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Volumn 129, Issue 43, 2007, Pages 12946-12947

Product deuterium isotope effect for orotidine 5′-monophosphate decarboxylase: Evidence for the existence of a short-lived carbanion intermediate

Author keywords

[No Author keywords available]

Indexed keywords

ANION; CARBANION; DEUTERIUM; ISOTOPE; OROTIDINE 5' PHOSPHATE DECARBOXYLASE; UNCLASSIFIED DRUG;

EID: 35848965479     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja076222f     Document Type: Article
Times cited : (44)

References (23)
  • 1
    • 35848948282 scopus 로고    scopus 로고
    • Residues are numbered according to the sequence for the enzyme from yeast
    • Residues are numbered according to the sequence for the enzyme from yeast.
  • 13
    • 35848964267 scopus 로고    scopus 로고
    • 1) and with suppression of the water peak. Baselines were subjected to first-order drift correction before integration of the signals.
    • 1) and with suppression of the water peak. Baselines were subjected to first-order drift correction before integration of the signals.
  • 14
    • 0001735348 scopus 로고    scopus 로고
    • Reaction mixtures were buffered with 50 mM 3-(N-morpholino) propanesulfonic acid (50% free base). Values of pL were obtained by adding 0.18 to the reading of the pH meter [Pentz, L.; Thornton, E. R. J. Am. Chem. Soc. 1967, 89, 6931-6938].
    • Reaction mixtures were buffered with 50 mM 3-(N-morpholino) propanesulfonic acid (50% free base). Values of pL were obtained by adding 0.18 to the reading of the pH meter [Pentz, L.; Thornton, E. R. J. Am. Chem. Soc. 1967, 89, 6931-6938].
  • 15
    • 35848969958 scopus 로고    scopus 로고
    • D (eq 1) remains constant over a period of ca. 20 hours. The variation in this ratio determined from integration of different NMR spectra is less than 3%.
    • D (eq 1) remains constant over a period of ca. 20 hours. The variation in this ratio determined from integration of different NMR spectra is less than 3%.
  • 22
    • 35848962176 scopus 로고    scopus 로고
    • The primary 13C KIE on OMPDC-catalyzed decarboxylation of OMP labeled at the carboxylate carbon decreases from 1.043 for reaction in H2O to 1.034 for the 25% slower reaction in D2O ref 7, which shows that decarboxylation is less rate-determining in D 2O than in H2O. This result is not easily rationalized by a mechanism in which proton transfer from Lys-93 to C-6 of OMP is concerted with the loss of CO2 because the change from H2O to D2O should raise the barrier to a reaction in which proton transfer is concerted with loss of CO2, as a result of a normal primary KIE. This would cause the loss of CO2 to become more rate-determining in a multistep enzymatic reaction in D2O and would result in an increase, rather than the observed decrease, in the 13C isotope effect
    • 13C isotope effect.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.