INTERPHASE SOLUBILITY AND CHROMATOGRAPHIC RETENTION

拟议的工作旨在为预测奠定基础 溶质分子在链中的分配和选择性 分子“中间相”，包括键合的固定相 反相液相色谱和两亲性 聚集体，如单层、双层、囊泡、脂质体和 胶束。 这项工作代表了一个小组在 佛罗里达大学与加州大学旧金山分校的一个小组，将理论和 做实验。我们发展了统计力学理论 中子散射支持的溶质吸收 溶质在双层膜中的分布实验，保留率与共价键 RPLC中的溶剂组成和光谱结果 胶束。我们在双层膜上的实验证实了预测 由于构型的原因，具有表面致密性的溶质排出 信息量。我们开发了合成粘结剂的新方法 不同表面密度的相，并已显示出分配到 是表面密度的函数。初步理论进一步 表明分子选择性随着表面密度的增加而增加。 研究了界面结构对保留率的影响。 在这里，我们旨在研究溶质结构对保留率的影响。 溶质将包括链、棒和盘；我们预计 分子间的高选择性是由于堆积在 间期。我们还计划研究长链溶质， 均聚物和杂聚体，与链长、组成 和温度。 我们的目标是开发一种分子框架来了解 分子分成链分子的半有序相， 包括：(I)滞留的分子机制和 RPC中的选择性，(II)RPC的基本物理化学 膜和胶束。这应该会产生广泛的影响， 小分子和蛋白质层析的优化； 将药物、代谢物和蛋白质插入膜中； 蛋白质在聚合物表面的吸附，因此与 分离和生物医学科学的基本问题。

The proposed work aims to establish a foundation for predicting partitioning and selectivities of solute molecules within chain molecule "interphases", including the bonded stationary phases of reversed-phase liquid chromatography, and amphiphilic aggregates, such as monolayers, bilayers, vesicles, liposomes, and micelles. This work represents a continuing collaboration of a group at the University of Florida with a group at UCSF, combining theory and experiment. We have developed statistical mechanical theory for solute uptake which is supported by neutron scattering experiments of solute distribution in bilayers, retention vs. co- solvent composition in RPLC, and spectroscopic results on micelles. Our experiments in bilayers confirm the predicted expulsion of solute with surface denisty, due to configurational entropy. We have developed new methods for synthesizing bonded phases of varying surface density, and have shown partitioning to be a function of surface density. Preliminary theory further suggests molecular selectivity will increase with surface density. We have studied effects of interphase structure on retention. Here we aim to study effects of solute structure on retention. Solutes will include chains, rods, and disks; we expect that the high selectivities among molecules result from packing in the interphase. We also plan to study long chain solutes, homopolymers and heteropolymers, vs. chain length, composition, and temperature. We aim to develop a molecular framework to understand how molecules partition into semi-ordered phases of chain molecules, including: (i) the molecular mechanisms of retention and selectivity in RPC, (ii) the fundamental physical chemistry of membranes and micelles. This should have broad implications for optimization in chromatography of small molecules and proteins; insertion of drugs, metabolites and proteins into membranes; adsorption of proteins at polymeric surfaces, and thus bear on fundamental issues of separations and biomedical sciences.