Application of enzymatically gelled chitosan solutions to water‐resistant adhesives

An investigation was undertaken on the application of dilute chitosan solutions gelled by tyrosinase‐catalyzed reaction with 3,4‐dihydroxyphenethylamine (dopamine). The tyrosinase‐catalyzed reaction with dopamine conferred water‐resistant adhesive properties to the semidilute chitosan solutions. The viscosity of the chitosan solutions increased highly by the tyrosinase‐catalyzed reaction and the subsequent reactions between o‐quinone compounds and chitosan. These highly viscous, gel‐like modified chitosan materials were allowed to spread onto the surfaces of the glass slides, which were tightly lapped together and held them in water. Tensile shear adhesive strength of over 400 kPa was observed for the modified chitosan samples. The increase in the amino group concentration of the chitosan solutions and the molecular mass of the chitosan used effectively led to the increase in adhesive strength of the glass slides. In addition, in the case where the chitosan solution was gelled by the enzymatic reaction with dopamine in the presence of poly(ethylene glycol), adhesive strength sharply increased at shorter reaction times concomitantly with the increase in the viscosity of the chitosan solutions because the tyrosinase activity effectively was retained by poly(ethylene glycol). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1818–1827, 2007     

Production of antimicrobially active silk proteins by use of metal‐containing dyestuffs

The work presented here discusses a new technique for preparing silk fibers and films with persistent antimicrobial activity through use of metallic dyestuffs during the fiber dyeing process. The length of the silk fibers investigated contracted when the fibers were immersed in concentrated neutral salt solutions, such as calcium or potassium nitrate, at elevated temperature levels. The birefringence and molecular orientation of the silk fibroin molecules became less ordered by the action of the neutral salt solutions, resulting in increased dyestuff absorption. Subsequently, contracted silk fibers were dyed with metallic dyestuffs containing Cr or Cu for the purpose of obtaining silk fibers with antimicrobial activity. Silk fibers dyed with metallic dyestuffs showed significant antimicrobial activity against the plant pathogen Cornebacterium and the human pathogen Coli bacillus. Tensile strength of the silk fibers after the salt shrinking and dyeing processes did not show a significant change, whereas the elongation at break was increased slightly. The techniques described here for preparing significantly active antimicrobial silk fibers are effective and economic ways of providing new materials for industrial and biomedical applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1181–1188, 2002     

Effect of medium-chain fatty acid positional distribution in dietary triacylglycerol on lymphatic lipid transport and chylomicron composition in rats

The present study was carried out to examine if the positional distribution of medium-chain fatty acid (MCF) in dietary synthetic fat influences lymphatic transport of dietary fat and the chemical composition of chylomicrons in rats with permanent cannulation of thoracic duct. Four types of synthetic triacylglycerol were prepared: (i) sn-1(3) MCF-sn 2 linoleic acid, (ii) interesterified sn-1(3) MCF-sn 2 linoleic acid, (iii) sn-2 MCF-sn-1(3) linoleic acid, and (iv) interesterified sn-2 MCF-sn-1(3) linoleic acid. A purified diet composed of equal amounts of the synthetic fat and cocoa butter was given to rats with permanent lymph duct cannulation. The positional distribution of MCF in the dietary fat had no significant effect on the lymph flow, triacylglycerol output, phospholipid output, lipid composition of chylomicrons, or the particle size. The positional distribution of MCF in the synthetic triacylglycerol was maintained in the chylomicron triacylglycerol. These results showed that MCF in the dietary triacylglycerol is transported into lymphatics and the positional distribution is well preserved in chylomicron triacylglycerol.     

Synthesis of tetramethyl-p-silphenylenesiloxanedimethylsiloxane triblock copolymer by employing living anionic polymerization

Dimethylsiloxane-tetramethyl-p-silphenylenesiloxane-dimethylsiloxane (DMS-TMPS-DMS) triblock copolymer was synthesized by employing living anionic polymerization of hexamethylcyclotrisiloxane (D₃). Two synthetic methods were carried out for the polymerization. One of those methods was the anionic polymerization of D₃ initiated at the silanolate anion which was prepared from the terminal hydroxyl group of silanol-terminated TMPS prepolymer by reaction with n-butyllithium (method 1). The other was the coupling reaction of vinyl-terminated TMPS prepolymer with hydrosilyl-terminated DMS prepolymer obtained from the anionic polymerization of D₃ by using diphenylmethylsilanolate anion as initiator (method 2). In method 1, DMS contents of the copolymers ranged from 25.8 to 72.5 wt% and the values agreed with the ratio of D₃ to TMPS prepolymer. The weight-average molecular weights ranged from 1.36×10⁴ to 19.4×10⁴ and were close to the predicted values calculated from the $\text{M}\text{?}{}_{\mathrm{v}}$ of the TMPS prepolymer and the amount of D₃ added. In the case of method 2, weight-average molecular weights ranged from 19.5×10⁴ to 24.2×10⁴. The high molecular weight copolymer could thus be obtained by method 2. Intrinsic viscosity values of the triblock copolymers agreed with calculated values obtained by considering the copolymer as a binary mixture of these homopolymers. Differential scanning calorimetry and thermogravimetry were carried out on the triblock copolymers. The equilibrium melting temperatures of each of the copolymers were very close to that of poly-TMPS (160°C). The glass transition temperature and heat of fusion were decreased as the DMS content was increased. The thermogravimetric curves for the copolymers indicated that the thermal stability of the triblock copolymer was intermediate between the DMS and TMPS homopolymers.     

Interfacial Reactions between Sapphire and Silver—Copper—Titanium Thin Film Filler Metal

Wetting and brazing studies of sputtering-deposited, submicrometer thin film filler metal in an Ag—Cu—Ti/Al₂O₃ system were performed. The interfacial reaction layer between the filler metal and Al₂O₃ was investigated. It is possible to make a brazing joint even with a reaction layer of less than 100 nm thickness. Different types of interfacial reaction layers were observed when the Ti content in the filler metal was varied. The Cu—Ti—O system compounds were observed in the samples with high wetting capabilities, but not in the sample with low wetting characteristics. It was found that these compounds are substances that promote effective brazing.     

FORMATION AND FLOW OF GAS BUBBLES IN A PRESSURIZED BUBBLE COLUMN WITH A SINGLE ORIFICE OR NOZZLE GAS DISTRIBUTOR

The characteristics of gas bubbles in a 5 cm diameter bubble column equipped with a single orifice of 1,3 or 5 mm diameter were investigated under system pressure of 0.1-15 MPa. The formation of gas bubbles was strongly affected by the system pressure. Under high pressures a dispersed gas jet was formed at gas velocities where spherical gas bubbles would have been formed at atmospheric pressure. The critical gas velocity between the bubbling regime and the jetting regime was correlated with the liquid phase Weber number and the gas phase Reynolds number based on the gas velocity at the orifice. Bubble size and gas holdup in the main part of the bubble column were also affected by the bubble formation pattern at the distributor     

Polymerization of propylene over metal oxides-supported TiCl3 catalysts

Summary Several metal oxides-supported TiCl₃ catalysts were prepared and propylene polymerization was conducted over them without cocatalysts. It was found that isotactic polymerization of propylene took place effectively over them.     

Polymerization of propylene over titanium exchanged Y-zeolite

Summary It was found that isotactic polymerization of propylene took place over titanium ion-exchanged Y-zeolite without organometallic compounds. The results obtained have led to the conclusions that Ti⁴⁺ species as well as Ti³⁺ species are active for the polymerization and that neither Ti-alkyl bonds nor Cl ligands are necessarily essential for polymerization of propylene.     

Preparation and characterization of electroplated amorphous gold-nickel alloy film for electrical contact applications

A process for electroplating amorphous gold-nickel alloy with the atomic ratio of unity was developed. The plating bath was prepared by adding potassium cyanoaurate(I) into a known plating bath which produces amorphous nickel-tungsten alloy. At a sufficiently high gold concentration, the alloy deposit did not contain any tungsten. The amorphous nature of the Au-Ni alloy produced in the new bath was confirmed by using TEM and THEED. Hardness, resistivity, and contact resistance of this new alloy were determined, and the results are discussed for applications as an electrical contact material.     

Comparative study of lipogenic enzymes in several vertebrates

The liver lipogenic enzymes are compared among rats, chickens, frogs and fish. Although the apparent Km values of glucose-6-phosphate dehydrogenase for glucose-6-phosphate are not much different among all the species, those of malic enzyme for malate are much higher in chickens and fish than in rats and frogs. Glucose-6-phosphate dehydrogenase showed very high activities compared with malic enzyme in fish liver, and malic enzyme showed high activities in chicken liver. Although the apparent Km values of acetyl-CoA carboxylase and fatty acid synthetase for substrates are in the same range among all the animals, the activity of acetyl-CoA carboxylase seems to be extremely low in fish and frog livers, and that of fatty acid synthetase is low in frog livers only. In addition, the apparent Km values of α-glycerophosphate acyltransferase of fish liver are very high, and the enzyme activity appears to be extremely low compared to the others. Therefore, the enzymes at the first steps of both fatty acid and glycerolipid syntheses of poikilothermos animals appear to be very low. On the other hand, the Ouchterlony double-diffusion patterns showed that the lipogenic enzymes of chickens, frogs and fish are immunologically different from those of rats, with the exception of acetyl-CoA carboxylase in chickens. Therefore, it is suggested that the fatty acid and glycerolipid forming systems of poikilothermos animals are quite different from those of homoiothermos and the lipogenesis is very low in poikilothermos.