Micellar effect on the electron transfer reaction of chromium(V) ion with organic sulfides

The rate of electron transfer from organic sulfides to [Cr^V(ehba)₂]⁻ (ehba-2-ethyl-2-hydroxy butyric acid) decreases with a decrease in the polarity of the medium. The anionic surfactant, SDS and the cationic surfactant, CTAB have different effects on the kinetics of this reaction. The micellar inhibition observed in the presence of SDS is probably due to the decrease in the polarity and the electrostatic repulsion faced by the anionic oxidant from the anionic micelle and the partition of the hydrophobic substrate between the aqueous and micellar phases. The micellar catalysis in the presence of CTAB is attributed to the increase in the concentration of both reactants in the micellar phase. This micellar catalysis is observed to offset the retarding effects of the less polar micellar medium and the unfavorable charge-charge interaction between the + charge developed on S center in the transition state and the cationic micelle. This catalysis is contrary to the enormous micellar inhibition observed with IO₄⁻, HSO₅⁻ and HCO₄⁻ oxidation of organic sulfides.     

Oxidation of Styrene to Benzaldehyde Catalyzed by Schiff Base Functionalized Triazolylidene Ni(II) Complexes

Four new Schiff base functionalized 1,2,3-triazolylidene nickel complexes, [Ni-(L₁NHC)₂](PF₆)₂; 3, [Ni-(L₂NHC)₂](PF₆)₂; 4, [Ni-(L₃NHC)](PF₆)₂; 7 and [Ni-(L₄NHC)](PF₆)₂; 8, (where L₁NHC = (E)-3-methyl-1-propyl-4-(2-(((2-(pyridin-2-yl)ethyl)imino)methyl)phenyl)-1H-1,2,3-triazol-3-ium hexafluorophosphate(V), 1, L₂NHC = (E)-3-methyl-4-(2-((phenethylimino)methyl)phenyl)-1-propyl-1H-1,2,3-triazol-3-ium hexafluorophosphate(V), 2, L₃NHC = 4,4′-(((1E)-(ethane-1,2-diylbis(azanylylidene))bis(methanylylidene))bis(2,1-phenylene))bis(3-methyl-1-propyl-1H-1,2,3-triazol-3-ium) hexafluorophosphate(V), 5, and L₄NHC = 4,4′-(((1E)-(butane-1,4-diylbis(azanylylidene))bis(methanylylidene))bis(2,1-phenylene))bis(3-methyl-1-propyl-1H-1,2,3-triazol-3-ium) hexafluorophosphate(V), 6), were synthesised and characterised by a variety of spectroscopic methods. Square planar geometry was proposed for all the nickel complexes. The catalytic potential of the complexes was explored in the oxidation of styrene to benzaldehyde, using hydrogen peroxide as a green oxidant in the presence of acetonitrile at 80 °C. All complexes showed good catalytic activity with high selectivity to benzaldehyde. Complex 3 gave a conversion of 88% and a selectivity of 70% to benzaldehyde in 6 h. However, complexes 4 and 7–8 gave lower conversions of 48–74% but with higher (up to 90%) selectivity to benzaldehyde. Results from kinetics studies determined the activation energy for the catalytic oxidation reaction as 65 ± 3 kJ/mol, first order in catalyst and fractional order in the oxidant. Results from UV-visible and CV studies of the catalytic activity of the Ni-triazolylidene complexes on styrene oxidation did not indicate any clear possibility of generation of a Ni(II) to Ni(III) catalytic cycle.     

Purification and Characterization of Gum-Derived Polysaccharides of Moringa oleifera and Azadirachta indica and Their Applications as Plant Stimulants and Bio-Pesticidal Agents

Plant gums are bio-organic substances that are derived from the barks of trees. They are biodegradable and non-adverse complex polysaccharides that have been gaining usage in recent years due to a number of advantages they contribute to various applications. In this study, gum was collected from Moringa oleifera and Azadirachta indica trees, then dried and powdered. Characterizations of gum polysaccharides were performed using TLC, GC-MS, NMR, etc., and sugar molecules such as glucose and xylose were found to be present. Effects of the gums on Abelmoschus esculentus growth were observed through root growth, shoot growth, and biomass content. The exposure of the seeds to the plant gums led to bio stimulation in the growth of the plants. Poor quality soil was exposed to the gum polysaccharide, where the polysaccharide was found to improve soil quality, which was observed through soil analysis and SEM analysis of soil porosity and structure. Furthermore, the plant gums were also found to have bio-pesticidal activity against mealybugs, which showed certain interstitial damage evident through histopathological analysis.     

Growth of CdGeAs2 single crystals by a microprocessor-controlled bridgman system

A microprocessor-controlled Bridgman system was designed and fabricated for the growth of II-IV-V₂ compounds and one of this group of compounds CdGeAs₂ has been grown using a two-zone vertical Bridgman systein. The grown crystals have been characterized by X-ray and Hall effect.     

Greener route for microwave enhanced syntheses of bioactive 1,5-benzodiazepines using heterogeneous calcium ferrite/graphene oxide nanocomposite as a novel and sustainable catalyst

In the present paper, a novel and benign protocol for microwave enhanced one pot syntheses of 2,3-dihydro-1,5 benzodiazepine derivatives from substituted acetophenones, aryl-aldehydes and o-phenylene diamine using heterogeneous calcium ferrite/graphene oxide (CF/GO) nanocomposite has been reported. The catalyst was prepared by ultrasonication method and characterized by spectral and analytical techniques. The CF/GO nanocomposite was employed for environmentally benign synthesis of 2,3-dihydro-1,5 benzodiazepines. The synthesized benzodiazepine derivatives were screened for their antimicrobial activities against various bacteria and fungi. The present synthetic strategy offered several advantages such as excellent yields in short span of time, simple modus operandi, ease of isolation and purification of products, simple recovery and reusability of the catalyst. A tentative mechanism for synthesis of 2,3-dihydro-1,5 benzodiazepine using CF/GO nanocatalyst has also been proposed.     

Performance of a 4×10 Gbit/s optical time domain multiplexed system using SMZ switching

Optical time division multiplexing (OTDM) is emerging and promising alternative for future high-speed photonic networks because of its ability to accommodate higher bit rate and flexible bandwidth. Among other factors the performance of an OTDM system largely depends upon the switching characteristics of a de-multiplexer (DEMUX). Symmetric Mach-Zehnder (SMZ) have been found to be most suitable than all the available de-multiplexing switches because of compact size, thermal stability, and low power operation. In this paper, we simulate four-channel OTDM systems (all channel multiplexer (MUX) and DEMUX) with a Mach-Zehnder modulator and SMZ DEMUX to investigate the impact of signal power, pulse width and control signal power on BER.     

Retaining positive definiteness in thresholded matrices

Positive definite (p.d.) matrices arise naturally in many areas within mathematics and also feature extensively in scientific applications. In modern high-dimensional applications, a common approach to finding sparse positive definite matrices is to threshold their small off-diagonal elements. This thresholding, sometimes referred to as hard-thresholding, sets small elements to zero. Thresholding has the attractive property that the resulting matrices are sparse, and are thus easier to interpret and work with. In many applications, it is often required, and thus implicitly assumed, that thresholded matrices retain positive definiteness. In this paper we formally investigate the algebraic properties of p.d. matrices which are thresholded. We demonstrate that for positive definiteness to be preserved, the pattern of elements to be set to zero has to necessarily correspond to a graph which is a union of complete components. This result rigorously demonstrates that, except in special cases, positive definiteness can be easily lost. We then proceed to demonstrate that the class of diagonally dominant matrices is not maximal in terms of retaining positive definiteness when thresholded. Consequently, we derive characterizations of matrices which retain positive definiteness when thresholded with respect to important classes of graphs. In particular, we demonstrate that retaining positive definiteness upon thresholding is governed by complex algebraic conditions.