ADVANCED ROTATIONAL ISOMERIC STATE SCHEME FOR MOLECULAR DESIGN OF ORGANIC AND POLMYERIC MATERIALS

用于有机和聚合物材料分子设计的先进旋转异构态方案

• 批准号: 11650920
• 负责人: SASANUMA Yuji
• 金额: $ 1.79万
• 依托单位: CHIBA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650920/
• 关键词: Conformation; RIS scheme; Poly (propylene oxide); Polysilane; Liquid crystal; Chemical shift; Deuterium NMR; Maximum entropy method; 炭素-13 NMR; 重水素 NMR; 特性比

In this project, we have developed an advanced rotational isomeric state (RIS) scheme for molecular design of organic and polymeric materials through the following three subjects.(1) Six dimeric model compounds of poly (propylene oxide), having different configurational sequences, were prepared, and investigated by carbon-13 NMR.The observed chemical shifts, assigned experimentally to the component carbon atoms, were well reproduced by the RIS scheme combined with substituent effects. The agreement between theory and experiment shows the validity of the conformational energies used in the calculations, the presence of the intramolecular (C-H)…O attraction, and the applicability of the RIS scheme to chemical-shift evaluation.(2) Unperturbed chain dimensions of poly (methyl n-propylsilane), poly (di-n-butylsilane), and poly (di-n-hexylsilane) were evaluated by static light scattering and size-exclusion chromatography-multichannel laser light scattering. For individual polymers, conformational energies including interactions of both main and side chains were determined from molecular dynamics simulations. The observed characteristic ratios were well reproduced by the RIS scheme using the conformational energies thus determined. Thus, we have developed a method for conformational analysis of polymers with long side chains.(3) Conformational and orientational characteristics of chain molecules such as n-alkanes and ethers dissolved in nematic solvents and amphiphilic molecules incorporated in hexagonal, lamellar, and reversed hexagonal aggregates have been investigated. Deuterium NMR quadrupolar splittings and proton-proton dipolar couplings were simulated by a combined use of the RIS scheme and the maximum entropy method. We have established a methodology for conformational analysis of chain molecules in anisotropic fields.

在本计画中，我们透过以下三个主题，发展出一个先进的旋转异构态（RIS）架构，以进行有机及高分子材料的分子设计。(1)制备了六种具有不同构型序列的聚环氧丙烷二聚模型化合物，并用碳-13核磁共振对其进行了研究，结合取代基效应的RIS方案很好地再现了实验上归属于组成碳原子的化学位移。理论和实验之间的协议表明，在计算中使用的构象能的有效性，分子内（C-H）... O吸引力的存在下，和化学位移评价的RIS计划的适用性。(2)用静态光散射和尺寸排阻色谱-多通道激光光散射法研究了聚甲基正丙基硅烷、聚二正丁基硅烷和聚二正己基硅烷的无扰链尺寸。对于单个聚合物，构象能，包括主链和侧链的相互作用，从分子动力学模拟确定。所观察到的特征比率，以及再现RIS计划使用的构象能，从而确定。因此，我们已经开发了一种方法的构象分析的聚合物与长侧链。(3)研究了链状分子如正构烷烃和醚类分子溶解在水溶性溶剂中的构象和取向特征，以及两亲分子在六方、层状和反六方聚集体中的构象和取向特征。采用RIS方案和最大熵方法相结合的方法，模拟了氘核磁共振四极分裂和质子-质子偶极耦合。我们建立了一种在各向异性场中分析链状分子构象的方法。

项目成果

Yuji Sasanuma: "Conformational Analysis of Chain Molecules in Liquid Crystalline Phases by a Rotational Isomeric State Scheme with Maximum Entropy Method II. ^2H NMR Quadrupolar Splittings from n-Decane and 1,6-Dimethoxyhexane Dissolved in 4'-Methoxybenzy

Yuji Sasanuma：“通过最大熵方法 II 的旋转异构态方案对液晶相中的链分子进行构象分析。^2H NMR 四极分裂来自溶解在 4-甲氧基苯中的正癸烷和 1,6-二甲氧基己烷

Akihiro Suzuki,Nobuyuki Miura,and Yuji Sasanuma: "Conformational Analysis of Amphiphilic Molecules Incorporated in Hexagonal, Lamellar, and Reversed Hexagonal Aggregates of a Ternary System of Sodium Octanoate, 1-Decanol, and Water by the Rotational Isome

Akihiro Suzuki、Nobuyuki Miura 和 Yuji Sasanuma：“通过旋转异构体对辛酸钠、1-癸醇和水三元系统中包含的六角形、层状和反六角形聚集体中的两亲分子进行构象分析

Yuji Sasanuma: "Conformational Analysis of Chain Molecules in Liquid Crystalline Phases by a Rotational Isomeric State Scheme with Maximum Entropy Method I. ^1H-^1H Dipolar Couplings from n-Alkanes Dissolved in a Nematic Solvent"Polym.J.. 32(10). 883-889

Yuji Sasanuma：“通过最大熵方法的旋转异构态方案对液晶相中的链分子进行构象分析 I.溶解在向列溶剂中的正烷烃的^1H-^1H偶极耦合”Polym.J.. 32(10

Yuji Sasanuma,Taisuke Iwata,Yasukazu Kato,Haruhisa Kato,Takashi Yarita,Shinichi Kinugasa,and Robert.V.Law: "Carbon-13 NMR Chemical Shifts of Dimeric Model Compounds of Ply (propylene oxide) : A Proof of Existence of the (C-H)…O Attraction"J.Phys.Chem.A. 1

Yuji Sasanuma、Taisuke Iwata、Yasukazu Kato、Haruhisa Kato、Takashi Yarita、Shinichi Kinugasa 和 Robert.V.Law：“Ply（环氧丙烷）二聚模型化合物的碳 13 NMR 化学位移：证明（ C-H)…O 吸引力"J.Phys.Chem.A. 1

Yuji Sasanuma: "Conformational Analysis of Chain Molecules in Liquid Crystalline Phases by a Rotational Isomeric State Scheme with Maximum Entropy Method I.^1H-^1H Dipolar Couplings from n-Alkanes Dissolved in a Nematic Solvent"Polym.J. 32 (10). 883-889 (

Yuji Sasanuma：“使用最大熵方法 I.^1H-^1H 偶极耦合从溶解在向列溶剂中的正烷烃通过旋转异构态方案对液晶相中的链分子进行构象分析”Polym.J。