Direct Probing and Modeling of Sorbent-Solute-Solvent Interactions in Chiral Separations

摘要提案题目：手性分离中吸附剂-溶质-溶剂相互作用的直接探测和建模，提案号：CTS-0625189，首席研究员：Nien-Hwa (Linda) Wang，机构：普渡大学。摘要：手性对映体的吸附分离，或称“外消旋混合物”，是制药和精细化工行业的一个关键问题。在这个项目中，一个新的官能团的方法来研究吸附剂-溶质-溶剂的相互作用将用于一类主要的手性吸附剂，衍生直链淀粉和纤维素。这些吸附剂用于超过50%的分析和制备吸附手性分离。利用洗脱色谱法研究了一系列具有一个或两个氢键官能团和疏水官能团的简单非手性溶质，以确定影响溶质在各种溶剂中保留时间的关键官能团及其相对重要性。红外光谱研究用于鉴定溶质、溶剂和吸附剂的关键官能团的氢键位点。了解单个官能团的特定相互作用将用于解释溶质在不同溶剂和不同温度下具有两个或两个以上官能团的保留行为和手性选择性。一个实用的预测模型将开发的溶剂和吸附剂的选择，以分离给定的手性溶质使用这类csp。这种分析结合了色谱研究、直接探测技术和分子模拟，在科学上是独一无二的。该结果将为选择溶剂、吸附剂和温度提供一般指导，以优化手性色谱的保留时间、选择性、生产率和溶剂消耗，用于分析分离应用和单对映体的大规模生产。官能团的研究可以应用于其他类型色谱的保留时间和选择性的进一步了解。在分子水平上提高对特定官能团相互作用和手性识别的科学理解在许多其他领域有应用，如传感器、生物材料、药物设计和纳米技术。更广泛的影响将出现在对医疗保健至关重要的领域。手性分离对于生产安全和负担得起的对映体药物至关重要。这项研究将改善研究生和本科生的教学和培训，并可能导致进一步的基础研究和创新材料和工艺。该项目将帮助培养一个重要技术领域的高级化学工程师。其中一些工程师将从代表性不足的群体中招聘。这项研究将有利于研究生和本科生的四门课程：分离学、界面工程、热力学和反应工程。该项目还将有助于提高美国工业界和美国大学在一个重要的先进技术领域的竞争力。

Abstract Proposal Title: Direct Probing and Modeling of Sorbent-Solute-Solvent Interactions in Chiral Separations, Proposal Number: CTS-0625189, Principal Investigator: Nien-Hwa (Linda) Wang, Institution: Purdue University.Abstract: Adsorptive separations of chiral enantiomer pairs, or "racemicmixtures", are a critical problem of the pharmaceutical and fine chemical industries. In this project, a new functional group approach to investigate sorbent-solutesolvent interactions will be used for a major class of chiral sorbents, derivatized amylose and cellulose. These sorbents are used in over 50% of all analytical and preparative adsorptive chiral separations. A series of simple non-chiral solutes with one or two hydrogen bonding (Hbonding) functional groups and hydrophobic functional groups are studied using elution chromatography, to identify the key functional groups that contribute to solute retention times in various solvents and their relative importance. IR studies are used to identify the H-bonding sites of the key functional groups of the solutes, the solvents, and the sorbents. Understanding the specific interactions of the individual functional groups will be used to interpret the retention behavior and chiral selectivities of solutes with two or more functional groups in different solvents and at different temperatures. A practicalpredictive model wil be developed for selection of solvent and sorbent for a separation of a given chiral solute using this class of CSPs. This analysis using a combination of chromatography studies, direct probing techniques, and molecular simulations is scientifically unique. The results should generate general guidelines for selecting solvents, sorbents, and temperatures to optimize retention times, selectivities, productivity, and solvent consumption in chiral chromatography for both analytical separation applications and large-scale production of single enantiomers. The functional group studies can be applied to advance understanding of retention times and selectivities in other types of chromatography. Improved scientific understanding of the interactions of the specific functional groups and chiral recognition at the molecular level has applications in many other areas, such as sensors, biomaterials, drug design, and nanotechnology. The broader impacts will be in the area critical to healthcare. Chiral separations are crucial for producing safe and affordable enantiomer drugs. The research will improve the teaching and training of graduate and undergraduate students and may lead to further fundamental research and innovative materials and processes. The project will help train advanced-level chemical engineers specializing in an important technology area. Some of these engineers will be recruited from underrepresented groups. The research will benefit four graduate and undergraduate courses, Separations, Interfacial Engineering, Thermodynamics, and Reaction Engineering. The project will also help enhance the competitiveness of the US industry and of the US universities in an important area of advanced technology.