Department of Chemistry

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The Ni/Co-natural clay catalysts have been prepared for the conversion of algae oil into diesel-grade hydrocarbons. Methyl oleate was used as a model compound for the present study. Ni/clay catalyst promotes decarboxylation/decarbonylation, whereas remarkable selectivity in hydrodeoxygenation (HDO) is achieved with Co/clay catalysts. Powder XRD and DRS studies of substrate mixed catalysts reveal a more prominent adsorption of substrate molecules over the Ni surface, which results in low HDO selectivity of nickel catalysts by surpassing the essential contribution of acidic sites. The HDO process provides higher carbon atom economy and energy value over decarboxylation/decarbonylation, while further reducing the formation of greenhouse gases such as CO2 and CH4. Total yield of saturated hydrocarbons from algae oil was 84-86 wt % with similar selectivity. The HDO rates of different fatty acids present in algae oil were independent of the fatty acid chain length. The catalysts are cost-effective and recyclable, and metal leaching during hydroprocessing is less than 1 ppm in all cases. This process is advantageous in terms of metal-to-substrate ratio, use of solvents and their concentration, and comparable HDO selectivity over the previously reported catalysts. A hydroprocessing reaction was also performed under solvent free conditions, which could be useful in industrial applications of this approach. © 2017 American Chemical Society.

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ACS Sustainable Chemistry and Engineering

Ni/Co-Natural Clay as Green Catalysts for Microalgae Oil to Diesel-Grade Hydrocarbons Conversion

Peptides synthesized in the likeness of their native interaction domain(s) are natural choices to target protein-protein interactions (PPIs) due to their fidelity of orthostatic contact points between binding partners. Despite therapeutic promise, intracellular delivery of biofunctional peptides at concentrations necessary for efficacy remains a formidable challenge. Peptide amphiphiles (PAs) provide a facile method of intracellular delivery and stabilization of bioactive peptides. PAs consisting of biofunctional peptide headgroups linked to hydrophobic alkyl lipid-like tails prevent peptide hydrolysis and proteolysis in circulation, and PA monomers are internalized via endocytosis. However, endocytotic sequestration and steric hindrance from the lipid tail are two major mechanisms that limit PA efficacy to target intracellular PPIs. To address these problems, we have constructed a PA platform consisting of cathepsin-B cleavable PAs in which a selective p53-based inhibitory peptide is cleaved from its lipid tail within endosomes, allowing for intracellular peptide accumulation and extracellular recycling of the lipid moiety. We monitor for cleavage and follow individual PA components in real time using a Förster resonance energy transfer (FRET)-based tracking system. Using this platform, we provide a better understanding and quantification of cellular internalization, trafficking, and endosomal cleavage of PAs and of the ultimate fates of each component. © 2017 American Chemical Society.

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Bioconjugate Chemistry

Cathepsin-Mediated Cleavage of Peptides from Peptide Amphiphiles Leads to Enhanced Intracellular Peptide Accumulation

The chiral Brønsted acid catalyzed enantioselective 1,2-addition of thiols to in situ generated ketimines, derived from 3-hydroxyisoindolinones, has been studied. The protocol provides a variety of isoindolinone-derived N,S-ketals in up to 98% yield and up to 99% enantioselectivity. The products have been converted to a known non-nucleoside HIV-1 reverse transcriptase inhibitor and a 1,3-thiazine derivative. © 2016 Elsevier Ltd

Tetrahedron Letters

Chiral phosphoric acid catalyzed enantioselective addition of thiols to in situ generated ketimines: Synthesis of N,S-ketals

In the present work, structural and spectroscopic investigations were carried out on a borreverine derivative. Borreverine is a class of alkaloid as well a natural antimalarial drug extracted from Borreria verticillata. With the aim of finding possible conformers, a detailed conformational analysis of a borreverine derivative was conducted utilizing density functional theory employing the B3LYP/6-31G(d,p) method. The crystallographic geometry was used for full geometry optimization, followed by a conformational analysis. The conformational investigation predicted the most stable conformer (conformer I), which was further compared with the initial crystallographic geometry (conformer V). The geometry optimization, vibrational frequency, and intensity of these two conformers (I and V) were calculated in the ground state using density functional theory with the B3LYP functional and 6-31G(d,p) basis set. The spectroscopic investigation was conducted using Fourier transform infrared (FT-IR) and Fourier transform Raman (FT-Raman) techniques. Tentative vibrational assignments of some selective modes were presented utilizing the observed FT-IR, FT-Raman, and calculated spectra. The scaled and observed wavenumbers were found to be in good agreement. The molecular electrostatic potential was computed and plotted so as to elucidate the reactive sites of the molecule. Natural bond orbital studies were performed to investigate the intramolecular charge transfer that results in molecular stability. © The Japan Society for Analytical Chemistry.

Analytical Sciences

Conformational study and vibrational spectroscopic (FT-IR and FT-Raman) analysis of an Alkaloid-Borreverine derivative

A streamlined total synthesis of the naturally occurring antitumor agents trioxacarcins is described, along with its application to the construction of a series of designed analogues of these complex natural products. Biological evaluation of the synthesized compounds revealed a number of highly potent, and yet structurally simpler, compounds that are effective against certain cancer cell lines, including a drug-resistant line. A novel one-step synthesis of anthraquinones and chloro anthraquinones from simple ketone precursors and phenylselenyl chloride is also described. The reported work, featuring novel chemistry and cascade reactions, has potential applications in cancer therapy, including targeted approaches as in antibody-drug conjugates. © 2017 American Chemical Society.

Journal of the American Chemical Society

Streamlined Total Synthesis of Trioxacarcins and Its Application to the Design, Synthesis, and Biological Evaluation of Analogues Thereof. Discovery of Simpler Designed and Potent Trioxacarcin Analogues

Enantioselective tandem Michael–aldol and oxidative Michael–aldol approaches have been achieved for the formation of diversely substituted cyclohexanes in total regio-, diastereo- and enantioselective fashion. The presence of nitro, hydroxy and keto groups in the product provides a wide scope for further structural transformations. Furthermore, the utility of the catalytic process is demonstrated in the context of enantioselective formal synthesis of ABT-341, a DPP4 inhibitor. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Chemistry - A European Journal

Enantioselective Tandem Oxidation/Michael–Aldol Approaches to Tetrasubstituted Cyclohexanes

The influence of water concentrations on phase transformations of a surfactant/co-surfactant/water system is investigated by using all atom molecular dynamics simulations. At higher water concentrations, where surfactant (behenyl trimethyl ammonium chloride, BTMAC) to co-surfactant (stearyl alcohol, SA) ratio is fixed, BTMAC and SA self-assemble into spherical micelles, which transform into strongly interdigitated one dimensional rippled lamellar phases upon decreasing water concentrations. Fragmentation or fusions of spherical micelles of different sizes are evident from the radial distribution functions at different temperatures. However, at lower water concentrations rippled lamellar phase transforms into an LβI phase upon heating. Our simulations reveal that the concentrations of water can influence available space around the head groups which couple with critical thickness to accommodate the packing fraction required for respective phases. This directs towards obtaining a controlling factor to design desired phases important for industrial and medical applications in the future. © 2016 Elsevier B.V.

Chemical Physics

Influence of water concentrations on the phase transformation of a model surfactant/co-surfactant/water system

In current research work, we are presenting dysprosium (Dy) doped spinel cathode materials LiMn2-xDyxO(4) (x=0.0, 0.01, 0.02, 0.03) and it's applications as cathode materials in lithium ion rechargeable batteries (LIRB) using a simple and sober sol-gel process. New materials were characterized using x-ray diffractometer and scanning electron microscope (SEM) which informed about the spinel phase purity and small grain size (similar to 1 mu m) compared to pristine LiMn2O4. The elementary electrochemical characterizations revealed that reversible and fast diffusion of Li+ ions have improved reversibility and initial specific capacity 124.18 and 124.68 mAhg(-1) for Dy01 and Dy02 respectively which 103\% of 120 mAhg-1 specific capacity LiMn2O4 at C/10 rate. The AC impedance spectra showed that the reduction in overall impedance via Dy doping in LiMn2O4. The galvenostatic chargedischarge study revealed the improved rate performance of doped LMO-Dy02 cathode (C) 2017 Elsevier Ltd. All rights reserved.

MATERIALS TODAY-PROCEEDINGS

Preliminary study of dysprosium doped LiMn2O4 spinel cathode materials

The prime focus of the present study is to employ NMR relaxation measurement to address the intermolecular interactions, as well as motional dynamics, of drugs, viz., paracetamol and aspirin, encapsulated within the β-cyclodextrin (β-CD) cavity. In this report, we have attempted to demonstrate the applicability of nonselective (R1ns), selective (R1se), and bi-selective (R1bs) spin-lattice relaxation rates to infer dynamical parameters, for example, the molecular rotational correlation times (τc) and cross-relaxation rates (σij) of the encapsulated drugs. Molecular rotational correlation times of the free drugs were calculated using the selective relaxation rate in the fast molecular motion time regime (ωH2τc2 ≪ 1 and R1ns/R1se ≈ 1.500), whereas that of the 1:1 complexed drugs were found from the ratio of R1ns/R1se in the intermediate motion time regime (ωH2τc2 ∼ 1 and R1ns/R1se ≈ 1.054), and these values were compared with each other to confirm the formation of inclusion complexes. Furthermore, the cross-relaxation rates were used to evaluate the intermolecular proton distances. Also, density functional theory calculations were performed to determine the minimum energy geometry of the inclusion complexes and the results compared with those from experiments. The report, thus, presents the possibility of utilizing NMR relaxation data, a more cost-effective experiment, to calculate internuclear distances in the case of drug-supramolecule complexes that are generally obtained by extremely time consuming two-dimensional nuclear Overhauser enhancement-based methods. A plausible mode of insertion of the drug molecules into the β-CD cavity has also been described based on experimental NMR relaxation data analysis. © 2017 American Chemical Society.

Journal of Physical Chemistry B

Analysis of Molecular Interaction of Drugs within β-Cyclodextrin Cavity by Solution-State NMR Relaxation

A combined experimental (FT-IR, 1H and 13C NMR) and theoretical approach is used to study the structure and properties of antimalarial drug dimethylisoborreverine (DMIB). Conformational analysis, has been performed by plotting one dimensional potential energy curve that was computed using density functional theory (DFT) with B3LYP/6-31G method and predicted conformer A1 as the most stable conformer. After full geometry optimization, harmonic wavenumbers were computed for conformer A1 at the DFT/B3LYP/6-311++G(d,P) level. A complete vibrational assignment of all the vibrational modes have been performed on the bases of the potential energy distribution (PED) and theoretical results were found to be in good agreement with the observed data. To predict the solvent effect, the UV-Vis spectra were calculated in different solvents by polarizable continuum model using TD-DFT method. Molecular docking studies were performed to test the biological activity of the sample using SWISSDOCK web server and Hex 8.0.0 software. The molecular electrostatic potential (MESP) was plotted to identify the reactive sites of the molecule. Natural bond orbital (NBO) analysis was performed to get a deep insight of intramolecular charge transfer. Thermodynamical parameters were calculated to predict the direction of chemical reaction. © 2015 Elsevier B.V.