Table 1.
Parameters obtained from the temperature and pressure dependence of the hydride transfer step in MR
| Parameters | NADH | NAD2H | KIE |
|---|---|---|---|
| k0, s−1 (25°C) | 50.2 ± 1.9 | 12.4 ± 0.3 | 4.0 ± 0.3 |
| ΔV‡, cm3·mol−1 (25°C) | −15.6 ± 0.8 | −11.6 ± 0.5 | −4.0 ± 1.3 |
| dΔΔV‡/dT, cm3·mol−1·K−1 | −0.09 ± 0.03 | −0.04 ± 0.03 | −0.05 ± 0.06 |
| ΔH‡, kJ·mol−1 | |||
| 1 bar | 32.0 ± 1.3 | 41.3 ± 2.5 | 9.3 ± 3.8 |
| 2 kbar | 30.1 ± 2.2 | 43.7 ± 1.5 | 13.6 ± 3.7 |
| dΔΔH‡/dp, kJ·mol−1·kbar−1 | 0.4 ± 0.7 | 1.0 ± 0.4 | 0.6 ± 1.1 |
| ΔS‡, J·mol−1·K−1 | |||
| 1 bar | −103 ± 5 | −83 ± 9 | 20 ± 13 |
| 2 kbar | −99 ± 8 | −66 ± 5 | 32 ± 13 |
| dΔΔS‡/dT, J·mol−1·K−1·kbar−1 | 6.8 ± 2.6 | 7.3 ± 1.6 | 0.5 ± 4.1 |
| lnA′, | 11.4 ± 0.6 | ||
| 1 bar | 13.8 ± 1.0 | 0.09 ± 0.15 | |
| 2 kbar | 11.8 ± 0.9 | 15.7 ± 0.6 | 0.02 ± 0.03 |
| dlnA′/dp, kbar−1 | 0.8 ± 0.3 | 0.9 ± 0.2 | 0.1 ± 0.5 |
KIE values are the differences in magnitude except for lnA′, where the prefactor ratio, A′H:A′D is given.