Selective hydrogenation of oleic acid to 9-octadecen-1-ol: Catalyst preparation and optimum reaction conditions

A new catalyst, ruthenium-tin-alumina is found to selectively hydrogenate oleic acid to 9-octadecen-1-ol (oleyl + elaidyl alcohol) at low pressure with high yield. Catalyst preparation methods, catalyst raw materials and activation conditions have a significant effect on the activity of the catalyst. The optimum atomic ratio of ruthenium to tin is about 1:2. Catalyst prepared by an improved sol-gel method shows higher activity and selectivity than catalysts prepared by impregnation and coprecipitation methods. Chloride is found to have a negative effect on catalytic activity. The best catalyst is prepared from chloride-free ruthenium and tin raw materials. Under the optimum reaction conditions of 250°C and 5.6 MPa, the selectivities for 9-octadecen-1-ol and total alcohol (9-octadecen-1-ol + stearyl alcohol) formation are 80.9% and 97%, respectively, at a conversion of 81.3%.     

Immobilization of glucose oxidase on nonwoven fabrics with bombyx mori silk fibroin gel

The enzyme glucose oxidase (GOD) was immobilized on the nonwoven fabrics, which have excellent properties in diffusivity of substrates, mechanical strength, and handling, with Bombyx mori silk fibroin gel. The nonwoven fabrics of silk fibroin, viscose rayon, poly-ethyleneterephthalate, 6-nylon, and polypropylene with activated surface by fluoline treatment were used. The stabilities of GOD to heat or pH changes were much improved by the immobilization as well as the case of the GOD immobilized in the silk fibroin membrane. Among nonwoven fabrics, silk fibroin was the most excellent support material for the immobilization of GOD although all nonwoven fabrics used here are able to be used as the support materials. The increase of the sensitivity was observed when the glucose sensor was made with the GOD immobilized on nonwoven silk fabrics as four times compared with the case of the GOD immobilized in the silk fibroin membrane.     

Effects of hydrophilicity of crosslinker on membrane properties of poly(N-hydroxyethyl-L-glutamine) hydrogels

Summary Poly(N-hydroxyethyl-L-glutamine) (PHEG) hydrogels were prepared by aminolysis of poly( -benzyl L-glutamate) with 2-aminoethanol and hydrophobic or hydrophilic crosslinkers, and the effect of the hydrophobicity of the crosslinkers was evaluated. The swelling properties, tensile properties and enzymatic degradation behavior were studied in phosphate buffered saline (PBS). The swelling ratio and degradation rate of these hydrogels were highly dependent on the hydrophobicity of the crosslinkers, while tensile properties were dependent on the swelling ratio, but not on the hydrophobicity of the crosskinkers.     

Copolymerization of Vinyl Chloride and Ethylene with Cp<Superscript>*</Superscript>Ti( OCH<Subscript>3</Subscript>)<Subscript>3</Subscript>/MAO Catalyst

Summary Copolymerization of vinyl chloride (VC) and ethylene with Cp^*Ti( OCH₃)₃/MAO catalyst was investigated. The Cp^*Ti( OCH₃)₃/MAO catalyst initiated the copolymerization of VC with ethylene, although the copolymer yields were low. In the ¹³C NMR spectra of the copolymers, the peaks based on junction part between VC and ethylene was observed, but the signals were small. From DSC measurement of the copolymers, only one glass transition temperature was observed. Thus, it is clear that the copolymerization with Cp^*Ti( OCH₃)₃/MAO catalysts gave the copolymer, and the copolymer consisting of block sequence rather than random copolymer. Received: 13 November 2002/Revised: 6 January 2003/Accepted: 10 January 2003 Correspondence to Kiyoshi Endo     

Electroless copper plating using Fe as a reducing agent

Although the electroless plating method is known to be an effective method for obtaining fine wiring in particular, 1 mol hydrogen gas is generated during 1 mol Cu deposition, and voids are generated in the wiring when electroless Cu plating is applied to fine wiring. To avoid the hydrogen evolution, the possibility of performing electroless Cu plating was confirmed using an inexpensive Fe^II compound as a reducing agent. The bath contains CuSO₄, FeSO₄, NaCl, ethylenediamine, sodium citrate, polyethylene glycol (PEG), and 2,2′-bipyridine. Under optimal conditions, over 1.7 μm of copper deposit with a smooth surface was obtained after 3 h of plating, which did not contain iron as an impurity. The electrical resistivity of the copper film is about 3-4 μΩ cm corresponding to that of electroplated copper films.     

A 31P-NMR study of peroxo species formed during oxidation of cyclohexene with hydrogen peroxide in tri-n-butylphosphate catalyzed by heteropolyacids

In the oxidation of cyclohexene with H₂O₂in monophasic tri-n-butylphosphate (TBP) solution catalyzed by Keggin-type 12-heteropolyacids, i.e., H₃PMo_12-xW _x O₄₀(x=0–12), several peroxo species were observed by ³¹P-NMR spectroscopy in lower field than the original heteropolyacids. Their composition varied regularly with that of the starting catalyst. The P-containing peroxo species formed was deduced as [PM₄O₈(O₂)₈]^3-(M = Mo, W). The peroxo species formed more easily with a decrease in the W content, x of H₃PMo_12-xW_xO₄₀. It was further indicated from the reactivity with cyclohexene and the comparison with catalytic performance that W-rich peroxo species were catalytically more active than Mo-rich peroxo species for the oxidation of cyclohexene in this reaction system.     

Expression and stabilization of galactose oxidase in Escherichia coli by directed evolution

We have used directed evolution methods to express a fungalenzyme, galactose oxidase (GOase), in functional form in Escherichiacoli. The evolved enzymes retain the activity and substratespecificity of the native fungal oxidase, but are more thermostable,are expressed at a much higher level (up to 10.8 mg/l of purifiedGOase), and have reduced negative charge compared to wild type,all properties which are expected to facilitate applicationsand further evolution of the enzyme. Spectroscopic characterizationof the recombinant enzymes reveals a tyrosyl radical of comparablestability to the native GOase from Fusarium.     

Structurally Diverse Polyamines: Solid‐Phase Synthesis and Interaction with DNA

A versatile solid‐phase approach based on peptide chemistry was used to construct four classes of structurally diverse polyamines with modified backbones: linear, partially constrained, branched, and cyclic. Their effects on DNA duplex stability and structure were examined. The polyamines showed distinct activities, thus highlighting the importance of polyamine backbone structure. Interestingly, the rank order of polyamine ability for DNA compaction was different to that for their effects on circular dichroism and melting temperature, thus indicating that these polyamines have distinct effects on secondary and higher‐order structures of DNA.