Table II.
Apparent First-Order Rate Constants (k obs) for the Photolysis of Riboflavin (k obs) in the Presence of Acetate Buffer (pH 3.8–5.6), for the Formation of Formylmethyflavin (k 1) and Lumichrome (k 2) and Second-Order Rate Constants for the Interaction of Riboflavin and Acetate Buffer (k′)
pH | Concentration (M) | k obs × 104 s−1 ± SD | k 0 × 104 s−1a ± SD | k 1 × 10−4 s−1 ± SD | k 2 × 104 s−1 ± SD | k′ × 104 (M−1 s−1) ± SD |
---|---|---|---|---|---|---|
3.8 | 0.1 | 0.60 ± 0.03 | 0.24 ± 0.01 | 0.44 ± 0.02 | 0.16 ± 0.01 | 4.10 ± 0.20 |
0.2 | 1.01 ± 0.05 | 0.71 ± 0.03 | 0.17 ± 0.02 | |||
0.3 | 1.42 ± 0.08 | 0.95 ± 0.05 | 0.23 ± 0.02 | |||
0.4 | 1.85 ± 0.07 | 1.22 ± 0.06 | 0.30 ± 0.04 | |||
0.6 | 2.40 ± 0.16 | 1.60 ± 0.08 | 0.40 ± 0.02 | |||
4.1 | 0.1 | 0.65 ± 0.03 | 0.25 ± 0.02 | 0.50 ± 0.03 | 0.22 ± 0.01 | 4.33 ± 0.22 |
0.2 | 1.12 ± 0.06 | 0.76 ± 0.04 | 0.37 ± 0.02 | |||
0.3 | 1.51 ± 0.08 | 1.05 ± 0.06 | 0.50 ± 0.03 | |||
0.4 | 1.93 ± 0.08 | 1.33 ± 0.07 | 0.63 ± 0.04 | |||
0.6 | 2.85 ± 0.10 | 1.98 ± 0.20 | 0.88 ± 0.06 | |||
4.3 | 0.1 | 0.66 ± 0.03 | 0.24 ± 0.01 | 0.51 ± 0.02 | 0.15 ± 0.01 | 4.31 ± 0.26 |
0.2 | 1.14 ± 0.06 | 0.80 ± 0.04 | 0.35 ± 0.02 | |||
0.3 | 1.70 ± 0.09 | 1.10 ± 0.05 | 0.47 ± 0.03 | |||
0.4 | 2.23 ± 0.11 | 1.40 ± 0.06 | 0.63 ± 0.03 | |||
0.6 | 2.88 ± 0.15 | 2.24 ± 0.20 | 0.98 ± 0.05 | |||
4.6 | 0.1 | 0.43 ± 0.02 | 0.22 ± 0.02 | 0.48 ± 0.02 | 0.15 ± 0.01 | 3.27 ± 0.18 |
0.2 | 0.63 ± 0.03 | 0.76 ± 0.04 | 0.26 ± 0.02 | |||
0.3 | 1.02 ± 0.05 | 1.00 ± 0.05 | 0.37 ± 0.02 | |||
0.4 | 1.10 ± 0.06 | 1.20 ± 0.07 | 0.48 ± 0.03 | |||
0.6 | 2.20 ± 0.11 | 1.87 ± 0.12 | 0.71 ± 0.03 | |||
4.9 | 0.1 | 0.39 ± 0.02 | 0.12 ± 0.01 | 0.37 ± 0.02 | 0.04 ± 0.03 | 3.10 ± 0.15 |
0.2 | 0.44 ± 0.03 | 0.56 ± 0.03 | 0.14 ± 0.05 | |||
0.3 | 0.97 ± 0.05 | 0.73 ± 0.04 | 0.32 ± 0.02 | |||
0.4 | 0.83 ± 0.05 | 0.95 ± 0.05 | 0.35 ± 0.02 | |||
0.6 | 1.62 ± 0.10 | 1.26 ± 0.08 | 0.59 ± 0.03 | |||
5.1 | 0.1 | 0.24 ± 0.02 | 0.10 ± 0.01 | 0.27 ± 0.01 | 0.17 ± 0.01 | 2.58 ± 0.13 |
0.2 | 0.44 ± 0.03 | 0.41 ± 0.02 | 0.22 ± 0.02 | |||
0.3 | 0.83 ± 0.05 | 0.54 ± 0.03 | 0.37 ± 0.02 | |||
0.4 | 0.83 ± 0.05 | 0.66 ± 0.03 | 0.41 ± 0.03 | |||
0.6 | 1.20 ± 0.07 | 0.89 ± 0.04 | 0.48 ± 0.03 | |||
5.3 | 0.1 | 0.20 ± 0.02 | 0.09 ± 0.04 | 0.14 ± 0.06 | 0.11 ± 0.05 | 2.04 ± 0.10 |
0.2 | 0.38 ± 0.02 | 0.16 ± 0.07 | 0.14 ± 0.06 | |||
0.3 | 0.67 ± 0.03 | 0.39 ± 0.02 | 0.27 ± 0.02 | |||
0.4 | 0.78 ± 0.04 | 0.49 ± 0.04 | 0.45 ± 0.03 | |||
0.6 | 0.95 ± 0.06 | 0.67 ± 0.06 | 0.79 ± 0.04 | |||
5.6 | 0.1 | 0.18 ± 0.01 | 0.08 ± 0.02 | 0.06 ± 0.03 | 0.03 ± 0.02 | 1.75 ± 0.08 |
0.2 | 0.34 ± 0.02 | 0.16 ± 0.07 | 0.14 ± 0.01 | |||
0.3 | 0.62 ± 0.03 | 0.34 ± 0.02 | 0.23 ± 0.02 | |||
0.4 | 0.76 ± 0.04 | 0.42 ± 0.03 | 0.33 ± 0.02 | |||
0.6 | 0.60 ± 0.04 | 0.64 ± 0.04 | 0.53 ± 0.03 |
a k 0 is the first-order rate constant for the photolysis of riboflavin in the absence of acetate buffer