Advanced Separation and Detection Methods for Supercritical Fluid Chromatography

超临界流体色谱的先进分离和检测方法

• 批准号: RGPIN-2021-02398
• 负责人: Thurbide, Kevin
• 金额: $ 4.66万
• 依托单位: University of Calgary
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2021
• 资助国家: 加拿大
• 起止时间: 2021-01-01 至 2022-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=741044
• 关键词: Advanced; Separation; Detection; Methods; Supercritical

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.

我们的工作旨在用环境更清洁的替代品取代有机溶剂，这是分析化学及其他领域的主要关注点。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吞吐量，由于其低成本，绿色性质和显着的特性，因此正在转向超临界CO2作为移动的相。例如，在超临界流体色谱（SFC）中，它比液相色谱产生更快的分离，并且可以分析比气相色谱更重的化合物。然而，超临界CO2是非极性的，需要添加极性有机改性剂如甲醇以分离极性分析物。这消除了SFC的绿色优点，并破坏了其使用非常理想的通用火焰离子化检测器（FID）和其他检测器的独特能力。这些限制可能会严重限制加拿大普遍存在的制药、石油和聚合物行业的SFC用户。 我们将开发我们发现并获得专利的新的SFC分离方法。它是基于使用水作为一种新的固定相，不采用有机改性剂，而只是纯超临界CO2。该方法可以很好地分析极性分子，并且与FID兼容，这使得它可能非常有用。我们的工作将极大地推进这种方法及其能力，并使其能够分析目前存在问题的重要分子类别。例如，我们将扩大改变水固定相组成，使手性分子分离，这是必不可少的药物发现。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分离不饱和有机化合物及其饱和类似物的潜力。这可以极大地帮助对复杂油中的化合物（如不饱和脂肪酸）进行无干扰分析。通过改变水相的pH值，还将努力分离和分析有机碱，这对石油化学，制药和其他工业具有广泛的重要性。在一个平行的方法，我们将作出一个非常规的尝试，积极改变水固定相的pH值在分离过程中，以操纵分析物的保留。如果它起作用，它可以允许在分离中进行最终控制，其中分析物按需洗脱。这种进步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型硫检测器也将在相关方法中与SFC一起进行检查。这些努力将大大简化原油等复杂样品中硫化合物的监管分析，为石化用户提供竞争优势，并为化学战剂等相关物质的气相检测开辟令人兴奋的新途径。该项目每年将培养6名学生。