VIBRATIONAL STUDIES OF LIPID STRUCTURE AND DYNAMICS

拉曼光谱已被广泛用于研究模型中的脂质双层 和真正的生物膜，最近红外光谱已经 作为一种同样可行的技术出现。这类信息可以 从这些研究中衍生出来的是多种多样和独特的，多种多样的 振动光谱对构象等因素的敏感性 环境，机动性，独一无二，因为快速的时间尺度 与产生光谱的事件有关。的目的 这项提议是为了为解释光谱提供必要的基础 并将这些知识应用于特定模型系统的研究。我们 我将通过对模型碳氢化合物链的研究来解决这个问题 正构烷烃、羧酸和磷脂等体系 建立在我们早期工作结果的基础上，建立量化 分子的振动光谱与结构和动力学的关系 脂肪帐单。我们将专注于分离静态和动态效果。 静态效应包括链构象的影响，确定 作为总平均值和脂链中的特定位置， 是我们的主要目标之一。另一个主要目标，与 动态效果，将通过分析来评估链的移动性 C-H拉伸带形状，从而提供了一种全新的 有关双层的信息。一种新的“平均链”分析方法 适用于脂谱的无序碳氢链的振动 将会被开发出来。我们能够识别不同类型的本地化 链中的构象缺陷将被用来建立关系 在双层的相和相关联的性质之间 构象无序。浅谈链条研究技术的应用 将构象和迁移率用于压力反转的研究 麻醉剂引起的模型膜系统的紊乱。

Raman spectroscopy has been much used to study the lipid bilayer in model and real biological membranes, and recently infrared spectroscopy has emerged as an equally viable technique. The kinds of information that can be derived from these studies are varied and unique, varied because of the sensitivity of vibrational spectra to factors such as conformation, environment, and mobility, and unique because of the fast time scale associated with the events that give rise to the spectra. The object of this proposal is to provide the needed groundwork for interpreting spectra and to apply this knowledge to the study of specific model systems. We will approach this problem through the study of model hydrocarbon chain systems such as n-alkanes, carboxylic acids, and phospholipids and will build on the results of our earlier work in establishing quantitative relations between vibrational spectra and the structure and dynamics of the lipid bilyer. We will focus on separating static and dynamic effects. Static effects include those of chain conformation, the determination of which as an overall average and at specific sites in the lipid chain will be one of our principal aims. Another principal aim, associated with dynamic effects, will be to evaluate chain mobility through an analysis of C-H stretching band shapes and thus provide a completely new kind of information about the bilayer. A new "average-chain" approach to analyzing the vibrations of disordered hydrocarbon chains applicable to lipid spectra will be developed. Our ability to identify different types of localized conformational defects in chains will be utilized to establish relations between the phase of the bilayer and the nature of the associated conformational disorder. Application of the techniques for studying chain conformation and mobility will be made to the study of pressure reversal of anesthetic induced disorder in model membrane systems.