Synthesis,spectral analysis,and <Emphasis Type="Italic">in vitro</Emphasis> microbiological evaluation of ethyl 7,9-diaryl-1, 4-diazaspiro[4.5]dec-9-ene-6- carboxylates as a new class of antibacterial and antifungal agents

A series of novel ethyl 7,9-diaryl-1,4-diazaspiro[4.5]dec-9-ene-6-carboxylates was synthesized by the reaction of ethyl 4,6-diaryl-2-oxocyclohex-3-ene-1-carboxylates with ethylenediamine in the presence of p-toluenesulfonic acid without a solvent under focused microwave irradiation. The title compounds were screened for their antimicrobial activities against a spectrum of clinically isolated microorganisms.     

Adsorption of collagen onto single walled carbon nanotubes: a molecular dynamics investigation

Classical molecular dynamics (MD) simulation has been carried out to understand the adsorption of collagen like peptides onto single walled carbon nanotubes (CNT) in an aqueous environment. It is observed that the triple helical structure of all the model collagen like peptides (CPs) has been unaltered upon adsorption onto CNT. The model CPs do not wrap around the CNT, however, the axis of the triple helix subtends a cross angle with respect to the axis of the CNT. The interaction between the CPs and CNT as well as that between the CPs and water molecules was observed by MD simulation snapshots. The inherent nature of the interaction of CPs with CNT facilitates the penetration of CPs into the water/CNT interface. During this process, water molecules trapped between the CPs and CNT are appreciably displaced. Although, hydrophobic-hydrophobic interaction is crucial for the interaction, the role of πR (R = OH and NH(2)) interactions are also observed from the geometrical parameters. The sequence specific interaction of CPs with CNT is evident from the results. It is found that the length of the CNT, curvature of the CNT and length of the CPs do not significantly influence interaction between the two systems. Overall the findings provide important information for the development of nanocomposite materials from collagen and CNT.     

Preparation,structure, and magnetic properties of isostructural La3MAlS7 and La3MFeS7 (M = Mg,Mn, Fe,Co, Ni,or Zn)

A series of quaternary metal sulfides of the general formula La₃MM′S₇ (M = Mn, Fe, Co; M′ = Al and M = Mg, Mn, Fe, Co, Ni; M′ = Fe) consisting of linear chains of face shared MS₆ octahedra and isolated M′S₄ tetrahedra has been prepared and studied. The aluminium compounds La₃MAlS₇ (M = Mn, Fe, Co) exhibit linear chain antiferromagnetism. Magnetic behavior of other La₃MFeS₇ sulfides has been examined in detail. The magnetic susceptibility of La₃MgFeS₇ shows that tetrahedral site Fe³⁺ undergoes a transition from $\text{S =}\text{5}\text{2}$ to S = 2 spin state around 150 K.     

Kinetics and mechanism of oxidation of some para-, meta-, and ortho-substituted ethyl S-phenylmercaptoacetates by chloramine-B(CAB)

The kinetics of oxidation of ethyl S-phenylmercapto acetate and several para-, meta-, and ortho-substituted ethyl S-phenylmercaptoacetates by chloramine-B have been studied in 50% (V/V) aqueous ethanol medium containing phosphate buffer. This oxidation is of first order with respect to substrate and zero order with respect to oxidant. A catalytic effect of mercury is observed and the order with respect to mercury is fractional (0.74). The increase in pH decreases the rate of oxidation and the order with respect to H⁺ is 0.05. In general electron-releasing substituents accelerate the rate while electron-attracting groups retard the rate. A good correlation is found to exist between log k ₁ and Hammett constants. Susceptibility of the reaction to the steric effect of ortho-substituents has been analyzed in the light of application of Taft's steric energy parameters. © John Wiley & Sons, Inc.     

Topotaxy in the oxidation of valentinite,Sb2O3, to cervantite,Sb2O4

The oxidation of orthorhombic Sb₂O₃, valentinite, to orthorhombic Sb₂O₄, cervantite, has been shown by single crystal x-ray diffraction techniques to be a topotactic reaction. The orientation relationships between the two lattices have been determined by making use of a hybrid crystal. It has been found that the individual axes in the two oxides are parallel. The two crystal structures have been compared in the appropriate orientation and their close similarity has been established. The shifts of the individual atoms in valentinite during the process of oxidation have been calculated to be not more than 0·6 Å. It has been established that the reduction of cervantite to valentinite also takes place topotactically.     

Synthesis, characterization, and growth rates of germanium silicalite-1 grown from clear solutions

The synthesis, characterization, and growth of Ge-silicalite-1 from optically clear solutions are reported. Ge-silicalite-1 is readily formed from optically clear solutions of TEOS, TPAOH, water, and a germanium source at 368 K. X-ray fluorescence (XRF) is used to determine the Si/Ge ratio and indicates that germanium inclusion is typically 30-50% of that in the actual mixture. Adsorption, power X-ray diffraction (PXRD), and 29Si NMR indicate the materials are crystalline and microporous. In situ small-angle X-ray scattering (SAXS) is applied to investigate the influences of germanium source (GeO2 and Ge(OC2H5)4) and content (Si/Ge 100:5) on the growth of Ge-silicalite-1 from clear solutions at 368 K. The in situ SAXS investigations show that for solutions with Si/Ge ratios of 100, 50, and 25 using Ge(OC2H5)4 the induction periods are approximately 6 h and the particle growth rates are 1.82 +/- 0.04, 2.52 +/- 0.13, and 2.85 +/- 0.08 nm/h, respectively, at 368 K, compared to those of pure silicalite-1 (6 h induction period, 1.93 +/- 0.1 nm/h growth rate). Further increasing the Si/Ge ratio to 15 and 5 shortens the induction period to approximately 4.5 h, and the growth rates are 3.07 +/- 0.16 and 2.05 +/- 0.10 nm/h, respectively, indicating the Si/Ge ratio that maximizes Ge-silicalite-1 growth is between 25 and 15. Similar trends are obtained with germanium oxide; however, the growth rates are all consistently larger than those for syntheses with Ge(OC2H5)4. The results indicate that Ge-silicalite-1 growth rates in the presence of germanium are increased as compared to those of pure-silica syntheses.     

Bio-energetic impairment in human calf muscle in thyroid disorders: a P MRS study

Mitochondrial metabolism particularly oxidative phosphorylation is greatly influenced by thyroid hormones. Earlier studies have described neuromuscular symptoms as well as impaired muscle metabolism in hypothyroid and hyperthyroid patients. In this study, we intend to look in to the muscle bioenergetics including phosphocreatine recovery kinetics based oxidative metabolism in thyroid dysfunction using in vivo ³¹P nuclear magnetic resonance spectroscopy (MRS). ³¹P MRS was carried out at resting state on 32 hypothyroid, 10 hyperthyroid patients and 25 control subjects. Nine out of 32 hypothyroid patients and 17 out of 25 control subjects under went exercise protocol for oxidative metabolism study and performed plantar flexion exercise while lying supine in 1.5 T magnetic resonance scanner using custom built exercise device. MRS measurements of inorganic phosphate (Pi), phosphocreatine (PCr), phosphodiesters (PDE) and adenosine triphosphate (ATP) of the calf muscle were acquired during rest, exercise and recovery phase. PCr recovery rate constant (k_PCr) and oxidative capacity were calculated by monoexponential fit of PCr versus time (t) at the beginning of recovery. During resting condition in hypothyroid patients, PCr/Pi ratio was reduced whereas PDE/ATP and Pi/ATP were increased. However, in case of hyperthyroidism, an increased PCr/Pi ratio and reduced PDE/ATP and Pi/ATP were observed. The results confirmed differential energy status of the muscle due to increased or decreased levels of thyroid hormone. Our results also demonstrate reduced oxidative metabolism in hypothyroid patients based on PCr recovery kinetics. PCr recovery kinetics study after exercise revealed decreased PCr recovery rate constant (k_PCr) in hypothyroid patients compared to controls that resulted in decrease in oxidative capacity of muscle by 50% in hypothyroids. These findings are consistent with a defect of high energy phosphate mitochondrial metabolism in thyroid dysfunction.     

Hydrated Clay for Catalyst Removal in Copper Mediated Atom Transfer Radical Polymerization

A simple method has been described to remove catalyst from the copper mediated atom transfer radical polymerization (ATRP) of benzyl methacrylate and methyl methacrylate in anisole at 25 °C using hydrated natural clay (sodium montmorillonite, Na‐clay). The method consists of (1) addition of hydrated clay (Cu^I/clay ≈ 5 wt.‐%) either during or after the polymerization, (2) oxidation of catalyst complex by exposing the terminated reaction mixture in air, and (3) filtration to obtain catalyst free polymer solution. A strong coordination of CuBr‐ligand complex onto hydrated clay (10 wt.‐% < H₂O/clay < 30 wt.‐%) upon oxidation resulted in polymers with no or insignificant residual catalyst (<1.74 ppm), as determined by UV‐vis and atomic absorption spectroscopy. The recovered clay exhibited expanded intercalary layers and absence of polymer within it.