# Extent of metal ion-sulfur binding in complexes of thiouracil nucleosides and nucleotides in aqueous solution

Odani, Akira and Kozlowski, Henryk and Swiatek-Kozlowska, Jolanta and Brasun, Justyna and Operschall, Bert P. and Sigel, Helmut. (2007) Extent of metal ion-sulfur binding in complexes of thiouracil nucleosides and nucleotides in aqueous solution. Journal of inorganic biochemistry, Vol. 101, H. 4. pp. 727-735.

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Official URL: http://edoc.unibas.ch/dok/A5248980

Previously published stability constants of several metal ion (M2+) complexes formed with thiouridines and their 5-monophosphates, together with recently obtained log K-M(U)(M) versus pK(U)(H) plots for M2+ complexes of uridinate derivatives (U-) allowed now a quantitative evaluation of the effect that the exchange of a (C)O by a (C)S group has on the stability of the corresponding complexes. For example, the stability of the Ni2+, Cu2+ and Cd2+ complexes of 2-thiouridinate is increased by about 1.6, 2.3, and 1.3 log units, respectively, by the indicated exchange of groups. Similar results were obtained for other thiouridinates, including 4-thiouridinate. The structure of these complexes and the types of chelates formed (involving (N3)(-) and (C)S) are discussed. A recently advanced method for the quantification of the chelate effect allows now also an evaluation of several complexes of thiouridinate 5-monophosphates. In most instances the thiouracilate coordination dominates the systems, allowing only the formation of small amounts of phosphate-bound isomers. Among the complexes studied only the one formed by Cu2+ with 2-thiouridinate 5`-monophosphate leads to significant amounts of the macrochelated isomer, which means that in this case Cu2+ is able to force the nucleotide from the anti to the syn conformation, allowing thus metal ion binding to both potential sites and this results in the formation of about 58 isomer. The remaining 42 coordinated to the thiouracilate residue; Cu2+ binding to the phosphate group occurs in this case only in trace amounts. (c) 2007 Elsevier Inc. All rights reserved.