Department of Chemistry

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IIT Jodhpur

A high degree of transparency in devices is considered highly desirable for futuristic technology. This demands that both the active material and the electrodes are made of transparent materials. In this work, a transparent Pd wire network (∼1 cm2), fabricated using crackle lithography technique with sheet resistance and transmittance of ∼200 Ohm per square and ∼80%, respectively, serves multiple roles; besides being an electrode, it acts as an active material for H2 sensing as well as an in-built electrothermal heater. The sensor works over a wide range of hydrogen (H2) concentration down to 0.02% with a response time of ∼41 s, which could be improved to ∼13 s by in situ Joule heating to ∼75 °C. Importantly, the device has the potential of scale-up to a window size transparent panel and to be flexible when desired. © 2016 American Chemical Society.

World University root node

ACS Applied Materials and Interfaces

Transparent Pd Wire Network-Based Areal Hydrogen Sensor with Inherent Joule Heater

Heater plates or sheets that are visibly transparent have many interesting applications in optoelectronic devices such as displays, as well as in defrosting, defogging, gas sensing and point-of-care disposable devices. In recent years, there have been many advances in this area with the advent of next generation transparent conducting electrodes (TCE) based on a wide range of materials such as oxide nanoparticles, CNTs, graphene, metal nanowires, metal meshes and their hybrids. The challenge has been to obtain uniform and stable temperature distribution over large areas, fast heating and cooling rates at low enough input power yet not sacrificing the visible transmittance. This review provides topical coverage of this important research field paying due attention to all the issues mentioned above. © 2016 American Chemical Society.

Visibly Transparent Heaters

This contribution aims to provide a brief account of the remarkable recent findings and advances in heterogeneous catalyst design based on facet rich Pt(111) on carbon materials. Platinum(111) hexagonal nanocrystals are prepared using Tween 20 as a facet directing agent via a simple, efficient and scalable thermolytic reduction process in air. These highly dispersed Pt(111) nanocrystals on carbon act as single site catalytic systems and exhibit exceptional activity (yield and ee ∼99%) and recyclability for the asymmetric hydrogenation of α-ketoesters. © 2016 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

New Journal of Chemistry

Asymmetric hydrogenation of α-ketoesters on the Pt(111) surface

N-methyl-d-aspartate (NMDA) receptor ion channel is activated by the binding of two pairs of glycine and glutamate along with the application of action potential. Binding and unbinding of ligands changes its conformation that plays a critical role in the open-close activities of NMDA receptor. Conformation states and their dynamics due to ligand binding are extremely difficult to characterize either by conventional ensemble experiments or single-channel electrophysiology method. Here we report the development of a new correlated technical approach, single-molecule patch-clamp FRET anisotropy imaging and demonstrate by probing the dynamics of NMDA receptor ion channel and kinetics of glycine binding with its ligand binding domain. Experimentally determined kinetics of ligand binding with receptor is further verified by computational modeling. Single-channel patch-clamp and four-channel fluorescence measurement are recorded simultaneously to get correlation among electrical on and off states, optically determined conformational open and closed states by FRET, and binding-unbinding states of the glycine ligand by anisotropy measurement at the ligand binding domain of GluN1 subunit. This method has the ability to detect the intermediate states in addition to electrical on and off states. Based on our experimental results, we have proposed that NMDA receptor gating goes through at least one electrically intermediate off state, a desensitized state, when ligands remain bound at the ligand binding domain with the conformation similar to the fully open state. © 2016 American Chemical Society.

Journal of the American Chemical Society

Single-Molecule Patch-Clamp FRET Anisotropy Microscopy Studies of NMDA Receptor Ion Channel Activation and Deactivation under Agonist Ligand Binding in Living Cells

Different rare-earth element (Dy, Gd, Tb and Yb) doped LiMn2O4 spinel active materials were prepared by a sol-gel method. The rare earth doping elements decrease the particle size but do not affect the formation of a cubic spinel structure. Furthermore, these dopants have a strong influence on the overall electrical properties of the cathodes prepared from them. In cyclic voltammetry measurements, two pairs of separated redox peaks are observed, regardless of the dopant. LiMn2O4 materials doped with gadolinium (Gd) and dysprosium (Dy) exhibit comparable room temperature rate capabilities to pristine LiMn2O4, with a discharge capacity of 94.5 mA h g-1 and 82.3 mA h g-1, respectively, versus 73.4 mA h g-1 for pristine LiMn2O4 at a rate of C5. Terbium (Tb) and ytterbium (Yb) doping shows, on the other hand, lower performance. After 50 cycles at C2, the capacity fade is 7% for LiMn1.95Dy0.05O4 and 14% for LiMn1.95Gd0.05O4, whereas for LiMn2O4 it is 32%. The improved cycling performance of LiMn2O4 doped with Gd and Dy is attributed to the powder size and atomic radii of the elements. The differences of the capacity retention on cycling are attributed to superior structural stability due to the rare earth doping. These results indicate that improved cathode materials doped with rare earth elements are suitable for lithium-ion battery applications. © 2016 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

Improved performance of rare earth doped LiMn2O4 cathodes for lithium-ion battery applications

We demonstrate a new method to achieve the maximum singlet fraction using an entangled mixed two-qubit state as a resource. For this, we establish a tight upper bound on singlet fraction and show that the maximal singlet fraction obtained in Verstraete and Verschelde (Phys Rev Lett 90:097901(1)–097901(4), 2003) does not attain the upper bound on the singlet fraction derived here. Interestingly, we found that the required upper bound can, in fact, be achieved using local filtering operations. © 2016, Springer Science+Business Media New York.

Fulltext

Quantum Information Processing

Upper bound on singlet fraction of two-qubit mixed entangled states

A simple, highly diastereoselective, Lewis acid catalyzed Friedel-Crafts coupling of a cyclic allylic alcohol with resorcinol derivatives has been developed. The method was applied for the enantiospecific total syntheses of structurally diverse natural products such as machaeriol-D, Δ8-THC, Δ9-THC, epi-perrottetinene and their analogues. Synthesis of both natural products and their enantiomers has been achieved with high atom economy, in a protecting group free manner and in less than 6 steps, the longest linear sequence, in a very good overall yield starting from R-(+) and S-(-)-limonene. © The Royal Society of Chemistry 2015.

Chemical Communications

Protecting group free enantiospecific total syntheses of structurally diverse natural products of the tetrahydrocannabinoid family

Objective: The objective of the present work is to develop a bi-layer tablet consisting of an Immediate Pulse Release [IPR] layer and a sustained release [SR] layer that can produce a distinct biphasic release having two different drug release rates. The IPR layer is intended to release a fraction of the dose rapidly at a faster rate and the SR layer is meant for slow release of the remaining dose at a slower rate for a desired period of time. Methods: The quantitative determination was carried out by UV spectrophotometer. Solid dispersion was prepared by melt method. IPR layer was prepared by direct compression method, SR layer was prepared by wet granulation method. In-vitro drug release study from tablets was carried out in USP II tablet dissolution rate test apparatus. FTIR, DSC, XRD studies were performed. Results: 89% of the incorporated drug was released within 30 min in acid solution of pH 1.2 from the IPR tablet prepared with the highest amount of gelucire due to solid state transformation of the drug. The SR layer (SR8) comprising of SAL, CG and CMC produced prolonged drug release (70% in 10 h). The optimized IPR3 layer and SR layers were compressed to form bi-layer tablets from which 23-37% drug was released immediately in 30 min, and the remaining drug was released slowly for 7 to 10 h depending upon the compositions of the tablets. Conclusion: This study revealed that bi-phasic release of GPZ consisting of an initial quick release and subsequent slow release could be achieved by formulating bi-layer tablets using the existing tablet technology, and such formulation may be able to control hyperglycaemia effectively for a longer period of time © 2015, International Journal of Pharmacy and Pharmaceutical Science. All rights reserved.

International Journal of Pharmacy and Pharmaceutical Sciences

Quick/slow biphasic release of a poorly water soluble antidiabetic drug from bi-layer tablets

We report a rhodium(II)-catalyzed highly enantioselective 1,3-dipolar cycloaddition reaction between the carbonyl moiety of tropone and carbonyl ylides to afford troponoids in good to high yields with excellent enantioselectivity. We demonstrate that α-diazoketone-derived carbonyl ylides, in contrast to carbonyl ylides derived from diazodiketoesters, undergo [6+3] cycloaddition reactions with tropone to yield the corresponding bridged heterocycles with excellent stereoselectivity. Decisive dipoles: In the rhodium(II)-catalyzed asymmetric 1,3-dipolar cycloaddition of tropone with carbonyl ylides, a programmable chemoselective reaction with the keto group or the 6 π system of tropone was controlled by the substrate (see scheme). The developed method enables the synthesis of complex products in highly enantiomerically enriched form. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Angewandte Chemie - International Edition

Rhodium(II)-catalyzed enantioselective synthesis of troponoids

The mechanism of the TEMPO mediated oxidative homo-coupling of aryl Grignard reagents is investigated in detail by experimental and computational studies. Experimental data reveal that the nitroxide-mediated homocoupling reaction of aryl Grignard reagents does not occur via free aryl radicals. Evidence for the presence of biaryl radical anions as intermediates in the coupling reaction is provided. It is also shown that PhMgPh under bromide free conditions in the presence of TEMPO does not undergo homocoupling. However, upon addition of MgBr2, C-C bond formation smoothly proceeds documenting the important role of the bromide anions in the oxidative homocoupling. DFT calculations show that an intramolecular electron transfer to a Mg-complexed TEMPO ligand with subsequent biaryl formation in a dimeric complex is viable and in agreement with experimental reaction conditions. This journal is © The Royal Society of Chemistry 2015.