Grant-in-Aid for Developmental Scientific Research (B)
|Allocation Type||Single-year Grants|
|Research Institution||University of Tokyo|
SUGAWARA Tadashi Univ.of Tokyo,Dept.of Arts and Sciences,Professor, 教養学部, 教授 (50124219)
IZUOKA Akira Univ.of Tokyo,Dept.of Arts and Sciences,Research Associate, 教養学部, 助手 (90193367)
TUKADA Hideyuki Yokohama City Univ., Associate, 総合理学研究所, 助教授 (40171970)
SATO Naoki Kyoto Univ., Professor, 化学研究所, 教授 (10170771)
YAMAGISHI Akihiko Univ.of Hokkaido,Dept.of Science, Professor, 理学部, 教授 (70001865)
KOBAYASHI Keiji Univ.of Tokyo,Dept.of Arts and Sciences,Professor, 教養学部, 教授 (50012456)
藤戸 輝昭 日本電子(株), 分析機器, 研究員
|Project Period (FY)
1990 – 1992
Completed(Fiscal Year 1992)
|Budget Amount *help
¥19,000,000 (Direct Cost : ¥19,000,000)
Fiscal Year 1992 : ¥400,000 (Direct Cost : ¥400,000)
Fiscal Year 1991 : ¥5,000,000 (Direct Cost : ¥5,000,000)
Fiscal Year 1990 : ¥13,600,000 (Direct Cost : ¥13,600,000)
|Keywords||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-ブ / 固体 ^1H高分解能測定 / 固相有機分子ダイナミックス / 光透過型プロ-ブ / 心体 ^1H高分解能測定|
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.