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Mechanism of non-enzymic transamination reaction between histidine and α-oxoglutaric acid

机译:组氨酸与α-氧代戊二酸之间的非酶转氨反应机理

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pNon-enzymic transamination reactions at 85° between various amino acids and α-oxoglutaric acid are catalysed by metal ions, e.g. Alsup3+/sup, Fesup2+/sup, Cusup2+/sup and Fesup3+/sup. The reaction is optimum at pH4·0. Of the 14 amino acids studied histidine is the most active. In the presence of Alsup3+/sup histidine transaminates with α-oxoglutaric acid, forming glutamic acid and Alsup3+/sup–imidazolylpyruvic acid complex as the end products. However, in the presence of Fesup2+/sup or Cusup2+/sup the products are glutamic acid and a 1:2 metal ion–imidazolylpyruvic acid chelate. The greater effectiveness of histidine in these reactions is attributed to the presence of the tertiary imidazole nitrogen atom, which is involved in the formation of stable sparingly soluble metal ion–imidazolylpyruvic acid complexes or chelates as end products of these reactions. Of the metal ions studied only Alsup3+/sup, Fesup2+/sup, Fesup3+/sup and Cusup2+/sup are effective catalysts for the transamination reactions, and EDTA addition completely inhibits the catalytic effect of the Alsup3+/sup. Spectrophotometric evidence is presented to demonstrate the presence of metal ion complexes of Schiff bases of histidine as intermediates in the transamination reactions. These results may contribute to understanding the role of histidine in enzyme catalysis./p
机译:各种氨基酸和α-氧代戊二酸之间在85°的非酶转氨反应是由金属离子催化的。 Al 3 + ,Fe 2 + ,Cu 2 + 和Fe 3 + 。该反应在pH4·0下最佳。在研究的14个氨基酸中,组氨酸最活跃。在存在Al 3 + 时,组氨酸与α-氧代戊二酸发生氨基转移反应,形成谷氨酸和最终产物Al 3 + -咪唑基丙酮酸复合物。但是,在Fe 2 + 或Cu 2 + 的存在下,产物是谷氨酸和1:2金属离子-咪唑基丙酮酸螯合物。组氨酸在这些反应中的更大功效归因于叔咪唑氮原子的存在,后者参与了稳定的难溶性金属离子-咪唑基丙酮酸复合物或螯合物的形成,这些络合物或螯合物是这些反应的最终产物。在研究的金属离子中,只有Al 3 + ,Fe 2 + ,Fe 3 + 和Cu 2 + 是转氨反应的有效催化剂,EDTA的添加完全抑制了Al 3 + 的催化作用。提出了分光光度的证据来证明组氨酸的席夫碱的金属离子络合物作为氨基转移反应的中间体。这些结果可能有助于了解组氨酸在酶催化中的作用。

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