Phenol Group in Pyridoxamine Acts as a Stabilizing Element for Its Carbinolamines and Schiff Bases

被引：14
作者：
Caldes, Catalina [1 ]
Vilanova, Bartolome [1 ]
Adrover, Miquel [1 ]
Munoz, Francisco [1 ]
Donoso, Josefa [1 ]
机构：
[1] Univ Illes Balears, Dept Quim, Inst Univ Invest Ciencies Salut IUNICS, ES-07122 Palma De Mallorca, Spain
来源：
CHEMISTRY & BIODIVERSITY | 2011年 / 8卷 / 07期
关键词：
AQUEOUS SYSTEMS; FORMALDEHYDE; EQUILIBRIA; AMINES; INHIBITOR; CATALYSIS; RESONANCE; ALDEHYDES; HYDRATION; KINETICS;
D O I：
10.1002/cbdv.201000296
中图分类号：
Q5 [生物化学]; Q7 [分子生物学];
学科分类号：
071010 ; 081704 ;
摘要：
Pyridoxamine (PM), a natural derivative of vitamin B(6), possesses a high biological and biomedical significance by virtue of its acting as enzyme cofactor in amino acid metabolism and as inhibitor in the nonenzymatic glycation of proteins. Both types of processes require the initial formation of a Schiff base. In this work, we used NMR spectroscopy to study the formation mechanism for a Schiff base between PM and formaldehyde (FA). This allowed the Schiff base and an intermediate carbinolamine (CA) to be detected. The Schiff base was found to be in isomeric equilibrium with a hemiaminal (HE) form. The formation equilibrium constants for the CA and HE over the pD range of 6.0-13.0 were determined and compared with those for the reaction between 4-picolylamine (PAM) and formaldehyde (FA). The comparison revealed a strong influence of the phenol group on the equilibrium constant. Based on the results, the phenol group in PM is a key structural element towards stabilizing the resulting carbinolamine and Schiff base.
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页码：1318 / 1332
页数：15
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