Table 2.
Kinetic isotope effects for the TcUP-catalyzed arsenolysis of uridine
| Heavy uridine | Light uridine | Type of KIE | Experimental KIE | Intrinsic KIE | Predicted KIE |
|---|---|---|---|---|---|
| 1′-3H | 5′-14Ca | α – Secondary | 1.103±0.004 | 1.132±0.005 | 1.126 |
| 1′-14C | 5′-3H2 | Primary | 1.080±0.003b | 1.103±0.004 | 1.109 |
| 5′-14C,2′-2H | 5′-3H2 | β – Secondary | 1.067±0.003b,c | 1.086±0.004 | 1.080 |
| 5′-14C,1,3-15N | 5′-3H2 | Primary and β – Secondary | 1.027±0.003b | 1.034±0.004 | 1.027 |
| 5′-14C,3-15N | 5′-3H2 | β – Secondary | 1.003±0.002b | 1.004±0.003 | 1.002 |
| 5′-14C,1-15N | – | Primary | 1.024±0.004d | 1.030±0.005 | 1.025 |
| 5′-3H2 | 5′-14C | δ – Secondary | 1.032±0.002 | 1.041±0.003 | 1.058 |
The remote 5′-14C KIE is assumed to be unity.
Experimental values corrected for remote 5′-3H2 KIE according to the equation .
Experimental values corrected for 2H content according to the equation , where F is the fraction of 2H in the substrate.
Experimental values corrected for 3-15N KIE according to the equation KIE = KIEobs/3-15N KIE.