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Radiation-induced destruction of hydroxyl-containing amino acids and dipeptides

机译:辐射诱导破坏含羟基氨基酸和二肽

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摘要

The yields of molecular products resulting from radiolysis of hydroxyl-containing amino acids and dipeptides under various conditions were determined. The possibility of a new radiation-induced destruction pathway has been shown for serine and threonine, as well as for the dipeptides having residues of these amino acids at the N-terminal part of the respective molecule. This process includes formation of N-centered radicals from the starting molecules followed by their decomposition with elimination of side substituents. On radiolysis, serine and threonine were also shown to undergo free-radical destruction to form acetaldehyde and acetone, respectively. A mechanism has been proposed including consecutive stages of fragmentation of a-hydroxyl-containing carbon-centered radicals with elimination of ammonia and decomposition of the secondary radicals with elimination of CO2. The yields of CO2 obtained on radiolysis of serine and threonine were significantly higher (except for solutions at pH 12) than those for alanine and valine, which have no hydroxyl groups in their structures. The obtained data indicate that the hydroxyl-containing amino acids occupy a special place among other amino acids as regards the variety of radiation-induced reactions which they may undergo due to their structural features.
机译:确定了在各种条件下由含羟基的氨基酸和二肽的辐射分解产生的分子产物的产率。对于丝氨酸和苏氨酸以及在相应分子的N-末端部分具有这些氨基酸残基的二肽,已经显示出新的辐射诱导的破坏途径的可能性。该过程包括由起始分子形成以N为中心的自由基,然后将其分解并消除侧取代基。在辐射分解中,丝氨酸和苏氨酸也被证明会遭到自由基破坏,分别形成乙醛和丙酮。已经提出了一种机制,其包括连续步骤的含α-羟基的碳中心自由基的裂解的连续阶段,其中消除了氨,以及继发自由基的分解,同时消除了CO2。通过丝氨酸和苏氨酸的放射分解获得的CO2产量(pH值为12的溶液除外)明显高于其结构中没有羟基的丙氨酸和缬氨酸。所获得的数据表明,由于它们的结构特征,含羟基的氨基酸在它们可能经历的各种辐射诱导反应方面在其他氨基酸中占有特殊的位置。

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