Stereospecific Organic Reactions in Functionalized Synthetic Bilayer Membranes

功能化合成双层膜中的立体定向有机反应

• 批准号: 58430016
• 负责人: MURAKAMI Yukito
• 金额: $ 20.54万
• 依托单位: Kyushu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (A)
• 财政年份: 1983
• 资助国家: 日本
• 起止时间: 1983 至 1985
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-58430016/
• 关键词: Bilayer Membrane; Stereospecific; Organic Reaction; Peptide Lipid; Nonbilayer Structure; Vitamin B6; Vitamin B12; アミノ基転移反応

1. Aggregate Morphology of Synthetic Peptide Lipids. -- Peptide lipids, which can form chemically and morphologically stable single-walled vesicles in aqueous media, were desinged by incorporation of amino acid residues as their structural components. Those peptide lipids having cationic, anionic, and nonionic head moieties were successfully prepared, and their morphological behavior in aqueous media was examined. In particular, nonbilayer aggregates, cubic and hexagonal phases, were constructed for the first time with these synthetic lipids.2. Fusion Behavior of Single-Walled Vesicles. -- Sintle-walled vesicles formed with equimolar mixtures of nonionic and anionic peptide lipids underwent fusion by adjusting pH or temperature via formation of nonbilayer aggregates. Single-walled vesicles having ionic head moieties underwent fusion instantaneously upon addition of ionic polymers having the opposite charges.3. Functional Model of Vitamin <B_6> -dependent Enzyme. -- A holoenzyme model formed with single-walled vesicles of the peptide lipid and a hydrophobic vitamin <B_6> catalyzed the transamination reaction between an amino acid and a keto acid with turnover behavior. Here, an artificial transaminase was obtained for the first time.4. Functional Model of Vitamin <B_(12)> -dependent Enzyme. -- A holoenzyme model formed with single-walled vesicles of the peptide lipid and a hydrophobic vitamin <B_(12)> catalyzed the carbon-skeletal rearrangement in a manner as observed with methylmalonyl-CoA mutase.

1. 合成肽脂质的聚集形态。 -- 肽脂质可以在水介质中形成化学和形态稳定的单壁囊泡，其设计是通过掺入氨基酸残基作为其结构成分。成功制备了具有阳离子、阴离子和非离子头部的肽脂质，并检查了它们在水介质中的形态行为。特别是，首次用这些合成脂质构建了非双层聚集体、立方相和六方相。2．单壁囊泡的融合行为。 -- 由非离子和阴离子肽脂质的等摩尔混合物形成的单壁囊泡通过形成非双层聚集体调节pH或温度进行融合。具有离子头部的单壁囊泡在添加具有相反电荷的离子聚合物后立即发生融合。 3．维生素<B_6>依赖性酶的功能模型。 -- 由肽脂质单壁囊泡和疏水性维生素<B_6>形成的全酶模型催化氨基酸和酮酸之间的转氨反应并具有周转行为。在此，首次获得了人工转氨酶。4．维生素<B_(12)>依赖性酶的功能模型。 -- 由肽脂质的单壁囊泡和疏水性维生素<B_(12)>形成的全酶模型以甲基丙二酸单酰辅酶A变位酶观察到的方式催化碳骨架重排。

项目成果

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J.Am.Chem.Soc.106-12. (1984)

J.Am.Chem.Soc.106-12。

Bull.Chem.Soc.Jpn.59-2. (1986)

Bull.Chem.Soc.Jpn.59-2。

J.Chem.Soc.,Perkin Trans.2. 12. (1985)

J.Chem.Soc.，Perkin Trans.2。

J. Am. Chem. Soc.107-7. (1985)

J. Am.