Kinetic study of the crosslinking reaction of 1,2‐polybutadiene with dicumyl peroxide in the absence and presence of vinyl acetate

The crosslinking reaction of 1,2-polybutadiene (1,2-PB) with dicumyl peroxide (DCPO) in dioxane was kinetically studied by means of Fourier transform near-infrared spectroscopy (FTNIR). The crosslinking reaction was followed in situ by the monitoring of the disappearance of the pendant vinyl group of 1,2-PB with FTNIR. The initial disappearance rate (R₀) of the vinyl group was expressed by R₀ = k[DCPO]^0.8[vinyl group]^−0.2 (120 °C). The overall activation energy of the reaction was estimated to be 38.3 kcal/mol. The unusual rate equation was explained in terms of the polymerization of the pendant vinyl group as an allyl monomer involving degradative chain transfer to the monomer. The reaction mixture involved electron spin resonance (ESR)-observable polymer radicals, of which the concentration rapidly increased with time owing to a progress of crosslinking after an induction period of 200 min. The crosslinking reaction of 1,2-PB with DCPO was also examined in the presence of vinyl acetate (VAc), which was regarded as a copolymerization of the vinyl group with VAc. The vinyl group of 1,2-PB was found to show a reactivity much higher than 1-octene and 3-methyl-1-hexene as model compounds in the copolymerization with VAc. This unexpectedly high reactivity of the vinyl group suggested that an intramolecular polymerization process proceeds between the pendant vinyl groups located on the same polymer chain, possibly leading to the formation of block-like polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4437–4447, 2004     

Determination of cyclosporin A in the serum of kidney transplant patients by rapid-flow fractionation and normal-phase high-performance liquid chromatography

High-performance liquid chromatography was used to determine cyclosporin A (CsA) concentrations in the serum of kidney transplant patients by rapid-flow fractionation (RFF) followed by silica gel normal-phase high-performance liquid chromatography (HPLC). The extraction of CsA from serum was achieved by RFF using a short diatomaceous earth column eluted with diethyl ether-n-hexane (50:50, v/v). The recovery was more than 80% at concentrations of 50-150 micrograms/l. The concentration of this compound was determined by HPLC using a conventional silica gel column with 3.3 M ammonia solution-ethanol-n-hexane (0.31:10.69:89, v/v) as eluent. Concentration calibration was made on the basis of the peak-height ratio of CsA to CsD as the internal standard. The coefficient of variation of this assay was less than 6.5% and the results were used for the therapeutic drug monitoring of CsA administered to kidney transplant patients. Measurements of the CsA concentrations in 160 serum specimens were also made by conventional radioimmunoassay (RIA) using commercial kits. The data obtained by RIA were on average 2.5 times those obtained by HPLC. Higher values in RIA were observed characteristically with patients with severe disfunction resulting from CsA hepatotoxicity. From the results, it appeared that HPLC rather than RIA provides more precise and reliable values for the concentration of this drug.     

Effect of Hydrolysis Conditions on the Direct Formation of Nanoparticles of Ceria–Zirconia Solid Solutions from Acidic Aqueous Solutions

The effect of the cation concentration, hydrolysis temperature, and composition in the CeO₂–ZrO₂ system on the direct precipitation of ceria–zirconia solid solutions and the structure of the precipitates from acidic aqueous solutions of (NH₄)₂Ce(NO₃)₆ and ZrOCl₂ by hydrolysis under hydrothermal conditions were investigated. Nanometer-sized (8–10 nm) ceria–zirconia solid solution particles in a composition range of 0 to 60 mol% ZrO₂ were directly precipitated from the solutions with total metal cation concentration less than 0.2 mol/dm³ by simultaneous thermal hydrolysis at 150–240°C. The crystalline phase of the precipitates gradually changed from cubic and/or tetragonal to monoclinic with increasing the cation concentration of the solution from 0.2 to 0.8 mol/dm³ at the starting composition of 50 mol% ZrO₂ under hydrolysis condition of 150°C for 48 h, which was attributed to decrease in the supply of hydrolyzed Ce component caused by decrease in the hydrolysis ratio of (NH₄)₂Ce(NO₃)₆. Ceria–zirconia solid solutions containing large amount of ZrO₂ maintained high specific surface area and small-sized crystallite after heat-treatment at 900–1000°C for 1 h.     

PEO-based composite lithium polymer electrolyte, PEO-BaTiO3-Li(C2F5SO2)2N

Polyethylene oxide (PEO) based polymer electrolytes with BaTiO₃ as filler and Li(C₂F₅SO₂)₂N as salt have been examined in lithium polymer batteries. The aluminum disolution potential in PEO-Li(C₂F₅SO₂)₂N was estimated to be 4.1 V vs. Li/Li⁺ at 80 °C, which was compared to that of 3.8 V vs. Li/Li⁺ in PEO-Li(CF₃SO₂)₂N. The electrical conductivity of the system was measured as a function of O/Li ratio. The highest conductivity was observed in O/Li=8. The conductivity was 1.65×10⁻³ S/cm at 80 °C and 1.5×10⁻⁵ S/cm at 25 °C. The interfacial resistance of Li/polymer electrolyte/Li annealed at 80 °C for 15 days was lower than 100 Ωcm². Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16 – 22, 2001.     

A Pseudo-Random Frequency Modulation Continuous Wave Coherent Lidar Using an Optical Field Correlation Detection Method

We propose a new detection method for a pseudo-random frequency modulation continuous wave (RM-CW) coherent lidar. The feature of this method is modulation of local beam with a time delayed pseudo-random sequence. Heterodyne detection and correlation detection between the received beam and the local beam are simultaneously carried out in an optical field. In the RM-CW coherent lidar using the optical field correlation detection method, the received equipment is greatly simplified. We carried out preliminary experiments and demonstrated that the new method is effective for detection of a CW coherent lidar.     

Copolymers containing a spiro orthoester moiety that undergo no shrinkage during cationic crosslinking

A spiro orthoester with an exomethylene group (exoSOE) was radically copolymerized with acrylonitrile or vinyl acetate at several feed ratios to obtain the corresponding copolymers having spiro orthoester moieties in the side chain. The obtained copolymers could be crosslinked via the double ring‐opening polymerization of the spiro orthoester moieties in their side chain by a treatment with BF₃OEt₂. The volume changes upon the crosslinking of the copolymers were evaluated by density measurements with a micromeritics gas pycnometer. The copolymers experienced less than 1% volume expansion instead of volume shrinkage during typical cationic crosslinking, regardless of the copolymer compositions. Negligible shrinkage was observed during the thermal cationic crosslinking of a film cast from a nitrobenzene solution of the copolymers containing a benzylthiophenium salt as a thermally latent cationic initiator. The constantly low volume changes during the crosslinking of the copolymers from exoSOE probably depended on the almost zero volume change during the cationic polymerizations of spiro orthoester derivatives. This indicates that exoSOE is an effective monomer for crosslinkable polymers without volume changes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3666–3673, 2006     

Inhibitory effects of 3-O-acyl-(+)-catechins on Epstein-Barr virus activation

In the course of an exploratory investigation of antitumor-promoting catechins, 3-O-acyl-(+)-catechins of varying carbon lengths from C(4) to C(18) were assessed for inhibitory effects on the activation of the Epstein-Barr virus early antigen. Like 3-O-acyl-(-)-epigallocatechins, the (+)-catechin derivatives showed promising effects with the C-3 acyl chain of C(8)-C(11) carbon atoms.     

In Situ Processing of Nano Crystalline Oxide Particles/Polymer Hybrid

Nano sized crystalline particles/polymer hybrids were synthesized form designed metal-organic precursors. The newly developed method is composed of the synthesis of organic matrix by polymerization and the in situ nucleation and growth of crystalline oxide particles in the organic matrix below 100°C. The design of metal-organic precursor modified with polymerizable ligand and the selection of reaction conditions does influence the size and crystallinity of ceramic particles in organic matrix. The nano-sized magnetic particle/polymer hybrid exhibits the interesting feature of superparamagnetism and quantum size effect. The crystalline particles of BaTiO₃/, PbTiO₃/, and KNbO₃/polymer hybrids behave to be dielectric and show the typical electro-rheological behavior.