Fast Proton Exchange in Histidine: Measurement of Rate Constants through Indirect Detection by NMR Spectroscopy

Owing to its imidazole side chain, histidine participates in various processes such as enzyme catalysis, pH regulation, metal binding, and phosphorylation. The determination of exchange rates of labile protons for such a system is important for understanding its functions. However, these rates are too fast to be measured directly in an aqueous solution by using NMR spectroscopy. We have obtained the exchange rates of the NH₃⁺ amino protons and the labile NH^ε2 and NH^δ1 protons of the imidazole ring by indirect detection through nitrogen‐15 as a function of temperature (272 K<T<293 K) and pH (1.3<pH<4.9) of uniformly nitrogen‐15‐ and carbon‐13‐labeled L ‐histidine ? HCl ? H₂O. Exchange rates up to 8.5×10⁴ s^?1 could be determined (i.e., lifetimes as short as 12 μs). The three chemical shifts δ_Hi of the invisible exchanging protons H_i and the three one‐bond scalar coupling constants ¹J(N,H_i) could also be determined accurately.     

Bimetallic Ag‐Pt Sub‐nanometer Supported Clusters as Highly Efficient and Robust Oxidation Catalysts

A combined experimental and theoretical investigation of Ag‐Pt sub‐nanometer clusters as heterogeneous catalysts in the CO→CO₂ reaction (COox) is presented. Ag₉Pt₂ and Ag₉Pt₃ clusters are size‐selected in the gas phase, deposited on an ultrathin amorphous alumina support, and tested as catalysts experimentally under realistic conditions and by first‐principles simulations at realistic coverage. In situ GISAXS/TPRx demonstrates that the clusters do not sinter or deactivate even after prolonged exposure to reactants at high temperature, and present comparable, extremely high COox catalytic efficiency. Such high activity and stability are ascribed to a synergic role of Ag and Pt in ultranano‐aggregates, in which Pt anchors the clusters to the support and binds and activates two CO molecules, while Ag binds and activates O₂, and Ag/Pt surface proximity disfavors poisoning by CO or oxidized species.     

New tetrazoloquinolinyl methoxyphenyl-4-thiazolidinones: synthesis and antihyperglycemic evaluation

Research on Chemical Intermediates - We report synthesis and in&nbsp;vivo antihyperglycemic evaluation of new 3-substituted...     

Oral intake of zirconia nanoparticle alters neuronal development and behaviour of <Emphasis Type="Italic">Drosophila melanogaster</Emphasis>

Zirconia nanoparticles (ZrO₂ NPs) have been extensively used in teeth and bone implants and thus get a chance to interact with the physiological system. The current study investigated the oral administration of various concentrations of ZrO₂ NPs synthesized by the hydrothermal method (0.25 to 5.0 mg L^?1) on Drosophila physiology and behaviour. The size of the currently studied nanoparticle varies from 10 to 12 nm. ZrO₂ NPs accumulated within the gut in a concentration-dependent manner and generate reactive oxygen species (ROS) only at 2.5 and 5.0 mg L^?1 concentrations. ROS was detected by nitroblue tetrazolium (NBT) assay and 2′,7′-dichlorofluorescein (H2DCF) staining. The ROS toxicity alters the larval gut structure as revealed by DAPI staining. The NP stress of larvae affects the Drosophila development by distressing pupa count and varying the phenotypic changes in sensory organs (eye, thorax bristle, wings). Besides phenotypic changes, flawed climbing behaviour against gravity was seen in ZrO₂ NP-treated flies. All together, for the first time, we have reported that a ROS-mediated ZrO₂ NP toxicity alters neuronal development and functioning using Drosophila as a model organism.

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Graphical abstract ?

     

Synthesis of novel pyrimidine nucleoside analogues owning multiple bases/sugars and their glycosidase inhibitory activity

A series of novel nucleoside analogues having dual bases (pyrimidine and triazole) and sugars have been synthesized by CuAAC reaction of azido sugars with propynylated pyrimidines. These compounds were evaluated for their in vitro α-glucosidase inhibitory activity. In this series, compounds 4b, 4d, 8a, 8b, 8c, 8e, 8g, 8h, and 8i exhibited very good inhibition of α-glucosidase enzyme. Nucleoside analogues 8a, 4b, 8h, and 8c displayed 47.4%, 41.8%, 39.4%, and 34.6% inhibition, respectively, comparable to the standard drug acarbose (53.4%).     

Studies on ionic solvation behavior of ionic liquid (tetrabutylphosphonium tetrafluoroborate) in some liquid media by volumetric,viscometric, and acoustic measurements

Physicochemical properties such as density (ρ), viscosity (η), ultrasonic speed (u) of ionic liquid tetrabutylphosphonium tetrafluoroborate in acetonitrile, tetrahydrofuran, 1,3-dioxolane, and their binaries have been studied over the entire range of composition at 298.15°K. Apparent molar volumes (? _V ) and viscosity B-coefficients supplemented with the data of densities and viscosities, respectively, have been interpreted in terms of ion–solvent interactions. The limiting apparent molar volumes (? _V ⁰ ), experimental slopes (S _V ^? ) derived from the Masson equation, and viscosity A and B-coefficients analyzed by the Jones–Dole equation have also been interpreted. The adiabatic compressibility (β) has been evaluated using the ultrasonic speed (u) values. Thereafter, limiting apparent molar adiabatic compressibilities (? _K ⁰  ) have been evaluated and discussed for the same.

A toxicity assessment of hydroxyapatite nanoparticles on development and behaviour of <Emphasis Type="Italic">Drosophila melanogaster</Emphasis>

The effects of oral intake of hydroxyapatite nanoparticles (HApNPs) were investigated on growth, development and behaviour of Drosophila. The Drosophila responses to various concentrations of HApNPs were compared. At lower concentrations, i.e. 5 mg L^?1 more amount of oxidative stress was produced than that of highest concentration, i.e. 80 mg L^?1. The increased amounts of oxidative stress reflect a higher amount of ROS production and increased cell damage within the larval gut. HApNPs was further shown to interfere with the calcium and phosphorus absorption pathway. Besides all these damage, HApNPs causes developmental delay in the late third instar larvae. The most significant anomaly was observed in pupae count, fly hatching after the feeding of HApNPs. Flies hatched from treated vials have decreased body weight with defective walking behaviour. Hatched flies have a phenotypic defect in the wing, eye and thorax of the bristles. Along with these changes, the adult fly becomes more prone towards stress. The findings hint that HApNPs persuade noxious effects and alter the development, structure, function and behaviour of the fly in a concentration-dependent manner.

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Graphical abstract Effect of Hydroxyapatite on the complete life cycle of Drosophila. Flies lay eggs in Hydroxyapatite containing food. As soon as the eggs hatch to larvae they start eating the NP contained food. The effect of Hydroxyapatite on various developmental stage is summerised by biochemical, immunohistochemical, behavioral, developmental and phenotypic defects.

     

Mechanical Motion in Crystals Triggered by Solid State Photochemical [2+2] Cycloaddition Reaction

Some special crystals respond to light by jumping, scattering or bursting just like popping of popcorn kernels on a hot surface. This rare phenomenon is called the photosalient (PS) effect. Molecular level control over the arrangement of light-responsive molecules in microscopic crystals for macroscale deformation or mechanical motion offers the possibility of using light to control smart material structures across the length scales. Photochemical [2+2] cycloaddition has recently emerged as a promising route to obtain photoswitchable structures and a wide variety of frameworks, but such reaction in crystals leading to macroscopic mechanical motion is relatively less explored. Study of chemistry of such novel soft crystals for the generation of smart materials is an imperative task. This minireview highlights recent advances in solid-state [2+2] cycloaddition in crystals to induce macroscale mechanical motion and thereby transduction of light into kinetic energy.     

Unimodular polynomial matrices over finite fields

Journal of Algebraic Combinatorics - We consider some combinatorial problems on matrix polynomials over finite fields. Using results from control theory, we give a proof of a result of Lieb, Jordan...