EXPLORING ARYLGLYOXALS AS THE ARGININE REACTIVITY PROBES - A MECHANISTIC INVESTIGATION USING THE BUFFER AND SUBSTITUENT EFFECTS

被引:14
作者
BABURAJ, K [1 ]
DURANI, S [1 ]
机构
[1] INDIAN INST TECHNOL,DEPT CHEM,BIOSCI & ENGN GRP,BOMBAY 400076,INDIA
关键词
D O I
10.1016/0045-2068(91)90049-U
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
The modification of arginine side chain by the α-dicarbonyl reagents was submitted to a mechanistic investigation. The reactivity of 4-substituted phenylglyoxals toward Nα-acetylarginine was found to be dependent on the substituent as well as buffer effects. Borate formed a complex with the glyoxal-hydrates to cause an activation of the electron-rich glyoxals and an inactivation of the electron-deficient glyoxals. The ρ{variant} value in the Hammett correlation in this buffer was found to be -1.0. Bicarbonate also complexed with the glyoxal-hydrates, to increase their reactivity irrespective of the substituent effects. The Hammett correlation in this buffer gave the ρ{variant} value of +1.0. On the basis of these and related observations, the mechanism in arginine modification has been formulated as a sequential process involving the intermolecular attack of guanidine at the α-dicarbonyl, the pH-dependent deprotonation of the resulting monocarbinolamine, and the intramolecular bond formation within this intermediate as the rate-determining step in the overall reaction. © 1991.
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页码:229 / 244
页数:16
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