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Acid-base and metal ion binding properties of 2-thiocytidine in aqueous solution

Brasun, Justyna and Matera, Agnieszka and Sochacka, Elzbieta and Swiatek-Kozlowska, Jolanta and Kozlowski, Henryk and Operschall, Bert P. and Sigel, Helmut. (2008) Acid-base and metal ion binding properties of 2-thiocytidine in aqueous solution. Journal of Biological Inorganic Chemistry, 13 (5). pp. 663-674.

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Official URL: http://edoc.unibas.ch/dok/A5248825

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Abstract

The thionucleoside 2-thiocytidine (C2S) occurs in nature in transfer RNAs; it receives attention in diverse fields like drug research and nanotechnology. By potentiometric pH titrations we measured the acidity constants of H(C2S)(+) and the stability constants of the M(C2S)(2+) and M(C2S-H)(+) complexes (M2+ = Zn2+ , Cd2+), and we compared these results with those obtained previously for its parent nucleoside, cytidine (Cyd). Replacement of the (C2)=O unit by (C2)=S facilitates the release of the proton from (N3)H+ in H(C2S)(+) (pK (a) = 3.44) somewhat, compared with H(Cyd)(+) (pK (a) = 4.24). This moderate effect of about 0.8 pK units contrasts with the strong acidification of about 4 pK units of the (C4)NH2 group in C2S (pK (a) = 12.65) compared with Cyd (pK (a) approximate to 16.7); the reason for this result is that the amino-thione tautomer, which dominates for the neutral C2S molecule, is transformed upon deprotonation into the imino-thioate form with the negative charge largely located on the sulfur. In the M(C2S)(2+) complexes the (C2)S group is the primary binding site rather than N3 as is the case in the M(Cyd)(2+) complexes, though owing to chelate formation N3 is to some extent still involved in metal ion binding. Similarly, in the Zn(C2S-H)(+) and Cd(C2S-H)(+) complexes the main metal ion binding site is the (C2)S- unit (formation degree above 99.99 chelate formation with N3 must be surmised for the M(C2S-H)(+) species in accord with previous solid-state studies of related ligands. Upon metal ion binding, the deprotonation of the (C4)NH2 group (pK(a) = 12.65) is dramatically acidified (pK (a) approximate to 3), confirming the very high stability of the M(C2S-H)(+) complexes. To conclude, the hydrogen-bonding and metal ion complex forming capabilities of C2S differ strongly from those of its parent Cyd; this must have consequences for the properties of those RNAs which contain this thionucleoside.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie
UniBasel Contributors:Sigel, Helmut
Item Type:Article, refereed
Article Subtype:Research Article
Bibsysno:Link to catalogue
Publisher:Springer
ISSN:0949-8257
e-ISSN:1432-1327
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
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Last Modified:21 Nov 2017 12:31
Deposited On:22 Mar 2012 14:15

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