Binding of polyanions by biogenic amines. III. Formation and stability of protonated spermidine and spermine complexes with carboxylic ligands

被引:20
作者
De Robertis, A
De Stefano, C
Gianguzza, A
Sammartano, S
机构
[1] Univ Messina, Dipartimento Chim Inorgan Chim Analit & Chim Fis, I-98166 Messina, Vill S Agata, Italy
[2] Univ Palermo, Dipartimento Chim Inorgan, I-90123 Palermo, Italy
关键词
biogenic amines; carboxylic ligands; anion coordination chemistry; formation constants; potentiometry; speciation of biological fluids;
D O I
10.1016/S0039-9140(98)00221-5
中图分类号
O65 [分析化学];
学科分类号
070302 ; 081704 ;
摘要
The formation and stability of protonated spermidine and spermine-carboxylic ligand complexes (seven systems) were studied potentiometrically (H+-glass electrode). ALH(r) species are formed (A = spermidine, spermine, Lz- = acetate, malonate, 1,2,3-propanetricarboxylate, 1,2,3,4-butanetetracarboxylate; r = 1...m + n - 1, where m and n are the maximum degree of protonation of the amine and of the carboxylic ligand, respectively), and their stability is a function of charges involved in the formation reaction. For the equilibrium H(i)A(i+) + HjL(j-z) = ALH(i+j)((i+j-z)) the linear relationship log K-ij = 0.46 zeta (zeta = \i(z - j)\) was found. By means of this simple equation a mean free energy value can be obtained per salt bridge (n), namely - Delta G degrees = 5.25 +/- 0.15 kJ mol(-1) n(-1). Species formed by the highest charged ligands are quite stable (K > 10(3) mol(-1) dm(3)) and potentially play an important role in the speciation of biofluids, as shown by speciation diagrams and simulated experiments. (C) 1999 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:119 / 126
页数:8
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