Selective oxidation of olefins and aromatic alcohols with tert‐butylhydroperoxide catalyzed by polymer‐anchored transition‐metal complexes

Three polymer‐anchored metal complexes (Co, Cu, and Pd) were synthesized and characterized. The catalytic performance of these complexes was tested for the oxidation of olefins and aromatic alcohols. These complexes showed excellent catalytic activity and high selectivity. These complexes selectively gave epoxides and aldehydes from olefins and alcohols, respectively. Individually, the effect of various solvents, oxidants, substrate oxidant molar ratios, temperatures, and catalyst amounts for the oxidation of cyclohexene and benzyl alcohol were studied. Under optimized reaction conditions, 96, 81, and 71% conversions of cyclohexene and 86, 79, and 73% conversions of benzyl alcohol were obtained with Co(II), Cu(II), and Pd(II) catalysts, respectively. The catalytic results reveal that these complexes could be recycled more than five times without much loss in activity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Non-aqueous titration of the acidic groups in coals: a warning!

Non-aqueous potentiometric titration using ethylenediamine as a solvent and sodium aminoethoxide as a titrant has been shown to be reliable for the estimation of total acidity only when the substrate is completely dissolved in the solvent.     

Synthesis and structure-activity relationship of the isoindolinyl benzisoxazolpiperidines as potent,selective, and orally active human dopamine D4 receptor antagonists

A new class of potent dopamine D(4) antagonists was discovered with selectivity over dopamine D(2) and the alpha-1 adrenoceptor. The lead compound was discovered by screening our compound collection. The structure-activity relationships of substituted isoindoline rings and the chirality about the hydroxymethyl side chain were explored. The isoindoline analogues showed modest differences in potency and selectivity. The S enantiomer proved to be the more potent enantiomer at the D(4) receptor. Several analogues with greater than 100-fold selectivity for D(4) over D(2) and the alpha-1 adrenoreceptor were discovered. Several selective analogues were active in vivo upon oral or intraperitoneal administration. A chiral synthesis starting from either D- or L-O-benzylserine is also described.     

Modelling the Effective Thermal Conductivity in Polydispersed Bed Systems: A Unified Approach using the Linear Packing Theory and Unit Cell Model

A comprehensive, unified approach, using the Linear Packing Theory and Unit Cell Model, is proposed for calculating of the effective thermal conductivity of polydispersed packed beds. In this new approach, the effect of packing density is incorporated by the use of (i) an initial porosity to take into account the packing of mono‐sized particles, and (ii) the packing size ratio as a measure of the particle‐particle interaction. The proposed approach was validated with the experimental measurements of binary and ternary beds. This new approach demonstrates that the effective thermal conductivity of beds composed of polydispersed particles can be simulated for any composition without the need to measure the in situ porosity.     

Synthesis and characterization of electrically conducting copolymer of aniline and o‐bromoaniline using methane sulfonic acid as dopant

Polyaniline (PAN), poly(o‐bromoaniline) (POBA), and poly(aniline‐co‐o‐bromoaniline) (PABA) were synthesized by oxidative coupling. These polymers are protonated by 10–20% methane sulfonic acid (MSA) and 1M HCl. The new polymer bases have greater solubility than that of PAN in common polar organic solvents; PAN–MSA was observed to be the most thermally stable of these polymers. POBA is associated with residual quinoid diimine units as illustrated in the IR and UV‐vis spectra, after reduction with hydrazine dihydrochloride. Both the doping agents cause a downward shift of the quinoid absorption in the IR spectra. MSA‐ and HCl‐doped PAN and PABA polymers exhibit a coil‐like conformation in DMSO, whereas only MSA‐doped PAN and PABA show an “expanded coil‐like” conformation in m‐cresol with a “free carrier tail” above 800 nm in their electronic spectra. XPS spectra indicated the presence of covalent bromine in the POBA and PABA polymers. Bromine retention was greater in the homopolymer as evidenced by the IR studies after aging at 350°C. Compared to HCl, MSA is found to be a more effective dopant, enhancing the conductivity of the copolymers by 10²–10³ times in magnitude. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2662–2669, 2002     

Half-of-the-sites reactivity of F235C {lambda}-repressor: implications for the structure of the whole repressor

A site-directed mutation, F235C, was created at the penultimateresidue of the -repressor. Measurement of dimer–monomerdissociation constant suggested that dimer–monomer dissociationof the mutant repressor is similar to that of the wild-type.Affinity towards a single operator O_R1 is also similar to thatof the wild-type repressor. The mutant repressor gene in a multi-copyplasmid confers immunity towards infection by a cI^- lambda phage,suggesting preservation of functional integrity. Far-UV circulardichroism spectra show no major change in the secondary structure.Fluorescence quenching experiments, however, suggest increasedexposure of some tryptophan residues. The urea denaturationprofile indicates decreased stability of a part of the C-terminaldomain. Under non-denaturing conditions, cysteine-235 showshalf-of-the-sites reactivity, i.e. on average only one out oftwo cysteine-235 residues in the dimer shows reactivity towardssulfhydryl reagents. Fluorescence energy transfer between randomlylabeled donor and acceptor fluorescent probes indicates thatonly one sulfhydryl per dimer is reactive, suggesting true half-of-the-sitesreactivity. The structural role of the C-terminal tail in thewhole repressor dimer is discussed.     

Composite polymeric microsponge-based long-acting gel formulation for topical delivery of mupirocin

Topical delivery of medicaments in a controlled manner is still a promising area of research. Drug-containing dammar gum-ethyl cellulose composite microsponge loaded gel formulation (D-MSPG) was developed for controlled topical delivery of mupirocin. The drug-loaded microsponges (D-MSPs) were formulated by the quasi-emulsion solvent diffusion method and were evaluated for morphology, particle size distribution, entrapment efficiency, thermal properties, and crystallinity. The optimized D-MSPs (entrapment efficiency 91.5 ± 4.0% and particle size of 55.15 ± 2.9 μm) were dispersed in carbopol 934 gel (D-MSPG). The final product was characterized for pH, viscosity, texture, spreadability, consistency, syneresis, in vitro drug release, and ex vivo skin penetration study. A comparative study with marketed formulation was performed. For optimized gel formulation (G4), drug content was 104.19 ± 1.68%, and drug release was 84.19% after 24 h. The pH of the optimized gel was observed to be 6.05 ± 0.04. Viscosity of the optimized gel formulation was found to be 1212.15 ± 434.85 mPa-s at 50 s⁻¹. The steady-state flux (J) in ex vivo skin permeation was observed to be 53.96 μg cm⁻² h⁻¹ and the permeability coefficient was 2.69 cm/h for the optimized gel formulation. According to the findings, the D-MSPG-based formulation strategy can act well to prolong the topical delivery of mupirocin or similar drug molecules.     

A local theory of heating in cross-ply carbon fiber thermoplastic composites by magnetic induction

For joining and repair of continuous fiber thermoplastic composites, induction heating has been viewed a strong candidate. Induction heating employs an applied alternating magnetic field, which induces a rotational emf in a grid of conductive carbon fibers, which are then used to carry resulting currents. In continuous carbon fiber crossply composites the available paths for “eddy current” loops are along the network of conductive carbon fibers. For this to occur, an electrical transfer must take place between crossing fibers in adjacent plies. Tests involving variable thicknesses of interply neat film layers have been performed to provide insight into the mechanisms taking place. These tests indicate that the primary mechanism for heating in such laminates is dielectric losses in the polymeric region between fibers in adjacent planes that form the conductive loop. Therefore, heating is not uniform in such composites despite a uniform magnetic flux. Heating patterns were viewed using liquid crystal materials and E-type thermocouples. Several factors leading to nonhomogeneous thermal distributions have been considered, including current density effects, internal emf cancellation, and rotational field effects. Global and local considerations are addressed, a localized model is proposed, and the corresponding theory is developed qualifying the early results. Additional testing has supported the theory.     

Anisotropy in mechanical and dynamic properties of composites based on carbon fiber filled thermoplastic elastomeric blends of natural rubber and high density polyethylene

The effects of short carbon fibers on static and dynamic properties of thermoplastic elastomeric blends of natural rubber (NR) and high density polyethylene (HDPE) have been studied. Both mechanical and dynamic properties are dependent on fiber concentration. The fiber aspect ratio ranges from 20 to 30. Adhesion between fiber and matrix is evident from the SEM photomicrographs of the failed composites and from variation of relative damping properties. Fiber orientation occurring during processing causes anisotropy in the physical properties. In composites with longitudinally oriented fibers, tensile failure occurs by both fiber pullout and breakage, while in composites with transversely oriented fibers, matrix failure dominates. The incorporation of fibers into the matrix lowers the tan δ_max value, but no change in glass transition temperature is observed.     

Effect of rare earth doping on sol-gel derived PZT thin films

We have studied the effect of rare earth dopants (Nd, Gd and Ce) on the phase formation behavior and electrical properties of sol-gel derived Pb_1.05(Zr_0.53Ti_0.47)O₃ thin films. In all these films the perovskite phase is obtained up to 5 at% doping and beyond that pyrochlore phase was found to coexist with the perovskite phase. Ce and Gd doping(1-2 at%) exhibited improved ferroelectric and dielectric properties as compared to the undoped PZT films. Nd doping (2 at%) was found to be effective to increase the retained switchable polarization of undoped PZT from 63% to 84%. The transition temperature of undoped PZT film was found to be reduced with Nd doping. The Nd doped films also exhibited typical relaxor behavior and a diffuse phase transition, characteristic of the relaxor material. Introduction of Nd into the PZT lattice probably introduces disorder in the B site of ABO₃ lattice which causes the observed relaxor behavior