Glass transition, fragility, and structural features of amorphous nickel–tellurate–vanadate samples

The experimental FTIR spectra and DSC curves of the ternary 40TeO₂–(60?x)V₂O₅–xNiO glasses with 0 ≤ x ≤ 30 (in mol%) have been investigated. The glass transition properties that have been measured and reported in this paper, include the glass transition temperature (T _g), glass transition width (ΔT _g), heat capacity change at glass transition (ΔC _P) and Fragility (F). Thermal stability, fragility, and glass-forming tendency of these glasses have been estimated. Also, Poisson’s ratio (μ) and IR spectra of the presented systems have been investigated, to determine relationship between chemical composition and the thermal stability or to interpret the structure of glass. In addition, Makishima and Makenzie’s theory was applied for determination of Young’s modulus, bulk modulus, and shear modulus, indicating a strong relation between elastic properties and structure of glass. In general, results of this work show that glasses with x = 0 and 30 have the highest shear and young’s modulus which make them as suitable candidate for the manufacture of strong glass fibers in technological applications; but it should be mentioned that glass with x = 30 has higher handling temperature and super resistance against thermal shock.     

Homogeneous geodesics and the critical points of the restricted Finsler function

In this paperwe study the set of homogeneous geodesics of a left-invariant Finsler metric on Lie groups. We first give a simple criterion that characterizes geodesic vectors. We extend J. Szenthe’s result on homogeneous geodesics to left-invariant Finsler metrics. This result gives a relation between geodesic vectors and restricted Minkowski norm in Finsler setting. We show that if a compact connected and semisimple Lie group has rank greater than 1, then for every left-invariant Finsler metric there are infinitely many homogeneous geodesics through the identity element.     

Homogeneous geodesics in homogeneous Finsler spaces

In this paper, we study homogeneous geodesics in homogeneous Finsler spaces. We first give a simple criterion that characterizes geodesic vectors. We show that the geodesics on a Lie group, relative to a bi-invariant Finsler metric, are the cosets of the one-parameter subgroups. The existence of infinitely many homogeneous geodesics on the compact semi-simple Lie group is established. We introduce the notion of a naturally reductive homogeneous Finsler space. As a special case, we study homogeneous geodesics in homogeneous Randers spaces. Finally, we study some curvature properties of homogeneous geodesics. In particular, we prove that the S-curvature vanishes along the homogeneous geodesics.     

Compensatory Adaptations of Structural Dynamics in an Intrinsically Disordered Protein Complex

Intrinsically disordered proteins (IDPs) play crucial roles in protein interaction networks and in this context frequently constitute important hubs and interfaces. Here we show by a combination of NMR and EPR spectroscopy that the binding of the cytokine osteopontin (OPN) to its natural ligand, heparin, is accompanied by thermodynamically compensating structural adaptations. The core segment of OPN expands upon binding. This “unfolding‐upon‐binding” is governed primarily through electrostatic interactions between heparin and charged patches along the protein backbone and compensates for entropic penalties due to heparin–OPN binding. It is shown how structural unfolding compensates for entropic losses through ligand binding in IDPs and elucidates the interplay between structure and thermodynamics of rapid substrate‐binding and ‐release events in IDP interaction networks.     

Antimicrobial Activity and Physical Characterization of Silver Nanoparticles Green Synthesized Using Nitrate Reductase from Fusarium oxysporum

Nanostructures from natural sources have received major attention due to wide array of biological activities and less toxicity for humans, animals, and the environment. In the present study, silver nanoparticles were successfully synthesized using a fungal nitrate reductase, and their biological activity was assessed against human pathogenic fungi and bacteria. The enzyme was isolated from Fusarium oxysporum IRAN 31C after culturing on malt extract-glucose-yeast extract-peptone (MGYP) medium. The enzyme was purified by a combination of ultrafiltration and ion exchange chromatography on DEAE Sephadex and its molecular weight was estimated by gel filtration on Sephacryl S-300. The purified enzyme had a maximum yield of 50.84 % with a final purification of 70 folds. With a molecular weight of 214 KDa, it is composed of three subunits of 125, 60, and 25 KDa. The purified enzyme was successfully used for synthesis of silver nanoparticles in a way dependent upon NADPH using gelatin as a capping agent. The synthesized silver nanoparticles were characterized by X-ray diffraction, dynamic light scattering spectroscopy, and transmission and scanning electron microscopy. These stable nonaggregating nanoparticles were spherical in shape with an average size of 50 nm and a zeta potential of ?34.3. Evaluation of the antimicrobial effects of synthesized nanoparticles by disk diffusion method showed strong growth inhibitory activity against all tested human pathogenic fungi and bacteria as evident from inhibition zones that ranged from 14 to 25 mm. Successful green synthesis of biologically active silver nanoparticles by a nitrate reductase from F. oxysporum in the present work not only reduces laborious downstream steps such as purification of nanoparticle from interfering cellular components, but also provides a constant source of safe biologically-active nanomaterials with potential application in agriculture and medicine.     

Pulse EPR Methods for Studying Chemical and Biological Samples Containing Transition Metals

This review discusses the application of pulse EPR to the characterization of disordered systems, with an emphasis on samples containing transition metals. Electron nuclear double‐resonance (ENDOR), electron‐spin‐echo envelope‐modulation (ESEEM), and double electron–electron resonance (DEER) methodologies are outlined. The theory of field modulation is outlined, and its application is illustrated with DEER experiments. The simulation of powder spectra in EPR is discussed, and strategies for optimization are given. The implementation of this armory of techniques is demonstrated on a rich variety of chemical systems: several porphyrin derivatives that are found in proteins and used as model systems, otherwise highly reactive aminyl radicals stabilized with electron‐rich transition metals, and nitroxide–copper–nitroxide clusters. These examples show that multi‐frequency continuous‐wave (CW) and pulse EPR provides detailed information about disordered systems.     

Clay Supported Bis-(trimethylsilyl)-chromate: An Efficient Reagent for Oxidative Deoximation

Summary.  A convenient method for the direct conversion of oximes to carbonyl compounds upon treatment with clay supported BTSC under classical heating as well as microwave irradiation in a solvent-free system is described.     

An experimental investigation of polyacrylamide and sulfonated polyacrylamides based gels crosslinked with cr(III)-acetate for water shutoff in fractured oil reservoirs

Abstract

Water injection as one of the most efficient and worldwide extensively employed approach in homogenous oil reservoirs suffers from early water breakthrough time as well as low oil sweep efficiency values in fractured oil reservoirs. This study investigates the potential application of Cr(III)-acetate based gel polymer system in a typical water injection process using one fractured micromodel. For this purpose, three sulfonated polyacrylamides, different in solfunation degree, and one hydrolyzed polyacrylamide were studied regarding gelation time, gel strength and stability to find the optimized conditions in terms of polymer type and concentration, and polymer/Cr(III)-acetate ratio, which were subsequently used for one dynamic test. Results illustrated the optimized conditions as AN 105 polymer with concentration of 5000?ppm and polymer/Cr(III) ratio of 5. Moreover, results showed that implementing such gel system yields an increased oil recovery value of 24.46% OOIP at 1.55 PV and delays the breakthrough time from 0.47 PV to 0.51 PV.     

Stereochemical consequences of oxygen atom transfer and electron transfer in imido/oxido molybdenum(IV, V, VI) complexes with two unsymmetric bidentate ligands

Two equivalents of the unsymmetrical Schiff base ligand (L(tBu))(-) (4-tert-butyl phenyl(pyrrolato-2-ylmethylene)amine) and MoCl(2)(NtBu)O(dme) (dme = 1,2-dimethoxyethane) gave a single stereoisomer of a mixed imido/oxido Mo(VI) complex 2(tBu). The stereochemistry of 2(tBu) was elucidated using X-ray diffraction, NMR spectroscopy, and DFT calculations. The complex is active in an oxygen atom transfer (OAT) reaction to trimethyl phosphane. The putative intermediate five-coordinate Mo(IV) imido complex coordinates a PMe(3) ligand, giving the six-coordinate imido phosphane Mo(IV) complex 5(tBu). The stereochemistry of 5(tBu) is different from that of 2(tBu) as shown by NMR spectroscopy, DFT calculations, and X-ray diffraction. Single-electron oxidation of 5(tBu) with ferrocenium hexafluorophosphate gave the stable cationic imido phosphane Mo(V) complex [5(tBu)](+) as the PF(6)(-) salt. EPR spectra of [5(tBu)](PF(6)) confirmed the presence of PMe(3) in the coordination sphere. Single-crystal X-ray diffraction analysis of [5(tBu)](PF(6)) revealed that electron transfer occurred under retention of the stereochemical configuration. The rate of OAT, the outcome of the electron transfer reaction, and the stabilities of the imido complexes presented here differ dramatically from those of analogous oxido complexes.