Cleavage of a RNA analog containing uridine by a bifunctional dinuclear Zn(II) catalyst

作者: C ROSSITER , R MATHEWS , I DELMUNDO , J MORROW

DOI: 10.1016/J.JINORGBIO.2008.09.004

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摘要: Abstract The macrocyclic ligand, 1,4-bis((1-oxa-4,7,10-triazacyclododecan-7-yl)methyl)benzene (L1) is prepared. L1 binds two Zn(II) ions at neutral pH to form Zn2(L1) as studied by using pH-potentiometric titrations. uridines 7.0, I = 0.100 M (NaCl) and the mononuclear analog Zn(L2) (L2 = 1-oxa-4,7,10-triazacyclododecane) a single uridine; dissociation constants for both complexes are in millimolar range. Both promote cleavage of simple RNA lacking nucleobase (HpPNP = 2-hydroxypropyl-4-nitrophenylphosphate), uridine containing UpPNP (uridine-3′-4-nitrophenylphosphate). Plots first-order rate constant HpPNP function concentration from 0.5 mM 20.0 mM linear, consistent with weak complexation substrate Kd > 20 mM. In contrast, or over similar ranges exhibit downward curvature, formation complex between catalyst UpPNP. Comparison second-order (k2 = kcat/Kd) shows that dinuclear better than cleavage.

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