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  • 1
    Electronic Resource
    Electronic Resource
    Oxford, UK : Blackwell Publishing Ltd
    Annals of the New York Academy of Sciences 672 (1992), S. 0 
    ISSN: 1749-6632
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Natural Sciences in General
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Oxford, UK : Blackwell Publishing Ltd
    Annals of the New York Academy of Sciences 613 (1990), S. 0 
    ISSN: 1749-6632
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Natural Sciences in General
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Oxford, UK : Blackwell Publishing Ltd
    Annals of the New York Academy of Sciences 799 (1996), S. 0 
    ISSN: 1749-6632
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Natural Sciences in General
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1432-0614
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Summary Bioconversion of three organosilicon compounds of different chain length between the silicon atom and the hydroxyl group (Me3Si(CH2)nOH, n = 1–3) by horse liver alcohol dehydrogenase (HLADH, EC 1.1.1.1.) was studied. Furthermore, the effect of the silicon atom on the HLADH-catalysed reaction was examined in comparison with the corresponding carbon compounds. HLADH could catalyse the dehydrogenation of trimethylsilyeethanol (n = 2) and trimethylsilylpropanol (n = 3). Trimethylsilylethanol was a better substrate than both its carbon analogue, 3,3-dimethylbutanol, and ethanol. The improved activity of HLADH on trimethylsilylethanol could be accounted for by a higher affinity toward HLADH and a lower activation energy of the reaction by HLADH than those of the carbon counterpart. These are derived from physical properties of the silicon atom, that is, the lower electronegativity and the bigger radius than those of the carbon atom. In contrast, HLADH showed no activity on trimethylsilylmethanol (n = 1), whereas it catalysed the dehydrogenation of the carbon analogue, 2,2-dimethylpropanol, fairly well. The reason for the inactivity of HLADH in the case of trimethylsilylmethanol based on the electric effect of the silicon atom is also discussed.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1432-0614
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Stereoselective esterification of three isomers of trimethylsilylpropanol, 1-trimethylsilyl-2-propanol, 1-trimethylsilyl-1-propanol, and 2-trimethylsilyl-1-propanol, was systematically studied with five kinds of hydrolases in an organic solvent system in connection with the structure of the compounds. The hydrolases were found to be able to esterify these organosilicon compounds, even β-hydroxyalkylsilanes, which are unstable under the conditions of acid-catalysed esterification, and the highly optically active organosilicon compounds were successfully prepared with the selected hydrolases. Even a primary alcohol, 2-trimethylsilyl-1-propanol, was stereoselectively esterified by lipase. Furthermore, comparative studies were made by using their carbon counterparts. The silicon atom in the substrates was found to enhance the enzyme stereoselectivity in some cases, but its effect on the substrate reactivity was dependent on the structure of the substrates. These results are discussed based on the specific characters of the silicon atom.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 1432-0614
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Streoselective dehydrogenation of three isomers of trimethylsilypropanol was carried out with horse liver alcohol dehydrogenase (HLADH, EC 1.1.1.1.) and optically active organosilicon compounds were obtained in a water-organic solvent two-layer system with coenzyme regeneration. Furthermore, we examined the effects of the silicon atom on stereoselectivity of HLADH compared to the corresponding carbon compounds. Substitution of the silicon atom for the carbon atom was found to improve the stereoselectivity of HLADH. For example, the optical purity of the remaining 1-trimethylsilyl-2-propanol was higher than 99% enantiomeric excess (ee) at 50% conversion, whereas that of the carbon analogue was 84% ee. This phenomenon was probably ascribable to the bulkiness of the organosilicon compounds derived from their longer Si-C bond. Kinetic analysis in an aqueous monolayer system demonstrated that the specific properties of the silicon atom greatly affected the reactivity of these substrate compounds.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 1432-0614
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Summary A “non-support bioreactor”, a novel column reactor packed with a free non-supported enzyme was constructed by applying the insolubility of the enzyme in organic solvents. Stereoselective esterification of 2-(4-chlorophenoxy)propanoic acid by lipase OF 360 from Candida cylindracea with n-tetradecanol was selected as a model reaction. Non-supported lipase revealed threefold higher activity than Celite-adsorbed lipase by maintaining high stereoselectivity in a batch reaction. In continuous operation, a non-support bioreactor produced the ester with fourfold higher productivity to that of a column reactor packed with Celite-adsorbed lipase (an adsorbed bioreactor). However, the optical purity of the remaining (S)-acid was low even when the conversion ration was kept at approximately 50%. Lipase recovered from the non-support bioreactor after continuous operation retained the original stereoselectivity in a batch reaction. Therefore, semi-continuous operation was conducted by recycling the substrate solution at a high flow rate. The non-support reactor showed high stereoselectivity and ten times the productivity compared with the adsorbed bioreactor. The reason for this high performance is discussed.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Applied microbiology and biotechnology 40 (1994), S. 653-656 
    ISSN: 1432-0614
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Thermolysin was able to catalyze enantioselective peptide synthesis with non-natural amino acids, halophenylalanines. However, the reactivity of thermolysin was considerably influenced by the kind and position of halogen substituents on these analogues. The manner of the recognition of the amino component by the enzyme was different from that of the carboxyl component in the synthesis of peptides with non-natural phenylalanine analogues. The phenomena observed are discussed, based on the kinetic parameters obtained.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Applied microbiology and biotechnology 40 (1994), S. 653-656 
    ISSN: 1432-0614
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract. Thermolysin was able to catalyze enantioselective peptide synthesis with non-natural amino acids, halophenylalanines. However, the reactivity of thermolysin was considerably influenced by the kind and position of halogen substituents on these analogues. The manner of the recognition of the amino component by the enzyme was different from that of the carboxyl component in the synthesis of peptides with non-natural phenylalanine analogues. The phenomena observed are discussed, based on the kinetic parameters obtained.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 1432-0614
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Summary Optical resolution of racemic carboxylic acids containing a halogen atom was attempted with stereoselective esterificatiob by Celite-adsorbed hydrolases in organic solvents. As lipase OF 360 from Candida cylindracea was found to stereoselectively esterify 2-(4-chlorophenoxy)propanoic acid, the (R)-enantiomer (d-isomer) of which is an important herbicide, the effects of alcohol chain length on stereoselectivity as well as reaction rate were investigated. The results revealed that the alcohol chain length markedly affected the stereoselective esterification of 2-(4-chlorophenoxy)propanoic acid: longer-chain alcohols, such as tetradecanol, served as excellent substrates for optical resolution of the acid, although the reaction rate was moderate.
    Type of Medium: Electronic Resource
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