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.

引用

页码：1318 / 1332

页数：15

共 35 条

[11] Substituent Effects on the Thermodynamic Stability of Imines Formed from Glycine and Aromatic Aldehydes: Implications for the Catalytic Activity of Pyridoxal-5′-phosphate [J].

Crugeiras, Juan ;

Rios, Ana ;

Riveiros, Enrique ;

Richard, John P. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (43) :15815-15824

[12] Pyridoxamine analogues scavenge lipid-derived γ-ketoaldehydes and protect against H2O2-mediated cytotoxicity [J].

Davies, Sean S. ;

Brantley, Eric J. ;

Voziyan, Paul A. ;

Amarnath, Venkataraman ;

Zagol-Ikapitte, Irene ;

Boutaud, Olivier ;

Hudson, Billy G. ;

Oates, John A. ;

Roberts, L. Jackson, II .

BIOCHEMISTRY, 2006, 45 (51) :15756-15767

[13] A PROTON RESONANCE INVESTIGATION OF EQUILIBRIA, SOLUTE STRUCTURES, AND TRANSAMINATION IN AQUEOUS SYSTEMS PYRIDOXAMINE-PYRUVATE-ZINC(2) AND -ALUMINUM(3) [J].

GANSOW, OA ;

HOLM, RH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1969, 91 (22) :5984-&

[14] A H-1 NUCLEAR MAGNETIC-RESONANCE STUDY OF THE DEPROTONATION OF L-DOPA AND ADRENALINE [J].

JAMESON, RF ;

HUNTER, G ;

KISS, T .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1980, (07) :1105-1110

[15] Structure, evolution and action of vitamin B6-dependent enzymes [J].

Jansonius, JN .

CURRENT OPINION IN STRUCTURAL BIOLOGY, 1998, 8 (06) :759-769

[16]

KALLEN RG, 1966, J BIOL CHEM, V241, P5864

[17] PYRIDOXAMINE AND 2-OXALOPROPIONIC ACID IN AQUEOUS SYSTEMS - CONDITIONAL IMINE FORMATION-CONSTANTS AND RATE CONSTANTS OF VITAMIN-B6 CATALYZED DECARBOXYLATION [J].

KUBALA, G ;

MARTELL, AE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (03) :449-455

[18] Program DYNAFIT for the analysis of enzyme kinetic data: Application to HIV proteinase [J].

Kuzmic, P .

ANALYTICAL BIOCHEMISTRY, 1996, 237 (02) :260-273

[19]

Laughton P.M., 1969, SOLUTE SOLVENT INTER, P399

[20] INFLUENCE OF PRESSURE ON EQUILIBRIUM OF HYDRATION OF ALIPHATIC ALDEHYDES [J].

LEWIS, CA ;

WOLFENDE.R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (20) :6685-6688

← 1 2 3 4 →