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-2016-03676
• 负责人: Thurbide, Kevin
• 金额: $ 3.35万
• 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: 2019
• 资助国家: 加拿大
• 起止时间: 2019-01-01 至 2020-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=689203
• 关键词: Advanced; Separation; Detection; Methods; Supercritical

Our research is aimed at replacing organic solvents with environmentally cleaner alternatives, which is a growing concern in analytical chemistry. Many analytical laboratories coping with mounting hazardous waste and slow sample throughput are now switching to supercritical CO2 as a mobile phase, due to its low cost, relatively green nature, and remarkable properties. For instance, in supercritical fluid chromatography (SFC), it provides faster separations than liquid chromatography and allows heavier compounds to be analyzed than gas chromatography. However, supercritical carbon dioxide 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). These limitations can seriously constrain SFC users, who frequently include the pharmaceutical, petroleum, and polymer industries, which are prevalent in Canada.***We will develop a new separation method for SFC that was recently discovered in our laboratory. It is based on using water as a novel stationary phase and does not employ organic modifiers but only pure supercritical carbon dioxide. The method also 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 attempt to alter the water stationary phase composition to allow it to separate chiral molecules, which are of tremendous importance to drug discovery. If possible, it will open a new avenue to customizing pharmaceutical separations. Through altering the pH of the water phase, efforts to separate ionizable analytes will also be made. This could allow a host of important analyses of organic acids and bases, which are of broad concern to pharmaceutical, petrochemical, and other industries. In a parallel approach, we will make an unconventional attempt to dynamically 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 can be 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 in heavy oil. In other work, we will examine if sulfur species can also be analyzed and to what extent. If so, we will pair the water phase with a sulfur specific detector and create one of the most selective approaches to sulfur analysis available. A powerful new sulfur detector that we invented will also be examined in a related approach. These efforts will greatly simplify the analysis of sulfur compounds in complex samples like crude oil and will give a competitive edge to petrochemical users.

我们的研究旨在用环境更清洁的替代品取代有机溶剂，这是分析化学中日益关注的问题。许多分析实验室正在应对日益增加的危险废物和缓慢的样品吞吐量，由于其成本低，相对绿色的性质和显着的性能，现在转向超临界CO2作为移动的相。例如，在超临界流体色谱（SFC）中，它提供比液相色谱更快的分离，并允许比气相色谱更重的化合物被分析。然而，超临界二氧化碳是非极性的，并且需要添加极性有机改性剂如甲醇以使其分离极性分析物。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）的独特能力。这些限制可能会严重限制SFC用户，他们经常包括制药，石油和聚合物行业，这些行业在加拿大很普遍。我们将开发一种新的分离方法，SFC是最近在我们的实验室发现的。它是基于使用水作为一种新的固定相，不使用有机改性剂，而只是纯超临界二氧化碳。该方法还可以很好地分析极性分子，并且与FID兼容，这使得它非常有用。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，我们将尝试改变水固定相的组成，使其能够分离手性分子，这对药物发现非常重要。如果可能的话，它将为定制药物分离开辟一条新的途径。通过改变水相的pH，也将努力分离可电离的分析物。这可以允许对有机酸和碱进行大量重要的分析，这些有机酸和碱与制药，石化和其他行业广泛相关。在一个平行的方法，我们将作出一个非常规的尝试，动态改变水固定相的pH值在分离过程中，以操纵分析物的保留。如果它工作，它可以允许在分离的最终控制，其中分析物可以按需洗脱。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。在其他工作中，我们将研究是否也可以分析硫物种以及在何种程度上。如果是这样的话，我们将把水相与硫特异性检测器配对，并创建一个最具选择性的硫分析方法。我们发明的一种功能强大的新型硫探测器也将在相关方法中进行检查。这些努力将大大简化原油等复杂样品中硫化合物的分析，并将为石化用户提供竞争优势。