Research into Formation and Structure of Helical Superstructure formed from Synthetic Bilayer Membrane

合成双层膜螺旋超结构的形成与结构研究

• 批准号: 01550687
• 负责人: YAMADA Norihiro
• 金额: $ 1.02万
• 依托单位: Chiba University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01550687/
• 关键词: Synthetic Bilayer Membrane; Helical Superstructure; Amphiphile; Even-Odd-Chain Effect; Chirality; Fourier Transform Infrared Spectrum; Aggregation Morphology; Hydrogen Bond; 二分子膜; ヘリックス; 光学顕微鏡; 可視・紫外分光; 偶奇効果; 疎水鎖

Bilayer aggregate which formed from amphiphilic compound in water sometimes transforms into helical superstructure by incubation at temperatures below the gel to liquid-crystal phase transition (Tc). We investigated the helical superstructure by using more than 20 amphiphiles to elucidate driving force of the helix-formation and molecular orientation or packing structure in the helices, and obtained following results.1. Chiral, double-chain ammonium amphiphiles possessing shorter hydrophobic chain formed the helical superstructures in preference to those possessing longer hydrophobic chain; dodecyl > tridecyl > tetradecyl > pentadecyl > hexadecyl.2. Although the formation of the helical aggregates were observed in aqueous solution of an achiral, single-chain ammonium amphiphile which contained a hydrogen bonding group, the helical superstructure was predominantly formed from chiral amphiphiles rather than achiral amphiphiles. The result means that the helix-formation is promoted by the presence of an asymmetric carbon and hydrogen bonding groups. And these structural moieties cooperatively act on the helix-formation.3. Annealing was more effective to form the helical superstructure than incubation at a constant temperature below Tc.4. Electronic and infrared spectra of the amphiphiles were not changed without respect to whether the amphiphiles formed large helices or fragmental helices. Thus the molecular orientation and packing is locally identical between large and small helices.5. Electronic and infrared spectra of aqueous bilayer membranes were alternatively changed with number of carbon atoms in the hydrophobic chain, which was independent of the helix-formation. Therefore, it became apparent that the even-odd-chain effect was an general phenomenon in the bilayer systems.

两亲性化合物在水中形成的双层聚集体，在低于凝胶相转变温度（Tc）时，有时会转变为螺旋超结构。我们用20多种两亲分子对螺旋超结构进行了研究，以阐明螺旋形成的驱动力和螺旋中的分子取向或堆积结构，得到了以下结果.疏水链较短的手性双链铵两亲物优先形成螺旋超结构;十二烷基>十三烷基>十四烷基>十五烷基>十六烷基.虽然在含有氢键基团的非手性单链铵两亲物的水溶液中观察到螺旋聚集体的形成，但螺旋超结构主要由手性两亲物而不是非手性两亲物形成。这一结果表明，螺旋的形成是由不对称的碳和氢键基团的存在下促进的。这些结构部分协同作用形成螺旋。退火是更有效地形成螺旋结构比在低于Tc的恒定温度下孵育。4。电子和红外光谱的两亲物没有改变，无论是形成大螺旋或片段螺旋。因此，大螺旋和小螺旋之间的分子取向和堆积是局部相同的.电子光谱和红外光谱随疏水链上碳原子数的变化而交替变化，与螺旋结构无关。因此，很明显，奇偶链效应是双层系统中的普遍现象。

项目成果

Norihiro Yamada: "Alternation of Absorption Maxima in Helical Superstructures of Chiral,Singleーchain Ammonium Amphiphiles" J.Chem.Soc.,Chem.Commun.568-569 (1990)

Norihiro Yamada：“手性单链铵两亲物螺旋超结构中吸收最大值的交替”J.Chem.Soc.，Chem.Commun.568-569 (1990)

Norihiro Yamada: "Alternation of Absorption Maxima in Helical Superstructures of Chiral, Single-chain Ammonium Amphiphiles" J. Chem. Soc., Chem. Commun.No. 7. 568-569. (1990)

Norihiro Yamada：“手性单链铵两亲物螺旋超结构中吸收最大值的交替”J. Chem。

Norihiro Yamada: "Alternation of Absorption Maxima in Helical Superstructures of Chiral,Single-chain Ammonium Amphiphiles" Journal of The Chemical Society,Chemical Communications(J.Chem.Soc.,Chem.Commun.). (1990)

Norihiro Yamada：“手性单链铵两亲物螺旋超结构中吸收最大值的交替”化学会杂志，化学通讯（J.Chem.Soc.，Chem.Commun.）。