Polymerization of pyrrole and processing of the resulting polypyrrole as blends with plasticised PVC

Polypyrrole was synthesized by chemical oxidation of pyrrole in water containing various sulphonic acids like toluene sulphonic acid (TSA), sulphosalicylic acid (SSA), and camphor sulphonic acid (CSA), as well as a combination of each sulphonic acid with sodium dodecyl benzene sulphonate (NaDBS) to investigate the effect of doping on conductivity, yield, and processability of the conducting polymer. Free-standing blend films of polypyrrole and plasticized polyvinyl chloride (PVC) were obtained by casting an homogeneous suspension of the two polymers in tetrahydrofuran. The maximum conductivity of the blend film is similar to 0.3 S/cm, corresponding to a weight fraction of 0.16 w/w polypyrrole. The blend film is semiconducting in the range 300-10 K. A TG-DTA scan indicates the blend film to be amorphous with a stepwise decomposition process similar to pristine PVC. The choice of a dual dopant system during synthesis and the plasticised polymer during subsequent processing were keys to obtaining homogeneous high-quality films. (C) 2001 John Wiley & Sons, Inc.

Synthesis and Properties of a Novel (Main-Chain)– (Side-Chain) Polymeric Peroxide

A novel (main-chain)-(side-chain) vinyl polyperoxide, poly(dipentene peroxide)(PDP), an alternating copolymer of dipentene (DP) and oxygen, has been synthesized by thermal oxidative polymerization of DP. The PDP was characterized by 1H NMR, 13C NMR, FTIR, DSC, TGA, and EI-MS studies. The overall activation energies of the degradation from Kissinger’s method were 28 and 33 kcal/mol, respectively, for the endocyclic and acyclic peroxide units. The side-chain peroxy groups were found to be thermally more stable than the main chain. Above 45°C the rate of polymerization increases sharply at a particular instant showing an “autoacceleration” with the formation of knee point. The kinetics of autoacceleration has been studied at various temperatures (45–70°C) and pressures (50–250 psi). © 2000 John Wiley&Sons, Inc. J Appl Polym Sci 79: 1549–1555, 2001

Synthesis, structural characterization, thermal studies and chain dynamics of poly(methacrylonitrile peroxide) by NMR spectroscopy

Poly(methacrylonitrile peroxide) (PMNP) has been synthesized from methacrylonitrile by free radical initiated oxidative polymerization and characterized by different spectroscopic methods. NMR spectroscopy confirmed the alternating copolymer structure with labile peroxy bonds in the main chain. The extreme instability of PMNP was noted from FTIR spectroscopy. Thermal degradation studies by using differential scanning calorimetry and thermogravimetry have revealed that PMNP degrades highly exothermically and the heat of degradation, 42.5 kcal mol−1, is of the same order as that reported for other vinyl polyperoxides. Mass spectral fragmentation pattern under electron impact (EI) condition has also been investigated. The mechanism of the primary exothermic degradation has been substantiated by thermochemical calculations. The chain dynamics of the polyperoxide chain has been studied by means of 13C spin–lattice relaxation times (T1) of the main chain as well as the side chain carbons. The temperature dependence of the spin–lattice relaxation times shows that the PMNP is more flexible compared to the analogous poly(styrene peroxide).

Toward a Mean Field Formulation of the Babcock-Leighton Type Solar Dynamo. I. α-Coefficient versus Durney's Double-Ring Approach

We develop a model of the solar dynamo in which, on the one hand, we follow the Babcock-Leighton approach to include surface processes, such as the production of poloidal field from the decay of active regions, and, on the other hand, we attempt to develop a mean field theory that can be studied in quantitative detail. One of the main challenges in developing such models is to treat the buoyant rise of the toroidal field and the production of poloidal field from it near the surface. A previous paper by Choudhuri, Schüssler, & Dikpati in 1995 did not incorporate buoyancy. We extend this model by two contrasting methods. In one method, we incorporate the generation of the poloidal field near the solar surface by Durney's procedure of double-ring eruption. In the second method, the poloidal field generation is treated by a positive α-effect concentrated near the solar surface coupled with an algorithm for handling buoyancy. The two methods are found to give qualitatively similar results.

Variable temperature x-ray crystal structure analysis of a type I langbeinite: Rb2Cd2(SO4)(3)

The structure of a type I langbeinite, Rb2Cd2(SO4)(3), displays three different phases, cubic with a = 10.378(5) Angstrom (space group P2(1)3) at room temperature, monoclinic at 120 K with a = 10.328(3), b = 10.322(3), c = 10.325(3) Angstrom, beta = 89.975(1)degrees (space group P2(1)), and orthorhombic at 85 K with a = 10.319(2), b = 10.321(2), c = 10.320(2) Angstrom (space group P2(1)2(1)2(1)), respectively. Precise single-crystal analyses of these phases indicate that Rb2Cd2(SO4)(3) distorts initially from cubic to monoclinic upon cooling followed by a significant reorientation of the SO4 tetrahedra, resulting in an orthorhombic symmetry upon further cooling. The three structures have been established unequivocally using the same crystal. There is no indication of the formation of an intermediate triclinic phase or any lattice disorder as conjectured in several earlier reports on compounds belonging to the type I langbeinite. The bond valence sum analyses of the coordination around the Rb sites indicate asymmetry in the bond strengths which could be the driving force of the ferroelectric behavior in these materials.

A new type II restriction endonuclease, OfoI from nonheterocystous cyanobacterium Oscillatoria foreaui

Although restriction enzymes are widely distributed in nature, many bacterial genera are yet to be explored for the presence of this important class of enzymes. We have purified and characterized a new type II restriction endonuclease, OfoI from a nonheterocyst cyanobacterium Oscillatoria foreaui. The recognition sequence has been determined by primer extension analysis. The purified enzyme OfoI recognizes and cleaves the palindromic hexanucleotide 5'-Cdown arrowYCGRG-3', generating 5'-protruding ends.

Efficient syntheses of benzothiazepines as antagonists for the mitochondrial sodium-calcium exchanger: Potential therapeutics for type II diabetes

Type II diabetes mellitus is a chronic metabolic disorder that can lead to serious cardiovascular, renal, neurologic, and retinal complications. While several drugs are currently prescribed to treat type II diabetes, their efficacy is limited by mechanism-related side effects (weight gain, hypoglycemia, gastrointestinal distress), inadequate efficacy for use as monotherapy, and the development of tolerance to the agents. Consequently, combination therapies are frequently employed to effectively regulate blood glucose levels. We have focused on the mitochondrial sodium-calcium exchanger (mNCE) as a novel target for diabetes drug discovery. We have proposed that inhibition of the mNCE can be used to regulate calcium flux across the mitochondrial membrane, thereby enhancing mitochondrial oxidative metabolism, which in turn enhances glucose-stimulated insulin secretion (GSIS) in the pancreatic beta-cell. In this paper, we report the facile synthesis of benzothiazepines and derivatives by S-alkylation using 2-aminobenzhydrols. The syntheses of other bicyclic analogues based on benzothiazepine, benzothiazecine, benzodiazecine, and benzodiazepine templates are also described. These compounds have been evaluated for their inhibition of mNCE activity, and the results from the structure-activity relationship (SAR) studies are discussed.

Electrical properties of ferroelectric YMnO3 films deposited on n-type Si(111) substrates

YMnO3 thin films were grown on an n-type Si substrate by nebulized spray pyrolysis in the metal-ferroelectric-semiconductor (MFS) configuration. The capacitance-voltage characteristics of the film in the MFS structure exhibit hysteretic behaviour consistent with the polarization charge switching direction, with the memory window decreasing with increase in temperature. The density of the interface states decreases with increasing annealing temperature. Mapping of the silicon energy band gap with the interface states has been carried out. The leakage current, measured in the accumulation region, is lower in well-crystallized thin films and obeys a space-charge limited conduction mechanism. The calculated activation energy from the dc leakage current characteristics of the Arrhenius plot reveals that the activation energy corresponds to oxygen vacancy motion.

Ternary copper(II) complexes of thiosemicarbazones and heterocyclic bases showing N3OS coordination as models for the type-2 centers of copper monooxygenases

Six ternary copper(II) complexes of general formulation [CuLB] (1-6), where L is dianionic ONS-donor thiosemicarbazones derived from the condensation of salicylaldehyde with thiosemicarbazides and B is NN-donor heterocyclic bases like 2,2'-bipyridine, 1,10-phenanthroline and 2,9-dimethyl-1,10-phenanthroline, are prepared from a reaction of copper(II) acetate hydrate with the heterocyclic base (B) and the thiosemicarbazone (H2L) in MeOH, and structurally characterized by X-ray diffraction technique. Crystal structures of the complexes display a distorted square-pyramidal (4 + 1) coordination geometry having the ONS-donor thiosemicarbazone bonded at the basal plane. The chelating heterocyclic bases exhibit axial-equatorial mode of bonding. The complexes are one-electron paramagnetic and they show axial X-band EPR spectra in DMF-toluene glass at 77 K giving g(parallel to)(A(parallel to)) and g(perpendicular to) values of similar to2.2 (175 x 10(-4) cm(-1)) and similar to2.0 indicating a {d(x2-y2)}(1) ground state. The complexes show a d-d band near 570 nm and a charge transfer band near 400 nm in DMF. The complexes are redox active and exhibit a quasireversible Cu(II)-Cu(I) couple in DMF-0.1 M tetrabutylammonium perchlorate near 0.1 V vs. SCE. They are catalytically active in the oxidation of ascorbic acid in presence of dioxygen. The complexes with a CuN3OS coordination model the ascorbate oxidation property of dopamine beta-hydroxylase and peptidylglycine a-hydroxylating monooxygeanase. (C) 2003 Elsevier Science B.V. All rights reserved.

The role of defects in carrier type reversal in bismuth doped Ge-Se glasses by photoluminescence spectroscopy

The role played by defects in bringing out n-type conduction in Ge20Se80-xBix and Ge20Se70-xBixTe10 glasses is using investigated photoluminescence (PL) spectroscopy. It was found that for both the systems, the compositions at lower Bi content exhibit luminescence with fine features associated while the compositions that show n-type conduction do not exhibit luminescence. The identification of the associated fine features, carried out by deconvoluting the experimental spectra, reveals that Bi addition brings out a relative diminishing in D+ defects as compared to D- ones. The study gives an overall indication for the role played by native defects in bringing out n-type conduction in Bi-doped glasses.

Synthesis of new (Bi, La)(3)MSb(2)O(11) phases (M = Cr, Mn, Fe) with KSbO(3)-type structure and their magnetic and photocatalytic properties

Synthesis and structure of new (Bi, La)(3)MSb(2)O(11) phases (M = Cr, Mn, Fe) are reported in conjunction with their magnetic and photocatalytic properties. XRD refinements reflect that Bi(3)CrSb(2)O(11), Bi(2)LaCrSb(2)O(11), Bi(2)LaMnSb(2)O(11) and Bi(2)LaFeSb(2)O(11) adopt KSbO(3)-type structure (space group, Pn (3) over bar). The structure can be described through three interpenetrating networks where the first is the (M/Sb)O(6) octahedral network and other two are the identical networks having Bi(6)O(4) composition. The magnetic measurements on Bi(2)LaCrSb(2)O(11) and Bi(2)LaMnSb(2)O(11) show paramagnetic behaviour with magnetic moments close to the expected spin only magnetic moments of Cr(+3) and Mn(+3). The UV-Visible diffuse reflectance spectra are broad and indicate that these materials possess a bandgap of similar to 2 eV. The photocatalytic activity of these materials has been investigated by degrading Malachite Green (MG) under exposure to UV light.

Aromatic, microporous polymer networks with high surface area generated in Friedel-Crafts-type polycondensations

A series of novel, microporous polymer networks (MPNs) have been generated in a simple, acid catalysed Friedel-Crafts-type self-condensation of A(2)B(2)- and A(2)B(4)-type fluorenone monomers. Two A2B4-type monomers with 2,7-bis(N, N-diphenylamino) A or 2,7-bis [4-(N, N-diphenylamino) phenyl] D substitution of the fluorenone cores lead to MPNs with high S(BET) surface areas of up to 1400 m(2) g(-1). Two MPNs made of binary monomer mixtures showed the highest Brunauer-Emmett-Teller (BET) surface areas S(BET) of our series (SBET of up to 1800 m(2) g(-1)) after washing the powdery samples with supercritical carbon dioxide. Total pore volumes of up to 1.6 cm(3) g(-1) have been detected. It is observed that the substitution pattern of the monomers is strongly influencing the resulting physicochemical properties of the microporous polymer networks (MPNs).