NON-IONIC LIPOSOMES AND REDOX ACTIVATED CATION PUMPS

在以前的工作中，我们已经建立了电化学 基于乙醚的离子载体的转换可以影响反式- 各种阳离子的膜运输。 在拟议的项目中， 我们将通过设计和合成高度 亲脂性、氧化还原活性冠醚和荚状配体。 使用这些 化合物，我们将开发阳离子泵技术，通过 化学和电化学梯度。 在此过程中， 工作中，我们发现这些高度亲脂的冠醚， 特别是那些有类固醇侧臂的，形成了一类新的 非离子脂质体（类脂质体）。 我们建议近距离探索这一点 处女区，并通过使用这些新的脂质体，探测 膜和囊泡形成的要求。 我们预计 这些化合物将导致新的，不寻常的结构， 生物型膜将增加阳离子的尺寸 在内外表面上都有陷阱。 这样的组件可以是 作为膜模型的价值，或可用于特定的 封装、药物递送等。此外，这些结构 可以允许详细了解之间的关系 结构刚性和阳离子选择性。 在结构上使用 相关的亲脂性冠醚化合物作为新的bol两亲物， 我们将构建新的单层囊泡。 使用这些小说 结构，再加上我们的核磁共振，ESR，环 伏安法、离子选择性电极和其他技术，将 使我们能够研究膜形成的机制， 破坏和阳离子运输。

In previous work, we have established that electrochemical switching of lariat ether-based ionophores can effect trans- membrane transport of various cations. In the proposed project, we will extend this work by the design and syntheses of highly lipophilic, redox-active crown ethers and podands. Using these compounds, we will develop techniques for cation pumping via chemical and electrochemical gradients. During the course of this work, we have discovered that these highly lipophilic crown ethers, especially those having steroid sidearms, form a novel class of non-ionic liposomes (niosomes). We propose to explore this nearly virgin area and, by use of these novel liposomes, probe the requirements for membrane and vesicle formation. We expect that such compounds will lead to new, unusual structures in which biological-type membranes will have the added dimension of a cation trap on both the inner and outer surfaces. Such assemblies may be of value as membrane models or may be used for specific encapsulation, drug-delivery, etc. In addition, these structures may permit a detailed understanding of the relationship between structural rigidity and cation selectivity. Using structurally related, lipophilic crown ether compounds as novel bolamphiphiles, we will construct novel monolayer vesicles. Use of these novel structures, coupled with our arsenal of NMR, ESR, cyclic voltammetry, ion-selective electrode, and other techniques, will permit us to study the mechanisms of membrane formation, membrane disruption, and cation transport.