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

多肽分子内一级跃迁过程中氢键协同转变的研究——^2H NMR分析在液晶态的应用

• 批准号: 15550111
• 负责人: ABE Akihiro
• 金额: $ 2.5万
• 依托单位: Tokyo Polytechnic University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550111/
• 关键词: 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

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.

1。α-螺旋式逆反转行为（左至右手，反之亦然），这实际上取决于侧链末端的酯基的化学结构（x）。通过构建相图作为溶液组成（TCE/TFA）和温度的函数，已经研究了聚合物之间这种现象学差异的原因。2。 NMR方法已经研究了M-Cresol（正常型跃迁）在M-Cresol（正常型跃迁）中聚冬天（X =苯甲酰和X =苯乙）的螺旋线圈转变。观察到的^1H-^1H附近_χ1键旋转周围的杂化耦合表明，随着从左手的随机螺旋状态的温度升高，G^概念的趋势从〜50％降低至〜30％。3。3.型固定型液体晶体的nematic构象，以检查室内的室内形成型的室内形成型的室内形成型的。光谱和热力学（PVT）分析得出的结论是，一组部分定向的会议持续存在于列表状态的整个范围内。这是新的化学结构分子设计的令人鼓舞的证据。

项目成果

Stepwise Phase Transition of Chain Molecules : Crystallization/Melting via a Nermatic LC Phase

链分子的逐步相变：通过向热 LC 相结晶/熔化

• 发表时间: 2005
• 期刊: Adv.Polym.Sci. (in press)
• 作者: A.Abe;H.Furuya;Z.Zhou;T.Hiejima;Y.Kobayashi
• 通讯作者: Y.Kobayashi

Phase Behavior of Ternary Systems Involving a Conformationally Variable Chain and a Randomly Coiled Polymer

涉及构象可变链和无规卷曲聚合物的三元体系的相行为

• 发表时间: 2003
• 期刊: Macromolecules 36
• 作者: J.Lin;S.lin;P.Liu;T.Hiejima;H.Furuya;A.Abe
• 通讯作者: A.Abe

H.Furuya, H.Iwanaga, T.Nakajima, A.Abe: "Nematic Confirmation of Oxyethylene Spacers Involved in Main-Chain Liquid Crystals"Macromol.Symp.. 192. 239-250 (2003)

H.Furuya、H.Iwanaga、T.Nakajima、A.Abe：“主链液晶中涉及的氧乙烯间隔基的向列确认”Macromol.Symp.. 192. 239-250 (2003)

Effect of the Pendant Ester Group Orientationon the Dipole Moment of Poly(alkyl acrylate)s

侧酯基取向对聚丙烯酸烷基酯偶极矩的影响

• 发表时间: 2003
• 期刊: Macromolecules 36
• 作者: Z.Zhou;A.Abe
• 通讯作者: A.Abe

Screw-sense inversion characteristic of α-helical poly(β-p-chlorobenzyl L-aspartate) and comparison with other related polyaspartates

• DOI: 10.1002/bip.20207
• 发表时间: 2005-01-01
• 期刊: BIOPOLYMERS
• 影响因子: 2.9
• 作者: Abe, A;Hiraga, K;Furuya, H
• 通讯作者: Furuya, H