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Pratheesh V. Nair
Photosciences & Photonics Group Chemical Sciences and Technology Division NIIST (CSIR) Trivandrum
What is nano ?
The prefix nano- comes from the Greek word for dwarf.
In science, nano means a measure of 10-9 units.
Nanomaterials Definition:- Particles of any matter having one of its dimensions in the range 1-100 nm
Capability to manipulate, control, assemble, produce and manufacture things at atomic precision
Importance Exhibit characteristic physical and chemical properties different from that of bulk Properties can be tailored by varying their size and shape
For any application their integration into higher order assemblies is essential
Au Nanorods
Quantum Dots
Carbon nanotubes
20 nm
Ag Nanoprisms
Quantum Rods
Fullerene clusters
20 nm
J. Am. Chem. Soc. 2006,128, 1385 PNAS, 2007, 104, 13574. Nano LEDs
Techniques for 2D and 3D NP assemblies; a) Solvent Evaporation b) Langmuir Blodgett Transfer c) Layer by layer assembly
Solvent Evaporation
The relatively weak attractions between nanocrystals, which are efficiently screened in
solution, become manifest as the solvent evaporates, initiating assembly of intricate, slowly evolving structures.
Layer by layer assembly Layer-by-layer (LBL) assembly is a simple and versatile method for material design with nanometer scale control over internal architecture
Scheme of the LBL film-deposition Steps 1 and 3 represent the adsorption of polyanion and polycation, steps 2 and 4 are washing steps.
Biomedical Applications
Polyelectrolytes
biomolecules
Polyelectrolytes are polymers whose repeating units bear an electrolyte group ; Dissociates in aqueous solutions, making the polymers charged. Polystyrene sulfonate (PSS)
Poly(2-vinylpyridine) (P2VP)
conformational transitions from stretched wormlike coil to necklace-like globule, and to compact globule the fraction of charged monomers decreases with an increase of pH and ionic strength.
Mineralization of PE
Electrostatic adsorption of PdCl42onto cationic P2VP chains
Reduction
with
dimethylamine
Biomolecules as templates
A perfect choice for 1 D assembly of nanoparticles !!!!!
The versatility of experimental methods for the manipulation of their structure Excellent experimental foundation for such studies developed in the life-science field
Biological templates, such as DNA, protein cages, viroid capsules, bacterial rhapidosomes, the deposition, multicellular assembly, superstructures, and patterning biolipid of Cylinders, linear fibrous and biomacromolecules like fibrin, dextran and collagen have been utilized to direct inorganic nanoparticles microstructures.
100 nm
Electrostatic assembly of cationic NPs onto the anionic backbone of DNA Wide range of structures including closely spaced linear arrays, ribbons or bundles and branched assemblies.
linear arrays
branched assemblies
ribbons or bundles
Linear arrays
Ribbons or bundles
Branched assemblies
Au Nanocrystal Growth on Nanotubes Controlled by Conformations and Charges of Sequenced Peptide Templates
Matsui et al, J. Am. Chem.Soc. 2003, 125, 5873. Self-assembly of bis(N-R-amido-glycylglycine)-1,7-heptane dicarboxylate molecules into nanowires. Immobilization of a histidine-rich peptide on the nanowires at the binding sites.
Addition of Au salt into nanowire solution and reduction using hydrazine hydrate
bis(N-R-amido-glycylglycine)-1,7heptane dicarboxylate
A-H-H-A-H-H-A-A-D
78 %
43 % pH - 8
Higher packing density at higher pH
pH - 12
Nature. 1993, 361, 333. Adv. Mater., 2000, 19, 1430. Chem. Mater., 2001, 13, 2864. Nano Lett. 2003, 3, 723.
Simple and reproducible procedure for the assembly of nanoparticles on carbon nanotubes in aqueous solution
SEM image of one monolayer of Au@SiO2 nanoparticles assembled onto a carbon nanotube;
TEM micrographs of thick (a) and thin (1) Polymer wrapping using poly(sodium 4-styrenesulfonate) (PSS). (bc) MWNTs (50 and 15 nm diameter), coated with 1 (ab) and 2 (2) Self-assembly of poly-(diallyldimethylammonium chloride) of (PDDA). (c) monolayers Au@SiO2 NPs.
Carbon replica
Au NP solution
Chain formation and anisotropy of magnetic NPs have been well-known in nature
Magnetotactic bacterium a biological compass
TEM image of a magnetotactic bacterium, Desulfovibrio magneticus strain RS-1, showing a chain of bullet-shaped magnetosomes aligned along the Earth's magnetic field.
Under an applied magnetic field, the nanostructures can be oriented aligning with the external magnetic field.
DLVO Theory
VT = VA + VR
VA = -A/(12 D2) - attractive forces VR = 2 a 2 exp(-D) - repulsive forces
Attractive forces van der Waals interactions and dipoledipole interactions Repulsive forces electrostatic interactions
Organization of CdTe NPs into nanowires upon partial removal of the of organic stabilizer
CdTe QDS
CdTe nanowire
Hydrazine is a Bronsted base and can gently react to remove the capping ligands from the nanocrystal surface. Hydrazine is a reducing agent, preventing oxidation of QD surface and repairing any
Oriented Aggregation
Oriented aggregation is a special case of aggregation that provides an important route by which nanocrystals grow and unique, often symmetry-defying, crystal morphologies are produced. Oriented attachment may occur by
collisions of aligned nanocrystals in suspension or rotation of misaligned NPs in contact toward low-energy interface configurations
Oriented attachment
misaligned NPs aligned NPs
1D growth Nanowires
Formation of Ag nanowires from Ag NPs through oriented attachment Liz-Marzan et al, J. Mater. Chem. 2004, 14, 607.
HRTEM images showing the various steps during the formation of Ag nanowires from individual Ag nanoparticles
Formation of high-quality single crystalline ZnO nanorods from spherical ZnO nanoparticles through oriented attachment.
individual nanoparticles
aligned nanoparticles
nanorods
lattice planes go straight through the contact areas particles are epitaxially fused together
Hydrogen Bonding
A hydrogen bond is the attractive force between the hydrogen
attached to an electronegative atom of one molecule and an electronegative atom of a different molecule.
Hydrogen-Bonding-Assisted Self-Assembly of polymers
Absorption spectra of gold nanorods recorded immediately after the addition of MPA
Drastic effects on the optical response from surface plasmon absorption is found when metallic NPs form rods, chains or sheets
Decrease in intensity of surface plasmon band at 520 nm and formation of a shoulder at higher wavelength
Nanochains of CdTe QDs formed from individual particles through dipole dipole interaction
Red shift of 36 nm
Presence of Frster resonance energy transfer (FRET) between QDs in the chain.
Gas sensors
Absorption of H2 led to the expansion of the crystalline lattice of Pd. Gap between Pd NPs in an array decreased, leading to higher electron transfer. On venting the H2, a reversible affect was observed.
George Thomas and co workers, J. Am. Chem. Soc. 2005, 127, 6516.
Future Perspectives
Development of preparation methods for large-scale production as well as
precise positioning of 1D NP arrays. Better understanding of the formation mechanism of template-free NP chains. Control of interparticle distances in NP chains, so that distance-dependent
Conclusions
Controlled organisation of nanoparticles is an essential step for the fabrication of nanomaterial based devices.
Thank You