Development and Application of Improved Methods for Coupling NMR and Capillary Isotachophoresis

堪萨斯大学的Cynthia Larive教授得到了分析和表面化学项目的支持，该项目用于开发毛细管等速电泳（cITP）与微线圈NMR光谱学相结合。具有纳升到微升检测体积的螺线管微线圈的发展极大地提高了核磁共振（NMR）检测的质量极限。 最近，这一技术已进一步通过耦合毛细管等速电泳（cITP）的样品浓缩和分析物分离与纳升微线圈NMR探针在线检测。这种新的方法显示了相当大的承诺，作为一个多功能的工具，用于分析质量有限的样品。该研究将推动在线cITP-NMR仪器的发展，并探索这种方法在化学分析中的应用。将开发和评价与核磁共振检测结合使用的电容耦合电导检测器。cITP的双电导率和NMR检测的实施将通过促进使用信号平均来利用NMR检测稀释分析物并监测NMR透明cITP带来推进该技术。该技术将作为一种工具，通过检查几种抗生素化合物作为简单的混合物和更复杂的样品基质的存在下，质量有限的样品的分析和结构阐明进行严格评价。最后，这种方法将被用来表征腐殖物质的结构，化学和物理性质，通过cITP分馏作为pH值和硼酸盐络合的函数，以及与一维和二维NMR实验。这些实验将检查分馏材料的官能团组成，从而解释cITP分离条带的常见和独特结构元素。 新的测量技术的发展促进了对许多复杂化学现象的理解。在环境化学领域尤其如此，科学家面临着分析含有低浓度物种的非常复杂的样品的问题。拟议的实验将开发新的分析方法，使NMR表征分子在复杂样品中的低浓度。NMR是化学分析中信息量最大的方法之一，能够揭示分子结构的微小细节。初步实验将侧重于相对简单的抗生素样品、由于在大规模农业中广泛使用而具有环境意义的化合物以及与抗生素耐药性发展有关的问题。 此外，cITP-NMR技术将用于研究一类对环境具有重要意义的化合物，即腐殖物质（腐殖酸和富里酸）。腐殖物质对环境具有重要意义，因为它们影响有机污染物和有毒金属离子的生物利用度和迁移。这些天然存在的有机酸在环境中通过动物和植物材料的分解形成非常复杂的混合物，这使得分子水平结构信息的测定非常困难。这些实验将推进腐殖物质的化学知识，从而增加对它们在环境中行为的理解。

Professor Cynthia Larive of the University of Kansas is supported by the Analytical and Surface Chemistry program for development of capillary isotachophoresis (cITP) in combination with microcoil NMR spectroscopy. The development of solenoidal microcoils with nanoliter to microliter detection volumes has greatly enhanced the mass limits of detection of nuclear magnetic resonance (NMR). Recently, this technology has been advanced further through the coupling of capillary isotachophoresis (cITP) for sample concentration and analyte separation with nanoliter microcoil NMR probes for on-line detection. This new methodology shows considerable promise as a versatile tool for the analysis of mass limited samples. The proposed research will advance the instrumentation for online cITP-NMR and explore the application of this methodology to chemical analysis. A capacitively coupled conductivity detector for use in conjunction with NMR detection will be developed and evaluated. The implementation of dual conductivity and NMR detection for cITP will advance this technology by facilitating the use of signal averaging to detect dilute analytes with NMR and monitor NMR transparent cITP bands. This technology will be critically evaluated as a tool for the analysis and structure elucidation of mass limited samples through the examination of several antibiotic compounds both as simple mixtures and in the presence of more complex sample matrices. Finally, this approach will be used to characterize the structure, chemical and physical properties of humic substances through cITP fractionation as a function of pH and borate complexation as well as with one and two-dimensional NMR experiments. These experiments will examine functional group composition of the fractionated materials allowing interpretation of both common and unique structural elements of the bands separated by cITP. The development of new measurement techniques has facilitated understanding of many complex chemical phenomena. This has been particularly true in the field of environmental chemistry, where scientists face the problem of analyzing very complex samples containing species at low concentrations. The proposed experiments will develop new analytical methods that will allow NMR characterization of molecules at low concentrations in complex samples. NMR is one of the most informative methods of chemical analysis, capable of revealing minute details of molecular structure. Initial experiments will focus on relatively simple samples of antibiotics, compounds of environmental interest due to their wide spread use in large scale agriculture and problems related to the development of antibiotic resistance. In addition, cITP-NMR technology will be used to study a class of environmentally important compounds, humic substances (humic and fulvic acids). Humic substances are environmentally important because they affect the bioavailability and transport of organic pollutants and toxic metal ions. These naturally occurring organic acids are formed in the environment by the breakdown of animal and plant material to form very complex mixtures, which makes the determination of molecular level structure information very difficult. These experiments will advance the knowledge of the chemistry of humic substances and in turn increase the understanding of their behavior in the environment.