Advanced Separation and Detection Methods for Supercritical Fluid Chromatography

我们的工作旨在用环境更清洁的替代品取代有机溶剂，这是分析化学和其他领域的一个主要问题。由于超临界二氧化碳的低成本、绿色特性和卓越的性能，许多分析实验室正在应对日益增长的危险废物和缓慢的样品处理能力，转而使用超临界二氧化碳作为流动相。例如，在超临界流体色谱(SFC)中，它的分离速度比液体色谱更快，而且比气相色谱能分析更重的化合物。然而，超临界二氧化碳是非极性的，需要添加像甲醇这样的极性有机改进剂来分离极性分析物。这消除了SFC的绿色优势，并破坏了其使用非常理想的通用火焰电离检测器(FID)和其他设备的独特能力。这些限制可能会严重限制SFC在制药、石油和聚合物行业的用户，这些行业在加拿大很普遍。他说：我们将为证监会开发一种新的分离方法，这是我们发现并获得专利的。它的基础是使用水作为一种新的固定相，并且不使用有机改性剂，而只使用纯超临界二氧化碳。该方法很好地分析了极性分子，并与FID兼容，使其具有潜在的非常有用的作用。我们的工作将极大地推进这一方法及其能力，并使其能够分析目前有问题的重要分子类别。例如，我们将扩展到改变水固定相组成以实现手性分子分离，这在药物发现中是必不可少的。这将为定制药物分离和大规模药物纯化开辟新的途径。我们还将探索这种水相从饱和类似物中分离不饱和有机化合物的前景。这将大大有助于复杂油脂中不饱和脂肪酸等化合物的无干扰分析。通过改变水相pH，还将努力分离和分析有机碱，这对石化、制药等行业具有广泛的重要性。在一种平行的方法中，我们将进行一种非常规的尝试，在分离过程中主动改变水固定相的pH值，以操纵分析物保留。如果它奏效，它可以在分离中实现最终控制，即按需洗脱分析物。这一进展可能会对分析大型复杂基质中的目标物质的能力产生巨大影响，例如重油中的环烷酸或胺。我们发明的一种功能强大的新硫探测器也将以相关的方法与SFC进行检查。这些努力将极大地简化对原油等复杂样品中硫化物的监管分析，为石化用户提供竞争优势，并为化学战剂等相关物种的气相检测开辟令人兴奋的新途径。拟议的工作将每年培训6000名学生。

Our work aims to replace organic solvents with environmentally cleaner alternatives, which is a major concern in analytical chemistry and beyond. Many analytical labs coping with growing hazardous waste and slow sample throughput are switching to supercritical CO2 as a mobile phase, due to its low cost, green nature, and remarkable properties. For instance, in supercritical fluid chromatography (SFC), it yields faster separations than liquid chromatography and can analyze heavier compounds than gas chromatography. However, supercritical CO2 is non-polar and requires a polar organic modifier like methanol to be added for it to separate polar analytes. This removes the green benefits of SFC and destroys its otherwise unique ability to use the highly desirable universal flame ionization detector (FID) and others. These limitations can seriously constrain SFC users in the pharmaceutical, petroleum, and polymer industries, which are prevalent in Canada.      We will develop a new separation method for SFC that we discovered and patented. It is based on using water as a novel stationary phase and does not employ organic modifiers but only pure supercritical CO2. The method analyzes polar molecules well and is FID compatible, making it potentially very useful. Our work will critically advance this approach and its capabilities, and allow it to analyze important classes of molecules that are currently problematic. For instance, we will expand on altering the water stationary phase composition to enable chiral molecule separations, which are essential in drug discovery. This will open new ways to customize pharmaceutical separations and large-scale drug purification. We will also explore the promising potential of this water phase to separate unsaturated organic compounds from their saturated analogs. This could greatly assist in the interference free analysis of compounds like unsaturated fatty acids in complex oils. Through altering the water phase pH, efforts will also be made to separate and analyze organic bases, which are of broad importance to petrochemical, pharmaceutical, and other industries. In a parallel approach, we will make an unconventional attempt to actively alter the water stationary phase pH during separations in order to manipulate analyte retention. If it works, it could allow for the ultimate control in separations, where analytes are eluted on demand. Such an advance could have huge impact in the ability to analyze for target substances in large complex matrices, such as naphthenic acids or amines in heavy oil. A powerful new sulfur detector that we invented will also be examined with SFC in a related approach. These efforts will greatly simplify regulatory analysis of sulfur compounds in complex samples like crude oil, giving a competitive edge to petrochemical users, and open exciting new routes for the gas phase detection of related species, such as chemical warfare agents. The proposed work will train 6 students per year.