Studies on the Cooperativie Transformation of Hydrogen-Bonds During the Intramolecular First-Order Transitions of Polypeptides-An Application of ^2H NMR Analysis in the Liquid Crystalline State
| Project/Area Number |
15550111
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Polymer chemistry
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| Research Institution | Tokyo Polytechnic University |
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Principal Investigator |
ABE Akihiro Tokyo Polytechnic University, Nano-Science Research Center, Professor, 工学研究科, 教授 (50114848)
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| Co-Investigator(Kenkyū-buntansha) |
HIEJIMA Toshihiro Tokyo Polytechnic University, Department of Nano-Chemistry, Associate Professor, 工学部, 助教授 (30288112)
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| Project Period (FY) |
2003 – 2004
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| Project Status |
Completed (Fiscal Year 2004)
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| Budget Amount *help |
¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 2004: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 2003: ¥2,800,000 (Direct Cost: ¥2,800,000)
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| Keywords | Poly(aspartate)s / Intramolecular hydrogen-bond / Helix-coil transition / Normal transition / Helix-helix transition / _χ1 conformer / Mainchain liquid crystal / Dipole moment / ポリL-アスパルテート / 共重合構造 / 分子内転移の相図 / 長い側鎖 / van der Waals解析 / ポリ(α-アミノ酸エステル) / ヘリックスらせんの反転 / 3成分系相図 / リオトロピック液晶 / ^2H-^1H交換反応速度 / ^2HNMR解析 |
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| Research Abstract |
1.Screw-sense inversion behaviors (left- to right-handed or vice versa) of α-helical polyaspartates differ substantially depending on the chemical structure (X) of the ester group at the side-chain terminals. The cause of such phenomenological differences among polymers (X=benzyl, chlorobenzyl, and phenethyl) have been investigated by constructing the phase diagram as a function of solvent composition (TCE/TFA) and temperature.
2.The helix-coil transition of polyaspartates (X=benzyl and X=phenethyl) in m-cresol at elevated temperature (a normal-type transition) has been studied by NMR methods. The observed ^1H-^1H vicinal coupling constant around the _χ1 bond rotation suggests that the g^- conformation decreases from 〜50% to 〜30% with increasing temperature in the transition region from the left-handed to random-coil state.
3.The nematic conformation of main-chain liquid crystals has been studied to examine the possible incorporation of the intramolecular hydrogen-bond. The spectroscopic as well as thermodynamic (PVT) analyses led to a conclusion that a group of partially oriented conformation persists over the entire range of the nematic state. This is an encouraging evidence for the molecular design of a new class of chemical structures.
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Report
(3 results)
Research Products
(21 results)
