Ring hydrogenation of naphthalene and 1-naphthol over supported metal catalysts in supercritical carbon dioxide solvent

Catalytic ring hydrogenations of naphthalene and 1-naphthol were studied over several supported metal catalysts in supercritical carbon dioxide solvent at low temperature. Higher concentration of hydrogen in supercritical carbon dioxide and lower reaction temperature were responsible for higher catalyst activity and selectivities to the desired partial ring hydrogenated products as compared with those observed in organic solvent for the same catalyst.     

Approach from physicochemical aspects in membrane filtration

In membrane filtration, solution environment factors such as pH and solvent density are important in controlling the filtration rate and the rejection of the particles and/or the macromolecules. The filtration rate and the rejection in membrane filtration have been investigated from physicochemical aspects. It was shown that the properties of the filter cake formed on the membrane surface play a vital role in determining the filtration rate in mem-brane filtration. It was clearly demonstrated that such filtration behaviors as the filtration rate and the rejection are highly dependent on the electrical nature of the particles and/or the macromolecules. Furthermore, it was shown that the solvent density ρ has a large effect on the steady filtration rate in upward ultrafiltration.     

Functional metal-porphyrazine derivatives and their polymers, 10. Secondary fuel cells based on oxygen reduction on platinum electrode modified by polymers and metal-phthalocyanines

Secondary fuel cells based on oxygen reduction of platinum electrode modified by polymers and metal-phthalocyanine (Mt = Fe(III), Co(II), Ni(II), and Cu(II)) were studied. The discharge curves for the platinum electrode modified by poly(2-vinylpyridine) (or polystyrene) and Co-phthalocyanine in 30% KOH aqueous solution, for a 30 min charge at 500 μA, followed by a 100 μA discharge showed a stable plateau at about ?0.24 V SCE (Saturated Calomel Electrode). The open circuit voltage (vs. Zn) of the cell was 1.2 V, and the discharge capacity was of 46 A · h/kg. For this battery there was no significant decay in its characteristics after more than 30 charge-discharge cycles. In Mt-phthalocyanines, the values decreased in the order of Co(II) > Fe(III) > > Cu(II) > Ni(II). From a cyclic voltammogram for the electrode modified by the polymer and Co-Pc, the cathodic reactions were discussed.     

Vinyl polymerization by metal complexes. XVIII. Kinetics of the polymerization of acrylonitrile initiated by imidazole-copper-(II) complexes

A study on the kinetics and mechanism of the polymerization of acrylonitrile initiated by imidazole and 2-substituted imidazole-copper-(II) complexes was made in dimethyl sulfoxide solution at 40–70°C. The rate of polymerization, Rp, could be expressed as follows: The overall activation energies of these polymerization processes are in a range from 14.2 to 69.1 KJ mole^-1. From the data of electronic spectra and electron paramagnetic resonance, it was confirmed that the polymerization in question could be initiated by free radicals which were formed by the reduction of copper-(II) complex to copper-(I) complex, and the latter formed a new complex with polyacrylonitrile resulted.     

Interactions oftrans-cinnamic acid,its related phenolic allelochemicals,and abscisic acid in seedling growth and seed germination of lettuce

Phenolic compounds have been identified as the most common allelochemicals produced by higher plants. Inhibitions of cinnamic acid, its related phenolic derivatives, and abscisic acid (ABA) on seedling growth and seed germination of lettuce were studied.trans-Cinnamic acid, ando-,m-, andp-coumaric acids inhibited the growth of etiolated seedlings of lettuce at concentrations higher than 10^–4 M and seed germination above 10^–3 M. Coumarin inhibited seedling growth and seed germination at 10^–5 M or above. Chlorogenic acid inhibited seedling growth above 10^–4 M, but did not inhibit seed germination at 10^–5–5×10^–3 M. Low concentrations (below 10^–3 M) of caffeic and ferulic acids promoted the elongation of hypocotyls, but higher concentrations (over 10^–3 M) inhibited seedling growth and seed germination. These phenolic compounds and abscisic acid had additive inhibitory effects both on seedling growth and seed germination. The inhibition on lettuce was reversed by caffeic and ferulic acids at concentrations lower than 10^–3 M except for the inhibition of germination by coumarin. These results suggest that in naturetrans-cinnamic acid,o-, m-, p-coumaric acids, coumarin, and chlorogenic acid inhibit plant growth regardless of their concentration. However, caffeic and ferulic acids can either promote or inhibit plant growth according to their concentration.     

Abnormal metabolism of polyunsaturated fatty acids and phospholipids in diabetic glomeruli

Studies were done on changes in phospholipid content and fatty acid composition of phospholipids and on the role of the acylation pathway in synthesis of phospholipids in the development of abnormal fatty acid composition in the glomeruli of rats 2 and 10 mo after induction of diabetes with streptozotocin. The proportions of individual phospholipids in the glomeruli of rats were not changed 2 mo after induction of diabetes, but the proportion of phosphatidylethanolamine (PE) decreased and that of sphingomyelin increased 10 mo after induction of diabetes. In contrast, in liver the proportion of PE was increased and that of phosphatidylcholine was decreased. These results showed that changes of individual phospholipids in glomeruli were time-dependent and tissue-specific. Two mo after induction of diabetes, the main change in the phospholipid fatty acid composition of diabetic glomeruli was a decrease in arachidonic acid (AA); the main change in serum free fatty acids (FFA) was an increase in linoleic acid (LA) and a decrease in AA. Ten mo after induction of diabetes, the main changes in the phospholipid fatty acid composition of glomeruli were an increase in LA and a decrease in AA; the main change of the serum FFA composition was a decrease in AA. Thus, the fatty acid composition of glomerular phospholipids was not directly correlated to that of the serum in diabetic rats. Acyl-CoA synthetase and acyltransferase activities increased in diabetic glomeruli with either AA or LA as substrate, but activity toward LA increased more at 2 mo after induction of diabetes. Acyl-CoA synthetase activity increased in diabetic glomeruli with LA as substrate, but that did not change with AA as substrate at 10 mo after induction of diabetes. Furthermore, acyltransferase activity decreased in diabetic glomeruli with AA as substrate, although that did not change with LA as substrate at 10 mo after induction of diabetes.     

Melt‐spinning process of a tetrafluoroethylene– hexafluoropropylene copolymer

An industrial melt‐spinning process of tetrafluoroethylene– hexafluoropropylene copolymer (FEP) using an extruder was studied. The novel “spinneret,” having both a large‐diameter spinning nozzle and a high‐temperature vessel, was used to solve the problem of filament breakage on the spinning line caused by high melting viscosity of FEP. The extruder, with its long feed zone, was newly designed to function with a geared pump. The strength of fibers increased with drawing of as‐spun fiber. FEP fibers up to six denier were continuously produced through long‐run production. According to this new process, FEP fibers can be supplied for textile or industrial application. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2366–2371, 2002     

Phase Formation and Microstructure of Titanium Oxides and Composites Produced by Thermal Plasma Oxidation of Titanium Carbide

The phase formation and microstructure of titanium oxides and composites produced by Ar–O₂ thermal plasma oxidation of titanium carbide powders were investigated in detail by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Relationships between the phase compositions and microstructures of the oxides were established by combined structural and phase analyses, in correlation with synthesis conditions and phase formation mechanisms. It is revealed that vapor condensation favored the formation of anatase, which existed as smaller particles, while liquid/solid oxidation favored the formation of rutile, which appeared as larger particles or composites. A higher oxygen input in the plasma gases (Ar + O₂) enhanced the formation of anatase due to impeded oxidation and evaporation. A small amount of Ti₄O₇ and Ti₃O₅ was detected in the larger particles coexisting with rutile or TiC. These suboxides were formed as intermediates in solid oxidation of TiC or precipitated from the Ti–C–O melt during cooling. Furthermore, extensive cracks, dislocations and stresses were observed in the monolithic rutile and composites, in association with the rapid quenching in this high-temperature in-flight oxidation process.     

Association and physical gelation of ABA triblock copolymer in selective solvent

Association behavior and physical gelation mechanism of ABA triblock copolymer dissolved in B-selective solvent have been studied systematically from dilute to moderately concentrated solutions. Static and dynamic light scattering and nuclear magnetic resonance measurements for dilute solutions of poly(methyl methacrylate)-block-poly(tert-butyl acrylate)-block-poly(methyl methacrylate) (PMMA-PtBuA-PMMA) in 1-butanol (PtBuA selective solvent) indicated that PMMA-PtBuA-PMMA chains are molecularly dissolved above 50 °C. With decreasing temperature, the triblock copolymers form associated micelles consisting PMMA associated core and PtBuA shell. Linear dynamic viscoelastic measurements for solutions with moderate concentration (3.9-12.0 wt%) revealed that the system was viscous sol state at 60 °C. Drastic increase of shear storage modulus (G′) occurred with decreasing temperature, and at 25 °C, G′ showed rubbery plateau with weak frequency dependency, means the formation of elastic physical gel. The consistency between the temperature for micelle formation and that at the increase in G′ indicates that the physical gelation is owing to the network formation as the result of the association of PMMA chains and the bridging PtBuA chains connecting the PMMA cores. Master curves for the dynamic moduli were derived by time-temperature superposition along the frequency axis. Just above sol-gel transition concentration (C_gel), the master curves suggest the existence of fairy amount of aggregate that is not incorporated in the macroscopic network. With the increase in polymer concentration, the master curves become to reveal Maxwell-type viscoelasticity with narrow relaxation time distribution, suggesting the formation of transient network with easily generation and destruction of crosslinks. Concentration dependency of the plateau modulus is stronger than the theoretically expected, means the macroscopic transient network grows with polymer concentration by increasing the fraction of elastically effective bridging PtBuA chain above C_gel.