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首页> 外文OA文献 >Structures of the subgel phases of n-saturated diacyl phosphatidylcholine bilayers: FTIR spectroscopic studies of 13C = O and 2H labeled lipids.
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Structures of the subgel phases of n-saturated diacyl phosphatidylcholine bilayers: FTIR spectroscopic studies of 13C = O and 2H labeled lipids.

机译：n-饱和二酰基磷脂酰胆碱双层分子亚凝胶相的结构：13 C = O和2H标记脂质的FTIR光谱研究。

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摘要

The subgel phases of unlabeled, specifically chain perdeuterated and specifically 13C = O labeled representative samples of the n-saturated diacylphosphatidylcholines were studied by Fourier-transform infrared spectroscopy. Our results indicate that the spectroscopic properties exhibited by the subgel phases of the longer chain homologues are not consistent with that of a pure phase and we suggest that this is because the observed spectrum is a summation of spectroscopic features arising from both their subgel and L beta gel phases. Using spectral subtraction techniques, we obtained a spectrum which we believe is more representative of the pure subgel phase and from it we suggest that the subgel phase of the long chain phosphatidylcholines is an ordered crystallike structure containing two vibrationally inequivalent populations of lipid molecules arranged with the zigzag planes of their hydrocarbon chains parallel. For dipalmitoylphosphatidylcholine, our data indicate that its stable subgel phase is generally similar to that of the longer chain homologues but it is a more ordered structure in which the polar/apolar interfacial region is probably less hydrated. With the medium chain (N = 13-15) compounds, two populations of vibrationally equivalent molecules are also present in the subgel phase, but unlike DPPC and the longer chain homologues, the zigzag planes of their sn1- and sn2- acyl chains are perpendicular to each other, and a sn1-ester C = O group of one of the populations is in relatively close contact with an sn2-ester C = O group of the other population. With the shorter chain (N = 10 - 12) compounds, our data is indicative of a very complex quasi-crystalline assembly in which there may be at least three vibrationally inequivalent populations of lipid molecules with rotationally disordered hydrocarbon chains. Moreover, the conformation of the glycerol backbone may well be very different from that usually expected of this class of phospholipids. With all of these lipids, the structural pictures which emerge from our studies of the various subgel phases are in many aspects incompatible with that deduced from the single crystal x-ray studies of dimyristoylphosphatidylcholine. We suggest that this is because under our experimental conditions, these lipids have effectively been crystallized from water, whereas the sample used for the single-crystal x-ray study was crystallized from organic solvents.
机译：通过傅立叶变换红外光谱法研究了未标记的，特别是链式氘代的和特别是13C = O标记的n-饱和二酰基磷脂酰胆碱代表性样品的亚凝胶相。我们的结果表明，较长链同系物的亚凝胶相表现出的光谱性质与纯相的光谱性质不一致，我们建议这是因为观察到的光谱是由其亚凝胶和Lβ产生的光谱特征的总和凝胶相。使用光谱减法技术，我们获得了一个我们认为更能代表纯亚凝胶相的光谱，并据此表明长链磷脂酰胆碱的亚凝胶相是一种有序的晶体状结构，包含两个振动不等价的脂质分子，并以它们的烃链呈锯齿形平面平行。对于二棕榈酰磷脂酰胆碱，我们的数据表明，其稳定的亚凝胶相通常类似于较长链的同系物，但它是一种更有序的结构，其中极性/非极性界面区域的水合程度可能较低。对于中链（N = 13-15）化合物，在亚凝胶相中也存在两个群体的振动等效分子，但是与DPPC和较长链的同系物不同，它们的sn1-和sn2-酰基链的锯齿形平面是垂直的彼此之间，并且其中一个种群的sn1-ester C = O组与另一种群的sn2-ester C = O组相对紧密接触。对于较短链的化合物（N = 10-12），我们的数据表明存在非常复杂的准晶体组装，其中可能存在至少三个振动不等价的脂质分子，它们具有旋转无序的烃链。而且，甘油主链的构象可能与这类磷脂通常预期的构象有很大不同。对于所有这些脂质，从我们对各种亚凝胶相的研究中得出的结构图在许多方面与由二肉豆蔻酰基磷脂酰胆碱的单晶X射线研究得出的结构图不兼容。我们认为这是因为在我们的实验条件下，这些脂质已从水中有效地结晶，而用于单晶X射线研究的样品已从有机溶剂中结晶。

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    Lewis, R N; McElhaney, R N;

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  • 年度 1992
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  • 正文语种 en
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