Natural stereospecific hydrogen isotope transfer in alcohol dehydrogenase-catalysed reduction

• Autorzy: Zhang B. , Pionnier S.
• Konferencja: Proceedings of the International Conference “2001 an Isotope Odyssey: New Application for a New Millenium", June 24-29, 2001, Zakopane, Poland
• Języki publikacji: EN

Abstrakty

EN

The enantiomeric purity of natural alfa-monodeuterated enantiomers, (R) and (S) ethanol-1-d1, in the alcohol produced by sugar fermentation with yeast was studied by 2H NMR using their esters derived from optical mandelic acid. The results of isotope tracing experiments show that the transfer pathways of the two enantiotopic hydrogens of the methylene group are different. It was observed that (S)-deuterium comes only from the medium water. The (R)-deuterium transfered by NADH in alcohol dehydrogenase reduction of the acetaldehyde is of complex origin. Some of them originates from carbon bound hydrogen of the sugar, especially from C(4) position of glucose and most of them comes from water. Only a small portion of the NADH deuterium is incorporated indirectly from water through enzyme catalysed exchange between the pro-S site of NADH and flavin. When a carbonyl compound (ethyl acetoacetate) was reduced under the same conditions during the alcoholic fermentation, among the NADH-transfered deuterium, only a small portion comes from water while most comes from the unexchangeable positions of the glucose.

Słowa kluczowe

EN

alcohol dehydrogenase; chiral isotopomers; deuterium; isotope tracing

• Wydawca: Institute of Nuclear Chemistry and Technology
• Czasopismo: Nukleonika
• Rocznik: 2002
• Tom: Vol. 47,suppl.1
• Strony: 29--31
• Opis fizyczny: Bibliogr. 7 poz., rys.

Twórcy

autor

Zhang B.

• Laboratoire d'Analyse Isotopique et Electrochimique de Métabolismes, CNRS UMR 6006, Université de Nantes, 2 rue de la Houssiniere, 44322 Nantes, France, Tel.: [phone], Fax: [phone]

autor

Pionnier S.

• Laboratoire d'Analyse Isotopique et Electrochimique de Métabolismes, CNRS UMR 6006, Université de Nantes, 2 rue de la Houssiniere, 44322 Nantes, France, Tel.: [phone], Fax: [phone]

Bibliografia

• 1. Cook PF, Blanchard JS, Cleland WW (1980) Primary and secondary deuterium isotope effects on equilibrium constants for enzyme-catalyzed reactions. Biochem 19:4853–4858
• 2. Günther H, Alizade MA, Kellner M, Biller F, Simon H (1973) Preparation of (1R)- and (1S)-1-2H labeled alcohols by exchange reactions catalysed by yeast or a couple enzyme system. Z Naturforsch 28c:241–246
• 3. Martin ML, Zhang BL, Martin GJ (1983) Natural chirality of methylene sites applied to the recognition of origin and to the study of biochemical mechanisms. FEBS Letters 158:131–133
• 4. Rabiller C, Mesbahi M, Martin ML (1990) 2H NMR resolution of the methylenic isotopomers of ethanol applied to the study of stereospecific enzyme-catalysed exchange. Chirality 2:85–89
• 5. Simon H, Kellner M, Günther H (1968) Synthesis, on a preparative scale, of ethanol stereospecifically labeled on hydrogen. Angew Chem Internat Edit 7;11:892
• 6. Zhang BL, Buddrus S, Martin ML (2000) Site-specific hydrogen isotope fractionation in the biosynthesis of glycerol. Bioorg Chem 28:1–15
• 7. Zhang BL, Yunianta Martin ML (1995) Site-specific isotope fractionation in the characterization of biochemical mechanisms. J Biol Chem 270:16023–16029