Kantrowitz E R, Lipscomb W N
J Biol Chem. 1976 May 10;251(9):2688-95.
Reaction of phenylglyoxal with aspartate transcarbamylase and its isolated catalytic subunit results in complete loss of enzymatic activity. This modification reaction is markedly influenced by pH and is partially reversible upon dialysis. Carbamyl phosphate or carbamyl phosphate with succinate partially protect the catalytic subunit and the native enzyme from inactivation by phenylglyoxal. In the native enzyme complete protection from inactivation is afforded by N-(phosphonacetyl)-L-aspartate. The decrease in enzymatic activity correlates with the modification of 6 arginine residues on each aspartate transcarbamylase molecule, i.e. 1 arginine per catalytic site. The data suggest that the essential arginine is involved in the binding of carbamyl phosphate to the enzyme. Reaction of the single thiol on the catalytic chain with 2-chloromercuri-4-nitrophenol does not prevent subsequent reaction with phenylglyoxal. If N-(phosphonacetyl)-L-aspartate is used to protect the active site we find that phenylglyoxal also causes the loss of activation of ATP and inhibition by CTP. The rate of loss of heterotropic effects is exactly the same for both nucleotides indicating that the two opposite regulatory effects originate at the same location on the enzyme, or are transmitted by the same mechanism between the subunits, or both.
苯乙二醛与天冬氨酸转氨甲酰酶及其分离出的催化亚基反应会导致酶活性完全丧失。这种修饰反应受pH值的显著影响,透析后部分可逆。氨甲酰磷酸或氨甲酰磷酸与琥珀酸可部分保护催化亚基和天然酶不被苯乙二醛灭活。在天然酶中,N-(膦酰乙酰基)-L-天冬氨酸可完全保护其不被灭活。酶活性的降低与每个天冬氨酸转氨甲酰酶分子上6个精氨酸残基的修饰有关,即每个催化位点1个精氨酸。数据表明,必需精氨酸参与氨甲酰磷酸与酶的结合。催化链上的单个巯基与2-氯汞基-4-硝基苯酚反应并不妨碍随后与苯乙二醛的反应。如果用N-(膦酰乙酰基)-L-天冬氨酸保护活性位点,我们发现苯乙二醛也会导致ATP活化丧失和CTP抑制作用丧失。两种核苷酸的异促效应丧失速率完全相同,这表明两种相反的调节效应起源于酶上的同一位置,或者通过相同的机制在亚基之间传递,或者两者皆是。