Table 5.
Quantitative interpretation of 13C and 18O IEs using the standard kinetic model (Scheme 1E).
| 13Keq3 | 18Keq3 | k3/k2 | k5/k4 | 13C FFa | Bond Orderb | Calc’d./Exptl.13C IE (%)c | (V/K)/[E]ok1 | [E]ok1 (%) | |
|---|---|---|---|---|---|---|---|---|---|
| OxDCd | 1.021 | 1.016 | 0.7 | 4.0 | 0.963 | 1.16 (1.14) | 1.2/1.5 | 0.375 | 100 |
| R92K | 1.017 | 1.011 | 2.4 | 2.6 | 0.968 | 1.22 (1.22) | 0.7/1.0 | 0.636 | 1 |
Fractionation factor for 13C at pH 4.2 calculated from the standard kinetic model for the OxDC-catalyzed reaction as described previously [4].
Bond orders are based on the results of BEBOVIB calculations [36] as reported previously [4]. Values in parentheses are the bond orders calculated on the basis of 18O fractionation factors (not shown here). nd – not computed.
13C IEs are calculated for the reaction at pH 4.2 using values of 13Keq3, 13k3, 13k5, k3/k2, k5/k4 computed from observations at pH 5.7. Experimental IEs are those observed at pH 4.2.
Measurements for wild type OxDC have been reported previously [4] and are included here for ease of comparison.