生命起源前手性对映体富集与放大的数学规律与实验  

Mathematic rule and the experiments of chiralenhancement/amplificationfor enantiomers before origin of life

作　　者：朱华结 李志伟[1] 贾云静 朱玉俊 Charles U.Pittman,Jr ZHU Huajie;LI Zhiwei;JIA Yunjin;ZHU Yujun;Charles U.Pittman,Jr(School of Chemical and Pharmaceutical Engineering,Hebei University of Science and Technology,Shijiazhuang,Hebei 050018,China;College of Life,Hebei University,Baoding,Hebei 071002,China;College of Pharmacy,Anhui Medical University,Hefei,Anhui 230012,China;Department of Chemistry,Mississippi State University,Starkville,MS 39762,US)

机构地区：[1]河北科技大学化学与制药工程学院,河北石家庄050018 [2]河北大学生命科学学院,河北保定071002 [3]安徽医科大学药学院,安徽合肥230012 [4]密西西比州立大学化学系,Starkville,MS 39762

出　　处：《河北科技大学学报》2023年第6期589-602,共14页Journal of Hebei University of Science and Technology

基　　金：国家自然科学基金(21877025);河北省医药联合重点项目(H2020201029,B2022208057)。

摘　　要：生命起源前的原始海洋(池)中,由于没有手性源,手性化合物在合成过程中可能受到其他不对称因素(如手性对称性破缺)等影响,它们几乎都是以极小%ee值的非外消旋体(non-racemic enantiomers)存在。从数学理论出发,结合化学反应原理,推导出这些非外消旋体在通过某种反应后,其较小的%ee值(%ee 1)可以富集到较大的%ee值(%ee 2),尤其在很低%ee值的情况下,理论上其放大倍数(%ee 2/%ee 1)可以是指数级别的增加,而这是生命起源前得到高含量对映体(如L-氨基酸)所需要的。进一步使用约1%ee值的L-色氨酸甲酯(L-TME),通过与双功能基团物质(如乙二醛)发生反应,在0℃~室温条件下,将其放大富集到3.4%(%ee 2)。系列实验表明:最大放大倍数(%ee 2/%ee 1)可达1.9(从6.1%的%ee 1提高到11.7%的%ee 2);单次最大增量(Δ%ee=%ee 2-%ee 1)达到12.3%(从44.2%(%ee 1)提高到56.5%(%ee 2))。The non-racemic enantiomers may exist with very small%ee values,which formed by some asymmetric factors(such as symmetry breaking)during their synthesis in the prebiotic pool in the absence of other chiral sources.We now conclude a mathematic formula by concerning the organic reaction principles.We found that the tiny%ee(%ee 1)values of non-racemic enantiomers can be enhanced to a reasonable large%ee values(%ee 2)after the non-racemic enantiomers react with bis-functional group reagents(such as oxalaldehyde).Theoretically,if the%ee 1 is extremely small,the enhancement/amplification multiples(%ee 2/%ee 1)should increase greatly.The is necessary to enrich the%ee values in prebiotic pool for the chiral compounds(such as L-amino acids)with very small%ee values.Finally,about 1%of L-tryptophan methyl ester(L-TME)was used to react with CHOCHO,and the%ee 2 of the L-TME remained in solution increased to 3.4%.The largest amplification multiple is 1.9(from 6.1%of%ee 1 to enrich to 11.7%(%ee 2));The largest increasement of the%ee(Δ%ee=%ee 2-%ee 1)is 12.3%(from 44.2%to 56.5%).

关 键 词：计算化学 手性富集/放大 对映体 史前时代 L-氨基酸 

分 类 号：O641.6[理学—物理化学]