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    化学所发展出界面超分子手性传递分子机理研究新方法
    来源:本站 发布时间:2022-12-20 点击数:581

      手性(xing)在(zai)自(zi)然(ran)界(jie)中(zhong)无处不在(zai)。界(jie)面所具(ju)有的非中(zhong)心对(dui)称(cheng)性(xing)为(wei)分子(zi)在(zai)界(jie)面的聚集和组(zu)(zu)装过程产生对(dui)称(cheng)性(xing)破缺创造了先(xian)天(tian)条(tiao)件,因此相(xiang)比于体相(xiang),研究(jiu)界(jie)面手性(xing)传递、自(zi)组(zu)(zu)装手性(xing)动力学对(dui)于探(tan)索手性(xing)起(qi)源(yuan)、探(tan)寻生命起(qi)源(yuan)、制备手性(xing)材料(liao)具(ju)有重要意义。  

      界(jie)(jie)面手(shou)(shou)性(xing)(xing)超(chao)分子(zi)(zi)(zi)自(zi)组装是(shi)近年来备(bei)受瞩(zhu)目(mu)的研(yan)(yan)(yan)究(jiu)领域之(zhi)一。它与(yu)(yu)手(shou)(shou)性(xing)(xing)生命系统密切相关,也是(shi)构(gou)建大型功能性(xing)(xing)手(shou)(shou)性(xing)(xing)材(cai)料(liao)的重(zhong)要方法(fa)。超(chao)分子(zi)(zi)(zi)手(shou)(shou)性(xing)(xing)与(yu)(yu)分子(zi)(zi)(zi)的手(shou)(shou)性(xing)(xing)相关,且取决于分子(zi)(zi)(zi)的空间排列。研(yan)(yan)(yan)究(jiu)超(chao)分子(zi)(zi)(zi)手(shou)(shou)性(xing)(xing)形成机制中重(zhong)要而困难的科学问(wen)题之(zhi)一是(shi)原(yuan)位(wei)研(yan)(yan)(yan)究(jiu)界(jie)(jie)面分子(zi)(zi)(zi)手(shou)(shou)性(xing)(xing)如何(he)被传递到超(chao)分子(zi)(zi)(zi)水平。迄今为(wei)止,这一问(wen)题尚未有明确答案(an)。非线性(xing)(xing)光学方法(fa)较其他研(yan)(yan)(yan)究(jiu)手(shou)(shou)段具(ju)有原(yuan)位(wei)、界(jie)(jie)面和手(shou)(shou)性(xing)(xing)研(yan)(yan)(yan)究(jiu)的敏感(gan)性(xing)(xing),为(wei)阐释手(shou)(shou)性(xing)(xing)物质结构(gou)与(yu)(yu)其特性(xing)(xing)之(zhi)间的关系提供了重(zhong)要技术(shu)和方法(fa)。  

      近年来,中国科(ke)学院化学研究所分子反应(ying)动(dong)力学实(shi)验室研究员张贞(zhen)课题组在界面超分子自组装单层膜的(de)结构手(shou)性(xing)、手(shou)性(xing)调(diao)控(J. Phys. Chem. B. 2020, 124, 8179-8187、界面(mian)生物膜磷(lin)脂分(fen)子由手(shou)性碳(tan)原子传递(di)至(zhi)宏观结构手(shou)性的分(fen)子机(ji)理(J. Chem. Phys. 2022156, 094704以(yi)及(ji)(ji)界面手性(xing)分(fen)子诱导(dao)非(fei)手性(xing)分(fen)子组装动力(li)学及(ji)(ji)其手性(xing)组装分(fen)子机(ji)理(J. Phys. Chem. Lett. 2022, 13, 3523-3528方面(mian)取得系列成果。近(jin)日,在上(shang)述(shu)研(yan)究的基础上(shang),科研(yan)人员使(shi)用自行(xing)研(yan)制的非线性光谱(pu)及成像(xiang)仪(yi)器并结合分子动力学(xue)模拟,从分子水平进一步探索了界面超分子手性构筑过程中手性从分子手性中心到超分子尺度的手性传递机制,建立了非线性光谱定量研究界面(mian)超(chao)分(fen)子长程手性传递的方法。 

      工作通过手(shou)性和(he)频振动(dong)光谱(chiral SFG结(jie)合(he)分子(zi)动力学(MD模拟研究了两亲分子L-/D-GAn (N, N’-bis (octadecyl)-L-/D-(anthracene-9-carboxamide)-glutamic diamide)单分子膜界面,原位探究在构筑超分(fen)子(zi)单层的过程(cheng)中,手性(xing)信(xin)息是如何(he)在分(fen)子(zi)各基(ji)团(tuan)间传递(di),并计算出分(fen)子(zi)各基(ji)团(tuan)的取(qu)向信(xin)息以(yi)及组(zu)装形成的氢键数目(mu)。研究发现,位于谷氨酸单元的手性中心通过分子间氢键诱导与之相连的酰胺基团发生轻微扭曲,将手性传递到酰胺基团、蒽环和疏水烷基链上。研究表明,手性中(zhong)心的手性信息可以(yi)通过分子间弱的非共价(jia)相互作用传(chuan)递到400-500 nm距离内(nei)的数百个分(fen)子中。该研究对于阐释分(fen)子本征手(shou)性(xing)和超分(fen)子手(shou)性(xing)之间的关系(xi)具(ju)有重要意(yi)义。  

      12月14日,相关研究成果在线发表在《自然-通讯》(Nature Communications上。研究工作得到国(guo)家自然(ran)科学基金、北京市自然(ran)科学基金和(he)中科院的支持。 

        

                                                                                     原位探(tan)索(suo)界面处的长程手性传递机(ji)制