Control of Molecular Weight and Polydispersity of Hyperbranched Polymers Using a Reactive B(3) Core: A Single-Step Route to Orthogonally Functionalizable Hyperbranched Polymers

Molecular weight and polydispersity are two structural features of hyperbranched polymers that are difficult to control because of the statistical nature of the step-growth polycondensation of AB(2) type monomers; the statistical growth also causes the polydispersity index to increase with percent conversion (or molecular weight). We demonstrate that using controlled amounts of a specifically designed B(3) core, containing B-type functionality that are more reactive than those present in the AB(2) monomer, both the molecular weight and the polydispersity can be readily controlled; the PDI was shown to improve with increasing mole-fraction of the B(3) core while the polymer molecular weight showed an expected decrease. Incorporation of a ``clickable'' propargyl group in the B(3) core unit permitted the generation of a core-functionalizable hyperbranched polymer. Importantly, this clickable core, in combination with a recently developed AB(2) monomer, wherein the B-type groups are allyl ethers and A is an hydroxyl group, led to the generation of a hyperbranched polymer carrying orthogonally functionalizable core and peripheral groups, via a single-step melt polycondensation. Selective functionalization of the core and periphery using two different types of chromophores was achieved, and the occurrence of fluorescence resonance energy transfer (FRET) between the donor and acceptor chromophores was demonstrated.

Control of Molecular Weight and Polydispersity of Hyperbranched Polymers Using a Reactive B(3) Core: A Single-Step Route to Orthogonally Functionalizable Hyperbranched Polymers

Molecular weight and polydispersity are two structural features of hyperbranched polymers that are difficult to control because of the statistical nature of the step-growth polycondensation of AB(2) type monomers; the statistical growth also causes the polydispersity index to increase with percent conversion (or molecular weight). We demonstrate that using controlled amounts of a specifically designed B(3) core, containing B-type functionality that are more reactive than those present in the AB(2) monomer, both the molecular weight and the polydispersity can be readily controlled; the PDI was shown to improve with increasing mole-fraction of the B(3) core while the polymer molecular weight showed an expected decrease. Incorporation of a ``clickable'' propargyl group in the B(3) core unit permitted the generation of a core-functionalizable hyperbranched polymer. Importantly, this clickable core, in combination with a recently developed AB(2) monomer, wherein the B-type groups are allyl ethers and A is an hydroxyl group, led to the generation of a hyperbranched polymer carrying orthogonally functionalizable core and peripheral groups, via a single-step melt polycondensation. Selective functionalization of the core and periphery using two different types of chromophores was achieved, and the occurrence of fluorescence resonance energy transfer (FRET) between the donor and acceptor chromophores was demonstrated.

Silver Nanoparticle Synthesis: Novel Route for Laser Triggering of Polyelectrolyte Capsules

We have demonstrated the synthesis of light-sensitive polyelectrolyte capsules (PECs) by utilizing a novel polyol reduction method and investigated its applicability as photosensitive drug delivery vehicle. The nanostructured capsules were prepared via layer by layer (LbL) assembly of poly(allylamine hydrochloride) (PAN) and dextran sulfate (DS) on silica particles followed by in-situ synthesis of silver nanoparticles (NPs). Capsules without silver NPs were permeable to low molecular weight (A(w), 479 g/mol) rhodamine but impermeable to higher molecular weight fluorescence labeled dextran (FITC-dextran). However, capsules synthesized with silver NPs showed porous morphology and were permeable to higher molecular weight (M(w) 70 kDa) FITC-dextran also. These capsules were loaded with FITC-dextran using thermal encapsulation method by exploiting temperature induced shrinking of the capsules. During heat treatment the porous morphology of the capsules transformed into smooth pore free structure which prevents the movement of dextran into bulk during the loading process. When these loaded capsules are exposed to laser pulses, the capsule wall ruptured, resulting in the release of the loaded drug/dye. The rupture of the capsules was dependent on particle size, laser pulse energy and exposure time. The release was linear with time when pulse energy of 400 mu J was used and burst release was observed when pulse energy increased to 600 mu J.

Near-infrared light-responsive graphene oxide composite multilayer capsules: a novel route for remote controlled drug delivery

A novel and simple route for near-infrared (NIR)-light controlled release of drugs has been demonstrated using graphene oxide (GO) composite microcapsules based on the unique optical properties of GO. Upon NIR-laser irradiation, the microcapsules were ruptured in a point-wise fashion due to local heating which in turn triggers the light-controlled release of the encapsulated anticancer drug doxorubicin (Dox) from these capsules.

Plasmonic Interactions at Close Proximity in Chiral Geometries: Route toward Broadband Chiroptical Response and Giant Enantiomeric Sensitivity

Chiral metamaterials can have diverse technological applications, such as engineering strongly twisted local electromagnetic fields for sensitive detection of chiral molecules, negative indices of refraction, broadband circular polarization devices, and many more. These are commonly achieved by arranging a group of noble-metal nanoparticles in a chiral geometry, which, for example, can be a helix, whose chiroptical response originates in the dynamic electromagnetic interactions between the localized plasmon modes of the individual nanoparticles. A key question relevant to the chiroptical response of such materials is the role of plasmon interactions as the constituent particles are brought closer, which is investigated in this paper through theoretical and experimental studies. The results of our theoretical analysis, when the particles are brought in close proximity are dramatic, showing a large red shift and enhancement of the spectral width and a near-exponential rise in the strength of the chiroptical response. These predictions were further confirmed with experimental studies of gold and silver nanoparticles arranged on a helical template, where the role of particle separation could be investigated in a systematic manner. The ``optical chirality'' of the electromagnetic fields in the vicinity of the nanoparticles was estimated to be orders of magnitude larger than what could be achieved in all other nanoplasmonic geometries considered so far, implying the suitability of the experimental system for sensitive detection of chiral molecules.

Vertically aligned ZnO nanorods on flexible substrates for multifunctional device applications: Easy and cost-effective route

Zinc oxide nanorods (ZnO NRs) have been synthesized on flexible substrates by adopting a new and novel three-step process. The as-grown ZnO NRs are vertically aligned and have excellent chemical stoichiometry between its constituents. The transmission electron microscopic studies show that these NR structures are single crystalline and grown along the < 001 > direction. The optical studies show that these nanostructures have a direct optical band gap of about 3.34 eV. Therefore, the proposed methodology for the synthesis of vertically aligned NRs on flexible sheets launches a new route in the development of low-cost flexible devices. (C) 2014 Elsevier B.V. All rights reserved.

Implication of a sigma-Methane Complex en Route to Elimination of Methane from a Ruthenium Complex: An Experimental and Theoretical Investigation

The five-coordinated 16-electron complex Ru(Me)(dppe)(2)]OTf] (3) undergoes methane elimination at room temperature to afford the ortho-metalated species (dppe){(C6H5)(C6H4)PCH2CH2P(C6H5)(2)}Ru]OTf] (7). Methane elimination, monitored using NMR spectroscopy, revealed no intermediate throughout the reaction. The NOE between Ru-Me protons and ortho phenyl protons and an agostic interaction trans to the methyl group were found in complex 3 by NMR spectroscopy, which form the basis for three plausible pathways for methane elimination and ortho metalation: pathway I (through spatial interaction), pathway II (through oxidative addition and reductive elimination), and pathway III (through agostic interaction). Methane elimination from complex 3 via pathway I was discounted, since it involves interactions through space and not through bonds. Moreover, the calculated energy barrier for the pathway I transition state was quite high (71.3 kcal/mol), which also indicates that this pathway is very unlikely. Furthermore, no spectroscopic evidence for oxidatively added seven-coordinated Ru(IV) species was found and the computed energy barrier of the transition state for pathway II was moderately high (41.1 kcal/mol), which suggests that this cannot be the right pathway for methane elimination and ortho-metalation of complex 3. On the other hand, indirect evidence in the form of chemical reactions point to the most plausible pathway for methane elimination, pathway III, via the intermediacy of a sigma-CH4 complex that could not be found spectroscopically. DFT calculations at several levels on this pathway showed an initial low-barrier rearrangement through TS1 to a square-pyramidal intermediate wherein methyl and agostic C-H are cis to each other. Migration of hydrogen from agostic C-H and elimination of methane proceed through the transition state TS2, which retains a weak metal-H bonding through most parts of the reaction coordinate. Upon comparison of all three pathways, pathway III was found to be the most likely for methane elimination and ortho-metalation of complex 3.

Kinetics of CO oxidation on palladium using microkinetics coupled with reaction route analysis

A plausible microkinetic model has been proposed for the CO oxidation reaction catalysed by palladium (Pd) with the kinetic parameters obtained from the literature. A robust rate expression using the reaction route analysis has been developed for the presented microkinetic scheme and the obtained rate expressions have been validated against the experimental data presented in the literature. A wide range of experimental conditions ranging from single Pd crystals under ultra-high vacuum conditions and impregnated Pd used for fixed bed experiments under atmospheric pressure has been used to validate the reaction mechanism. (C) 2015 Elsevier Ltd. All rights reserved.

Tailoring of Electronic Structure and Thermoelectric Properties of a Topological Crystalline Insulator by Chemical Doping

Topological crystalline insulators (TCIs) are a new quantum state of matter in which linearly dispersed metallic surface states are protected by crystal mirror symmetry. Owing to its vanishingly small bulk band gap, a TCI like Pb0.6Sn0.4Te has poor thermoelectric properties. Breaking of crystal symmetry can widen the band gap of TCI. While breaking of mirror symmetry in a TCI has been mostly explored by various physical perturbation techniques, chemical doping, which may also alter the electronic structure of TCI by perturbing the local mirror symmetry, has not yet been explored. Herein, we demonstrate that Na doping in Pb0.6Sn0.4Te locally breaks the crystal symmetry and opens up a bulk electronic band gap, which is confirmed by direct electronic absorption spectroscopy and electronic structure calculations. Na doping in Pb0.6Sn0.4Te increases p-type carrier concentration and suppresses the bipolar conduction (by widening the band gap), which collectively gives rise to a promising zT of 1 at 856 K for Pb0.58Sn0.40Na0.02Te. Breaking of crystal symmetry by chemical doping widens the bulk band gap in TCI, which uncovers a route to improve TCI for thermoelectric applications.

Controllable chemical vapor deposition of large area uniform nanocrystalline graphene directly on silicon dioxide

Metal-catalyst-free chemical vapor deposition (CVD) of large area uniform nanocrystalline graphene on oxidized silicon substrates is demonstrated. The material grows slowly, allowing for thickness control down to monolayer graphene. The as-grown thin films are continuous with no observable pinholes, and are smooth and uniform across whole wafers, as inspected by optical-, scanning electron-, and atomic force microscopy. The sp 2 hybridized carbon structure is confirmed by Raman spectroscopy. Room temperature electrical measurements show ohmic behavior (sheet resistance similar to exfoliated graphene) and up to 13 of electric-field effect. The Hall mobility is ∼40 cm 2/Vs, which is an order of magnitude higher than previously reported values for nanocrystalline graphene. Transmission electron microscopy, Raman spectroscopy, and transport measurements indicate a graphene crystalline domain size ∼10 nm. The absence of transfer to another substrate allows avoidance of wrinkles, holes, and etching residues which are usually detrimental to device performance. This work provides a broader perspective of graphene CVD and shows a viable route toward applications involving transparent electrodes. © 2012 American Institute of Physics.

Direct chemical vapor deposition of large-area carbon thin films on gallium nitride for transparent electrodes: A first attempt

Direct formation of large-area carbon thin films on gallium nitride by chemical vapor deposition without metallic catalysts is demonstrated. A high flow of ammonia is used to stabilize the surface of the GaN (0001)/sapphire substrate during the deposition at 950°C. Various characterization methods verify that the synthesized thin films are largely sp 2 bonded, macroscopically uniform, and electrically conducting. The carbon thin films possess optical transparencies comparable to that of exfoliated graphene. This paper offers a viable route toward the use of carbon-based materials for future transparent electrodes in III-nitride optoelectronics, such as GaN-based light emitting diodes and laser diodes. © 1988-2012 IEEE.

Chemical nano-gardens: growth of salt nanowires from supramolecular self-assembly gels.

In this article, we examine the phenomenon of single-crystal halide salt wire growth at the surface of porous materials. We report the use of a single-step casting technique with a supramolecular self-assembly gel matrix that upon drying leads to the growth of single-crystal halide (e.g., NaCl, KCl, and KI) nanowires with diameters ~130-200 nm. We demonstrate their formation using electron microscopy and electron-dispersive X-ray spectroscopy, showing that the supramolecular gel stabilizes the growth of these wires by facilitating a diffusion-driven base growth mechanism. Critically, we show that standard non-supramolecular gels are unable to facilitate nanowire growth. We further show that these nanowires can be grown by seeding, forming nanocrystal gardens. This study helps understand the possible prefunctionalization of membranes to stimulate ion-specific filters or salt efflorescence suppressors, while also providing a novel route to nanomaterial growth.

Simple Electrochemical Route to Nanofiber Junctions and Dendrites of Conducting Polymer

We first report a simple and rapid electrochemical approach to synthesize novel nanofiber junctions and dendrites of conducting poly(o-phenylenediamine) without any surfactant or template. Through controlling some parameters such as the time and potential of electrodeposition and concentration of the reactant, nanofiber junctions and dendrites of conducting polymer can be easily obtained on the solid surface.