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     

Organometallic chemistry related to applications for microelectronics in Japan

This is meant to be a brief overview of the developments of research activities in Japan on organometallic compounds related to their use in electronic and optoelectronic devices. The importance of organometallic compounds in the deposition of metal and semiconductor films for the fabrication of many electronic and opto-electronic devices cannot be exaggerated. Their scope has now extended to thin-film electronic ceramics and high-temperature oxide superconductors. A variety of organometallic compounds have been used as source materials in many types of processing procedures, such as metal–organic chemical vapor deposition (MOCVD), metalorganic vapor-phase epitaxy (MOVPE), metal–organic molecular-beam epitaxy (MOMBE), etc. Deposited materials include silicon, Group III–V and II–VI compound semiconductors, metals, superconducting oxides and other inorganic materials. Organometallic compounds are utilized as such in many electronic and optoelectronic devices; examples are conducting and semiconducting materials, photovoltaic, photochromic, electrochromic and nonlinear optical materials. This review consists of two parts: (I) research related to the fabrication of semiconductor, metal and inorganic materials; and (II) research related to the direct use of organometallic materials and basic fundamental research.     

Numerical analysis of finite amplitude motion of waves and a moored floating body under severe storm conditions

The motion of a moored floating body under the action of wave forces, which is influenced by fluid forces, shape of the floating body and mooring forces, should be analysed as a complex coupled motion system. Especially under severe storm conditions or resonant motion of the floating body it is necessary to consider finite amplitude motions of the waves, the floating body and the mooring lines as well as non-linear interactions of these finite amplitude motions. The problem of a floating body has been studied on the basis of linear wave theory by many researchers. However, the finite amplitude motion under a correlated motion system has rarely been taken into account. This paper presents a numerical method for calculating the finite amplitude motion when a floating body is moored by non-linear mooring lines such as chains and cables under severe storm conditions.     

Approximate Solution of the Saha Equation — Temperature as an Explicit Function of Particle Densities

The Saha equation for a plasma in thermodynamic equilibrium (TE) is approximately solved to give the temperature as an explicit function of population densities. It is shown that the derived expressions for the Saha temperature are valid approximations to the exact solution. An application of the approximate temperature to the calculation of TE plasma parameters is also described.     

Determination of midodrine in human plasma by high-performance liquid chromatography with fluorescence detection.

A simple and sensitive fluorometric high-performance liquid chromatographic method was developed for the determination of midodrine in human plasma. After liquid-liquid extraction from plasma, the drug and 2-phenylglycinol (internal standard) were convened into the corresponding fluorescent derivatives by reaction with 3,4-dihydro-6,7-dimethoxy-4-methyl-3-oxoquinoxaline-2-carbonyl chloride, a fluorescence derivatization reagent for amines. The derivatives were separated within 30 min on a reversed-phase column using isocratic elution with acetonitrile-methanol-water (10:30:60, v/v) and were detected spectrofluorometrically at 485 nm with excitation at 400 nm. The detection limit for midodrine was 0.3 pmol (76 pg) per mL plasma at a signal-to-noise ratio of 3.     

Reaction kinetics and pathway of hydrothermal decomposition of aspartic acid

The kinetics and pathway of hydrothermal decomposition of aspartic acid were studied using a continuous‐flow tubular reactor. The reaction was carried out in the temperature range of 200–260°C and at a pressure of 20 MPa. Deamination was the primary reaction, indicated by the presence of significant amount of ammonia, fumaric acid, or maleic acid in the products. Other reaction products were pyruvic acid, malic acid, and traces of succinic and lactic acid. Traces of alanine were also detected, showing the possibility of decomposing high‐molecular weight amino acids to obtain simple amino acids such as glycine or alanine. Results on the effect of reaction parameters demonstrated that decomposition of aspartic acid is highly temperature dependent under hydrothermal conditions. For a slight temperature difference of 60°C (from 200 to 260°C), the first‐order reaction rate constants of 0.003 significantly increased to 0.231 s^?1. The activation energy was 144 kJ/mol, as calculated by the Arrhenius equation. No significant effect was exhibited by other reaction parameters such as pH and pressure. The results are useful in controlling the hydrolysis of proteinaceous materials toward high yield of aspartic acid under hydrothermal conditions. © 2007 Wiley Periodicals, Inc. 39: 175–180, 2007     

Breakage of λ-DNA by inorganic tin and organotin compounds as environmental pollutants

In proportion to the environmental pollution problems caused by organotin compounds, the genotoxicities of tin compounds in the environments have become of interest so as to estimate their safety in recent years. In this work, isolated λ-DNA (double-strand DNA) was incubated with inorganic tin(II) and tin(IV) and five organotin compounds [n-butyltin trichloride, di(n-butyltin) dichloride, methyltin trichloride, dimethyltin dichloride and trimethyltin chloride] in reaction systems both with and without hydrogen peroxide (H₂O₂) content. The tin compounds tested in this study did not induce DNA breakage in the absence of hydrogen peroxide. Divalent inorganic tin (SnCl₂) and tetravalent inorganic tin (SnCl₄) caused DNA breakage in the presence of hydrogen peroxide (10 mM), and the DNA damage activity of inorganic tin was much more potent in divalent inorganic tin (SnCl₂) than in tetravalent inorganic tin (SnCl₄). Divalent inorganic tin (SnCl₂) induced DNA breakage in a concentration-dependent fashion at concentrations greater than 0.1 mM of SnCl₂ in the presence of hydrogen peroxide (10 mM). DNA breakage was not caused by n-butyltin compounds and methyltin compounds either in the presence or in the absence of hydrogen peroxide.     

Stereocontrol of diene polymers by topochemical polymerization of substituted benzyl muconates and their crystallization properties

We report the stereocontrol of diene polymers by the topochemical polymerization of alkoxy-substituted benzyl muconates in the solid state. A monomer stacking structure is controlled by the weak intermolecular interactions in the monomer crystals, depending on the structure and position of the alkoxy-substituent. The translational and alternating types of molecular stacking structures in a column provide diisotactic and disyndiotactic polymers, respectively, by the solid-state polymerization under UV and γ-ray irradiation. On the other hand, the meso and racemo structures of the resulting polymers are determined by the molecular symmetry of the used muconate monomers. The various substituted benzyl ester polymers are transformed into the same ethyl ester polymers with the four types of tacticities. The structure and crystallization behavior of the substituted benzyl ester polymers as well as the ethyl ester polymers have been revealed in detail. We clarify the effects of the tacticity on the crystallization property of the stereoregular polymuconates. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4952–4965, 2006