Eu(III) Macrocyclic Complexes Promote Cleavage of and Bind to Models for the 5‘-Cap of mRNA. Effect of Pendent Group and a Second Metal Ion
- 25 April 2000
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 39 (10) , 2130-2134
- https://doi.org/10.1021/ic9912068
Abstract
The interaction of three Eu(III) macrocyclic complexes Eu(THED)3+, Eu(ATHC)3+, and Eu(S-THP)3+ with two 5‘-cap model compounds, GpppG and m7GpppG is studied (THED = 1,4,7,10-tetrakis(2-hydroxyethyl)-1,4,7,10-tetraazacyclododecane, ATHC = 1-(carbamoylmethyl)-4,7,10-tris(2-hydroxyethyl)-1,4,7,10-tetraazacyclododecane, S-THP = 1S,4S,7S,10S-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane). Laser-induced excitation luminescence spectroscopy is used to study the binding of Eu(S-THP)3+ to GpppG (K = 5.9 × 104 M-1) and to characterize the Eu(S-THP)−GpppG complex. Both Eu(THED)3+ and Eu(S-THP)3+ bind to m7GpppG as monitored by use of fluorescence spectroscopy with binding constants of 5.9 × 103 and 4.4 × 104 M-1, respectively. The kinetics of cleavage of GpppG by two macrocyclic complexes is studied. Cleavage of GpppG by Eu(THED)3+ is accelerated by 15-fold in the presence of an equivalent of Zn(NO3)2 at pH 7.3, 37 °C, suggesting that two metal ions accelerate the cap cleavage reaction. Eu(ATHC)3+ promotes cleavage of GpppG with a pseudo-first-order rate constant of 2.6 × 10-5 s-1 at pH 7.3, 37 °C, and 0.30 mM complex.Keywords
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