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. Author manuscript; available in PMC: 2012 Jun 29.
Published in final edited form as: J Am Chem Soc. 2011 Jun 3;133(25):9923–9931. doi: 10.1021/ja2031294

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
a

The remote 5′-14C KIE is assumed to be unity.

b

Experimental values corrected for remote 5′-3H2 KIE according to the equation KIE=KIEobs×5H32KIE.

c

Experimental values corrected for 2H content according to the equation KIE=(KIEobs1+F)/F, where F is the fraction of 2H in the substrate.

d

Experimental values corrected for 3-15N KIE according to the equation KIE = KIEobs/3-15N KIE.