Development of a high resolution solid-steate NMR spectrometer and investigation dynamical behavior of organic molecules in the solid state.

开发高分辨率固态核磁共振波谱仪并研究固态有机分子的动力学行为。

• 批准号: 02554016
• 负责人: SUGAWARA Tadashi
• 金额: $ 12.16万
• 依托单位: University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02554016/
• 关键词: Solid-state high resolution NMR; Dynamical behavior of organic molecules in the solid state; Tautomerization in the solid state; Polymerization in the solid state; Polydiacetylene; beta-Hydroxyphenalenone; ヒドロキシフェナレノン; 固体高分解能核磁気共鳴装置; パルス系列; 光透過プロ

The purpose of the project is to produce a new type of a high resolution solid-state NMR spectrometer for investigating dynamical behavior of organic molecules in the solid state.1. The main instrumental problems to be innovated are as follows.(1) Optimize pulse frequencies in order to perform CRAMPS experiments (high resolution solid state ^1HNMR) by introducing a four-phase shifter and other hardwares.(2) Improve a lower limit of variable temperatures for CP/MAS experiments by modifying a cooling system of the probe.(3) Prepare a photo-transmission probe in order to irradiate a sample during CP/MAS measurements.The first problem was successfully solved. High resolution ^1H NMR spectra of maleic acid and citric acid were obtained with a resolution of 0.32 ppm. Technical solutions concerning to the latter two points were proposed, although instrumental modifications could not be achieved due to the financial condition.2. Utilizing the novel spectrometer, CP/MAS measurement were performed on solid samples to elucidate intriguing dynamical behaviors. Typical studies are as follows.(1) Investigate the solid state tautomerization of b-hydroxyenones which exhibit paraelectric and (anti)ferroelectric behaviors(2) Prepare new host molecules such as twin-donors or fused thiophenes and elucidate dynamical behaviors of guest molecules in inclusion complexes.(3) Prepare photolabile diacetylenes carrying a mesogenic group and monitor the photo-induced polymerization by CP/MAS measurements.In summery, novel physical properties and chemical reactions, which are derived from a dynamical behavior of organic molecules in the solid state, have been elucidated by using the newly developed high resolution solid state NMR spectrometer.

该项目的目的是生产一种新型高分辨率固态核磁共振波谱仪，用于研究固态有机分子的动力学行为。 1．主要需要创新的仪器问题如下：（1）通过引入四移相器等硬件，优化脉冲频率，以进行CRAMPS实验（高分辨率固态^1HNMR）。（2）提高通过修改探头的冷却系统，实现CP/MAS实验的可变温度。(3)准备光透射探头，以便在CP/MAS测量时照射样品。第一个问题成功解决。获得了马来酸和柠檬酸的高分辨率^1H NMR谱，分辨率为0.32 ppm。针对后两点提出了技术解决方案，但由于财务状况无法进行仪器修改。 2．利用新型光谱仪，对固体样品进行 CP/MAS 测量，以阐明有趣的动力学行为。典型研究如下：（1）研究具有顺电和（反）铁电行为的b-羟基烯酮的固态互变异构（2）制备新的主体分子，如孪生供体或稠合噻吩，并阐明客体分子的动力学行为(3) 制备带有介晶基团的光不稳定丁二炔，并通过 CP/MAS 测量监测光诱导聚合。化学反应源于固态有机分子的动力学行为，已通过使用新开发的高分辨率固态核磁共振波谱仪得到了阐明。

项目成果

Stereospecificity of the 1,2-Wittig Rearrangement: How Chelation Effects Influence Stereochemical Outcome

1,2-Wittig 重排的立体特异性：螯合效应如何影响立体化学结果

• DOI: 10.1021/ja981696n
• 发表时间: 1998-08-05
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: R. Maleczka;F. Geng
• 通讯作者: F. Geng