Table 2.
Benzoic acid (1) | 4‐Methylbenzoic acid (2) | 4‐Methoxybenzoic acid (3) | 3‐Methoxybenzoic acid (4) | 2‐Methoxybenzoic acid (5) | 4‐Nitrobenzoic acid (6) | 3‐Nitrobenzoic acid (7) | 2‐Nitrobenzoic acid (8) | ||
---|---|---|---|---|---|---|---|---|---|
Hammett | 0 | −0.17 | −0.27 | 0.12 | – | 0.71 | 0.78 | – | |
σ constants28 | |||||||||
mpCAR | k cat [min−1] | 140±20* | 122±3 | 132±4 | 104±3 | NA | NA | 3.7±0.5 | NA |
K m [mm] | 20±4* | 3.7±0.2 | 2.8±0.2 | 3.0±0.2 | NA | NA | 0.3±0.1 | NA | |
k cat/K m [min−1 mm −1] | 7±1* | 33±2 | 48±5 | 35±3 | NA | NA | 11±4 | NA | |
msCAR | k cat [min−1] | 197±4 | 154±6 | 179±6 | 18±1* | NA | NA | 40±10 | NA |
K m [mm] | 3.4±0.2 | 0.16±0.02 | 0.19±0.02 | 12±1* | NA | NA | 0.5±0.2 | NA | |
k cat/K m [min−1 mm −1] | 57±4 | 900±100 | 930±80 | 1.4±0.2* | NA | NA | 100±50 | NA | |
tpCAR | k cat [min−1] | 142±3 | 152±2 | 130±2 | 186±2 | 19±3 | 13±1 | 33±2 | NA |
K m [mm] | 2.0±0.1 | 0.69±0.03 | 0.45±0.02 | 0.56±0.02 | 9±3 | 0.6±0.1 | 0.7±0.1 | NA | |
k cat/K m [min−1 mm −1] | 72±6 | 220±10 | 290±10 | 334±10 | 2.2±0.7 | 22±6 | 44±8 | NA | |
noCAR | k cat [min−1] | 183±6 | 135±5 | 138±4 | 136±5 | NA | NA | 59±2 | NA |
K m [mm] | 2.1±0.2 | 1.2±0.2 | 1.1±0.1 | 0.9±0.1 | NA | NA | 2.5±0.3 | NA | |
k cat/K m [min−1 mm −1] | 89.1±8 | 110±20 | 130±10 | 150±10 | NA | NA | 24±3 | NA | |
niCAR | k cat [min−1] | 98±7 | 94±2 | 49±1 | 93±1 | NA | NA | 18±1 | NA |
K m [mm] | 0.9±0.1 | 1.0±0.1 | 0.25±0.01 | 0.68±0.03 | NA | NA | 5.6±0.7 | NA | |
k cat/K m [min−1 mm −1] | 103±9 | 97±6 | 200±10 | 137±6 | NA | NA | 3.2±0.4 | NA |
NA: no activity was detected with that substrate. *: K m was unusually large and substrate concentrations could not reach a high enough concentration to be able to determine the kinetic constants accurately. Errors represent the standard error. No Hammett constants are shown for substrates substituted in the 2‐position as steric effects cannot be accounted for properly.