Recognition of protonated aliphatic α,ω-diamines by coproporphyrin I tetraanion in water

被引:3
作者
Flores-Villalobos, A [1 ]
Morales-Rojas, H [1 ]
Escalante-Tovar, S [1 ]
Yatsimirsky, AK [1 ]
机构
[1] Univ Nacl Autonoma Mexico, Fac Quim, Mexico City 04510, DF, Mexico
关键词
diarmines; recognition; coproporphyrin I;
D O I
10.1002/poc.454
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Interactions of aliphatic alphaomega-diamines [H2N(CH2)(n)NH2, 2 less than or equal to n less than or equal to 8] with coproporphyrin I tetraanion (CP) were studied by spectrophotometry, fluorimetry and H-1 NMR spectroscopy in the pH range 7-10 and ionic strengths 0.01 -0.1 M. Diprotonated diammonium cations induce dimerization of CP by forming 1: 1 complexes with CP which undergo much stronger self-aggregation than free CP tetraanions. On increasing the number of methylene units n connecting the ammonium groups, the binding constants for the complex formation with monomeric CP (K-L) increase but the dimerization constants of the resulting complexes decrease. A hydrophobic contribution to the binding free energy of - 1.6 +/- 0.2 kJ mol(-1) per methylene unit was obtained from the Linear correlation of logK(L) values extrapolated to zero ionic strength vs the number of methylene units (n = 2-6). A model for diammonium-induced porphyrin dimerization is proposed, which involves complexation of diammonium cations with CP monomer via a combination of electrostatic and hydrophobic interactions and subsequent formation of porphyrin face-to-face dimers in which diammonium cations serve as the stabilizing bridges via ion pairing to carboxylate groups of two CP monomeric units. Copyright (C) 2001 John Wiley Sons, Ltd.
引用
收藏
页码:83 / 93
页数:11
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