H. Sigel et B. Lippert, THE EFFECTS OF N7-COORDINATED CIS-DIAMMINE-PLATINUM(II) ON THE ACID-BASE PROPERTIES OF GUANINE DERIVATIVES, Pure and applied chemistry, 70(4), 1998, pp. 845-854
The effect of the cis-(NH3)(2)Pt2+ unit, if coordinated to the N7 site
of guanine residues, on the acid-base properties of complexes of the
type cis-(NH3)(2)Pt(9-EtG)(2)(2+), cis-(NH3)(2)Pt(dGuo)(dGMP), or cis-
(NH3)(2)Pt(dGMP)(2)(2-), where 9-EtG = 9-ethylguanine, dGuo = 2'-deoxy
guanosine, and dGMP(2-) = 2'-deoxyguanosine 5'-monophosphate, is summa
rized and various micro acidity constants sue derived, which allow to
quantify the intrinsic acidities of H(N1) and -P(O)(2)(OH)(-) sites. I
n total the acid-base properties of more than 20 different species are
considered. The deprotonation of -P(O)(2)(OH)(-) groups in nucleobase
-platinated nucleotide complexes is only slightly facilitated (Delta p
K(a) similar or equal to 0.4). The acidification of H(N1) sites by N7-
bound platinum(II) is more pronounced, e.g., it amounts on average to
Delta pK(a) similar or equal to 0.8 in cis-(NH3)(2)Pt(dGuo)(dGMP). Thi
s allows conclusions regarding the situation in intrastrand crosslinks
formed between cis(NH3)2Pt2+ and adjacent guanine residues in DNA.