Enzymatic ring-opening polyaddition for chitin synthesis: A cationic mechanism in basic solution?

The in vitro synthesis of chitin via a nonbiosynthetic path has been achieved for the first time by enzymatic ring-opening polyaddition of a chitobiose oxazoline monomer ( C2O ). Chitinase, a hydrolysis enzyme of chitin, recognized and polymerized the monomer regio- and stereoselectively. The structure of artificial chitin was confirmed by comparison with an authentic natural chitin sample with the use of CP/MAS ¹³C NMR and IR spectroscopy. X-ray diffraction as well as NMR analysis showed its crystal structure of α-chitin. Characteristic features of the present polymerization are described.     

Theoretical calculation of structures and proton transfer in hydrated ammonia-hydrogen chloride clusters

Ab initio molecular orbital calculations have been performed to investigate the structures and quantum effects of the proton motion in NH(3):HCl:(H(2)O)(n) (n = 0-3) clusters using a MP2/aug-cc-pVDZ level of theory. Three new stable structures and one transition-state structure are investigated for these clusters. The detailed analyses of the intermolecular interactions suggest that three-body interactions play an important role to determine the relative stability in each size of cluster. The quantum effects of the proton motion result in frequency shifts for proton-stretching modes. Our one-dimensional and two-dimensional models fairly closely reproduce the experimental proton-stretching vibrational frequency of the NH(3):HCl cluster. The most stable isomer for n = 1 has a proton-transfer structure, which is weakened by the quantum effects of the proton motion.     

A comparative study on chemical conversion of cellulose between the batch-type and flow-type systems in supercritical water

Microcrystalline cellulose (avicel) was treated in supercritical waterusing batch-type and flow-type systems. The flow-type system made it possibletoshorten the heating, treating and cooling times, compared with the batch-typesystem. As a result, the flow-type system was able to liquefy avicel withoutproducing any supercritical water-insoluble residue. Although hydrolyzedproducts such as glucose and fructose, and pyrolyzed products such aslevoglucosan, 5-hydroxymethyl furfural, erythrose, methylglyoxal,glycolaldehydeand dihydroxyacetone were found in common from the water-soluble portiontreatedby both systems, the flow-type system gave a water-soluble portion with morehydrolyzed and less pyrolyzed products, together with water-solubleoligosaccharides consisting of cellobiose to cellododecaose and theirdecomposedproducts at their reducing end of glucose, such as[–glucopyranosyl]_1–11 –levoglucosan,[–glucopyranosyl]_1–11 –erythrose and[–glucopyranosyl]_1–11 –glycolaldehyde. Inaddition, the precipitates of polysaccharides were recovered after 12h setting of the water-soluble portion. These results indicatedthat the flow-type system can hydrolyze cellulose with minimizing pyrolyzedproducts. On the other hand, the batch-type system resulted in a higher yieldof the pyrolyzed products due to the longer treatment, but a higher yield ofglucose due possibly to the higher pressure and concomitantly higher ionicproduct of water. Based on these lines of evidence, the process to increase theyield of the sugar is discussed under supercritical water treatment.     

Micro-thermal analysis of thermal conductance distribution in advanced silicon nitrides

A micro-thermal analysis technique was applied to investigate advanced silicon nitride materials, which exhibit high thermal conductivity. Local thermal properties in the microstructure were evaluated, and the grain boundaries were observed to have lower thermal conductance than the Si₃N₄ grains. It was found that thermal conductance both in the grains and boundaries was lowered by the addition of the sintering aid Al₂O₃, which is soluble in Si₃N₄ grains. This indicates that high thermal conductivity in silicon nitride ceramics is achieved both by grain growth, leading to a reduction in boundary density, and by eliminating soluble elements in silicon nitride grains. This revised version was published online in August 2006 with corrections to the Cover Date.     

Two-step preparation for catalyst-free biodiesel fuel production

Biodiesel fuel was prepared by a two-step reaction: hydrolysis and methyl esterification. Hydrolysis was carried out at a subcritical state of water to obtain fatty acids from triglycerides of rapeseed oil, while the methyl esterification of the hydrolyzed products of triglycerides was treated near the supercritical methanol condition to achieve fatty acid methyl esters. Consequently, the two-step preparation was found to convert rapessed oil to fatty acid methyl esters in considerably shorter reaction time and milder reaction condition than the direct supercritical methanol treatment. The optimum reaction condition in this two-step preparation was 270°C and 20 min for hydrolysis and methyl esterification, respectively. Variables affecting the yields in hydrolysis and methyl esterification are discussed.