Improving the Understanding of the Properties and Retention Behavior of Chemically Bonded Stationary Phases Employing Spectroscopic and Chromatographic Characterization Techniques

该项目旨在利用主要研究人员的相互补充的专业知识[新型高效液相固定相(JP)的合成和核磁共振表征以及高效液相/核磁共振耦合(KA)的发展]，为色谱保留提供新的见解，以便更好地设计新的分离方案和新的固定相。智能优点：各种固定相将使用固体核磁共振和悬浮态核磁共振技术进行表征。后者是了解色谱行为的一个有价值的工具，因为它可以检测溶质与固定相以及色谱载体材料之间的相互作用。这些能力将为各种类型的分子如何在分离过程中保留提供答案。将研究常规固定相(由有机硅烷化产生的固定相)和新型氢化物固定相(通过硅烷化/硅氢化形成氢化物取代硅醇基团的新表面)。氢化物为基础的相可以保留极性和非极性化合物，并在从100%水到完全有机的流动相中运行。了解在这些材料上的保留对于解决蛋白质组学、代谢组学、临床分析和环境监测中具有挑战性的分离问题将特别有价值。核磁共振表征将得到使用常规LC、毛细管LC、LC-MS和LC-核磁共振的层析评估的支持。各种氢化物固定相的合成将在开发这些材料的圣何塞州立大学进行，核磁共振研究将在首次使用悬浮态核磁共振方法的图宾根大学进行。每个实验室将进行不同的高效液相色谱法评估，利用核磁共振进行检测的研究将在图宾根进行，图宾根正在为进一步开发这种方法做出相当大的努力。该项目将解决已存在多年的固定相上的溶质保留问题，并研究最新开发的分离材料。更广泛的影响：该项目是一项合作努力，包括合成化学以及分析方法的发展。指标的背景和专门知识涵盖了本提案中概述的所有主要方向。该项目将以面向国际团队的形式培训本科生和研究生。两个小组之间的互动将包括交流意见以及适当的人员，以实现项目的目标。SJSU的学生群体是一个多元化的群体，没有少数民族占多数，因此该项目的人力发展方面将对科学界代表性不足的群体产生重大影响。项目人员中包括一个教授博士后的职位，该人员50%的时间致力于研究，50%的时间参与教学活动。这些调查的结果还将提交给分析化学和材料科学的同行评议期刊，并将在这些学科的重要国家和国际专业会议上发表演讲。

This project intends to capitalize on the mutually complementary expertise [synthesis of novel HPLC stationary phases (JP) and NMR characterization and development of HPLC/NMR coupling (KA)] of the principal investigators to provide new insights into chromatographic retention in order to better design new separation protocols as well as new stationary phases. Intellectual Merit: A variety of stationary phases will be characterized using solid-state NMR and suspended-state NMR techniques. The latter is a valuable tool for understanding chromatographic behavior because it can detect interactions between solutes and the stationary phase as well as the chromatographic support material. These capabilities will provide answers to how various types of molecules are retained in the separation process. Conventional stationary phases (those produced by organosilanization) and new hydride based stationary phases (fabricated by silanization/hydrosilation creating a new surface where hydrides replace silanol groups) will be studied. The hydride-based phases can retain both polar and nonpolar compounds and operate in mobile phases from 100% aqueous to completely organic. Understanding retention on these materials will be particularly valuable for solving challenging separation problems in proteomics, metabolomics, clinical analysis and environmental monitoring. The NMR characterizations will be supported by chromatographic evaluations using conventional LC, capillary LC, LC-MS and LC-NMR. The synthesis of the various hydride stationary phases will be done at San Jose State University where these materials were developed and the NMR investigations will take place at the University of Tubingen where the suspended state NMR method was first used. Each lab will conduct various HPLC evaluations with those studies utilizing NMR for detection taking place in Tubingen where considerable effort is ongoing in the further development of this method. This project will address questions about solute retention on stationary phases that have existed for many years and also investigate the most recently developed separation materials. Broader Impacts: The project is a collaborative effort that encompasses synthetic chemistry as well as development of analytical methodology. The background and expertise of the PIs encompass all of the major directions outlined in this proposal. The project will involve the training of undergraduate and graduate students in an international team oriented format. Interactions between the two groups will involve exchange of ideas as well as personnel as appropriate to fulfilling the goals of the project. The SJSU student body is a diverse group where there is no ethnic majority so that the manpower development aspects of the project will have a significant impact on underrepresented groups in science. A teaching postdoctoral position is included in the project personnel that involves 50% of the time being devoted to research and a 50% commitment to participation in instructional activities. The results of these investigations will also be submitted to peer reviewed journals in analytical chemistry and materials science and will be described in presentations at significant national and international professional meetings in these disciplines.