Polymer synthesis by means of germylene and stannylene

Divalent group 14 metal species, a germylene(la) and a stannylene(lb), behaved as a comonomer(reductant monomer) in the copolymerization with p-benzoquinone derivatives(oxidant monomer)(“oxidation-reduction copolymerization”) and as an initiator for anionic monomers. The copolymerization took place without initiator at a lower temperature to give an alternating copolymer. N-phenyl-p-quinoneimine also behaved as a reactive oxidant monomer toward la and lb. These species have been shown to induce the polymerization of anionically polymerizable monomers such as methyl methacrylate, methacrylonitrile, and 4-vinylpyridine. Based on the mechanistic examination of the polymerization, a new alternating copolymerization between la and 2-cyclohexene-l-one has been developed to produce a copolymer having a metal-enolate structure, which involves the oxidation-reduction process during the copolymerization.     

One‐Pot Synthetic Procedure for2,2′‐Disubstituted Biaryls via the Suzuki Coupling Reaction of Aryl Triflates in a Biphasic Solvent System

A one‐pot synthetic procedure for 2,2′‐disubstituted biaryls was developed via a Suzuki cross‐coupling reaction of aryl triflates in a biphasic solvent system. The effects of various bases and solvents were investigated. Results showed that the Na₂CO₃–toluene/H₂O combination gave the highest yields.     

Quantum Mutual Entropy Defined by Liftings

A lifting is a map from the state of a system to that of a compound system, which was introduced in Accardi and Ohya (Appl. Math. Optim. 39:33–59, 1999). The lifting can be applied to various physical processes.     

Relativistic correlating basis sets for 57La and 89Ac

Developed and reported are compact yet efficient correlating basis sets for the ₅₇La and ₈₉Ac atoms, missing in the literature. Good performance of these correlating sets is exemplified in molecular applications to diatomic oxides and fluorides. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

On Short Time Asymptotic Behavior of Some Symmetric Diffusions on General State Spaces

For conservative symmetric diffusions on a general state space (X,m), the short time asymptotic behavior of tlog _X 1 _A T _t 1 _B dm is investigated, where T _t is the associated semigroup and A and B are measurable subsets of X. It is proved that the superior limit is dominated by the inferior limit up to some absolute constant. When ₂ of the associated Dirichlet form is lower bounded, it is shown that the limit exists for any A and B, and is described by the intrinsic metric between them. Applications to infinite-dimensional spaces and fractals are given.     

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.     

Metallic conductivity and ferromagnetic interaction of iron(III) d spins in the needle crystals of (ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide)(2).FeBr(4) salt

The 2:1 charge-transfer (CT) salts (1(2).FeBr(4) and 1(2).GaBr(4)) of ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide (1) with FeBr(4)(-) and GaBr(4)(-) counteranions were obtained as needle crystals, whose structures are almost the same as each other. The 1 molecules form a one dimensionally stacked column with alternation of their molecular axis direction, while the counteranions are aligned in parallel with the 1-stacked columns with the direction of their distorted-tetrahedral geometry maintained. The room-temperature electrical conductivities measured on the single crystals of 1(2).FeBr(4) and 1(2).GaBr(4) were 4.6 and 2.1 S cm(-1), respectively. From the temperature dependences of their electrical conductivities in both cases the electrical conducting properties were metallic between ca. 170 and 300 K, but below ca. 170 K converted to be semiconducting and continued till 5 K, although the activation energies are very small (4-10 meV). For 1(2).FeBr(4) very weak and antiferromagnetic interaction occurred between the d spins of FeBr(4)(-) ions in the temperature range of ca. 1-300 K. However, below ca. 15 K the ferromagnetic interaction was reversely preferential possibly by participation of the pi spin of 1.