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

摘要提案标题：手性分离中吸附剂-溶质-溶剂相互作用的直接探测和模拟，提案号：CTS-0625189，主要研究者：Nien-Hwa（琳达）Wang，机构：普渡大学摘要：手性对映体对（或“外消旋混合物”）的吸附分离是制药和精细化工行业的关键问题。在本计画中，一种新的官能基方法将被用来研究一种主要的手性吸附剂，衍生化直链淀粉和纤维素。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（H键合）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。IR研究用于确定溶质、溶剂和吸附剂的关键官能团的H-键合位点。了解单个官能团的特定相互作用将用于解释具有两个或更多个官能团的溶质在不同溶剂和不同温度下的保留行为和手性选择性。该模型可用于手性分离溶剂和吸附剂的选择。这种结合色谱研究、直接探测技术和分子模拟的分析在科学上是独一无二的。这些结果将为选择溶剂、吸附剂和温度以优化手性色谱中的保留时间、选择性、生产率和溶剂消耗提供一般指导，用于分析分离应用和单一对映体的大规模生产。官能团的研究可以应用于其他类型的色谱保留时间和选择性的理解。对特定官能团的相互作用和分子水平上的手性识别的科学理解的提高在许多其他领域中具有应用，例如传感器、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可负担的对映体药物至关重要。该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。该项目将有助于培养专门从事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募。本研究将有益于分离、界面工程、热力学和反应工程四门研究生和本科生课程。该项目还将有助于提高美国工业和美国大学在先进技术这一重要领域的竞争力。

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.