Sequence analysis and kinetic study of the polymerization of 1,4-bis(hydroxydimethylsilyl)benzene with sir2Cl2

²⁹Si NMR rate studies of the bulk reaction of 1,4-bis(hydroxydimethylsilyl)benzene (BHB) with dichlorodimethylsilane, dichloromethylphenylsilane, and dichlorodiphenylsilane show a very rapid kinetic equilibrium giving aryl-SiMe₂Cl groups in place of the aryl-SiMe₂OH of the BHB and OH groups in place of Cl in the dichlorosilane. This is followed by a slow condensation polymerization of the 1,4-bis(chlorodimethylsilyl)benzene with the hydroxy terminated disilane groups. The very rapid initial rates could be followed with ²⁹Si NMR using the INEPT pulse sequence despite the very long ²⁹Si relaxation times. Condensation polymerization is complete within minutes for BHB + SiMe₂Cl₂, but hours and days are required for the SiMePhCl₂ and SiPh₂Cl₂, respectively, at +22°C. Initial reaction kinetics in the presence of Cr(acac)₃ are not identical to those obtained using the INEPT pulse sequence and no relaxation reagent.     

Free radical reactions at the Ru(0 0 0 1) surface: Atomic oxygen and dissociated NH3

X-ray photoelectron spectroscopy was used to study the effect of atomic oxygen on Ru(0 0 0 1), and the effect of dissociated ammonia on RuO₂/Ru(0 0 0 1), in UHV conditions at ambient temperature. The Ru(0 0 0 1) surface was exposed, at ambient temperature, to a mixed flux of atomic and molecular oxygen generated by dissociation of O₂ in a thermal catalytic cracker, with 45% dissociation efficiency. The detailed study of the XPS spectra shows the formation of a disordered multilayer oxide (RuO₂). No formation of higher oxides of Ru was observed. The formation of RuO₂ proceeded without saturation for total oxygen exposures of up to 10⁵ Langmuir, at which point an average oxide thickness of 68 Å was observed. RuO₂ formed by the reaction with atomic oxygen was exposed to a flux of NH_x (x = 1, 2) + H generated by the cracker. The reduction of RuO₂ to Ru metal was observed by XPS. An exposure of 3.6 × 10² L of NH_x + H, resulted in the observation of adsorbed H₂O and OH, but no evidence of lattice oxide. The chemisorbed species were removed by additional NH_x + H exposure. No nitrogen adsorption was observed.     

Uncovering giant nanowheels for magnesium ion–based batteries

The giant wheel-shaped Na₁₅{[Mo₁₅₄O₄₆₂H₁₄(H₂O)₇₀]_0.5[Mo₁₅₂O₄₅₇H₁₄(H₂O)₆₈]_0.5}·ca. 400 H₂O (Mo₁₅₄) is one of the fascinating clusters with the open host framework, which is designed by simple metal-oxygen fragment–linked coordination modes. The generation of structural vacancies (here referred to as defects), the substitution of ligands, and incorporation of heterometallic centers in Mo₁₅₄ could offer several attractive possibilities to achieve good electrochemical performance such as high specific capacity and stability in multivalent batteries. Herein, we have introduced electronically rich giant nanowheel Mo₁₅₄ as a potential cathode material in magnesium-rechargeable batteries (MRBs). The experimental evidence indicates that the Mo₁₅₄ wheels offer a reversible capacity of ～150 mAh g^?1 at 50 mA g^?1 in MRBs, which was retained to about 55 mAh g^?1 after a long cycling life (>500 cycles). Typically, the divalent alkali metals (Mg²⁺) suffer from diffusion and insertion reactions in host materials; however, the stable and high rate performance against cycling with good Coulombic efficiency was achieved for Mo₁₅₄ electrodes. Thus, the work demonstrates that the complex inorganic clusters are promising cathode materials in multivalent ion batteries.     

Influence of polyfurfuryl alcohol (PFA) loading on the properties of Nafion composite membranes

Composite membranes based on Nafion (N115) loaded with furfuryl alcohol (FA) were prepared by in situ acid-catalyzed polymerization technique, with the aim to improve the ionic conductivity of Nafion membranes. The functionalization, thermal stability, electrical properties and mechanical strength of N115-PFA composites was analyzed by means of Fourier transform infrared (FT-IR) attenuated total reflection (ATR) spectroscopy, small- and wide-angle X-ray scattering (SAXS/WAXS), thermogravimetric analysis (TGA), electrical impedance spectroscopy, dynamic vapor sorption (DVS) and dynamic mechanical analyser (DMA). The FA loading in the resultant composites had a positive correlation with the water uptake (W_u), water vapor uptake (W_vu), ionic conductivity and thermo-mechanical stability. At low polyfurfuryl alcohol (PFA) loading, these membranes displayed higher W_u and improved ionic and electrical properties. Further, the thermo-mechanical stability also gradually increased with the PFA loading. All the composites showed a well-defined glass transition temperature in DMA, which shifted to higher temperature with repeated PFA loading. Overall, the results indicate that the developed composite membrane are promising for low temperature polymer electrolyte membrane (PEM) fuel cells.     

Efficient Production of Prebiotic Gluco-oligosaccharides in Orange Juice Using Immobilized and Co-immobilized Dextransucrase

Dextransucrase from Leuconostoc mesenteroides NRRL B-512F was subjected to immobilization and co-immobilization with dextranase from Chaetomium erraticum. Immobilization has enhanced the operational and storage stability of dextransucrase. Two hundred milligrammes (2.4 IU/mg) of alginate beads (immobilized and co-immobilized) were found to be optimum for the production of gluco-oligosaccharides (GOS) in orange juice with a high degree of polymerization. The pulp of the orange juice did not interfere in the reaction. In the batch process, co-immobilized dextransucrase (41 g/L) produced a significantly higher amount of GOS than immobilized dextransucrase (37 g/L). Alginate entrapment enhanced the thermal stability of dextransucrase for up to 3 days in orange juice at 30 °C. The production of GOS in semi-continuous process was 39 g/L in co-immobilized dextransucrase and 33 g/L in immobilized dextransucrase. Thus, immobilization technology offers a great scope in terms of reusability and efficient production of a value added functional health drink.     

Thermal Cycloimidization Study of Polyimides and Poly(amide imide)s Synthesized from Low-Temperature Solution Polymerization

Polyimides (PI)s and Poly(amide imide)s (PAI)s containing di/tri-structural arrangements of monomer constituents were synthesized from 1,2,4,5 benzenetetracarboxylic anhydride/3,3′,4,4′ benzophenonetetracarboxylic dianhydride, diamines and trimellitic dianhydride chloride, i.e., a mixture of dianhydrides and diamines, using low-temperature solution polymerization. The majority of the resulting polymers were readily soluble in polar aprotic solvents such as dimethylformamide, dimethylsulfoxide, dimethylacetamide, etc. Thermal cycloimidization studies by thermogravimetic analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR) revealed that the rate of cycloimidization was much faster during the initial 15 min, and then occurred at much slower rates till the completion. The activation energies (Ea) for thermal cycloimidization of poly(amic acid)s was calculated from the rate of mass loss of the polymer heated at different temperatures according to the Coats and Redfern method. PI and PAIs derived from diamines containing single cyclic/benzene ring structures, such as m-phenylenediamine and 1,3-cyclohexanebis(methylamine), showed less amount of char yield than those having two benzene rings and separated by methylene, sulfone, or ether linkages. The structure of both diamine and trimellitic chloride had a profound effect on the polymer chain mobility, as indicated by the big variation in the glass transition temperatures. Thermally stable polymers were developed into membranes and tested for their mechanical strength by dynamic mechanical analysis(DMA).     

Spiro‐heterocycles from substituted pyridines,pyrans and thiopyrans

A new class of spiro‐pyrimidines, pyrazoles and isoxazoles are prepared by nucleophilic reaction of 3,5‐diaroyl‐2,6‐diaryl‐piperidine‐4,4‐dicarbonitrile (1), 3,5‐diaroyl‐2,6‐diaryl‐tetrahydropyran‐4,4‐dicarbonitrile (2) and 3,5‐diaroyl‐2,6‐diaryl‐tetrahydrothiopyran‐4,4‐dicarbonitrile (3) with urea, N,N'‐dimethyl urea, thiourea, hydrazine hydrate and hydroxylamine hydrochloride.     

Copolymerization of 2-hydroxypropyl methacrylate with alkyl acrylate monomers

2-Hydroxypropyl methacrylate has been copolymerized with methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate in bulk at 60°C using benzoyl peroxide as initiator. The compositions of copolymers have been determined by the estimation of the hydroxyl group by acetylation process. The copolymerization parameters have been determined by conventional scheme of copolymerization.     

Preparation and characterization of mixed-ligand dihydrazone complexes of nickel(II)

Summary New complexes of Ni^II-containing dihydrazones derived from dehydroacetic acid as primary ligands and ammonia or pyridine as secondary ligand were prepared and characterized by elemental analysis, conductance, spectral and magnetic data. The dihydrazones react with NiCl₂ in their enolic forms as bis-tridentate complexing agents, forming dinuclear dihydrazido-diamine-dinickel complexes with ammino co-ligands. The ammino complexes were treated with pyridine to give the pyridino complexes. Squareplanar geometries are proposed for all the complexes and preliminary studies show that they possess antifungal activity.