THE MECHANISM OF SYNTHESIS OF AMINO ACIDS BY ELECTRIC DISCHARGES
THE MECHANISM OF SYNTHESIS OF AMINO ACIDS BY ELECTRIC DISCHARGES
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DOI：
10.1016/0006-3002(57)90366-9
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发表时间：
1957-01-01
期刊：
影响因子：
--
通讯作者：
MILLER, SL
中科院分区：
文献类型：
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作者：
MILLER, SL
研究了CH4、NH3、H2O和H2放电合成氨基酸和羟基酸的机理。火花放电以良好的产率产生氰化氢和醛，反应形成氨基和羟基腈（Strecker 合成）。由火花放电产物形成的氨基腈的水解速率足以占火花放电一周后氨基酸的总产率。 β-丙氨酸和琥珀酸可能是通过将氨和氰化氢加到丙烯腈中并水解成酸来合成的。诸如羟基酸/氨基酸和琥珀酸/β-丙氨酸之类的产物的比率可以通过考虑所涉及的平衡和速率来预测，并且实验比率与预测的一致性为这些机制提供了进一步的证据。向火花放电装置中添加硫酸亚铁铵并没有显着改变产物的产率，这表明铁或硫酸盐均不产生催化合成或分解。激发 CH4、H2O、H2 和 N2（而不是 NH3）的混合物可得到相同的产物，但收率较低。除之前鉴定出的产物外，还明确鉴定出N-甲基丙氨酸、亚氨基二乙酸、琥珀酸和尿素。通过色谱 RF 值鉴定 a,a''-亚氨基乙酸丙酸、α-羟基丁酸、天冬氨酸和谷氨酸以及甲基脲。未检测到嘌呤或嘧啶。根据这些实验结果，讨论了原始地球上有机化合物合成的某些方面。
The mecha-nism of the electric discharge synthesis of amino and hydroxy acids from CH4, NH3, H2O, and H2 was investigated. Hydrogen cyanide and aldehydes, which are produced in good yield by the spark discharge, react to form amino and hydroxynitriles (Strecker synthesis). The rate of hydrolysis of the aminonitriles formed from the products of the spark discharge is sufficient to account for the total yield of amino acids after a week''s sparking. The [beta]-alanine and succinic acid were probably synthesized by addition of ammonia and hydrogen cyanide to acrylonitrile and hydrolysis to the acids. The ratios of products such as hydroxy acid/amino acid and succinic acid/[beta]-alanine can be predicted by considering the equilibria and rates involved, and the agreement of the experimental ratios with the predictions offers further evidence for these mechanisms. The addition of ferrous ammonium sulfate to the spark discharge apparatus did not alter significantly the yield of products, indicating that neither iron or sulfate produced catalytic syntheses or decompositions. Sparking a mixture of CH4, H2O, H2, and N2 (instead of NH3) gave the same products but in lower yield. In addition to the products previously identified, N-methylalanine, iminodiacetic acid, succinic acid, and urea were definitely identified. a,a''-Iminoacetic-propionic, a-hydroxybutyric, aspartic, and glutamic acids, and methyl-urea were identified by chromatographic RF values. No purines or pyrimidines could be detected. Some aspects of the synthesis of organic compounds on the primitive Earth are discussed on the basis of these experimental results.