Ionic liquid-based sodium ion-conducting composite gel polymer electrolytes: effect of active and passive fillers

Journal of Solid State Electrochemistry - We report the studies on composite gel polymer electrolytes (GPEs) comprising 0.5 M solution of sodium trifluoromethane sulfonate (Na-triflate or...     

Synthesis of potential impurities of cloxacillin sodium drug substance

The present work describes the synthesis and characterization of six related compounds of cloxacillin sodium ( 1 ) viz penicilloic acid of cloxacillin (2) , (3-(2-chlorophenyl)-5-methylisoxazole-4-carbonyl) glycine (Glycine analogue of cloxacillin) (3), CMICAA adduct of cloxacillin (4) , (4S)-2-(carboxy(3-(2-chlorophenyl)-5-methylisoxazole-4-carboxamido) methyl)-3-(2-ethylhexanoyl)-5,5-dimethylthiazolidine-4-carboxylic acid (N-2-ethylhexanoyl penicilloic acid of cloxacillin) ( 5 ), N-Acetylated penicilloic acid of cloxacillin ( 6 ), and Cloxacillin Penicillamide (7) . These related compounds are very essential in the process development of cloxacillin sodium and are used as reference standards to determine the quality of the drug substance.     

Studies of iron(II) and iron(III) complexes with fac-N2O, cis-N2O2 and N2O3 donor ligands: models for the 2-His 1-carboxylate motif of non-heme iron monooxygenases

Enzymes in the oxygen-activating class of mononuclear non-heme iron oxygenases (MNOs) contain a highly conserved iron center facially ligated by two histidine nitrogen atoms and one carboxylate oxygen atom that leave one face of the metal center (three binding sites) open for coordination to cofactor, substrate, and/or dioxygen. A comparative family of [Fe(II/III)(N(2)O(n))(L)(4-n))](±x), n = 1-3, L = solvent or Cl(-), model complexes, based on a ligand series that supports a facially ligated N,N,O core that is then modified to contain either one or two additional carboxylate chelate arms, has been structurally and spectroscopically characterized. EPR studies demonstrate that the high-spin d(5) Fe(III)g = 4.3 signal becomes more symmetrical as the number of carboxylate ligands decreases across the series Fe(N(2)O(3)), Fe(N(2)O(2)), and Fe(N(2)O(1)), reflecting an increase in the E/D strain of these complexes as the number of exchangeable/solvent coordination sites increases, paralleling the enhanced distribution of electronic structures that contribute to the spectral line shape. The observed systematic variations in the Fe(II)-Fe(III) oxidation-reduction potentials illustrate the fundamental influence of differential carboxylate ligation. The trend towards lower reduction potential for the iron center across the [Fe(III)(N(2)O(1))Cl(3)](-), [Fe(III)(N(2)O(2))Cl(2)](-) and [Fe(III)(N(2)O(3))Cl](-) series is consistent with replacement of the chloride anions with the more strongly donating anionic O-donor carboxylate ligands that are expected to stabilize the oxidized ferric state. This electrochemical trend parallels the observed dioxygen sensitivity of the three ferrous complexes (Fe(II)(N(2)O(1)) < Fe(II)(N(2)O(2)) < Fe(II)(N(2)O(3))), which form μ-oxo bridged ferric species upon exposure to air or oxygen atom donor (OAD) molecules. The observed oxygen sensitivity is particularly interesting and discussed in the context of α-ketoglutarate-dependent MNO enzyme mechanisms.     

Synthesis,structural and electrical properties of Ti modified Bi2Sn2O7 pyrochlore

Polycrystalline ceramic samples of Bi₂Sn_2−xTi_xO₇ (x=0.00, 0.2, 0.4, 0.6 and 0.8) have been synthesized by standard high temperature solid state reaction method. The effect of homovalent cation (titanium) substitution on the Sn-site on the structural and electrical properties of the pure Bi₂Sn₂O₇ ceramic have been studied by X-ray diffraction followed by SEM, dielectric and dc conductivity studies. The structural analysis indicates that the increase of titanium contents do not lead to any secondary phase. The frequency and temperature dependent dielectric studies have been carried out. It is found that the Ti doping reduces the material particle size. The size of the particles are strongly influenced by the addition of titanium to the system. The substitution of Ti for Sn ions affected the degree of disorder and modified the dielectric properties leading to more resistive ceramic compounds. The activation energies of all the compounds were calculated using the relation σ=σ₀exp(−Ea/kT).     

Structure of Three Related Diphosphorus Ligands: Highlighting the Significance of the Backbone

Abstract  

The three compounds contained in this report—4,6-bis(diphenylphosphino)-10,10-dimethylphenoxasilin (sixantphos), 1; 4,5-bis(diphenylphosphino)-9-isopropylidenexanthene, (isopropxantphos) 2 and bis-(2-diphenylphosphino)-p-tolyl) ether (PTEphos) 3, all contain a common ether-linked diphenylphosphino backbone. These structures are of interest with respect to the intra-molecular P···P distance which is 3.884(2), 4.104(2) and 5.151(2) ? for 1, 2 and 3 respectively. The differences in the P···P distances are as a result of the variations in the backbones. Structure 1 shows a significant roof-like bending of the backbone along the axis of planarity involving the oxygen and Si donor atoms. Compound 2 is also folded with a larger dihedral angle of 35.85(2)° as compared to 24.14(2)° found in 1. The backbone in structure 3 is significantly bent and twisted with a dihedral angle of 67.34(2)°. These data show the effect on the intra-molecular P···P distance of varying the backbone of three xantphos-type ligands, with respect to the nature of the heterocycle donor 1, the substituent on the donor 2 and total loss of xanthene character 3.     

Effect of hydrophilic polymer on complexing efficiency of cyclodextrins towards efavirenz-characterization and thermodynamic parameters

The present work describes the effect of PVP on the complexation efficiency of cyclodextrins towards efavirenz, a poorly soluble antiretroviral agent imparting irritating sensation to buccal cavity. The phase solubility study indicates 1:1 stoichiometry for binary and ternary systems. DSC and XRPD revealed complete inclusion only in the lyophilized systems. The ternary systems were autoclaved before being lyophilized for the best results. Proton NMR suggests that the chlorobenzene part of benzoxazinone ring of the drug is involved in inclusion and was confirmed by 2D-COESY. The thermodynamic parameters, indicative of complexation efficiency were calculated calorimetrically by determining the interaction enthalpy of efavirenz with cyclodextrins in the presence and absence of PVP. The value of stability constants increased in the order β-CD?<?HP-β-CD?<?M-β-CD and is still higher in the presence of PVP illustrating the facilitation of the inclusion. Molar enthalpy of interaction of autoclaved solid formulation determined calorimetrically indicated stronger interaction for efavirenz:M-βCD-PVP system (?12.20?kJ/mol) which showed highest solubility and dissolution rate. The in vitro measurement of permeability showed a ten fold increase in the flux for the autoclaved formulation containing efavirenz-M-β-CD-PVP. In conclusion, encapsulation by cyclodextrins increases the solubility and suppresses the oral irritation of efavirenz. PVP further increases the complexation efficiency and decreases the bulk of cyclodextrins.     

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.     

High yield synthesis of intrinsic, doped and composites of nano-zinc oxide using novel combinatorial method

A novel synthesis of the production of luminescent zinc oxide (ZnO), either in its intrinsic, metal, non-metal-doped or composite forms with high yield has been developed by parallel iterative techniques, within a combinatorial library prepared by the reduction of nitroarenes. The reduction of nitroarenes by aluminium/zinc dusts in alkaline medium (pH 10±2) forms azoxy compounds, whereas in acidic medium (pH 4.9±0.2) forms phenyl hydroxylamine and zinc/aluminium dust gets oxidised into respective hydroxide. Here, we demonstrate the reduction of nitroarenes at neutral pH (7.0±0.2), which forms intrinsic as well as doped ZnO at 50±5°C using zinc dust alone or mixtures of salts of several transition and non-transition metals in presence of 1:10 ratio of solvent and water. Interestingly, it is observed that the photoluminescence emission could be tuned in a wide range from 390 to 615 nm useful for many display related devices.