Matthews C N
Orig Life. 1975 Jan-Apr;6(1-2):155-62. doi: 10.1007/BF01372400.
Evidence from laboratory and extraterrestrial chemistry is presented consistent with the hypothesis that the original heteropolypeptides on Earth were synthesized spontaneously from hydrogen cyanide and water without the intervening formation of chi-amino acids, a key step being the direct polymerization of atmospheric hydrogen cyanide to polyaminomalononitrile (IV) via dimeric HCN. Molecular orbital calculations (INDO) show that the most probable structure for (HCN)2 is azacyclopropenylidenimine. Successive reactions of hydrogen cyanide with the reactive nitrile side chains of IV then yield heteropolyamidines which are converted by water to heteropolypeptides. To study this postulated modification of a homopolymer to a heteropolymer, poly-chi-cyanoglycine (IX) was prepared from the N-carboxyanhydride of chi-cyanoglycine. Hydrolysis of IX, a polyamide analog of the polyamidine IV, yielded glycine. However, when IX was hydrolysed after being treated with hydrogen cyanide, other chi-amino acids were also obtained including alanine, serine, aspartic acid and glutamic acid, suggesting that the nitrile groups of IX (and therfore of IV) are indeed readily attacked by hydrogen cyanide as predicted. Further theoretical and experimental studies support the view that hydrogen cyanide polymerization along these lines is a universal process that accounts not only for the past formation of primitive proteins on Earth, but also for the yellow-brown-orange colors of Jupiter today and for the presence of water-soluble compounds hydrolyzable to chi-amino acids in materials obtained from environments as diverse as the moon, carbonaceous chondrites and the reaction chambers used to simulate organic synthesis in planetary atmospheres.
本文提供了来自实验室和外星化学的证据,这些证据与以下假设一致:地球上最初的杂多聚肽是由氰化氢和水自发合成的,无需经过关键步骤即手性氨基酸的中间形成过程,其中一个关键步骤是大气中的氰化氢通过二聚体HCN直接聚合成聚氨基丙二腈(IV)。分子轨道计算(INDO)表明,(HCN)2最可能的结构是氮杂环丙烯基亚胺。氰化氢与IV的活性腈侧链的连续反应随后产生杂多脒,这些杂多脒被水转化为杂多聚肽。为了研究这种假设的从均聚物到杂聚物的修饰,由手性氰基甘氨酸的N-羧基酐制备了聚手性氰基甘氨酸(IX)。IX是聚氨基丙二腈IV的聚酰胺类似物,其水解产生甘氨酸。然而,当IX在用氰化氢处理后水解时,还获得了其他手性氨基酸,包括丙氨酸、丝氨酸、天冬氨酸和谷氨酸,这表明IX(因此也是IV)的腈基确实如预测的那样容易受到氰化氢的攻击。进一步的理论和实验研究支持了这样一种观点,即沿着这些路线的氰化氢聚合是一个普遍过程,它不仅解释了过去地球上原始蛋白质的形成,还解释了如今木星的黄棕色或橙色以及从月球、碳质球粒陨石和用于模拟行星大气中有机合成的反应室等不同环境中获得的材料中可水解为手性氨基酸的水溶性化合物的存在。