Joint Study on Structure of Polymers by New Solid State NMR

新固态核磁共振联合研究聚合物结构

基本信息

批准号：
06044075
负责人：
ASAKURA Tetsuo
金额：
$ 3.65万
依托单位：
Tokyo University of Agriculture and Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for international Scientific Research
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1996
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06044075/
关键词：
Solid State NMR Silk Isotope Labelling Angular-dependent NMR REDOR NMR Structural Analysis Amorphous Structure Dynamics Chemical shift Anisotropy CROWN スピン拡散

项目摘要

The objective of this international joint study is development of novel analytical methods using angular-and distance-dependent theory of solid state NMR in atomic level and its application to structural analysis of polymers in atomic level. Orientation-dependent NMR interactions such as dipole-dipole, quadrupole and chemical shielding yield structural information on polymers in the solid state. If these parameters are observed for each site in oriented polymers, the solid state NMR methods can give even the atomic co-ordinates of the polymers. This is especially effective in the determination of the atomic co-ordinates of uniaxially oriented peptides or proteins in which the X-ray technique gives only little structural information. This analytical method could be applied to obtain structural information of oriented polyamide fibers such as poly (p-phenylene terephthalamide) (PPTA), and poly (m-phenylene isophthalamide) (PMIA) and poly (4-methyl-m-phenylene terephthalamide) (P4M-MPTA) fibers without isotope labelling of the samples. The oriented carbonyl carbon labelled poly (ethylene terephthalate) (PET) films are also analyzed with this method. Especially, more quantitative structural information was obtained for a locally ordered domain which has been recognized as an amorphous domain in X-ray diffraction analysis in heterogeneous polymer samples. The REDOR (Rotational Echo Double Resonance) technique has been applied to structure determination of a silk fibroin model compound. In general, this does not require the orientation of the samples in the analysis, but selective isotope labelling between specified nuclear pairs in the samples is required which becomes frequently to be a problem.

这项国际联合研究的目的是使用原子水平的固态NMR的角度和距离依赖性理论开发新的分析方法及其在原子水平的聚合物结构分析中的应用。方向依赖性的NMR相互作用，例如偶极 - 偶极子，四极杆和化学屏蔽产生固态聚合物的结构信息。如果在定向聚合物中观察到每个位点的这些参数，则固态NMR方法甚至可以给出聚合物的原子坐标。这对于确定单轴向肽或蛋白质的原子坐标尤其有效，在这些肽或蛋白质中，X射线技术仅提供很少的结构信息。这种分析方法可以应用于获得定向聚酰胺纤维的结构信息，例如聚（P-phenylene tetrephalamide）（PPTA）和聚（M-苯基二苯丙胺）（PMIA）和聚（4-甲基 - 苯基苯基treephathalamide）（p4m-mptle）（p4mmpta）fiber nickepabipa biber nict same bibers bibers bibers，该方法还分析了定向的碳碳标记的聚（乙二醇乙二醇化）（PET）膜。特别是，在异质聚合物样品中，在局部有序域中获得了更定量的结构信息，该域中已被认为是X射线衍射分析中的无定形结构域。 REDOR（旋转回声双共振）技术已应用于丝纤维蛋白模型化合物的结构测定。通常，这不需要分析中样品的方向，但是需要在样品中指定的核对对之间选择性同位素标记，这通常是一个问题。