Ether-like Si-Ge hydrides for applications in synthesis of nanostructured semiconductors and dielectrics.
Hydrolysis reactions of silyl-germyl triflates are used to produce ether-like Si-Ge hydride compounds including H(3)SiOSiH(3) and the previously unknown O(SiH(2)GeH(3))(2). The structural, energetic and vibrational properties of the latter were investigated by experimental and quantum chemical simulation methods. A combined Raman, infrared and theoretical analysis indicated that the compound consists of an equal mixture of linear and gauche isomers in analogy to the butane-like H(3)GeSiH(2)SiH(2)GeH(3) with an exceedingly small torsional barrier of approximately 0.2 kcal mol(-1). This is also corroborated by thermochemistry simulations which indicate that the energy difference between the isomers is less than 1 kcal mol(-1). Proof-of-principle depositions of O(SiH(2)GeH(3))(2) at 500 degrees C on Si(100) yielded nearly stoichiometric Si(2)Ge(2)O materials, closely reflecting the composition of the molecular core. A complete characterization of the film by RBS, XTEM, Raman and IR ellipsometry revealed the presence of Si(0.30)Ge(0.70) quantum dots embedded within an amorphous matrix of Si-Ge-O suboxide, as required for the fabrication of high performance nonvolatile memory devices. The use of readily available starting materials coupled with facile purification and high yields also makes the above molecular approach an attractive synthesis route to H(3)SiOSiH(3) with industrial applications in the formation of Si-O-N high-k gate materials in high-mobility SiGe based transistors.
Synthetic pathways to disilylmethane, H3SiCH2SiH3, and methyldisilane, CH3SiH2SiH3
Disilylmethane is available in a four-step synthesis starting with phenylsilane. This is converted into chlorophenylsilane by HCl/AlCl3. The reaction of PhSiH2Cl and dibromomethane with magnesium in tetrahydrofuran affords bis(phenylsilyl)-methane, which yields bis(bromosilyl)methane by treatment with anhydrous hydrogen bromide. (BrH2Si)2CH2 is converted into disilylmethane by reduction with LiAlH4 in a two-phase system using a phase-transfer catalyst. - Methyldisilane is available by alkylation of a monohalodisilane, XSi2H5 (X Cl, Br), with methyllithium in a high-boiling ether or by silylation of bromomethylsilane with silylpotassium. Due to secondary silylation reactions the overall yields of methyldisilane are low in all cases.
New method for analysis of enzymatic reactions: Thermolysin-catalyzed synthesis of aspartame precursor
Aspartame is an artificial sweetener which is 200 times sweeter than sucrose. A precursor of aspartame, N-(benzyloxycarbonyl)-l-aspartyl-l-phenylalanine methyl ester (Z-APM) was synthesized and hydrolyzed with thermolysin in an aqueous monophasic system. Graphical plotting methods and/or nonlinear regression have been used to analyze enzymatic reactions because of the nonlinearity of enzymatic rate equations. There are, however, problems: the former require accurate measurement of the initial reaction rate and the latter gives no analytical information. The authors proposed a method to solve the nonlinear enzymatic rate equations with respect to the concentration of a product with the Taylor expansion, especially for the reversible Theorell-Chance mechanism (Murakami, Y., Hirata, M., and Hirata, A., J. Ferment. Bioeng., 82, 246–252, 1996). This solution, however, is complex for practical use. In this paper, a simpler solution to explain the thermolysin-catalyzed synthesis of Z-APM is obtained. New methods to determine the kinetic parameters, especially for the reversible Theorell-Chance mechanism, based on the approximated solution are proposed. The results calculated using the obtained kinetic parameters can satisfactorily explain the experimental results, which demonstrates the effectiveness of the proposed analysis. We must know the relation between the concentrations of substrates and a product, and accurately evaluate of the result obtained using Taylor expansion when we determine the kinetic parameters using our newly developed methods. The methods to determine the kinetic parameters of the reversible Theorell-Chance mechanism described in this paper is, however, expected to be applied to general enzymatic reactions.