Vibrational Dynamics and Heat Capacity of Poly(3-methylthiophene): A Conducting Polymer

Using the Urey–Bradley force field and Wilson's GF matrix method as modified by Higgs, normal modes of vibration and their dispersions in poly(3-methylthiophene) have been obtained. They provide a detailed interpretation of its I.R. and Raman spectra. Characteristic features of the dispersion curves, such as regions of high density-of-states, repulsion, and character mixing of dispersive modes, are discussed. Predictive values of the heat capacity as a function of temperature have been calculated.     

Efficient and Convenient Polyethylene Glycol (PEG)‐Mediated Synthesis of Spiro‐oxindoles

Polyethylene glycol (PEG) has been reported as an efficient and convenient medium for the three‐component synthesis for spiro‐oxindole.     

Polydimethylsiloxane–cristobalite composite adhesive system for aerospace applications

The effect of phase‐pure cristobalite (a high temperature crystalline polymorph of silica) on the adhesive characteristics of hydroxyl terminated polydimethylsiloxane (PDMS) was studied. The potential advantages of PDMS/cristobalite composite system as an adhesive for aerospace applications are also discussed. A PDMS/cristobalite composite adhesive system containing different filler contents (0–46 volume percentage, vol%) was prepared. The filler material, phase‐pure cristobalite, was synthesized by the pyrolysis of fused silica at 1400°C. The mechanical, rheological, and thermal characteristics of the composites were studied. A high yield stress (0.151 Pa), shear‐thinning index (1.051), and fast recovery rate were observed for ～34 vol% cristobalite loading, which indicate that PDMS retains its excellent adhesive and flow characteristics even at high filler loading with enhanced mechanical characteristics. Thermal analysis shows the onset of degradation of PDMS shifts to higher temperatures, 372–438°C and 317–417°C in nitrogen and air atmosphere respectively, which shows excellent thermal stability. The residual component yields after thermal degradation of PDMS/cristobalite composite system in nitrogen and air atmosphere show different degradation mechanisms. Copyright © 2008 John Wiley & Sons, Ltd.     

The loss of carbon dioxide from activated perbenzoate anions in the gas phase: unimolecular rearrangement via epoxidation of the benzene ring

The unimolecular reactivities of a range of perbenzoate anions (X-C6H5CO3-), including the perbenzoate anion itself (X = H), nitroperbenzoates (X = para-, meta-, ortho-NO2), and methoxyperbenzoates (X = para-, meta-OCH3) were investigated in the gas phase by electrospray ionization tandem mass spectrometry. The collision-induced dissociation mass spectra of these compounds reveal product ions consistent with a major loss of carbon dioxide requiring unimolecular rearrangement of the perbenzoate anion prior to fragmentation. Isotopic labeling of the perbenzoate anion supports rearrangement via an initial nucleophilic aromatic substitution at the ortho carbon of the benzene ring, while data from substituted perbenzoates indicate that nucleophilic attack at the ipso carbon can be induced in the presence of electron-withdrawing moieties at the ortho and para positions. Electronic structure calculations carried out at the B3LYP/6-311++G(d,p) level of theory reveal two competing reaction pathways for decarboxylation of perbenzoate anions via initial nucleophilic substitution at the ortho and ipso positions, respectively. Somewhat surprisingly, however, the computational data indicate that the reaction proceeds in both instances via epoxidation of the benzene ring with decarboxylation resulting--at least initially--in the formation of oxepin or benzene oxide anions rather than the energetically favored phenoxide anion. As such, this novel rearrangement of perbenzoate anions provides an intriguing new pathway for epoxidation of the usually inert benzene ring.     

Quaternionic Formulation of Supersymmetric Quantum Mechanics

Quaternionic formulation of supersymmetric quantum mechanics has been developed consistently in terms of Hamiltonians, super partner Hamiltonians, and supercharges for free particle and interacting field in one and three dimensions. Supercharges, super partner Hamiltonians and energy eigenvalues are discussed and it has been shown that the results are consistent with the results of quantum mechanics.     

New bis-macrocyclic complexes with transition metal ions

Template condensation of benzidine, formaldehyde, ethylenediamine or 1,3-diaminopropane, metal salt and 1-phenyl-1,3-butanedione or 2,3-butanedione in a 1:4:2:2 molar ratio results in the formation of two new series of binuclear pentaaza macrocyclic complexes: dichloro[1,1-phenylbis(7-methyl-9-phenyl-1,3,6,10,13-pentaazacyclotetradeca-6,9-diene) metal(II)], [M₂LCl₄] (M = Co^II, Cu^II, Fe^III and Zn^II) and dichloro[1,1-phenylbis(8,9-dimethyl-1,3,7,10,14-pentaazacyclopentadeca-7,9-diene) metal(II)], [M₂LCl₄] (M = Ni^II, Co^II, Cu^II and Cd^II). Both series were characterized by i.r., ¹H-n.m.r., u.v.–vis. spectral studies, conductivity and magnetic susceptibility measurements.     

Correlation analysis of structure and reactivity in the oxidation of substituted benzyl alcohols by bis(2,2′-bipyridyl) copper(II) permanganate

The oxidation of substituted benzyl alcohols by bis(2,2′-bipyridyl) copper(II) permanganate (BBCP), leading to the corresponding benzaldehydes is first-order with respect to BBCP. Michaelis-Menten type kinetics were observed with respect to the alcohols. The oxidation of a,a-dideuteriobenzyl alcohol indicated the presence of a substantial kinetic isotope effect. The rates of oxidation of meta- and para-substituted benzyl alcohols were correlated in terms of Charton's triparametric LDR equation whereas ortho- substituted benzyl alcohols were correlated with a four parametric LDRS equation. The results of correlation analyses point to an electron-deficient reaction center in the transition state. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 9–16, 1997.     

Protective Role of Quercetin in Carbon Tetrachloride Induced Toxicity in Rat Brain: Biochemical,Spectrophotometric Assays and Computational Approach

Carbon tetrachloride (CCL4) induces oxidative stress by free radical toxicities, inflammation, and neurotoxicity. Quercetin (Q), on the other hand, has a role as anti-inflammatory, antioxidant, antibacterial, and free radical-scavenging. This study explored protection given by quercetin against CCL4 induced neurotoxicity in rats at given concentrations. Male Wistar rats were divided into four groups Group C: control group; Group CCL4: given a single oral dose of 1 mL/kg bw CCL4; Group Q: given a single i.p injection of 100 mg/kg bw quercetin; and Group Q + CCL4: given a single i.p injection of 100 mg/kg bw quercetin before two hours of a single oral dose of 1 mL/kg bw CCL4. The results from brain-to-body weight ratio, morphology, lipid peroxidation, brain urea, ascorbic acid, reduced glutathione, sodium, and enzyme alterations (aspartate aminotransferase (AST), alanine aminotransferase (ALT), catalase, and superoxide dismutase) suggested alterations by CCL4 and a significant reversal of these parameters by quercetin. In silico analysis of quercetin with various proteins was conducted to understand the molecular mechanism of its protection. The results identified by BzScore4 D showed moderate binding between quercetin and the following receptors: glucocorticoids, estrogen beta, and androgens and weak binding between quercetin and the following proteins: estrogen alpha, Peroxisome proliferator-activated receptors (PPARγ), Herg k+ channel, Liver x, mineralocorticoid, progesterone, Thyroid α, and Thyroid β. Three-dimensional/four-dimensional visualization of binding modes of quercetin with glucocorticoids, estrogen beta, and androgen receptors was performed. Based on the results, a possible mechanism is hypothesized for quercetin protection against CCL4 toxicity in the rat brain.