On the regioselectivity for the Michael addition of thiols to unsymmetrical fumaric derivatives

The regiochemistry of the Michael addition of thiols to unsymmetrical fumaric derivatives was investigated. Conjugate addition of thiols to unsymmetrical fumaric diester was well controlled by the presence of lithium cation and one of the two possible regioisomers was prepared in a highly selective manner. Fumaric ester amides underwent the regioselective Michael addition that was controlled by the presence or absence of the base; either of the regioisomers was prepared as an almost diastereomerically pure form. The present control of the regiochemistry can be explained by the factors of change of active site for the addition by the coordination or non-coordination of proton or lithium cation to the carbonyls. To clarify the origin of the regioselectivity, the relative rates of the conjugate addition of thiol to acrylate derivatives were measured under competitive conditions. Ethyl acrylate reacted with thiol faster than tert-butyl acrylate and the rate difference was enhanced by the presence of lithium cation. In the presence of base, ethyl acrylate gave the adducts much faster than acrylamide, while under non-basic conditions acrylamide showed higher reactivity than the ester. This regioselectivity was also observed in the Michael/aldol reaction and multi-substituted γ-butyrolactones were prepared in a stereoselective manner. The thio groups introduced here served as a leaving group and a convenient stereoselective synthesis of β-, γ- and δ-lactams was developed.     

Kinetic analysis of photopolymerization reaction of lauryl acrylate with a photoinduced chemical reaction calorimeter

Calorimetric studies on kinetics of photopolymerization reactions made previously have been limited by the structures of the calorimeters. This report suggests a thermal-leak type of calorimeter for carrying out kinetic analysis of the photopolymerization reaction. The method was applied to the photopolymerization system consisting of lauryl acrylate and benzoin methyl ether. The results obtained illustrate the utility of this apparatus.     

A PL homotopy continuation method with the use of an odd map for the artificial level

This note presents a new piecewise linear homotopy continuation method for solving a system of nonlinear equations. The important feature of the method is the use of an odd map for the artificial level of the homotopy. Some sufficient conditions for the global convergence of the method are given. They are different from the known conditions for the global convergence of the existing homotopy continuation methods. Specifically, they cover all the systems of nondegenerate linear equations. Partially supported by the Sakkokai Foundation and by the Grand-in-Aid for Scientific Research of the Ministry of Education and Culture No. 58750265. Partially supported by the Grant-in-Aid for Scientific Research of the Ministry of Education and Culture No. 56460103.     

Potentiometric sensor for sulfur oxides using NASICON as a solid electrolyte

The ac conductivity of NASICON is higher by two orders of magnitude than that of Na₂SO₄ at 1000 K. The dc polarization measurement reveals that NASICON shows sodium ion conduction even at the temperature of about 1200 K, and that the electronic transference number is of the order of 10^?5. The SO₂-O₂-SO₃ concentration cell using NASICON electrolyte gives essentially the same electromotive force as in the cell using Na₂SO₄ electrolyte because a thin layer of Na₂SO₄ if formed on NASICON at the electrodes. The high sinterability of NASICON offers a dense electrolyte without permeation of gases. The SO_x sensor using NASICON electrolyte exhibits good response and excellent selectivity against CO₂ and NO₂.     

Genetic and expression analysis of all non‐synonymous single nucleotide polymorphisms in the human deoxyribonuclease I‐like 1 and 2 genes

Members of the human DNase I family, DNase I‐like 1 and 2 (DNases 1L1 and 1L2), with physiological role(s) other than those of DNase I, possess three and one non‐synonymous SNPs in the genes, respectively. However, only limited population data are available, and the effect of these SNPs on the catalytic activity of the enzyme remains unknown. Genotyping of all the non‐synonymous SNPs was performed in three ethnic groups including six different populations using the PCR‐RFLP method newly developed. Asian and African groups including Japanese, Koreans, Ghanaians and Ovambos were typed as a single genotype at each SNP, but polymorphism at only SNP V122I in DNase 1L1 was found in Caucasian groups including Germans and Turks; thus a Caucasian‐specific allele was identified. The DNase 1L1 and 1L2 genes show relatively low genetic diversity with regard to these non‐synonymous SNPs. The level of activity derived from the V122I, Q170H and D227A substituted DNase 1L1 corresponding to SNPs was similar to that of the wild‐type, whereas replacement of the Asp residue at position 197 in the DNase 1L2 protein with Ala, corresponding to SNP D197A, reduced its activity greatly. Thus, SNP V122I in DNase 1L1 exhibiting polymorphism exerts no effect on the catalytic activity, and furthermore SNP D197A in DNase 1L2, affecting its catalytic activity, shows no polymorphism. These findings permit us to postulate that the non‐synonymous SNPs identified in the DNase 1L1 and 1L2 genes may exert no influence on the activity levels of DNases 1L1 and 1L2 in human populations.     

Hydrostatic pressure effects on polymer cholesteric liquid-crystalline structure. I. Equilibrium structure of hydroxypropyl cellulose aqueous solution

The effect of pressure on the polymer cholesteric liquid-crystalline structure of hydroxypropyl cellulose aqueous solutions was studied using reflection spectra measurements. Pressures applied to the polymer liquid crystals ranged from 1 to 2000 bar. The equilibrium reflection spectrum of the cholesteric structure shifted to longer wavelengths, showing that the cholesteric pitch of the liquid-crystalline structure increases as the applied pressure increases. At pressures higher than 200 bar the maximum wavelength of reflection shifted linearly with the increase in applied pressure. At lower pressures, the cholesteric structure was influenced by the surface plane of the quartz window.