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首页> 外文期刊>Chemistry: A European journal >Synthesis and Vesicle Formation from Dimeric Pseudoglyceryl Lipids with (CH_2)_m Spacers: Pronounced m-Value Dependence fo Thermal Properties, Vesicle Fusion, and Cholesterol Complexation
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Synthesis and Vesicle Formation from Dimeric Pseudoglyceryl Lipids with (CH_2)_m Spacers: Pronounced m-Value Dependence fo Thermal Properties, Vesicle Fusion, and Cholesterol Complexation

机译：具有（CH_2）_m间隔基的二聚伪甘油脂质的合成和囊泡形成：热性质，囊泡融合和胆固醇络合的明显m值依赖性

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摘要

Eight new dimeric lipids, in which the two Me_2N~+ ion headgroups are separated by a variable number of polymethylene units [-(CH_2)_m-], have been synthesized. The electron micrograph (TEM) and dynamci light scattering (DLS) of their aqueous dispersions confirmed the formation of vesiculartype aggregates. The vesicle sizes and morphologies were found to depend strongly on the m value, the method, and thermal hitory of the vesicle preparation, Information on the thermotropic properties of the resulting vesicles was obtianed from microcalorimetry and temperautre-dependent fluorescence anisotropy measurements. Interestingly, the T_m values for these vesicles revealed a nonlinear dependence on spacer chain length (m value). These vesicles were able to entrap riboflavin. The rates of permeation of the OH~- ion under an imposed transmembrnae pH gradient were also found to depend significantly on the m value. X-Ray diffraction ofhte cast films fo the lipid dispersions elucidated the nature and the thickness of these membrane organizations, and it was revealed that these lipdis organize in three different ways depending on teh m value. The EPR spin-probe method with the doxylstearic acids 5NS, 12NS, and 16NS, spin-labeled at various positions of stearic acid, was used to establish the chain-flexxibiltiy gradient and homogeneity of these bilayer assemblies. Teh apparent fusogenic propensities of these bipolar tetraether lipids were investigated in the presence of Na_2SO_4 with fluorescence-resonance energy-transfer fusion assay. Small unila mellar vesicles formed from 1 and three representative biscationic lipids were also studied with fluorescence anisotropy and ~1H NMR spectroscopic techniques int eh absence and the presence of varying amounts of cholesterol.
机译：合成了八个新的二聚脂质，其中两个Me_2N〜+离子头基被可变数量的多亚甲基单元[-（CH_2）_m-]隔开。其水分散体的电子显微照片（TEM）和动态光散射（DLS）证实了囊泡状聚集体的形成。发现囊泡的大小和形态在很大程度上取决于囊泡制备物的m值，方法和热特性。通过微量热法和与温度有关的荧光各向异性测量，获得了关于所得囊泡的热力学性质的信息。有趣的是，这些囊泡的T_m值显示出对间隔链长度（m值）的非线性依赖性。这些囊泡能够捕获核黄素。还发现，在施加的跨膜pH梯度下，OH〜-离子的渗透速率明显取决于m值。通过流延膜的X射线衍射分析了脂质分散体的性质和膜组织的厚度，发现这些脂膜根据其值以三种不同的方式组织。使用在硬脂酸的不同位置上进行旋转标记的，具有二硬脂酸5NS，12NS和16NS的EPR旋转探针方法来建立这些双层组件的链柔性梯度和均匀性。在Na_2SO_4存在下，通过荧光共振能量转移融合分析研究了这些双极四醚脂质的表观融合倾向。还用荧光各向异性和〜1H NMR光谱技术研究了由1个和3个代表性的双阳离子脂质形成的单核小囊泡，其中不存在胆固醇，并且存在数量不等的胆固醇。

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