手性有机分子的自识别理论计算及在对映体萃取分离中的应用研究

The self-replicating catalytic research of chiral organic molecule is the forward field in asymmetric chemistry, and offers the key small molecular model system for theoretically simulating the homochiral evolution of life activities. Based on the thermodynamics mechanism of the self-replicating catalystic process of chiral organic molecules, the project proposes the concept "self-recognition of chiral organic molecule" to develop an entirely new research field of important scientific significance. By quantum chemical method, the relationship between chiral molecular self-recognition process and the self-replicating catalytic process will be calculated for screening the chiral organic molecule system with possible self-replicating catalytic property. The screened systems will be tested by experiment. By chemical modification, a lipophilic (or hydrophilic) functional group is introduced on a single optically pure isomers of the screened hydrophilic (or lipophilic) chiral organic molecule with high self-recognition capabilities, to change the hydrophilic / lipophilic property. The modified single optically pure isomers is designed as chiral extraction selector in the organic (or water) phase. The designed chiral selector is used to separate its precursory isomers by extration, which is defined as self-recognition chiral extration. Enantioselective extraction research of the precursory enantiomers by the modified selector will carry out. A number of important extraction process variables will be obtained by experiment and modeling. The high extraction efficiency will be obtained at the optimized conditions, which would give us a new method for designing chiral extraction selector, and develop the chiral extraction technology.

手性有机分子的自复制催化研究是不对称化学领域的崭新前沿研究内容，也是在理论上为模拟生命活动中同手性演化提供关键的小分子模型系统。基于手性有机分子自复制催化过程的热力学机理，本项目提出手性有机分子自识别的概念，开拓一个具有重要科学意义的全新研究领域。采用量子化学理论方法研究手性分子自识别过程及自复制催化过程的关联，筛选具有自复制催化可能的手性有机分子体系，通过实验加以验证。将筛选的具有高自识别能力的亲水（或亲油）手性有机分子的单一光学纯异构体进行化学改性，引入亲油（或亲水）官能团，改变其亲水/亲油性能，将之设计为有机相（或水相）手性萃取剂。这种采用改性的单一光学纯的手性分子作为手性萃取剂萃取分离其前驱对映体的方法称为自识别手性萃取。通过实验和计算模拟，优化手性萃取工艺参数，获得高的萃取效率。这将为我们提供一个设计手性萃取试剂的新方法，拓展手性萃取分离的应用。

手性有机分子的自复制催化研究是不对称化学领域的崭新前沿研究内容，也是在理论上为模拟生命活动中同手性演化提供关键的小分子模型系统。Soai还原反应证明了结构明确的单个小分子化合物可以像生物大分子那样进行精确的自我复制。. 本项目采用全新的方法合成了系列炔基嘧啶醛衍生物，通过Soai反应获得系列炔基嘧啶醇衍生物，采用手性柱对嘧啶醇化合物进行分离。通过理论计算，研究了Soai反应自催化机理，结果表明：起催化作用的是手性催化剂二聚体。反应中手性催化剂二聚体占据主导地位，同手性催化剂二聚体于异手性催化剂二聚体的反应活性是不同的，同手性催化剂二聚体更活泼一些。. 合成了系列杂原子自催化诱导试剂，包括杂环硫醚类化合物、硝基烯类化合物、酰氧基酮类化合物、3-硫醚-4-羟基香豆素类化合物、嘧啶并噻唑类化合物、噻二唑类化合物。. 通过Soai反应自催化诱导实验，发现葡萄糖、蔗糖、淀粉、环糊精等天然产物具有一定的自催化诱导效应，进一步拓展了Soai自催化诱导反应的范围，具有一定的理论意义。. 将自催化现象用于手性萃取，结果表明分离因子比较低，萃取效果不理想。.