Department of Chemistry

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IIT Jodhpur

Capturing structure and dynamics of both lipids and water near membranes using simulations as in experiments is a challenging task till date. Dimyristoylphophatidylcholine (DMPC) lipid bilayers with Berger and CHARMM36 force-fields have been investigated at fluid phase with TIP3P and TIP4P/2005 water models. Interfacial water molecules (IW) near lipid bilayers exhibit local distorted tetrahedrality within the first hydration shell of interface water for both water models. Anomalous diffusion exponents of IW hydrogens show oscillations without decaging at an intermediate length scale slightly larger than the intermolecular separation. The non-Gaussian parameters of bulk water decay to zero for both water models at a time-scale consistent with previously reported neutron scattering experiments, whereas IW exhibit β to α relaxations which are universal signatures of glassy dynamics. These results provide insights on the choice of force-fields to apprehend underlying physical laws of water relaxations near membranes and will be useful to study membrane phase transitions in future. © 2019

World University root node

Chemical Physics

Heterogeneity in structure and dynamics of water near bilayers using TIP3P and TIP4P/2005 water models

In this study, the oxidative conversion of 5-hydroxymethylfurfural into essential chemicals on recyclable metal (Pt, Pd, Ru, Co, & Ni)- supported catalysts is reported. While most of the catalytic reactions require a base as an additive, this current study provided a base-free environmentally benign heterogeneous catalytic system. The reactions were performed on various M/CNT catalysts. As a support, CNT played an important role in the reaction mechanism. These catalysts showed a high activity for the base free oxidation of HMF under air in aqueous media. The CNT-supported Pt, Pd, and Ru catalysts were found to be more selective towards FDCA (>97%) compared to Ni and Co for DFF (>96%). The conversion and selectivity of the products were determined using NMR and HPLC. The (1 wt%) M/CNT catalysts were prepared via solution processing and were characterized using BET, XRD, TEM, TGA, FTIR, and XPS. © 2019 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

New Journal of Chemistry

Metal-functionalized carbon nanotubes for biomass conversion: Base-free highly efficient and recyclable catalysts for aerobic oxidation of 5-hydroxymethylfurfural

The present study aims at the development and characterization of zinc oxide (ZnO) nanoparticles as a carrier for various anti-cancerous drugs viz. 5-Fluorouracil (5-FU), Doxorubicin (DOX) and Daunorubicin (DNR). ZnO nanoparticles were prepared by standard precipitation method. The measurement of optical band gap using UV-Visible Diffuse Reflectance Spectroscopy (DRS) analysis reveals the lowering of ZnO band gap after the drug loading. Crystallite size of free and drug loaded ZnO nanoparticles were determined using X-ray Diffraction (XRD) analysis. The crystallite size of ZnO nanoparticles increases after the drug loading. Both the techniques confirm the adsorption of drug molecules on ZnO surface. © 2019 American Institute of Physics Inc.. All rights reserved.

AIP Conference Proceedings

Optical band gap and crystallite size investigations of anticancer drug loaded ZnO nanoparticles

The scalability and stability of electrocatalysts is one of the biggest challenges for their practical applicability. In this context, Co3O4 nanoparticles conformally coated on a light weight, 3D and highly conducting carbon cloth are fabricated using an easily synthesized cobalt hexadecylthiolate complex as ink. This method is especially useful for large-scale production as the complex is synthesized in large quantities and coated on 3D substrates by a simple dip-coating method. The optimum loading of the catalyst is achieved through a layer-by-layer (LbL) assembly of a cobalt hexadecylthiolate complex via repeated dip coating of the carbon cloth electrode in the solution. The Co3O4/CC undergoes electrochemical oxidation and converts to CoOOH as an active species and acts as a highly efficient electrocatalyst with optimized loading. The Co3O4-16/CC with 16 times dip coating exhibits remarkable stability over 24 h with an overpotential of 300 mV at 10 mA cm−2 and a Tafel slope of 77.06 mV dec−1. The electrocatalytic activity of Co3O4-16/CC prepared by LbL coating is better than conventional Co3O4 and comparable to IrO2 and RuO2 electrocatalysts with the future possibility of commercial-scale production at lower cost. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Energy Technology

Layer-by-Layer Coating of Cobalt-Based Ink for Large-Scale Fabrication of OER Electrocatalyst

An economical approach for the diastereoselective synthesis of highly functionalized carbocyclic spiropyrazolone derivatives having one quaternary and two tertiary stereocenters along with one exocyclic double bond exploiting dual organo-silver sequential catalysis has been developed. The unified method to both cyclohexyl and cyclopentyl spirocompounds involves the reaction of γ- and β-nitroalkynes with alkylidene pyrazolones catalyzed by Hünig's base followed by carbophilic activation of the triple bond with a Ag(I) salt leading to cyclization via hydroalkylation. © 2018

Tetrahedron Letters

An efficient and highly diastereoselective synthesis of carbocyclic spiropyrazolones via one-pot sequential dual organo-silver catalyzed Michael-hydroalkylation reactions

We analyse the ping-pong (PP) protocol [K. Bostrom and T. Felbinger, Phys. Rev. Lett. 89, 187902 (2002)] using different sets of partially entangled three-qubit states. Interestingly, our results show that the partially entangled nonorthogonal three-qubit states are more useful as resources in comparison to three-qubit maximally entangled Greenberger-Horne-Zeilinger (GHZ) states. The properties of orthogonal set of partially entangled states as resources for PP protocol, however, are similar to that of maximally entangled GHZ states - both the states are not preferable due to the vulnerability towards eavesdropping. On the other hand, partially entangled nonorthogonal basis set holds importance for transferring two-bit information, one each from a sender, to a single receiver. The protocol is further analysed for various eavesdropping attacks, and the results are compared with the use of two shared Bell pairs for two-bit information transfer. Surprisingly, the use of partially entangled nonorthogonal set of states is found to offer better qubit efficiency and increased security, as against the use of two separate maximally entangled Bell states with orthogonal basis. In addition, we also propose a mixed-state sharing protocol to further enhance the security of the PP protocol. ©2019 Walter de Gruyter GmbH, Berlin/Boston 2019.

Fulltext

Zeitschrift fur Naturforschung - Section A Journal of Physical Sciences

An Improved Ping-Pong Protocol Using Three-Qubit Nonmaximally Nonorthogonal Entangled States

Design and development of multifunctional materials have drawn incredible attraction in recent years. Herein, we report the design and construction of versatile star-shaped intramolecular charge transfer (ICT)-coupled excited-state intramolecular proton transfer (ESIPT)-active mechanoresponsive and aggregation-induced emissive (AIE) luminogen triaminoguanidine-diethylaminophenol (LH3) conjugate from simple precursors triaminoguanidine hydrochloride and 4-(N,N-diethylamino)salicylaldehyde. Solvent-dependent dual emission in nonpolar to polar protic solvents implies the presence of ICT-coupled ESIPT features in the excited state. Aggregation-enhanced emissive feature of LH3 was established in the CH3CN/water mixture. Furthermore, this compound exhibits mechanochromic fluorescence behavior upon external grinding. Fluorescence microscopy images of pristine, crystal, and crushed crystals confirm the naked-eye mechanoresponsive characteristics of LH3. In addition, LH3 selectively sensed a Cu2+ ion through a colorimetric and fluorescence "turn-off" route, and subsequently, the LH3-Cu2+ ensemble could act as a selective and sensitive sensor for S2- in a "turn-on" fluorescence manner via a metal displacement approach. Reversible "turn-off-turn-on" features of LH3 with Cu2+/S2- ions were efficiently demonstrated to construct the IMPLICATION logic gate function. The Cu2+/S2--responsive sensing behavior of LH3 was established in the paper strip experiment also, which can easily be characterized by the naked eye under daylight as well as a UV lamp (λ = 365 nm). © 2019 American Chemical Society.

ACS Omega

Star-shaped ESIPT-active mechanoresponsive luminescent AIEgen and its on-off-on emissive response to Cu2+/S2-

Graphitic carbon is the ultimate source of carbon electrodes for practical application in energy storage devices as it is commercially available at a much lower cost in contrast to other forms of nanostructured carbon. Recently, fluorinated carbon with improved electrical conductivity and wettability has been found to possess better and efficient electrochemical storage properties. However, the development of a simple fluorination process is still a challenge. Herein, Selectfluor (F-TEDA) is explored as a fluorinating agent for Vulcan carbon. Fluorination of carbon material results in the formation of semi-ionic C—F (F = 8.02 at%) and ionic C—F (F = 2.71 at%) bonds as observed in X-ray photoelectron spectroscopy analysis along with an increase in defect density (ID/IG) by 33.4%. Symmetric two-electrode supercapacitor cells are assembled in Swagelok-type geometry, and the specific capacitance of fluorinated carbon is found to increase by ≈15 times in contrast to pristine carbon due to induced surface polarization despite the decrease in specific surface area by ≈34%, which is remarkable. The fabricated device is stable with ≈96% capacitance retention over 10 000 cycles, resulting in enhanced supercapacitive performance. © 2019 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim

Electrophilic Fluorination of Graphitic Carbon for Enhancement in Electric Double-Layer Capacitance

In the present study, we have tried to characterize the inclusion complex of Hexaflumuron (HFM) with ß-cyclodextrin (ß-CD) using 1H &amp; 19F NMR experiments. HFM is a pesticide (anti-termite) belonging to benzoylphenylurea family that contains three classes of fluorine. Its' very low aqueous solubility can lead to facile accumulation in water or soil causing rapid poisoning of the environment. Therefore, elimination of HFM requires scavenging agents such as ß-CD that can encapsulate HFM resulting in better aqueous solubility. A significant change in 19F and 1H NMR chemical shift, 1H &amp; 19F longitudinal (T1) and 19F transverse relaxation (T2) time was observed for HFM in the presence of CD that confirms HFM-CD association. Jobs Plot demonstrated that ß-CD was found to form 2:1 inclusion complex with HFM. Association constant was determined from chemical shift titration method using modified Benesi-Hildebrand plot. The present study for the first time provides an insight in understanding formulation of HFM in ß-CD enhancingthe solubility giving rise to a possible soil remediation method. © 2019 American Institute of Physics Inc.. All rights reserved.

Hexaflumuron_ß-cyclodextrin inclusion complex as improved pesticide formulation: A NMR case study

Purpose: Motility of spermatozoa helps not only in planning the type of infertility treatment but also directly reflects the success rate in assisted reproductive technology (ART). Previously, biotin, a water-soluble vitamin, has been shown to increase the motility and longevity of cryopreserved human spermatozoa. The present study was designed to understand the molecular basis of the beneficial effects of presence of biotin in sperm wash medium on early embryo development. Methods: The effect biotin supplementation to sperm wash medium on the sperm parameters were assessed in swim-up fraction of normozoospermic and asthenozoospermic ejaculates collected from infertile men. Fertilization and early embryo development was studied using Swiss albino mice. Results: Even though both biotin and pentoxifylline (PTX) enhanced the motility of spermatozoa from normozoospermic and asthenozoospermic samples, biotin group exhibited higher in vitro survival. Using mouse model, we observed that presence of biotin or PTX in sperm wash medium improved the fertilization rate and blastocyst rate compared to control. Blastocysts from these groups had significantly higher total cell number (P < 0.01) and lower apoptotic index. In silico target prediction revealed that GTPase HRas (HRas), tyrosine-protein phosphatase nonreceptor type 1 (PTP1B), and glucokinase are the probable targets for biotin. Solution-state Nuclear Magnetic Resonance (NMR) studies confirmed that biotin interacts both with human HRas and PTP1B. Conclusion: Our results indicate that presence of biotin in sperm wash medium can improve the fertilization potential and preimplantation embryo development and can be considered as a safe alternate to PTX. © 2018, Springer Science+Business Media, LLC, part of Springer Nature.