Synthesis of sodium-polystyrenesulfonate-grafted nanoparticles by core-cross-linking of block copolymer micelles

Sodium poly(styrenesulfonate)(polySSNa)-grafted polymer nanoparticles were synthesized by core-cross-linking of block copolymer micelles and subsequent chemical transformation. Block copolymers, poly(p-((1-methyl)silacyclobutyl)styrene-block-poly(neopentyl p-styrenesulfonate)s, polySBS-b-polySSPen, were synthesized by nitroxy-mediated living radical polymerization. The block copolymers formed micelles (R_h=15-23 nm, where R_h represents the hydrodynamic radius) with a polySBS core and polySSPen shell in acetone. The micelle core was cross-linked by ring-opening polymerization of silacyclobutyl groups in polySBS. Hydrolysis of the neopentyl groups provided polySSNa-grafted nanoparticles. The R_h of the particles before the hydrolysis ranged from 12 to 21 nm in acetone, while they varied to the range from 50 to 110 nm in water after the hydrolysis.     

Thermal degradation of poly[(tetramethyl-p-silphenylene) siloxane]

For the purpose of studying the mechanism of thermal degradation of poly[(tetramethyl-p-silphenylene) Siloxane] (poly TMPS) a series of polymers with silphenylene and siloxane bonds in the main chain were prepared and subjected to thermogravimetry (TG) and pyrolysis study. Analyses of products from poly TMPS degradation (in vacuum at a constant temperature) by gas chromatography (GC), infrared (IR), nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry (GC–MS) revealed that degradation occurs at the silphenylene bonds. The TG curves obtained in He for heating rates of 1,2,2.5,7.5, and 10°C/min were analyzed by the Ozawa method; activation energies of 39 ± 1 and 45 ± 2 kcal/mol were obtained respectively for the initial cleavage of the methyl side group and the later-stage scission of the main-chain silphenylene bond which leads to a major weight loss. The results agree with those obtained for other structurally similar polymers.     

High resolution capillary gas chromatographic hydrocarbon-type analysis of naphtha and gasoline

A slightly modified, commercially available high resolution capillary gas chromatograph and a PC-based data processing system running proprietary software (“PONA”) have been employed in the development of a system for petroleum type analysis which would be equivalent or superior to the FIA (fluorescent indicator adsorption) method in terms of ease of use and the speed, variety, and accuracy of the analytical data produced. The system is capable of performing identification and quantitation of most of the individual components in a complex gasoline sample consisting of more than 230 components and can report weight percentage and/or volume percentage for each component as well as types by carbon number (e.g., isoparaffins, normal paraffins, olefins, naphthenes, aromatic compounds) within a ca. 70 minute analysis cycle. Precolumn sulfonation to trap olefins and aromatic compounds has been used as an complementary technique to the basic mass spectrometric identification of components of interest. The estimation of correction factors for weight percentage (or volume percentage) calculation are also discussed. Comparisons are made between this system and others, and the results indicate that the proposed method supersedes the conventional method employing FIA.     

Solvent effect on protein binding by polymer brush grafted onto porous membranes

An epoxy-group-containing polymer chain was grafted onto the hollow-fiber form of a porous polyethylene membrane by the immersion of the electron beam-irradiated trunk polymer in glycidyl methacrylate diluted with methanol and 1-butanol. The epoxy group density ranged from 8.5 to 13.4 mol per kg of the trunk polymer. Subsequently, the epoxy groups produced were converted into sulfonic acid and diethylamino groups. The density of -SOH and -N(C2H5), groups was 0.40 and 2.2 mol per kg of the product. respectively. The polymer brush, defined as a polymer chain extending from the surface of a pore toward the interior of the pore, was evaluated from the determination of an equilibrium binding capacity of hen egg lysozyme (HEL) and bovine serum albumin (BSA). The polymer brush prepared in 1-butanol was found to be longer than that prepared in methanol from the determinations of liquid permeability and protein adsorptivity. The proteins were bound to the polymer brush prepared in 1-butanol, followed by the functionalization, at higher degrees of multilayer binding: about 30 for HEL and 6 for BSA.     

Organometallic compounds : XII. stereochemical interconversion reactions between 1,1′−bis(α-hydroxyalkyl)ferrocenes and 7-oxa[3]ferrocenophanes

Meso and racemic isomers of 1,1′-bis(α-hydroxyalkyl)ferrocene derivatives, and trans and cis isomers of 7-oxa[3]ferrocenophanes have been isolated. The configurations of these isomers have been determined both by spectroscopy and from their reaction behavior. It has been found that the ring-closure and ring-opening interconversion reactions between 1,1′-bis(α-hydroxyalkyl)ferrocenes and 7-oxa[3]ferrocenophanes are stereospecific. PMR spectra of the diols and ethers have been examined at 100 MHz in CF₃COOH, and the existence of α-[1′-(α-hydroxyalkyl)ferrocenyl]carbonium ions has been demonstrated in this acid. A mechanism for the various interconversion reactions is proposed on the basis of their stereospecific reactivity and from the PMR spectra of the carbonium ions.     

Measurement of the product ion ratio N4+/N3+ in the radiolysis of nitrogen

The ratio of N₄⁺ to N₃⁺ formed in the radiolysis of gaseous nitrogen has been measured to be 4.7 ± 0.4 using a time-resolved atmospheric pressure ionization mass spectrometer. The limit of error has been evaluated from the ion mass discrimination of the apparatus.     

Soluble polymer-supported catalysts containing pendant quaternary onium salts for the addition reaction of oxiranes with carbon dioxide

The addition reaction of oxiranes ( 15a-d ) with carbon dioxide (CO₂) was carried out using 1 mol % of soluble polymer-supported quaternary onium salts as catalysts under atmospheric pressure. The reaction of 15a-d with CO₂ proceeded very smoothly to give the corresponding five-membered cyclic carbonates ( 16a-d ) in high yields at 90-100°C. The catalytic activity of the soluble polymer-supported quaternary onium salts was strongly affected by the following factors: kind of reaction solvent, degree of introduction of the pendant onium salt residues in the polymer chain, and type of alkyl group on the onium salts due to the balance between lipophilicity and steric hindrance of the onium salt residue. Furthermore, these soluble polymer-supported quaternary onium salts were found ordinarily to have higher catalytic activity than low molecular weight quaternary onium salts under the same reaction conditions. It was also found that the rate of reaction was proportional both to catalyst concentration and to oxirane concentration. © 1995 John Wiley & Sons, Inc.     

Electrochemical characterization of negative electrodes consisting of surface-modified Zr0.9Ti0.1(Ni1.1Co0.1Mn0.5V0.2Cr0.1)x Laves-phase alloys

Laves-phase hydrogen storage alloy has a high potential for use as negative electrode material as alternative for the misch-metal-based material. In order to improve the energy density and the rate capability of negative electrode, chemical and mechanical modification of Lavesphase alloy with different stoichiometric ratios was carried out. Discharge capacity and high-rate dischargeabilty was evaluated by electrochemical methods and the characterization of Laves-phase alloy was made by X-ray diffraction, SEM observation and PCT measurement. The best result in discharge capacity could be obtained for stoichiometric Laves-phase alloy with a composition of Zr_0.9Ti_0.1Ni_1.1Co_0.1Mn_0.5V_0.2Cr_0.1 by boiling in 10 M KOH solution. On the other hand, the high-rate dischargeability was increased remarkably by introducing mechanical grinding before alkali treatment. The cause for improved performance was discussed on the basis of thermodynamic stability of metal hydride and changes in crystal structure and surface morphology influencing on diffusion coefficient and diffusion path length of hydrogen.     

Stereoselective synthesis of 2-methylenepyrrolizidines by tandem cyclization of N-propargylaminyl radicals

Tandem cyclization of N-propargylaminyl radicals, generated by N-chlorination of (E)-alk-4-enylamines 2a-d and 2f followed by treatment with tributyltin radical, afforded 2-methylenepyrrolizidines 3a-d and 3f in a highly stereoselective manner. A similar radical cyclization of (Z)-N-propargyl-1-methyl-5-phenylpent-4-enylamine (2e) gave pyrrolizidine 3b having the same stereochemistry as that obtained from the E isomer 2b.     

Synthesis and nanostructure of strong polyelectrolyte brushes in amphiphilic diblock copolymer monolayers on a water surface

We synthesized an ionic amphiphilic diblock copolymer, poly(hydrogenated isoprene)-b-poly(styrenesulfonic acid) (PIp-h2-b-PSS), by living anionic polymerization, and the nanostructure of its monolayer spread on a water surface was directly investigated by the in situ X-ray reflectivity technique. The monolayer of the diblock copolymer on a water surface had a smooth hydrophobic PIp-h2 layer on water and a "carpet"/polymer brush double layer in a hydrophilic sodium polystyrene sulfonate (PSSNa) layer under the water. The surface pressure dependence and PSSNa chain length dependence of the PIp-h2 layer thickness and the brush nanostructure were quantitatively studied. The effect of salt concentration in the subphase was also investigated in aqueous solutions containing 0-2 M NaCl. The salt effect on monolayer structure occurred at around 0.2 M. The thickness of the PSS brush layer decreased at salt concentrations above 0.2 M, while no structural change was observed below 0.2 M. This critical salt concentration is thought to be related to the balance of ionic concentrations inside the brush and in bulk solution.