introduction to nanotechnology basic principles of...
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Mohd Zobir HusseinProgramme Leader for Nanomaterials
Materials Synthesis and Characterization Laboratory (MSCL)Institute of Advanced Technology (ITMA)
UNIVERSITI PUTRA MALAYSIA
Visiting Professor, 3 in 1 Programme 2019, 30 Sept-4 Oct 2019, Fakultas Kedoktoran Gigi, UBI
INTRODUCTION TO NANOTECHNOLOGYBasic principles of nanoscience and nanotechnology
Content• Introduction• Examples of nanomaterials• Nanoscale • Theory• Opportunities and challenges• Applications• Risks• Classification of nanomaterials• Nanomedicines; drug and theranostics nanodelivery systems• Commercialised nanomedicines: nanodrugs• Nanodelivery system: Design, synthesis and characterisation• Supramolecular chemistry; host-guest and applications• Advantages of nanomedicine• Controlled release properties of drug• Some examples of nanomaterials
INTRODUCTION
Green plants convert more energy and synthesize a greater tonnage of fine chemicals than the combined global chemical industry. This is an example of amazing nanobiotechnology process (Drexler, 1999)
High performance teeth in human (Risnes, 1998), strong shells of shellfish are as a result of smart and complex bionanotechnology processes (Lin and Meyers, 2005).
Example of nanocomposite material: teeth
Example of nanocomposite material:Layered Nanohybrid Materials
Paua abalone
Example of nanocomposite material:Layered Nanohybrid Materials
Paua abalone
Nanoscale - a dimension of fascinating properties
Nano = dwaft (Greek)
1 nm = 1 x 10-9 m=10 atoms
1 Å = 1 x 10-10 m
Nanoscience and nanotechnology
Nanoscience and nanotechnology
Nanoscience is the study of phenomena and manipulation of materials at atomic, molecular and macromolecular scales, where properties differ significantly from those at a larger scale.
Nanotechnology is the design, characterisation, production and application of structures, devices and systems by controlling shape and size at nanometer scale:~ (0.2–100) nm(where unique phenomena enable novel applications)
Encompassing nanoscience, engineering and technology, nanotechnology involves imaging, measuring, modeling and manipulating matter at this length scale. (The Royal Society 2004)
Nanoscience and nanotechnology
Nanoscience is concerned with understanding these effects and their influence on the properties of materials
Nanotechnology aims to exploit these effects to create structures, devices and systems with novel properties and functions due to their ultra small size (nm)
Nanomedicines: The use of nanoscience and nanotechnology for medicine (applications, processes, etc.)
Nanodrug delivery systemsNanodiagnosticNanotheranosticsMultifunctional NanotheranosticsMultimodal NanotheranosticsNanodentistryetc.
Nanomaterials
Nanomaterial and nanobiomaterialsize: 0.2 - 100 nm
At nanometer size regimeLarger surface areaChemically more reactiveHas quantum size effects
electricalmagnetic optical
Nanoscale - a dimension of fascinating properties
At the nanoscale regime,materials exhibit unusual and attractive properties; ü lower resistance to electricityü lower melting points and ü faster chemical reactions
Their extremely small size allows; direct interaction with enzymes, proteins, DNA and other biomolecules, opening great possibilities for ü drug deliveryü gene therapyü medical diagnosticsü etc.
Gold nanoparticles showing the change in optical properties as a function of size
NANOMEDICINE
Nanoscience/Nanotechnology - a multidisciplinary approachOpportunities/Challanges
Nanomedicine - a multidisciplinary approach(Opportunities/Challenges)
Application of nanomaterials for
different areas
Application of graphene and CNTs for nanomedicines
Current and emerging applications of nanomaterials for nanomedicine
THE OPPORTUNITIES TO CONTRIBUTE TO NANOSCIENCE/NANOTECHNOLOGY
§ Synthesis of Nanostructures: new materials/nanostructures for new discovery of new phenomena and novel applications.
§ Materials: the invention and development of materials whose properties depend on nanoscale structure, which ultimately, be important in producing these materials reproducibly, economically, and in quantity.
§ Molecular Mechanisms in Nanobiotechnology: By understanding the molecular mechanisms of functional nanostructures in biology-the light-harvesting apparatus of plants, ATPases, the ribosome, the structures that package DNA-Physical and analytical chemistry will help to build the tools that define these structures.
§ Risk Assessment and Evaluation of Safety: Understanding the risks of nanostructures and nanomaterials will require cooperation across disciplines that range from chemistry to physiology, and from molecular medicine to epidemiology.
THE INDUSTRY OPPORTUNITIES
1) Tools for Research: To produce new tools and equipment for research (Instruments for nanoscience/nanotechnology).
2) New Materials: Nanomaterials for electrically/magnetically/optically functional polymers, particles, and composites for a range of applications, from spray-painted automobile bumpers and nanoscale bar-coded rods, to the printed organic electronics of electronic newspapers and smart shipping labels.
3) New Processes for Fabrication: The development of new processes to make new nanomaterials at affordable cost.
4) Nanoelectronics: The development of new fabricating method with the sub-50-nm dimensions required by nanoelectronics will present immediate opportunities for materials science and chemistry.
5) Nanoparticle Technology: Specialized kinds of nanoparticles will become important in a wide range of applications—from drugs to improve bioavailability, to electrodes and lumiphores for new kinds of graphic displays, etc.
6) The Revolutionary Unknown: A final class—and the one that is the most exciting—comprises the revolutionary ideas, for example, nano-CDs (read by an array of parallel atomic force microscope tips known as the “centipede”), quantum computers, and biocompatible nanoparticles able to reach, recognize, and report presymptomatic disease.
RISKS OF NANOTECHNOLOGYA new technology sparks conflict between those wishing to exploit it as rapidly as possible and those wishing to wait — to have it proved absolutely safe.
Nanotechnology is new; although parts of it are quite familiar, parts are unfamiliar, and it is not a surprise that the public is wary of its potential for harm, as well as excited by its potential for good.
Therefore, Risk Assessment and Evaluation of Safety is important
Standard? MSDS, etc.
AND REMEMBER
Nanoscience is now an important, central thread in fundamental research, and it will soon become an important part of technology.
In our enthusiasm for “nano”, we must not forget “micro”,
For many applications, microtechnology is more important than nanotechnology. For example, assay systems based on mammalian cells for use in developing drugs, nanotechnology NEEDS microworld: a mammalian cell is an object that is a few micrometers (not nanometers) in size.
Research and development must be focused on the development of science and technology at the right size—and that size may range from nanometers to millimeters (for the technologies of small things): “nano” is not always the best or only answer.
Nanoscience is now a thread woven into many fields of science. Nanotechnology—certainly evolutionary, and perhaps revolutionary—will emerge from it.
Classification approach
Classification (dimension) - Siegel
The dimensionality and shape play a major role in determining the characteristics of nanomaterials; physical, chemical and biological characteristics.
Size ↓, → surface-to-volume ratio ↑
The smaller size of the nanomaterials give higher surface area.
Raman and FTIR spectroscopy (vibrational spectroscopy) are also based on shapes
Classification (dimension) - Siegel
0 D 1 D 2 D 3 D
Carbon nanomaterials/allotrope
nanodiamond Graphene graphite ionsdaleite
Fullerene- C60 Fullerene- C540 Fullerene=- C70
Amorphous/activated carbon SWNT
MWNT
Carbon nanospheres
Carbon Nano Fibers
0D NANOMATERIALS
Basel = selasih = kemangi?
QD
fullerene
1D NANOMATERIALS
SWNTCNT
CNF
2D NANOMATERIALS
2D layered structure: ZLH, LDH, etcGraphene, graphene oxide
3D NANOMATERIALS
activated carbon with 3D pores
NANOMATERIALS
2
0
1
3 0D
1D2D
3D
Carbon nanomaterials/allotrope
nanodiamond Graphene graphite ionsdaleite
Fullerene- C60 Fullerene- C540 Fullerene=- C70
Amorphous/activated carbon SWNT
MWNT
Carbon nanospheres
Carbon Nano Fibers
a) 0 D
g) 3 D
h) 1 D
b) 2 D 3D c) 3 D
d) 0 D e) 0 D f) 0 D
NANOMEDICINE
Is the application of nanotechnology in medicine (US NNI)
Science and technology, diagnostic, treatment and prevention of diseases and injuries leading to pain relief, preserving and improving human health using tools and molecular level knowledge of the human body (Europe Science Foundation)
Generally nanomedicine is a comprehensive monitoring, management, repair, protection and improvement of all human biological systems, operating at the molecular level – and this purposely created using nanodevices and nanostructures, ultimately leading to improve health status of individuals.
Caruana, BioMedical Physics, University of Malta
• Doxil (pegylated liposomal doxorubicin) – the 1st FDA approved (1995) nanodrug - used to treat cancers; ovarian cancer and AIDS-related Kaposi's sarcoma.
• To improve the balance between the efficacy and toxicity of doxorubicin therapy.
Nanodelivery system (NDS)
refers to approaches, formulations, technologies and systems for transporting active agents (pharmaceutical/target/diagnostic/energy,etc.) to achieve its desired effect using nanotechnology platform
Nanodelivery provides a means to control a) stability b) solubility c) bioavailability, d) controlled release properties.
Nanodelivery System (NDS)
Advantage of NDS the compatibility of nanoparticle properties with the properties of the bioactive and the desired applications.
Physicochemical properties of nanoparticles such as size, charge, hydrophobicity, and targeting molecules affect the absorption, distribution, metabolism and excretion (ADME) of NDS.
The fate of the bioactive depends on its physicochemical properties and the location of its release.
The safety of NDS is largely unknown. Toxicological studies consisting of a combination of in silico, in vitro, and in vivo are needed to reveal the safety of NDS for successful applications.
Design, synthesis and charaterisations of host-guest materials for nanodelivery systems (NDS)
Factors1) The physico-chemical properties of the host and the guest 2) The final desired tailor-made physico-chemical properties to be exploited 3) The interaction (bonding) of the host and the guest
for the formation of pure-phase nanomaterials4) Method of synthesis to get pure-phase5) Physico-chemical characterisations
Supra (Latin) = above or beyond•Chemistry beyond the molecules•Chemistry of tailor-shape intermolecular interaction
Supramolecular ChemistryThe chemistry of the intermolecular bondcovering the structures and functions of the entit ies formed by the association of 2 chemical species (J.M. Lehn)
The chemistry based upon intermolecular interactions (the association of 2 building blocks which are held together by intermolecular bonds (F. Vogtle)
Supramolecules•Information is stored in the form of structural uniqueness•The combined action and characteristic parts of the design component molecules resulted in new properties or synergistic effect
Supramolecular Chemistry
INTRODUCTIONSupramolecular Chemistry
v One of the fastest growing areas in parallel with the nanotechnology era – bottom up approach v Interdisciplinary fieldv One of the fields is host-guest chemistry
Host-guest
Method of synthesis = f(host-guest chemistry) – TYPE OF BONDSIntercalation, encapsulation, dispersion, adsorption, conjugation, etc.
HOST(inorganic)
GUEST(active agent) HOST
(inorganic)
GUEST(active agent)
+
INTRODUCTION
Type of interaction E KJ/Mol strengthIon-ion 100 - 350 strongestIon-dipole 50 - 200 Dipole-dipole 5 - 50 H-bonding 4 - 120 p-systems 0 - 50 Van der Walls forces 5 Close packing hydrophobic weakest
The supramolecular chemistry: has had a profound effect on structures of different sizes and shapes especially for nanomaterials (1 to 100 nm)
INTRODUCTIONHost-guest chemistry
A molecule (host) and another molecule (guest) can bind together to produce a “host-guest” complex via noncovalent bond
Host possesses convergent binding siteGuest possesses divergent binding site
Host/Guest A monoatomic cationA simple inorganic anionA complex molecule such as hormones, drugs, DNA, etc
INTRODUCTIONHost-guest Chemistry
Host Guest
Crystal lattice inclusion = Clathrand
Molecular inclusion = Cavitand
Electrostatic interaction = Complex
+ -
INTRODUCTIONClassification of supramolecular host-guest compounds
Interaction between the host and the guest
a) Electrostatic the host-guest system is a complex
b) Nondirectional, less specific such as hydrophobic, VDW or crystal close-packing then
i) Cavitand = host with intramoleular cavities Host-guest aggregate is cavitate
ii) Clathrand = host with extramolecular cavities Host-guest aggregate is clathrate
INTRODUCTIONApplication of host-guest nanomaterials
SensorsMolecular recognitionSynthesis: di- and poly-merization, etc.Separation and PurificationOrganic ElectronicsCrystal EngineeringSolar Energy PolymersHydrogels for Soft NanotechnologyProteins and Nucleic Acids TargetingMagnetic Resonance Imaging and Contrast AgentsFood and Textile IndustriesDrug and Theranostic Delivery SystemsEnergyetc.
INTRODUCTIONApplication a) Dimerization/polymerization
INTRODUCTIONApplication b) molecular recognition
Design, synthesis and characterisation of drug/theranostic nanodelivery systems
Methods: f = (host-guest chemistry)Intercalation, encapsulation, dispersion, adsorption, conjugation, etc.
DESIGNAPPLICATIONSf=(active agent)
HOST(nanomaterial)
GUEST(active agent)
Synthesismethod
Parametric optimisation
characterisations
Pure phase
HOST(nanomaterial)
GUEST(active agent)
drug
diagnostic
targetphotothermal
etc.
0D1D2D3D
Design, synthesis and characterisations of NDS
Target tailor-made properties
Synthesis methods
Parametric optimization
Phase-pureproduct
Physico-Chemical characterisations
TARGET APPLICATION
STUDIESTherapeutic DSDiagnostic DS
Theranostic DSMultimodal DS
etc.
Selection of the host and the guest Host-guest
interaction
Design of drug delivery systems(2D nanomaterials - by intercalation process)
Active agents-intercalated nanomaterial (NDDS)
Layered 2D nanomaterial
Active agents
therapeutic ( )
Design of theranostics delivery system (by intercalation + adsorption)
Therapeutic and diagnostic active agents-
loaded nanomaterial (TDS)
Layered nanomaterial
Active agents
therapeutic ( ) diagnostic ( )
eg. imaging probe
Design of multifunctional theranostics delivery system (MTDS) (by intercalationn + adsorption + conjugation)
Active agents-loaded nanomaterial (MTDS)
Layered nanomaterial
Active agents
therapeutic ( ) diagnostic ( )
Eg. imaging probe
Target agent ( )
Theranostics nanodelivery systemMultifunctional theranostics nanodelivery system (MTDS)
DRUGS – as guests
ANTI-CANCER
CNS/BBB
ANTI-HISTAMINE
ANTI-MICROBIAL
ANTI-TB
Sun protection
etc.
Advantages of NDS with controlled release property
Prevent harmful side-effects
Controlled-release capability
Therapeutic window
Toxic side effects
Ineffective levelMinimize drug degradation & loss
Increase compliancy
Tailor-made property (> 2 drugs)
Advantages of NANOMEDICINE
NDS
NANOEMULSION
2D LAYERED NANOHYBRID POLYMER NANOPARTICLE
MAGNETIC NANOPARTICLELYPOSOME NANOPARTICLE
CNSs Graphene, GO, GQD,
etc.
AND MANY MORE
Carbon Nanostructures (CNS)
Carbon nanomaterials/allotrope
nanodiamond Graphene graphite ionsdaleite
Fullerene- C60 Fullerene- C540 Fullerene=- C70
Amorphous/activated carbon SWNT
MWNT
Carbon nanospheres
Carbon Nano Fibers
a) 0 D
g) 3 D
h) 1 D
b) 2 D 3D c) 3 D
d) 0 D e) 0 D f) 0 D
Carbon Nanotubes (CNTs)
Carbon Nanotubes (CNTs)
Some Important Propertiesi) Metallic, semi-conducting or superconducting ii) The largest elastic modulus of any material ever known.iii) The hollow structure - able to store guest molecules
(such as Lithium) iv) Functional groups can be generated to anchor biological
materials or drugs, etc. for transportation to the target
Carbon Nanotubes (CNTs)
CNT for multifunctional biomedical application
Therapeutic molecule
Imaging probe
Targeting moiety
ü One of the thinnest and strongest materialsü 2D sheet of carbon just one atom thickü ‘honeycomb’ structure ü 100 times stronger than steelü highly conductive and flexible
GRAPHENE
The Nobel Prize in Physics for 2010 was awarded to Andre Geim and Konstantin Novoselov, for groundbreaking experiments for the 2D material.
Ø Is the most important derivatives of graphene Ø contains many oxygenated functional groups: (hydroxyls, epoxides and carboxylic acids) - confer on the tremendous biocompatibility, water solubility)Ø Has dual-characteristics (hydrophilic edges and hydrophobic basal plane) Ø high surface area ~ 2600 m2/g.Ø All of these characteristics are ideal for drug delivery applications.
Ref. Nano Lett. 2010, 10, 4328–4334., ). Nano Lett. 2009, 9, 2654–2660, Science 2006, 313, 951–954, Nat Nanotechnol 2008;3:101-5, J Mater Chem 2010:3448-54, J Am Chem Soc: 2010;132(23):8180–6.
GRAPHENE OXIDE (GO)
Preparation of GO
stirred for 12 hrs at 50 °C, sonication & work up
[Marcano et al. ACS VOL. 4 ▪ NO. 8 ▪ 4806–4814 ▪ 2010]
XRD Analysis
10 20 30 40
Graphite Flakes
Graphene oxide
2ϴ/degrees
9.0 Å
3.7 Å
inte
nsity
/cps
Graphite
GO INH-GO
F. Liu, et al., Adv. Mater.,2013, 25 3657
GRAPHENE QUANTUM DOTS
F. Liu, et al., Adv. Mater., 2013, 25 3657
Kim, et al., ACS Nano, 2012, 6(9) 8203-8208
Synthesis of strongly green-photoluminescent graphene quantum dots for drug carrier, Wang, et al., Coll. Surf Sc., Coll Surf B: Biointerface 2013, 112 192-196.
Green GQD
Synthesis of strongly green-photoluminescent graphene quantum dots for drug carrier, Wang, et al., Coll. Surf Sc., Coll Surf B: Biointerface 2013, 112 192-196.
Green GQD
Application of nanotechnology for dentistry (nanodentistry)
Nanotechnology based on nanoscience is multidiciplinary studies. Nanomaterials show fascinating properties compared to their bulk counterparts. They show promising opportunities and challenges beside their possible risks.
Various types of nanomaterials with different dimensions; 0, 1, 2 and 3D can be designed to be used for nanomedicine especially as multifunctional delivery systems for various drugs, target and imaging agents. This can be extended for dentistry or NANODENTISTRY.
CONCLUSIONS
• Examples of nanomaterials• Nanomaterials and their properties• Opportunities and challenges• Applications and risks• Classification of nanomaterials• Nanomedicine for drug and theranostics nanodelivery systems• Commercialised nanomedicines: nanodrugs• Nanodelivery system: Design, synthesis and characterisation• Supramolecular chemistry; host-guest and their applications• Advantages of nanomedicine, controlled release properties• Specific examples of nanomaterials: CNTs, graphenes and their derivatives.
Take home keywords