Solvent- and Substrate-Induced Chiroptical Inversion in Amphiphilic,Biocompatible Glycoconjugate Supramolecules: Shape-Persistent Gelation,Self-Healing,and Antibacterial Activity

We have shown solvent- and substrate-dependent chiral inversion of a few glycoconjugate supramolecules. (Z)-F-Gluco, in which d -glucosamine has been attached chemically to Cbz-protected l -phenylalanine at the C terminus, forms a self-healing hydrogel through intertwining of the nanofibers wherein the gelators undergo lamellar packing in the β-sheet secondary structures with a single chiral handedness. Dihybrid (Z)-F-gluco nanocomposite gel was prepared by in-situ formation of silver nanoparticles AgNPs in the gel; this enhances the mechanical properties of the composite gel through physical crosslinking without altering the packing pattern. In contrast, (Z)-L-gluco bearing an l -leucine moiety does not form a hydrogel but an organogel. Interestingly, the chiral handedness of the aggregates of (Z)-L-gluco can be reversed by choosing suitable solvents. In addition to self-healing behavior, (Z)-L-gluco gel revealed shape persistency. Further, (Z)-F-gluco hydrogel is benign, nontoxic, non-immunogenic, and non-allergenic in animal cells. AgNP-loaded (Z)-F-gluco hydrogel showed antibacterial activity against both Gram-positive and Gram-negative bacteria.     

The ABC of Insulin: The Organic Chemistry of a Small Protein

Insulin is a small protein crucial for regulating the blood glucose level in all animals. Since 1922 it has been used for the treatment of patients with diabetes. Despite consisting of just 51 amino acids, insulin contains 17 of the proteinogenic amino acids, A- and B-chains, three disulfide bridges, and it folds with 3 α-helices and a short β-sheet segment. Insulin associates into dimers and further into hexamers with stabilization by Zn²⁺ and phenolic ligands. Selective chemical modification of proteins is at the forefront of developments in chemical biology and biopharmaceuticals. Insulin's structure has made it amenable to organic and inorganic chemical reactions. This Review provides a synthetic organic chemistry perspective on this small protein. It gives an overview of key chemical and physico-chemical aspects of the insulin molecule, with a focus on chemoselective reactions. This includes N-acylations at the N-termini or at Lys^B29 by pH control, introduction of protecting groups on insulin, binding of metal ions, ligands to control the nano-scale assembly of insulin, and more.     

Ionic liquid‐based dispersive liquid–liquid microextraction followed by RP‐HPLC determination of saquinavir in rat serum: application to pharmacokinetics

An ionic liquid‐based dispersive liquid–liquid microextraction followed by RP‐HPLC determination of the most commonly prescribed protease inhibitor, saquinavir, in rat plasma was developed and validated. The effects of different ionic liquids, dispersive solvents, extractant/disperser ratio and salt concentration on sample recovery and enrichment were studied. Among the ionic liquids investigated, 1‐butyl‐3‐methylimidazolium hexafluorophosphate was found to be most effective for extraction of saquinavir from rat serum. The recovery was found to be 95% at an extractant/disperser ratio of 0.43 using 1‐butyl‐3‐methylimidazolium hexafluorophosphate and methanol as extraction and dispersive solvents. The recovery was further enhanced to 99.5% by addition of 5.0% NaCl. A threefold enhancement in detection and quantification limits was achieved, at 0.01 and 0.03 µg/mL, compared with the conventional protein precipitation method. A linear relationship was observed in the range of 0.035–10.0 µg/mL with a correlation coefficient (r²) of 0.9996. The method was validated and applied to study pharmacokinetics of saquinavir in rat serum. Copyright © 2014 John Wiley & Sons, Ltd.     

Kantorovich variant of a new kind of q‐Bernstein–Schurer operators

Ren and Zeng (2013) introduced a new kind of q‐Bernstein–Schurer operators and studied some approximation properties. Acu et al. (2016) defined the Durrmeyer modification of these operators and studied the rate of convergence and statistical approximation. The purpose of this paper is to introduce a Kantorovich modification of these operators by using q‐Riemann integral and investigate the rate of convergence by means of the Lipschitz class and the Peetre's K‐functional. Next, we introduce the bivariate case of q‐Bernstein–Schurer–Kantorovich operators and study the degree of approximation with the aid of the partial modulus continuity, Lipschitz space, and the Peetre's K‐functional. Finally, we define the generalized Boolean sum operators of the q‐Bernstein–Schurer–Kantorovich type and investigate the approximation of the Bögel continuous and Bögel differentiable functions by using the mixed modulus of smoothness. Furthermore, we illustrate the convergence of the operators considered in the paper for the univariate case and the associated generalized Boolean sum operators to certain functions by means of graphics using Maple algorithms. Copyright © 2017 John Wiley & Sons, Ltd.     

Photosynthetic,Biochemical and Secondary Metabolite Changes in a Medicinal Plant Chlorophytum borivillianum (Safed musli) against Low and High Doses of UV-B Radiation

Plants are inevitably grown in presence of sunlight, therefore bound to be exposed to natural UV-B radiation. Several studies have already been conducted with UV-B and medicinal plants and only few studies showed dose dependent variation. The present study aims to find out the variations and adaptation in Chlorophytum borivillianum under two different doses of UV-B radiation; ambient + low (3.2 kJm⁻² d⁻¹) and high (7.2 kJm⁻² d⁻¹) UV-B dose, denoted as LD and HD, respectively. Reduction in photosynthetic rate was higher at HD, while plants receiving LD displayed nonsignificant variation. During vegetative and reproductive stage, significant reduction (P ≤ 0.001) in stomatal conductance was obtained when exposed to HD-eUV-B. F_v/F_m showed more reductions in HD-eUV-B (12.6%) followed by LD-eUV-B (7.9%). Low and high doses of UV-B enhanced the anthocyanin content but the increase was significant in HD, indicates epidermal protection strategy by the plants. Under LD-eUV-B, the content of saponin, a major phytochemical constituent was enhanced by 26%. Phytochemical analysis of roots revealed reduction mostly in fatty acid components whereas the steroidal components (stigmasterol and sarsasapogenin) showed enhancement in response to LD. The study suggests the importance of LD-eUV-B in the stimulation of medicinal compounds in C. borivillianum.     

Dynamic responses of orthotropic plates under moving masses

Summary The problem considered is that of heavy masses moving on lightweight rectangular plates of orthotropic materials, slated for use in space structures. The dynamic equation of motion for orthotropic plates which contains singularities in both space and time variables is first presented. The response is expressed as a summation of double series of eigenfunctions. The equation of motion is transformed into an integro-differential equation for modal amplitudes using the Green's function. The Green's function is chosen to satisfy the initial conditions, the boundary conditions, and the transient conditions due to the moving masses. The solution series exhibits a good convergence. The effect of orthotropicity on natural frequencies and dynamic responses is demonstrated.

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Dynamische Antwort orthotroper Platten auf bewegte Massenpunkte

übersicht Behandelt wird die Bewegung von Massenpunkten auf rechteckigen Leichtbau-Platten aus orthotropem Werkstoff, die für Raumfahrtkonstruktionen vorgesehen sind. ZunÄchst wird die Bewegungsgleichung orthotroper Platten mit singulÄren Ausdrücken in den Raum- und Zeitkoordinaten angegeben. Die Antwort wird als Doppelsumme einer zweifachen Reihenentwicklung dargestellt und die Bewegungsgleichung mit Hilfe der Greenschen Funktion in eine Integro-Differentialgleichung für die Modalamplituden transformiert. Die Greensche Funktion ist so gewÄhlt, da\ sie die Anfangs- und Randbedingungen sowie die übergangsbedingungen unter der bewegten Masse erfüllt. Die Lösung durch Reihenentwicklung zeigt gute Konvergenz. Der Einflu\ der Orthotropie auf die Eigenfrequenzen und die dynamischen Antworten wird veranschaulicht.

     

Application of rainbow schlieren deflectometry for concentration measurements in an axisymmetric helium jet

 The rainbow schlieren deflectometry technique was used to measure oxygen concentrations in a laminar, isothermal helium jet discharged vertically into ambient air. The concentration distributions were inferred from the color schlieren image by taking into consideration the sampling interval and noise in measurements, especially near the jet center. Excellent quantitative agreement was reached between measurements from schlieren and a continuous sampling probe. This work demonstrates the capability of the schlieren technique for providing accurate, spatially-resolved, nonintrusive, full-field of view measurements of species concentration in an isothermal binary system. Because the basic quantity measured is the refractive index, the present schlieren technique can be extended for quantitative measurements of other scalar flow properties related to the refractive index. Received: 21 April 1997 / Accepted: 14 November 1997     

Integral equation formulation for buoyancy-driven convection problems

An integral equation formulation for buoyancy-driven convection problems is developed and illustrated. Buoyancy-driven convection in a bounded cylindrical geometry with a free surface is studied for a range of aspect ratios and Nusselt numbers. The critical Rayleigh number, the nature of the cellular motion, and the heat transfer enhancement are computed using linear theory. Green's functions are used to convert the linear problem into linear Fredholm integral equations. Theorems are proved which establish the properties of the eigenvalues and eigenfunctions of the linear integral operator which appears in these equations.     

Properties of vortices in the self-similar turbulent jet

Instantaneous, two-dimensional velocity measurements were conducted in the axial plane of a self-similar turbulent axisymmetric jet. The velocity fields were high-pass filtered to expose the vortical structures. An automated method was used to identify the radial and axial coordinates of the vortex centers and rotational sense, and to measure their size, circulation, vorticity, and energy. New insights into turbulent jets are obtained by plotting statistical distributions for vortex properties as functions of Reynolds number and radial position. While the probability of finding a vortex is uniform up to the edge of the jet, the strongest eddies in the high-pass filtered field occur near the jet axis. The average circulation is directly proportional to the vortex size. The Reynolds number strongly affects the average vorticity, circulation, and energy of the eddies. However, the normalized curves show a good collapse implying that the jet is indeed self-similar. Results for the left and right half-planes of the jet are also presented. Interestingly, we find that contrary to customary drawings of jet flows, a substantial number of both clockwise and counter-clockwise rotating eddies exist on both sides of the jet axis, with almost equal numbers of oppositely rotating vortices close to the jet axis. Further, the disparity in the number of oppositely rotating eddies in each half-plane increases with the eddy size. Nevertheless, these results are consistent with the well-known radial vorticity distribution of axisymmetric jets.     

In situ synthesis of Ag-SiO2 Janus particles with epoxy functionality for textile applications

A facile method for the synthesis of silver-silica（Ag-SiO₂） Janus particles with functionalities suitable for textile applications is reported.Silica nanoparticles prepared by the Stober method were functionalized with epoxy,amine,and thiol groups,which were confirmed by Fourier transform infrared analysis.The functionalized silica nanoparticles were used to produce Pickering emulsions,and the exposed surface was used for the attachment of silver nanoparticles（AgNPs） via the low-temperature chemical reduction method.The morphology and structure of the Ag-SiO₂ Janus particles were characterized by scanning electron microscopy,scanning transmission electron microscopy,high-resolution transmission electron microscopy,energy-dispersive X-ray analysis,and UV-vis spectroscopy.Because of their specific functionalities,these Ag-SiO₂ Janus particles are proposed for applications on textile substrates,as they can overcome several drawbacks of direct application of AgNPs on textiles,such as leaching,agglomeration,and instability during storage.