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Application of biocatalysts for development of non-natural organosilicon compounds

Research Project

Project/Area Number 04805102
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field 発酵工学
Research InstitutionKYUSHU UNIVERSITY (1993)
Kyushu Institute of Technology (1992)

Principal Investigator

SONOMOTO Kenji  Kyushu University, Faculty of Agriculture, Assoc.Prof., 農学部, 助教授 (10154717)

Project Period (FY) 1992 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1993: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1992: ¥1,300,000 (Direct Cost: ¥1,300,000)
KeywordsOrganosilicon compounds / Sila-substitution effects / Sila-substituted alcohols / stereoselective esterification / Alcohol dehydrogenase / Lipase / Trimethylsilyl group / beta-effect / 電子的安定化効果 / エステル化反応 / 光学分割 / Candida cylindraceaリパーゼ / Pseudomonas sp.リポプロテインリパーゼ / 2-(4-クロロフェノキシ)プロピオン酸
Research Abstract

Comparative studies were made of the use as acyl acceptor of organosilicon compounds [Me_3Si(CH_2)_nOH] and the corresponding carbon compounds [Me_3C(CH_2)_nOH] in the stereoselective esterification of 2-(4-chlorophenoxy)propanoic acid by the use of lipase OF 360 of candida cylindracea in water-saturated benzene. The organosilicon compounds were effectively used as the substrates for the esterification of D-acid enantiomer. Of the organosilicon compounds of different chain-length between the silicon atom and the hydroxyl group, trimethylsilylmethanol (n=1) enabled the esterification reaction to be both fast and highly stereoselective, which was difficult with conventional substrates such as its carbon counterpart. On the other hand, no difference was observed between trimethylsilylethanol (n=2) and its carbon analogue (3,3-dimethylbutanol) in the enzymatic activity and the stereoselectivity. These results indicate that the silicon atom behaved as a mimic carbon atom for lipase in the c … More ase of trimethylsilylethanol but was effective in enhancing the reactivity of trimethylsilylmethanol. The difference could be explained on the basis of the properties of silicon atom, such as its low electronegativity and big atomic radius compared with the carbon atom.
Among the commercially available alcohol dehydrogenases from different sources tested, equine lliver alcohol dehydrogenase (HLADH) recognized several organosilicon compounds, sila-substituted alcohols, as a substrate and exhibited the oxidative activity. Especially, large differences in catalytic rates were observed between trimethylsilyl alcohols [Me_3Si(CH_2)_nOH] but not between the carbon analogues. Thus, the activity of HLADH was extremely and peculiarly affected by trimethylsilyl group in the organosilicon compounds [trimethylsilylmethanol (n=1), 27% ; trimethylsilylethanol (n=2), 212% ; trimethylsilylpropanol (n=3), 65% ; ethanol, 100%]. These differences might result from beta-effect of trimethylsilyl group (stabilization of a negative charge in the carbon to the silicon and ・ a positive charge on the carbon to the silicon) by considering the possible mechanisms for hydrogen transfer at HLADH active site. As a result of kinetic investigations with HLADH, trimethylsilylethanol was found to show high affinity compared with the others. Furthermore, enhancement of HLADH activity derived from sila-substitution was not easily provided even by the use of the corresponding carbon analogues with electron attractive group (for example, 3-methoxy-3-methylbutanol). Less

Report

(3 results)
  • 1993 Annual Research Report   Final Research Report Summary
  • 1992 Annual Research Report
  • Research Products

    (33 results)

All Other

All Publications (33 results)

  • [Publications] M.Kawase: "Inspection of an acyl-enzyme intermediate in a lipase reaction by gas-chromatography-mass spectrometry and modeling of the reaction mechanism." Biocatalysis. 6. 43-50 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] K.Sonomoto: "Enzymatic conversion of artificial organosilicon compounds by alcohol dehydrogenase." Enzyme Microb.Technol.14. 640-643 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] K.Sonomoto: "Effects of sila-substitution of substrates on activity of alcohol dehydrogenase." Ann.N.Y.Acad.Sci.672. 66-70 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] C.-S.Rui: "A flow-injection biosensor system for the amperometric determination of creatinine:simultaneous compensation of endogenous interferents." Anal.Biochem.210. 163-171 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] A.Uejima: "Efficient kinetic resolution of organosilicon compounds by stereo-selective esterification with hydrolases in organic solvent." Appl.Microbiol.Biotechnol.38. 482-486 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] K.Sonomoto: "Integrated bioreactor system for biologically active peptides from isolated soybean protein." Ann.N.Y.Acad.Sci.(in press). (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] 田中渥夫: "バイオリアクターの世界-実践者のためのその基礎と応用-" ハリオ研究所, 329 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] 園元謙二: "バイオプロセスシステム工学" アイピーシー(印刷中), (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Kawase: "Inspection of an acyl-enzyme intermediate in a lipase reaction by gas-chromatography-mass spectrometry and modeling of the reaction mechanism." Biocatalysis. 6. 43-50 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] K.Sonomoto: "Enzymatic conversion of artificial organosilicon compounds by alcohol dehydrogenase." Enzyme Microb.Technol. 14. 640-643 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] K.Sonomoto: "Effects of sila-substitution of substrates on activity of alcohol dehydrogenase." Ann.N.Y.Acad.Sci.672. 66-70 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] C.-S.Rui: "Amperometric assay of creatinine in urine by flow injection analysis based on conjugated reactions of immobilized enzymes. Simultaneous compensation of endogenous ammonia." Ann.N.Y.Acad.Sci.672. 264-271 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] C.-S.Rui: "Amperometric flow-injection biosensor system for the simultaneous determination of urea and creatinine." Anal.Sci.8. 845-850 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] C.-S.Rui: "A flow-injection biosensor system for the amperometric determination of creatinine : simultaneous compensation of endogenous interferents." Anal.Biochem.210. 163-171 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] C.-S.Rui: "Multifunctional flow-injection biosensor for the simultaneous measurement of creatinine, glucose and urea." Biosci.Biotech.Biochem.57. 191-194 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] A.Uejima: "Efficient kinetic resolution of organosilicon compounds by stereoselective esterification with hydrolases in organic solvent." Appl.Microbiol.Biotechnol. : 38. 482-486 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] K.Sonomoto: "Integrated bioreactor system for biologically active peptides from isolated soybean protein." Ann.N.Y.Acad.Sci.in press. (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] C.-S.Rui: "A multifunctional flow-injection biosensor for the simultaneous determination of ammonia, creatinine and urea." Ann.N.Y.Acad.Sci.in press. (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] T.Yamakido: "Enzymatic hydrolysis of castor oil for valuable fatty acid production." Ann.N.Y.Acad.Sci.in press. (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] C.-S.Rui: "A flow-injection biosensor system for the amperometric determination of creatinine: simultaneous compensation of endogenous interferents." Anal. Biochem.210. 163-171 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] C.-S.Rui: "Multifunctional flow-injection biosensor for the simultaneous measurement of creatinine, glucose and urea." Biosci. Biotech. Biochem.57. 191-194 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] A.Uejima: "Efficient kinetic resolution of organosilicon compounds by stereoselective esterification with hydrolases in organic solvent." Appl. Microbiol. Biotechnol.38. 482-486 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Sonomoto: "Integrated bioreactor system for biologically active peptides from isolated soybean protein." Ann. N. Y. Acad. Sci.(in press). (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] C.-S.Rui: "A multifunctional flow-injection biosensor for the simultaneous determination of ammonia,creatinine and urea." Ann. N. Y. Acad. Sci.(in press). (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] T.Yamakido: "Enzymatic hydrolysis of castor oil for valuable fatty acid production.21GC06:Ann. N. Y. Acad. Sci." (in press). (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] 園本謙二: "バイオプロセスシステム工学" アイピーシー(印刷中), (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] Masaya Kawase: "Inspcction of an acyl-enzymc intermediate in a lipase reaction by gas chromatography-mass spectrometry and modeling of the reaction mechanism." Biocatalysis. 6. 43-50 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Kenji Sonomoto: "Enzymatic conversion of artificial organosilicon compounds by alcohol dehydrogenase." Enzyme Microb.Technol.14. 640-643 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Kenji Sonomoto: "Effects of sila-substitution of substrates on activity of alcohol dehydrogenase." Ann.N.Y.Acad.Sci.672. 66-70 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Chang-Sheng Rui: "Amperometric assay of creatinine in urine by flow injection analysis based on conjugated reactions of immobilized enzymes.Simultaneous compensation of endogenous ammonia." Ann.N.Y.Acad.Sci.672. 264-271 (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Chang-Sheng Rui: "Amperometric flow-injection biosensor system for the simultaneous determination of urea and creatinine." Anal.Sci.8. 845-850 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Chang-Sheng Rui: "A flow-injection biosensor system for the amperometric determination of creatinine:simultaneous compensation of endogenous interferents." Anal.Biochem.印刷中. (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] 田中 渥夫: "バイオリアクターの世界-実践者のためのその基礎と応用-" ハリオ研究所, 329 (1992)

    • Related Report
      1992 Annual Research Report

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Published: 1992-04-01   Modified: 2016-04-21  

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