核磁共振残留偶极耦合在立体化学研究中的应用
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- 英文论文题名：Residual Dipolar Couplings as a Powerful NMR Parameter for the Determination of Organic Molecules
- 论文作者：雷新响 ; 宗文
- 英文论文作者：Xinxiang Lei ; Zong Wen ; College of Pharmacy ; South-Central University for Nationalities ; College of Chemistry & Materials Engineering ; Wenzhou University
- 年：2016
- 作者机构：中南民族大学药学院;温州大学化学与材料工程学院;
- 论文关键词：核磁共振 ; 残留偶极耦合 ; 立体化学 ; 氧化石墨烯液晶
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第四十五分会：物理有机
- 语种：中文
- 分类号：O621.13
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第四十五分会 ; 物理有机
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：207k
- 原文格式：D
- 会议级别：全国
摘要
有机分子的结构鉴定一直是有机分析化学的基础课题,核磁共振波谱法则是众多结构分析方法中的一种有效手段,能够提供有机分子构造、构型以及优势构象的重要信息。随着核磁共振波谱技术的发展,残留偶极耦合RDC[1](Residual Dipolar Couplings)可以提供分子内两个距离在8?的原子空间排列信息,它与分子内原子的空间排列有关,反映了分子的构造、构型以及优势构象,是有机分子结构解析的一项重要参数,因此,越来越受到有机化学家的重视[2]。但是由于缺乏有效的有机溶剂兼容的定向介质,限制了其在有化合物立体结构分析中的应用。本课题组发现氧化石墨烯液晶作为一种RDC提取介质表现出了良好效果[3]。
Residual dipolar couplings(RDCs) have proven to be an invaluable anisotropic NMR parameter for the structural elucidation of complex biopolymers and organic molecules. However, a remaining bottleneck limiting its wider use by organic and natural product chemists is the lack of a range of easily applicable aligning media for diverse organic solvents. In this study, graphene oxide(GO)-based liquid crystals(LCs) were developed to induce partial orientation of organic molecules to allow RDC measurements. These LCs were determined to be remarkably stable and broadly compatible with organic solvents such as dimethyl sulfoxide. Moreover, compared with those for other alignment media, no background signals were acquired with the GO molecules in solution because of their rigidity and high molecular weight.
Residual dipolar couplings(RDCs) have proven to be an invaluable anisotropic NMR parameter for the structural elucidation of complex biopolymers and organic molecules. However, a remaining bottleneck limiting its wider use by organic and natural product chemists is the lack of a range of easily applicable aligning media for diverse organic solvents. In this study, graphene oxide(GO)-based liquid crystals(LCs) were developed to induce partial orientation of organic molecules to allow RDC measurements. These LCs were determined to be remarkably stable and broadly compatible with organic solvents such as dimethyl sulfoxide. Moreover, compared with those for other alignment media, no background signals were acquired with the GO molecules in solution because of their rigidity and high molecular weight.
引文
[1]Tjandra,N.;Bax,A.Science,1997,278,1111.
[2](a)Gil,R.R.Angew.Chem.Int.Ed.,2011,50,7222.(b)Sun,H.;Reinscheid,U.M.;Whitson,E.L.;Edward J.D.;Ireland,C,M.;Va?zquez,A.N.;Griesinger,C.J.Am.Chem.Soc.,2011,133,14629.(c)B?ttcher,B.;Schmidts,V.;Raskatov,J.A.;Thiele,C.M.Angew.Chem.Int.Ed.,2010,49,205.(d)Kummerl?we,G.;Luy,B.Trends in Analytical Chemistry,2009,28,483.
[3](a)Lei.X.X.;Xu.Z.;Sun.H.,et al.J.Am.Chem.Soc.2014,136,11280;(b)Zong W.;Li,G.W.;Cao,J.M.;Lei,X.X.;Hu,M.L.;Sun,H.;Griesinger,C.;Tan,R.X.Angew.Chem.Int.Ed.2016,55,3690
[2](a)Gil,R.R.Angew.Chem.Int.Ed.,2011,50,7222.(b)Sun,H.;Reinscheid,U.M.;Whitson,E.L.;Edward J.D.;Ireland,C,M.;Va?zquez,A.N.;Griesinger,C.J.Am.Chem.Soc.,2011,133,14629.(c)B?ttcher,B.;Schmidts,V.;Raskatov,J.A.;Thiele,C.M.Angew.Chem.Int.Ed.,2010,49,205.(d)Kummerl?we,G.;Luy,B.Trends in Analytical Chemistry,2009,28,483.
[3](a)Lei.X.X.;Xu.Z.;Sun.H.,et al.J.Am.Chem.Soc.2014,136,11280;(b)Zong W.;Li,G.W.;Cao,J.M.;Lei,X.X.;Hu,M.L.;Sun,H.;Griesinger,C.;Tan,R.X.Angew.Chem.Int.Ed.2016,55,3690