Formation of Superstructural Bilayers and Enzyme Model Reaction by Telomer-type Surfactants.

调聚物型表面活性剂的超结构双层的形成和酶模型反应。

• 批准号: 60470112
• 负责人: YAMADA Kimiho
• 金额: $ 3.46万
• 依托单位: Kumamoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1985
• 资助国家: 日本
• 起止时间: 1985 至 1986
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-60470112/
• 关键词: Telomer; Polypeptide; Surfactant; Micelle; Bilayer; Helix; Superstructure; 不斉選択性

1. Double-chain alkyl derivatives with poly(L-glutamic acid)- and poly(L-aspartic acid)-head groups were synthesized and their aggregate morphologies in dilute aqueous solutions were investigated. These polyamino acid derivatives were dispersed in water at above pH 4 to form a variety of helical superstructures composed of single-walled bilayer membranes, whose morphologies were closely related to the chemical structures of hydrophilic head groups. The helical structures were not observed in the corresponding ammonium amphiphiles without polyamino acid-head groups and the amphiphile with low-molecular head groups or with poly(DL-amino acid) head groups. The developmental mechanism to helical superstructures was concluded by following the metamorphosis of bilay reaggregates from poly(L-aspartic acid) derivatives in aqueous solutions:the helical forms are induced via the formation of double or multiple helix among the untwisted filaments produced by incubating.2. Chiral ester cleavage by … More achiral hydroxamic acids was investigated in the presence of chiral matrix micelles formed from amphiphiles with poly-L-lysine-head groups. The results are summarized as follows. (1) The enantioselectivity was not observed in the alkaline hydrolysis in chiral micelles only. This matrix possesses no selectivity. When an achiral hydroxamic acid was added to the system,selectivity was induced. (2) The direction of selectivity is reversed by the conformational change of the secondary structure formed by the peptide moiety of matrix micelles. L-Selectivity in the random coil and D-selectivity in the <alpha> -helix condition were observed. (3) The degree of selectivity is dependent on the chemical structure of hydroxamic acid;for example, an N-H type hydroxamic acid gives higher selectivity than an N-methyl type one. Thus, it is supposed that enantioselectivity is introduced by the chiral interaction between chiral micelles and achiral nucleophiles, in which the conformation of polypeptide moiety plays an important role. Less

1.合成了含聚L-谷氨酸和聚L-天冬氨酸头部基团的双链烷基衍生物，并研究了它们在稀水溶液中的聚集形态。这些聚氨基酸衍生物分散在pH 4以上的水中，形成由单壁双层膜组成的各种螺旋超结构，其形态与亲水性头部基团的化学结构密切相关。在相应的不含聚氨基酸头基的铵两亲物和含低分子量头基或聚DL-氨基酸头基的两亲物中没有观察到螺旋结构。通过对聚L-天冬氨酸衍生物在水溶液中形成的bilay重聚集体的变态过程的观察，得出了螺旋超结构的形成机制：螺旋结构的形成是通过在培养过程中产生的解捻丝之间形成双螺旋或多螺旋而实现的.手性酯裂解 ...更多信息 研究了具有聚-L-赖氨酸-头基的两亲物形成的手性基质胶束存在下的非手性异羟肟酸。结果总结如下。(1)在碱性条件下，仅在手性胶束中水解没有观察到对映体选择性。该基质不具有选择性。当一个非手性异羟肟酸加入到系统中，诱导的选择性。(2)选择性的方向是由基质胶束的肽部分形成的二级结构的构象变化逆转。观察到无规卷曲中的L-选择性和-螺旋条件中的D-选择性<alpha>。(3)选择性的程度取决于异羟肟酸的化学结构;例如，N-H型异羟肟酸给出比N-甲基型异羟肟酸更高的选择性。因此，推测手性胶束与非手性亲核试剂之间的手性相互作用是导致对映选择性的主要原因，其中多肽部分的构象起着重要的作用。少

项目成果

伊原博隆: Polymer Journal. 18. 463-469 (1986)

井原弘隆：聚合物杂志 18. 463-469 (1986)

Hirotaka, Ihara: "Amphiphiles with polypeptide-head groups <III> . Regulation of enantioselectivity in micellar hydrolysis." Polymer Journal. 18. 463-469 (1986)

Hirotaka, Ihara：“具有多肽头基 <III> 的两亲物。胶束水解中对映选择性的调节。”

Hirotaka, Ihara: "Exceptional morphologies and metamorphosis of bilayer membranes formed from amphiphiles with poly(L-aspartic acid)-head groups." Polymer Communication. 27. 282-285 (1986)

Hirotaka, Ihara：“由带有聚（L-天冬氨酸）头基的两亲物形成的双层膜具有特殊的形态和变态。”

伊原博隆: Polymer Communication. 27. 282-285 (1986)

井原弘隆：聚合物通讯。27. 282-285 (1986)

伊原博隆: 日本化学会誌. 3月号. (1987)

Hirotaka Ihara：日本化学会杂志三月号（1987 年）。