Studies on the 14α-hydroxylation of progesterone in mucor piriformis

Cell-free extracts with high 14?-hydroxylase activity were prepared from induced vegetative cell cultures of Mucor piriformis by grinding in potassium phosphate buffer (0.05 M, pH 8.0) containing glucose (0.25 M), KCl (1 mM), glutathione (1.0 mM) and glycerol (10%). Although the ideal pH for preparing the cell-free extract from vegetative cells was 8.0, the pH optimum of the hydroxylase was found to be 7.6. Microsomes (2.0 mg) prepared from the crude cell-free extract hydroxylated progesterone to 14?-hydroxyprogesterone in not, vert, similar60% yields in 30 min in the presence of NADPH and O2. Microsomes prepared from the uninduced cells did not contain any 14?-hydroxylase activity. The hydroxylase activity was inhibited to a significant extent by CO and p-chloromercuribenzoate whereas moderate inhibition was noticed in the presence of SKF-525A, metyrapone and N-methylmaleimideindicating the possible involvement of the cytochromeP-450 system in the reaction. The membrane bound hydroxylase was solubilized using Triton X-100 and the solubilized fraction contained nearly 35% of the original hydroxylase activity.

Electrical switching and thermal studies on bulk Ge-Te-Bi glasses

Bulk, melt quenched Ge18Te82-xBix glasses (1 <= x <= 4) have been found to exhibit memory type electrical switching behavior, which is in agreement with the lower thermal diffusivity values of Ge-Te-Bi samples. A linear variation in switching voltages (V-th) has been found in these samples with increase in thickness which is consistent with the memory type electrical switching. Also, the switching voltages have been found to decrease with an increase in temperature which happens due to the decrease in the activation energy for crystallization at higher temperatures. Further. V-th of Ge18Te82-xBix glasses have been found to decrease with the increase in Bi content, indicating that in the Ge-Te-Bi system, the resistivity of the additive has a stronger role to play in the composition dependence of V-th, in comparison with the network connectivity and rigidity factors. In addition, the composition dependence of crystallization activation energy has been found to show a decrease with an increase in Bi content, which is consistent with the observed decrease in the switching voltages. X-ray diffraction studies on thermally crystallized samples reveal the presence of hexagonal Te, GeTe, Bi2Te3 phases, suggesting that bismuth is not taking part in network formation to a greater extent, as reflected in the variation of switching voltages with the addition of Bi. SEM studies on switched and un-switched regions of Ge-Te-Bi samples indicate that there are morphological changes in the switched region, which can be attributed to the formation of the crystalline channel between two electrodes during switching. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis and studies of Rh(I) catalysts within and across poly(alkyl aryl ether) dendrimers

In order to study the efficiencies of catalytic moieties within and across dendrimer generations, partially and fully functionalized dendrimers were synthesized. Poly(alkyl aryl ether) dendrimers from zero to three generations, presenting 3 to 24 peripheral functionalities, were utilized to prepare as many as 12 catalysts. The dendrimer peripheries were partially and fully functionalized with triphenylphosphine in the first instance. A rhodium(I) metal complexation was performed subsequently to afford multivalent dendritic catalysts, both within and across generations. Upon synthesis, the dendritic catalysts were tested in the hydrogenation of styrene, in a substrate-to-catalyst ratio of 1:0.001. Turn-over-numbers were evaluated for each catalyst, from which significant increases in the catalytic activities were identified for multivalent catalysts than monovalent catalysts, both within and across generations. (C) 2010 Elsevier B.V. All rights reserved.

EXAFS and MAS NMR studies of sodium molybdophosphate and sodium tungstophosphate glasses

he local order around molybdenum and tungsten atoms in various sodium molybdophosphate and sodium tungstophosphate glasses has been investigated using extended X-ray absorption fine structure (EXAFS). Both molybdenum and tungsten atoms are present in six-coordinated environment in these glasses. Magic angle spinning nuclear magnetic resonance (MAS NMR) of P-31 suggests that metaphosphate or neutral [POO3/2] groups are present in these glasses.

Mechanistic studies on the effect of ferrocene bonding agents in composite solid propellents

Five compounds, viz. 1,1'-ferrocenediyldiethylidene bis(thiocarbonohydrazide) (DAFT), 1,1-diacetylferrocene disemicarbazone (DAFS), 1,1-diacetylferrocenebenzoyl hydrazone (FDBAH), 1,1-diacetylferrocene-p-nitrobenzoyl hydrazone (FDNBAH), and p-toluenesulfonic acid 1,1'-ferrocenediyldiethylidene dihydrazide (TFDD) were found to be bonding agents as well as burning-rate modifiers for the ammonium perchlorate + hydroxy-terminated polybutadiene system. The tensile strength and percentage elongation significantly increased in the presence of these bonding agents (except FDBAH). The bonding agents generally did not adversely affect the slurry viscosity during processing. The bonding sites were located by infrared spectroscopy, supported by determination of the dissolution kinetics of the bonding agents and scanning electron microscopy. The bonding agents did not undergo any side-reactions with the curing agents.

Optical absorption and photoluminescence studies of Nd3 doped alkali boro germanate glasses

Optical absorption and photoluminescence studies have been carried out at room temperature in 25 R2O-25 GeO2-49.5 B2O3-0.5 Nd2O3 glass systems, (Composition in mol%, R= Li, Na, K and Rb). Judd Ofelt Intensity parameters and other parameters like Racah (E-1, E-2 and E-3), Slater-Condon-Shortley (F-2, F-4 and F-6) Spin-Orbit Coupling (xi(4f)) and Configuration Interaction (alpha,beta and gamma) for Nd3+ ion in the glass system are calculated. The variation of the 02 parameters are interpreted in terms of the covalency of the RE ion in the glass matrix. Further the hypersensitive transition I-4(9/2) -> (4)G(5/2), (2)G(7/2) is analyzed with respect to the intensity ratio I-L/I-S and is found to be dependent on the type of alkali in the glass matrix. The Photoluminescence studies do not show any appreciable shift in the peak emission wavelength of the F-4(3/2) to I-4(11/2) transition with the change in alkali type. (C) 2010 Elsevier B.V. All rights reserved.

Electrical switching studies on Ge-Te-Tl chalcogenide glasses: Effect of thallium on the composition dependence of switching voltages

Bulk Ge(17)Te83_,JI glasses (05x.5_13), have been found to exhibit memory type electrical switching. The switching voltages (also known as threshold voltage V-th) of Ge17Te83-xTlx glasses are found to decrease with increasing thallium content. The rate of decrease of Vtry is greater at lower concentrations and \textbackslashid, falls at a slower rate for higher thallium concentrations (x 6). The addition of thallium to the Ge-Te network fragments the covalent network and introduces ionic nature to it; the reduction in network connectivity leads to the decrease in switching voltages with thallium content. The decrease in the glass transition temperatures of Ge17Te83-xTlx glasses with increasing thallium concentration supports the idea of decrease in network connectivity with TI addition. The more metallic nature of TI also contributes to the observed reduction in the switching voltages of Ge17Te83-xTlx glasses with TI content. Further, there is an interesting correlation seen between the threshold voltage V-th and the average bond energy, as a function of TI content. In addition, the switching voltages of Ge17Te83-xTlx glasses have been found to decrease with sample thickness almost linearly. The set-reset studies indicate that the Ge17Te83-xTl2 sample can be switched for more than 10 cycles, whereas other glasses could not be reset beyond two switching cycles. (C) 2010 Elsevier B.V. All rights reserved.

Preparation, Structural, and Electrical Studies of Polyaniline/ZnFe2O4 Nanocomposites

Polyaniline/ZnFe2O4 nanocomposites were synthesized by a simple and inexpensive one-step in situ polymerization method in the presence of ZnFe2O4 nanoparticles. The structural, morphological, and electrical properties of the samples were characterized by wide angle X-ray diffraction (WAXD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). WAXD and SEM revealed the formation of polyaniline/ZnFe2O4 nanocomposites. Infrared spectroscopy indicated that there was some interaction between the ZnFe2O4 nanoparticles and polyaniline. The dc electrical conductivity measurements were carried in the temperature range of 80 to 300 K. With increase in the doping concentration of ZnFe2O4, the conductivity of the nanocomposites found to be decreasing from 5.15 to 0.92 Scm(-1) and the temperature dependent resistivity follows ln rho(T) similar to T-1/2 behavior. The nanocomposites (80 wt % of ZnFe2O4) show a more negative magnetoresistance compared with that of pure polyaniline (PANI). These results suggest that the interaction between the polymer matrix PANI and zinc nanoparticles take place in these nanocomposites. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 120: 2856-2862, 2011

Mechanistic studies on the effect of ferrocene bonding agents in composite solid propellents

Five compounds, viz. 1,1'-ferrocenediyldiethylidene bis(thiocarbonohydrazide) (DAFT), 1,1-diacetylferrocene disemicarbazone (DAFS), 1,1-diacetylferrocenebenzoyl hydrazone (FDBAH), 1,1-diacetylferrocene-p-nitrobenzoyl hydrazone (FDNBAH), and p-tolenesulfonic acid, 1,1'-ferrocenediyldiethylidene dihydrazide (TFDD) were found to be bonding agents as well as burning-rate modifiers for the ammonium perchlorate + hydroxy-terminated polybutadiene system. The tensile strength and percentage elongation significantly increased in the presence of these bonding agents (except FDBAH). The bonding agents generally did not adversely affect the slurry viscosity during processing. The bonding sites were located by infrared spectroscopy, supported by determination of the dissolution kinetics of the bonding agents and scanning electron microscopy. The bonding agents did not undergo any side-reactions with the curing agents.

Kinetic evolution studies of silver nanoparticles in a bio-based green synthesis process

Silver nanoparticles are being extensively studied due to their widespread applications and unique properties. In the present study, the growth kinetics of silver nanoparticles as synthesized on reduction of silver nitrate solution by aqueous extract of Azadirachta indica leaves was investigated. The formation of silver nanoparticles was preliminarily monitored by measuring the absorption maxima at different time intervals after adding the reducing agent to the silver salt solution (0.5, 1, 1.5, 2, 2.5, 3, 3.5 and 4 h). At different time points characterization studies were conducted using X-ray diffraction studies, FT-IR techniques, zeta potential studies and transmission electron microscopy. The total available silver in the reaction medium was determined at different durations using ICP-OES. The changes in reduction potential in the medium were also monitored using potentiometric analysis. The results confirm a definite change in the medium pertaining to formation of the stable nanoparticles after 2 h, and a significant increase in the agglomeration tendency after 4 h of interaction. The growth kinetic data of the nanoparticles till 3.5 h was found to fit the LSW model confirming diffusion limited growth. (C) 2011 Elsevier B.V. All rights reserved.

Reaction of normal and pseudo 2-formylbenzenesulfonyl chlorides with amines:experimental and theoretical studies on the structure of 2-formyl benzenesulfonamides in solid, solution and gas phases

The reaction of 2-formylbenzenesulfonyl chloride 1 and its pseudo isomer 2 with primary amines give either the corresponding sulfonamido Schiff bases or the corresponding 2-formylbenzenesulfonamide depending on the concentration of the amine used. The derivatives exist as an equilibrium mixture of the corresponding sulfonamide and 2-alkyl-3-hydroxy(or 3-aminoalkyl)-benzisothiazole-1,1-dioxide. Spectroscopic studies suggest that 2-formylbenzenesulfonamides exist as benzisothiazole-1,1-dioxides in the solid state, as a mixture of 2-formylbenzenesulfonamide and the corresponding benzisothiazole-1,1-dioxide in solution and as 2-formyl-benzenesulfonamides in the gas phase.

Synthesis and studies on pyridinium pentafluorozirconate and pyridinium oxotetrafluoroniobate

Pyridinium pentafluorozirconate, (C5H5NH)ZrF5, and pyridinium oxotetrafluoroniobate, (CH5NH)NbOF4, have been synthesised by the reaction of pyridinium poly(hydrogen fluoride), PPHF, with ZrOCl2 and Nb2O5, respectively. These new complexes have been characterised by chemical analysis, thermal analysis, X-ray diffraction and infrared spectra.

Time-resolved fluorescence studies on covalently linked porphyrin�nitroarene complexes. Conformational control of photoinduced electron transfer reactions

Time-resolved fluorescence studies were carried out on a series of free-base and zinc(II) derivatives of meso-tetraphenylporphyrins covalently linked to either 1,3-dinitrobenzene (DNB) or 1,3,5-trinitrobenzene (TNB) acceptor units. These acceptor units were linked at different sites (at the ortho, meta or para positions of one of the phenyl groups of meso-tetraphenylporphyrin) to the donor porphyrins such that the resulting isomeric intramolecular donor-acceptor complexes exhibit different centre-to-centre (ctc) distances and relative orientations. Biexponential fluorescence decay profiles observed for several of these covalently linked complexes were rationalized in terms of the presence of ''closed'' and ''extended'' conformers. Detailed analyses of the fluorescence decay data have provided a comprehensive understanding of the photoinduced electron transfer (PET) reactions occurring in systems containing zinc(II) porphyrin donors. It is observed that although DNB-linked zinc(II) complexes follow the trends predicted for the efficiency of PET with respect to donor-acceptor distance, the TNB-linked zinc(II) porphyrins exhibit a behaviour which is dictated by steric effects. Similarly, although the thermodynamic criteria predict a greater efficiency of charge separation in TNB-linked complexes compared with DNB-linked complexes, the reverse trend observed has been attributed to orientational effects. In the complexes containing free-base porphyrin donors, PET is expected to be less efficient from a thermodynamic viewpoint. In a few of these cases, fluorescence quenching seems to occur by parallel mechanisms other than PET.