed

Surface cationization of NFC

Synthesis and FTIR characterization of propargyl-terminated cationic salt

+

Standard spectrum of a propargyl-bearing quaternary

ammonium saltFTIR spectrum of synthesized propargyl-bearing quaternary

ammonium salt

Sun et. Polymer,2012,2884-2889.

4000 3500 3000 2500 2000 1500 1000 500

0

20

40

60

80

100

Tra

nsm

ittan

ce (

%)

Wavelength (cm-1)

2116 cm-1

Characterization of cationized NFC (FTIR & zeta-potential)

2 4 6 8 10 12

0

10

20

30

40

Anna's results

Click reaction

Re-do anna's method

Zeta

pote

ntia

l (m

V)

pH4000 3500 3000 2500 2000 1500 1000 500

Tra

nsm

itta

nce (

%)

Wavelength (cm-1)

Before cationization

After cationization

Disappeareance of azide stretching band

indicates successful click reaction

Resulting cationic charge is lower than

that achieved using EPTMAC

EPTMAC cationization for pulp and

NFC suspension

Click cationization

Synthesis of gold nanoparticles (Au NPs)

Preparation: Turkevich method (simplest method)

NP size: 10-20 nm

Reaction: hot chloroauric acid reduced by sodium citrate solution

300 400 500 600 700 800 900

0

1

2

Inte

nsity(a

.u.)

Wavelength (nm)

pH=4.91

Immobilization of Au NPs on NFC

Electrostatic interactionDirect click reaction

Gehan et. Langmuir,2010,3975-3980.

Transmission electron microscopy of Au NP decorated NFC

Au NP decorated NFC surface using electrostatic attraction

Conclusions & future plans

Alkyne- and azide-modified NFCs were successfully synthesized

Alkyne-terminated cationic salt were synthesized and “clicked” with

azide-modified NFC

Gold nanoparticles were immobilized on modified NFC surface

Magnetic propargyl-terminated FePt nanoparticles will be

synthesized and then attached to cellulosic nanomaterials

LIGNOCELLVALUE-ADDED MATERIALS AND FUNCTIONAL STRUCTURES FROM

LIGNOCELLULOSICS

Bacterial cellulose as biomolecule carrier

Luis Morales


Bacterial cellulose (BC)

Gluconacetobacter,

Rhizobium

Cellulose synthesis and

extrusion from cellsNetwork of BC fibrils

BC is highly pure and crystalline

BC applications

Biomedical (wound healing, drug deliver, tissue engineering, dental

implants)

Nutritional values (food additives, thickener)

Cosmetics

Electronics

Nonwoven fabric

High water holding capacity

Nanoporous structure

Partially dehydrated membrane is able to absorb fluid up to its original

capacity

Sterile, easy to use, and inexpensive

Ability to be molded in situ, high elasticity and conformability, high

mechanical strength

Biocompatible, nonpyrogenic, nontoxic

Advantages of using BC in wound healing

Aim of the study

Explore the possible use of BC as biomolecule carrier for

micronutrient and drug delivery

Molecules of interest

Nicotinic acid

(vitamin B3)

Riboflavin

(vitamin B2)

Essential human nutrient

Reduce cholesterol

Essential human nutrient

Plays major roles in metabolism

Wound healing

QCM-D (Quartz Crystal Microbalance with Dissipation)

Electromechanical technique

Vibrating quartz crystal

V~

Substrate

Adsorption

Aqueous phase

Ampli-

tude

Time Circuit off

Q-Sense E4

Frequency changes are proportional to mass adsorb on the crystals

BC model films

BC, Gluconacetobacter

medellinensis

5 passes,

constant shear rate, 55 MpaMicrofluidized BC

0.6% Microfluidized BC was spin coated on SiO2 crystals

Nicotinic acid adsorption on BC films, QCM-D study

Continuous nicotinic acid (0.5 g/L) injection at 100 µl/min, T= 25ºC, pH 7

Nanofibrillated cellulose (NFC)

Softwood kraft pulp (81.7% cellulose, 9.2% xylan, 9% glucomannan, < 0.5% lignin)

10 passes,

constant shear rate, 55 Mpa

NFC (1,67 g/L), sonicated and centrifuged 10400 rpm, 25ºC and the supernatant

was used to make model films on SiO2 surface

Riboflavin adsorption on NFC films, QCM-D study

Riboflavin H2O

Continuous riboflavin (0.5 g/L) injection at 100 µl/min, T= 25ºC, pH 7

Carboxymethylcellulose (CMC) modification, SEM images

BC

BC-CMC

Surface Cross section

Adsorption of Riboflavin on pre-adsorbed CMC NFC films

CMC CaCl2H2O

H2ORiboflavin

Continuous riboflavin (0.5 g/L) injection at 100 µl/min, T= 25ºC, pH 7

Future plans

Elucidate the binding mechanisms of Riboflavin on pre-adsorbed CMC NFC films

Test binding and release of ibuprofen, indomethacin and other drugs used in

wound healing on NFC and BC using QCM-D

Measure drug and nutrient binding on NFC and BC using HPLC

Study drug/micronutrient relase from NFC and BC(?) films

Thank you for your attention


Lignin is awesome!


Ester Rojo

MOTIVATION

NFC, NFLC

Reinforcement

Soybean oil resin

Matrix

Adhesion

Substrate of Printed Circuit Boards (electronic applications)Matrix: Epoxy (petroleum-based) Soybean oil

Reinforcement: E-glass (high energy requires) NFCOthers: Coupling agents (chemicals) Lignin (NFLC)

Lignin, NFLC

BIOCOMPOSITES

STUDY OF THE REINFORCEMENT

Effect of lignin content on the properties of nanopapers

NFC, NFLC

Reinforcement

Soybean oil resin

MatrixAdhesion

Lignin, NFLC

4% L 14% L0% L

Spruce

Nanopaper

EFFECT OF LIGNIN CONTENT ON THE PROPERTIES OF NANOPAPERS

Experimental procedure

Wiley Mill (30 mesh screen)

Polytron (dispersing and mixing)

Microfluidazer

6 passes

NFC(0.8% dry)

Cold press

Hot press

Filtering

Pulps< 2% dry content

2.5 bar, 15 min

4 bar, 4 min

100 °C1800kg, 225 kg/cm2, 220 bar

2 h

04

14%L

1* 400-200 nm6 * 200-100 nm

62

0

20

40

60

80

100

120

140

160

0 5 10 15

Filte

red

wate

r (m

L)

Filtration time (min)

0% L

4% L

14% L

0

20

40

60

80

100

0 5 10 15

Filte

red

wate

r (%

)

Filtration time (min)

0% L

4% L

14% L

0 %

4 %

14 %

Volume

Time

EFFECT OF LIGNIN CONTENT

Filtration time

63

4 % L 14 % L0 % L

0 % Lignin 4 % Lignin 14 % Lignin

Density (g/cm3) 1.24 ± 0.03 1.18 ± 0.05 1.20 ± 0.02

Tensile Strength, MPa 164 ± 17 156 ± 17 116 ± 7

Tensile Index, kN/g 1942 ± 565 1625 ± 134 1306 ± 80

Breaking Strain, % 2.88 ± 0.12 2.83 ± 0.35 1.71 ± 0.25

Elastic modulus, GPa 14.3 ± 0.5 13.4 ± 0.9 12.2 ± 0.2

TEA, kJ/m2 161 ± 18 154 ± 34 66 ± 15

TEA, J/g 1904 ± 269 1598 ± 319 737 ± 167 0

50

100

150

200

0 1 2 3St

ress

(M

Pa)

Strain (%)

0% L

4% L

14% L


Mechanical properties

64

4 %

14 %

0 %

100

200

300

4

8

12

16

A B C D E F G H I J K L0

3

6

9

12

Str

eng

th (

MP

a)

Mod

ulu

s (

GP

a)

Str

ain

(%

)

Softwood Hardw. Non-w.

A

A : Present work

B-L: Literature values- L

+ L


Mechanical properties

65

0% L 4% L 14% L

20

30

40

50

60

70

80

90

WC

A (

°)

4 % L 14 % L0 % L

76.2°61.8°35.7°


Water contact angle: static (goniometer)

30

40

50

60

70

80

90

0 10 20 30 40 50 60 70

WC

A

t (s)

0% L

4% L

14% L

66

EFFECT OF LIGNIN CONTENT:

Water contact angle: dynamic

Hyster. (°)θa (°) θr (°)

0% L 35.4 ± 0.5 25.8 ± 1

14% L 77.7 ± 3 25.8 ± 1.8 51.9

9.6

4% L 60.9 ± 4.1 25.9 ± 1.7 35.1

θa (°) θr (°) Hyster. (°)

27.5 47.5

0% L 36.2 26.2 10.0

4% L 67.4 26.0 41.4

14% L 75.0

GONIOMETER Optical (direct measurements of WCA) Method: Sessile drop

TENSIOMETER Force (indirect measurements of WCA)

Method: Wilhelmy plate

20

30

40

50

60

70

80

90

2 4 6 8 10

Co

nta

ct

an

gle

(°)

Depth (mm)

0% L

4% L

14% L

Advancing (θa)-hydrophobic parts-

Receding (θr)-hydrophilic parts-

Hysteresis = θa – θr

• Roughness

• Heterogeneity

Advancing (θa) Receding (θr)

Comparable results

67


Surface energy: Contact angle (goniometer)Intermolecular forces in a material

Surface energyWork required to extract molecules

from the bulk of a material and create a new unit area of surface molecules

(mJ/m2)

Surface energy is the combination of

d: Dispersion (non polar) energy, LW Associated with London-van der Waals interactions

p: Polar energy, or Lewis acid-base component, ABAssociated with electron-donor = base (γ-), and electron-acceptor = acid (γ+) interactions

SURFACE ENERGY CALCULATIONS:

Geometric mean method = 2 component theory = Owens, Wendt, Rabel and Kaelble (OWRK)Assumes that the interfacial free energy across the cellulose-liquid interface is related to the geometric mean of the polar anddispersion surface free energies of the cellulose and the liquid

Acid-base theory = 3 component theory = Van Oss, Good, ChaudhuryIncludes Lewis acid-base components

1 + 𝑐𝑜𝑠𝜃 ∙ 𝛾𝑙𝑣 = 2 ∙ 𝛾𝑑𝑙∙ 𝛾𝑑

𝑠+ 𝛾

𝑝

𝑙∙ 𝛾

𝑝

𝑠

1 + 𝑐𝑜𝑠𝜃 ∙ 𝛾𝑙𝑣 = 2 ∙ 𝛾𝐿𝑊𝑙∙ 𝛾𝐿𝑊

𝑠+ 𝛾−

𝑙∙ 𝛾+

𝑠+ 𝛾+

𝑙∙ 𝛾−

𝑠


Surface energy: Contact angle, sessile drop

Lignin

WaterFormamideDiiodomethaneEthylglygol

0%L 4%L 14%L

Contact angle (°)

Water (γ=72.8) 35.4 60.9 77.8

Formamide (58) 15.4 20.7 36.2

Diiodomethane (50.8) 19.5 31.1 33.8

Ethyleneglycol (48) 17.6 19.5 33.7

Surface energy (mJ/m2)

γd, LW (apolar) 48.62 44.51 43.20

γ+ (polar, acid) 0.10 1.29 1.36

γ- (polar, base) 40.21 11.81 2.28

γAB (polar) 4.02 7.82 3.52

γs (total) 52.64 ± 0.46 52.34 ± 0.55 46.72 ± 0.48

𝛾 𝑠 = 𝛾𝐿𝑊 + 2 𝛾+𝛾−


Surface energy: Contact angle, sessile drop

Acid-base theory

𝛾𝐴𝐵

0%L 4%L 14%L

46.72

52.34

52.64

1.361.29

0.102.28

11.81

40.21

43.2044.51

s (

mN

/m)

% Lignin

-, base

+, acid

d, LW

48.62

𝛾𝑠 =

For spruce… (M. Gindl et al. 2001, Colloids and Surfaces A, 181, 279-287)

Non polar component (γLW) is larger than the acid-base component (γAB)

The base component (γ-) is stronger than the acid component (γ+)

- Wood is acidic in bulk but basic in the surface -

Lignin

γ -

γ +

γ LW

γ s

Water, Formamide, Diiodomethane, Ethylglygol

70


Relative water absorption capacity (RWAC)

RWAC: 38 %WAC: 30.6 g/m2

0 20 40 60 80 100 120 6000

0

5

10

15

20

25

30

35

40

45

50

RW

AC

(%

)

t (min)

0%L 4%L 14%L

RWAC: 27.8 %WAC: 24.9 g/m2

RWAC: 11.1 %WAC: 9.4 g/m2

RWAC =gwatergdry solid

∙ 100

WAC =gwater𝑚2

71

Water vapor transmission rate (23 °C, 50% RH "wet cup")

Oxygen permeability


Barrier properties

% L WVTR (g*mm/m2*day) StDev

0 55 0.5

4 58 2.0

14 54 2.5

% L ≤ 50% RH StDev 80% RH StDev

0 0.2280 0.0869 1.2945 0.1128

4 0.1574 0.1086 1.9043 0.4387

14 0.0144 0.0104 2.3918 0.2557

OP (cc*mm/m2/day)H2OO2

• ↓RH: ↑L --- ↓O2 permeability

• ↑ RH: ↑L --- ↑ O2 permeability

72

EFFECT OF LIGNIN CONTENT : AFM (2 x 2 µm)

0 % L 4 % L 14 % L

-40

0

40

0 0.5 1 1.5 2

n m

-40

0

40

0 0.5 1 1.5 2

n m

-40

0

40

0 0.5 1 1.5 2

n m

L

Rq

Rq = 17.1 nm Rq = 9.97 nm Rq = 8.63 nm

(Root mean square roughness)

73

EFFECT OF LIGNIN CONTENT : SEM (surface&cross section)

0 % L

4 % L

14 % L

L

74


Pore size distribution: Differential scanning calorimetry (DSC)

Porous nanopaper

THERMOPOROSIMETRY:Freeze the sample: Measure the energy when the water is meltedWater contained within pores is at an elevated pressure and thus

has a depressed melting temperature (< 0 °C)Isothermal melting method: Water in the nanopaper is melted

isothermally at different temperatures approaching 0 °C

𝐷 =−4 ∙ 𝑉 ∙ 𝜎𝑙𝑠

𝐻𝑚 ∙ 𝐿𝑛𝑇𝑚𝑇0

T (°C) D (nm)

-33 1.2

-20 2.1

-17 2.5

-14 3.0

-11 3.8

-9 4.7

-7 6.1

-5 8.5

-3.5 12.2

-2.5 17.2

-1.6 26.9

-0.8 53.8

-0.4 107.7

-0.2 215.4

~ 0 Non bound water

FBW (Freezing bound water)

Water in micropores

NFBW (Non freezing bound water)

Water in the fiber wall which does not freeze

FNBW (Freezing non bounded water)

Bulk water & water in macropores

TBW

TFW

Gibbs-Thomson:

75


Pore size distribution: DSC

^Exo

time (min)

T=-33 °CD=1.2 nm

T=-11 °CD=3.8 nm

T=-2.5 °CD=17.2 nm

T=-0.2 °CD=215.4 nm

FBW (Water in micropores)

TBW (-35 → 30 °C)

(microp.+macrop.+bulk)

76

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.0 50.0 100.0 150.0 200.0

W (

g/g)

D (nm)

0% L

4% L

14% L


Pore size distribution: DSC

FBW (Freezing bound water)

NFBW (Non freezing bound water)

FNBW (Freezing non bounded water)

TBW

TFW

0%L 4%L 14%L

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

Bo

und

wate

r co

nte

nt

(g/g

)

Lignin content

FBW

NFBW

Lignin

NFBW = constant

FBW & TBW

0.2

0.4

0.6

0.8

1

1.2

1.0 10.0 100.0

Cu

mu

lati

ve p

ore

wat

er

(g/g

)

Pore diameter (nm)

0% L

4% L

14% L

53.8 nm

NFBW

8.5 nm26.9 nm

FBW

Micro

po

res

77

SUMMARY: Effect of lignin content

LIGNIN

Competitive mechanical properties

Increases WCA and

hydrophobicity

Increases hysteresis (WCA) and chemical

heterogeneity

Reduces water absorption

capacityImproves barrier oxygen properties at

low RH

Reduces roughness

Reduces surface energy (base component)

Reduces size and number of micropores

Reduces filtration

time


Thank you!






5. Cellulose Nanocrystal Nano-Forest: A Cilia Mimic (ArcotLokanathan)


Cellulose Nanocrystal Nano-

Forest: A Cilia Mimic

Dr. Arcot Lokanathan

Dept of Forest Products and Technology

Aalto University, Finland

Outline

I. Motivation

II. Introduction

III. CNC nano-forest formation

IV. Protein adsorption on CNC nano-forest

QCM-D studies

IV. Summary

MotivationSmart materials from renewable resources

Requirements for high end applications

- Controlling nano-scale architecture

- Manipulating the self assembly processes

Building blocks for nano-architecture

- Something well defined: structurally and chemically

- Electro-mechanical (Piezoelectric) - Photosensitive, light emitting devices

- Magnetically active - self healing, self cleaning

- pH/thermal responsive - Semiconducting/ Conducting

Meas. Sci. Technol., 2011, 22, 024005

Reducingend

Non-reducingend

Renewable building blocks for nano-architecture

Something well defined: structurally and chemically

CNC reducing end thiolation

Ag NP tagging

TEM

CNC-SH CNC

SH

Self assembly on Au QCM-D

Gold

• The thiolation significantly increases CNC adsorption on Au

CNC-SH CNC

SH

Self assembly on Au QCM-D

S SS SS

Gold

• CNC-SH adlayer is far more flexible than CNC adlayer

• CNC-SH adlayer 1mg/ml has higher rigidity relative to 0.1mg/ml

Aligning CNCs using convective flow

• Evaporation front driven alignment

• Drop casting technique

2 steps

- Chemisorption of CNC-SH

- Evaporating a drop of water

Atomic force microscopy

CNC-SH adsorbed on Au followed

by drying a drop of water

*All images: 2mm×2mm, Tapping

mode, Air, Force constant : 46 N/m

CNC adsorbed on Au followed by

drying a drop of water

Nano

Forest

CNC-SH

165 nm

CNC-SH

+

PEG - (NH3)+

139 nm

Inter-CNC distance in Nanoforest

• Electro-steric stabilization

• Partial replacement of electrostatic repulsion with steric

Flexible hairy surface - Biomimic

Biological cilia

Size selective exclusion of particles

Lokanathan et al. Biomacromolecules, 2013,14, 8, 2807-13.

Brian Button et al. Science, 2012, 337, 937-41

Protein adsorption on CNC nano-forest

Cytochrome C BSA Fibrinogen

Mw (kDa) 12.3 66 340

Dimensions (nm) 3.1 × 3.1 × 3.1 14 × 4 × 4 45 × 9 × 9

pKa 10.2 4.7 5.8

Note: at pH 7.4 Cyto +ve charge; Fibro & BSA – ve charge


Cyto C and BSA adsorb on Au – hydrophobic interactions

Fibrinogen adsorbs mainly on CNC – reversible interaction

Effect of this on rigidity

D 7

F 7


– The extent of protein adsorption is inversely related to the Mw

of protein

– Smaller proteins are likely to adsorb onto Au

– Larger proteins may get entangled in CNC nano-forest

Vs.

Summary– Reducing ends of CNCs thiolated

– The thiolated CNCs self assemble on Au, form nano-forest

– The inter CNC distance can be decreased

– Protein adsorption on CNC nanoforest, cilia mimic

Publications1. Cilia-Mimetic Hairy Surfaces Based on End-Immobilized Nanocellulose Colloidal

Rods; Accepted: Biomacromolecules, 2013, 14 (8), pp 2807–2813; DOI:

10.1021/bm400633r

2. The unusual interactions between polymer grafted cellulose nanocrystal

aggregates; Accepted: Soft Matter, 2013,9, 8965-8973; DOI:

10.1039/C3SM51494C

3. Cellulose nanocrystal-mediated synthesis of silver nanoparticles: Role of sulfate

groups in nucleation phenomena; Submitted: Biomacromolecules

4. Tailoring electrostatic and steric interactions to control self-assembly of

topochemically thiolated cellulose nanocrystals on gold; To be submitted

Thank you for your time

Acknowledgements

Aalto University

Prof. Laine Janne

Prof. Orlando Rojas (NCSU/Aalto)

Prof. Ikkala Olli

Dr. Johansson Leena-Sisko

Dr. Campbell Joseph

Dr. Filpponen Ilari

Dr. Kontturi Eero

Prof. Österberg Monika

Funding

Aalto School of Chemical Technology,

Academy of Finland,

The Finnish Funding Agency for Technology and

Innovation,

ERC

Modification of nanofibrillated

cellulose (NFC) using luminescent

carbon dots (CDs)

Karoliina Junka, Jiaqi Guo, Ilari Filpponen, Janne Laine, Orlando J. Rojas

Outline

• Background

• Adsorption studies using NFC model films

• Bulk modification of NFC gel with CDs

• Cellulose nanopaper modification

• Summary

• Acknowledgements

Background

• Carboxymethylated NFC: -0.3 mmol/g

• CDs: a) AFM image

b) phase image

c) TEM image

• CDs: contain NH3: +0.5 mmol/g at pH 4.5

• EDC/NHS assisted coupling

reaction:

– covalent attachment of CDs on

carboxymethylated NFC

1x1 µm2

a)

b)

c)

EDC: 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide

hydrochloride

NHS: N-hydroxysuccinimide

Image: Bioconjugate Techniques 2nd edition (2008), Greg T. Hermanson, Academic Press

Methods

• NFC model surfaces:

QCM-D: SPR:

Procedure for the covalent attachment of

CDs on NFC

1. Stabilization of the NFC film at pH 4.5 and 10 mM ionic

strength

2. EDC/NHS activation of the film (pH=4.5, I=10 mM)

3. CD attachment (pH=4.5, I=10 mM)

4. Rinsing (pH=4.5, I=10 mM)

5. Rinsing (pH=8.5, I= 10 mM)

6. Rinsing (pH=4.5, I=10 mM)

CDs attach covalently on EDC/NHS

activated NFC

• SPR

-100

-70

-40

-10

20

50

80

0 50 100

ΔFre

quen

cy/3 (Hz)

Time (min)

0.24

0.26

0.28

0.3

0.32

0.34

30 80

∆SPR a

ng

le(

)

Time (min)

CDs

pH=8.5

Rinsing

4.5

a) b)

CDs

pH=4.5

pH=8.5

4.54.5

EDC/

NHS

Reference (red line): no EDC/NHS activation of the NFC

Bound water is removed from NFC film

upon CD attachment

-100

-70

-40

-10

20

50

80

0 50 100

ΔFre

quen

cy/3 (Hz)

Time (min)

0.24

0.26

0.28

0.3

0.32

0.34

30 80

∆SPR a

ngl

e(

)

Time (min)

CDs

pH=8.5

Rinsing

4.5

a) b)

CDs

pH=4.5

pH=8.5

4.54.5

EDC/

NHS

• QCM-D

Reference (red line): no EDC/NHS activation of the NFC

AFM imaging shows change in NFC

surface topography due to CD coating

-10

0

10

20

0 1000z-sc

ale

(n

m)

-10

0

10

20

0 1000z-sc

ale

(n

m)

a) CNF (1x1 µm2)

c) CNF-CD (1x1 µm2)

b)

d)

e)

f)

NFC

CD-NFC

NFC

CD-NFCCD-NFC:

NFC:

Carbon nanodot attachment on NFC

1. without carboxyl group activation:

2. carboxyl groups are EDC/NHS activated:

CDs

pH 4.5

CDs

pH 4.5

pH 8.5 to

pH 4.5

pH 8.5 to

pH 4.5

H2O

H2O

Bulk modification of NFC gel

• EDC/NHS activation of carboxymethylated NFC gel

• CD attachment

• Dialysis

• CD dosages:

– 3 and 30 mg/g

0

50

100

150

200

0 3 30

Su

rface

ch

arg

e(µ

eq

/g)

Amount of carbon nanodots

added (mg/g)

pH=8.5

pH=4.5

COO-

COO-

COO-

COO-

COO-

+

NH3+

NH3+ NH3

+

Polyelectrolyte titration as a tool for NFC

gel characterization

0

50

100

150

200

0 3 30

Su

rfa

cech

arg

e(µ

eq/g

)

Amount of carbon nanodots

added (mg/g)

pH=8.5

pH=4.5

COO-

COO-

COO-

COO-

COO-

+

NH3+

NH3+ NH3

+

Carbon dot loading based on the titration: 11 ± 6 mg/g and 26 ± 6 mg/g

Changes in the thermal behavior of NFC

due to CDs: increase in degradation T

• Thermogravimetric analysis

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

100 200 300 400 500 600 700 800

Weig

ht

deriv

ati

ve (

%/º

C)

Temperature (ºC)

Application: Cellulose nanopaper

• Transparent nanopaper (~8.4 mg/cm2) was made of NFC and

CD-NFC

1 g/L pressing drying (40C)

The CM-NFC nanopaper is very moisture sensitive (wrinkles),

but does not brake in water can be modified by dipping

The filtration time decreases 20 % when the NFC is CD-modified

CM-NFC

CD-NFC

Fluorescent cellulose nanopaper

• The NFC film (a, d, g,) is not fluorescent

• Dipped film (b, e, h): CDs on the surface

– A thin fluorescent layer

• CD-NFC film (c, f, i): 30 mg/g CDs

– Fluorescent film

• AFM images:

– Roughness of the film is lower

when the film has been modified

with CDs (a:46 nm, b:30 nm, c:31 nm)

e)f)

a) b) c)

e)d) f)

i)g) h)

Summary

• CDs were covalently attached to NFC using QCM-D and SPR

to monitor the adsorption

– CDs are removed by alkaline rinsing if the NFC film is not

EDC/NHS activated

• CDs remove bound water from NFC

• Bulk modification of NFC was done with CDs

• CD-modified NFC resulted in fluorescent nanopaper

– Surface modified nanopaper was made by dipping

• Application possibilities: anti-counterfitting, biosensing

applications

CD-modified NFC:

application areas

• Anti-counterfitting:

• Fluorescent imaging in

biological systems:

• Sensor applications:

Goh et al. 2012 Biomacromolecules, DOI: dx.doi.org/10.1021/bm300796q

Zhu et al. 2013 Angewandte Chemie, DOI: 10.1002/anie.201300519

Acknowledgements• Special thanks goes to Dr.Tiina Nypelö, Dr.Yanxia Zhang,

Ms. Barbara White and Dr. Ingrid Hoeger for help in the

laboratory (North Carolina State University)

• Funding:

Administration / Budget

115

€

LignoCell Budget

steering committee meeting / 26.11 - nc state universityojrojas/lignocell/report nov 2013.pdf ·...

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