Mechanistic imperatives for enzymatic catalysis of aldose-ketose isomerization: Isomerization of glyceraldehyde in weakly alkaline aqueous solution occurs with intramolecular transfer of a hydride ion

Journal of the American Chemical Society

Volumn 118, Issue 31, 1996, Pages 7432-7433

  Nagorski, R W ^a   Richard, John P ^a  

^a UNIVERSITY AT BUFFALO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

GLYCERALDEHYDE;

ARTICLE; CATALYSIS; ISOMERISM; REACTION ANALYSIS;

EID: 0029769672     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja961259d     Document Type: Article

References (18)

1. 2O proceeds through a common enolate reaction intermediate (Kooyman, C.; Vellenga, K.; de Wilt, H. G. J. Carbohydr. Res. 1977, 54, 33-44).
2. 2O proceeds through a common enolate reaction intermediate (Kooyman, C.; Vellenga, K.; de Wilt, H. G. J. Carbohydr. Res. 1977, 54, 33-44).
3. 2O proceeds through a common enolate reaction intermediate (Kooyman, C.; Vellenga, K.; de Wilt, H. G. J. Carbohydr. Res. 1977, 54, 33-44).
4. Henrick, K.; Collyer, C. A.; Blow, D. M. J. Mol Biol. 1989, 208, 129-157.
5. Collyer, C. A.; Blow, D. M. Proc. Nat. Acad. Sci. U.S.A. 1990, 87, 1362-1366.
6. Collyer, C. A.; Henrick, K.; Blow, D. M. J. Mol Biol. 1990, 212, 211-235.
7. Allen, K. N.; Lavie, A.; Farber, G.; Glasfeld, A.; Petsko, G.; Ringe, D. Biochemistry 1994, 33, 1481-1487.
8. Farber, G. K.; Glasfeld, A.; Tiraby, G.; Ringe, D.; Petsko, G. A. Biochemistry 1989, 28, 7289-7297.
9. Richard, J. P. J. Am. Chem. Soc. 1984, 106, 4926-4936.
10. Knowles, J. K.; Albery, W. J. Acc. Chem. Res. 1977, 10, 105-111.
11. 15,16 and the observed first-order rate constants for deuterium exchange were determined by treating the data as described in ref 14.
12. 2O at 25 °C using Varian VXR-400S or INOVA-500 spectrometers. Chemical shifts are reported relative to HOD at 4.65 ppm. (b) These values were calculated by correcting the observed ratios of 5.7 (Figure 1A) and 4.1 (Figure 1B) for the presence of 0.15% of dihydroxacetone in our preparation of D,L GA.
13. This argument is developed in greater detail in ref 16.
14. The progress of isomerization of D,L-GA was determined by comparison of the integrated areas of the peaks for the hydroxymethylene protons of DHA and for the C-1 proton of the hydrate of D,L-GA, with appropriate corrections for the differences in the extent of hydration of DHA (16% hydrate) and D,L-GA (95% hydrate).
15. CHD during the first 1%-4% of the isomerization reaction in dilute alkaline solution showed that this ratio is reproducible to within ± 10%.
16. Halkides, C. J.; Frey, P. A.; Tobin, J. B. J. Am. Chem. Soc. 1993, 115, 3332-3333.
17. Amyes, T. L.; Richard, J. P. J. Am. Chem. Soc. 1992, 114, 10297-10302.
18. Amyes, T. L.; Richard, J. P. J. Am. Chem. Soc. 1996, 118, 3129-3141.