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: 2018
• 资助国家: 加拿大
• 起止时间: 2018-01-01 至 2019-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=666825
• 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替代有机溶剂，这在分析化学领域日益受到关注。许多分析实验室应对不断增加的危险废物和缓慢的样品通量，现在改用超临界二氧化碳作为流动相，因为它成本低廉、相对绿色且具有卓越的性能。例如，在超临界流体色谱 (SFC) 中，它比液相色谱提供更快的分离速度，并且比气相色谱可以分析更重的化合物。然而，超临界二氧化碳是非极性的，需要添加极性有机改性剂（如甲醇）才能分离极性分析物。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离子化检测器 (FID) 的独特能力。这些限制会严重限制 SFC 用户，这些用户通常包括加拿大盛行的制药、石油和聚合物行业。***我们将开发一种新的 SFC 分离方法，这是我们实验室最近发现的。它基于使用水作为新型固定相，不使用有机改性剂，而仅使用纯超临界二氧化碳。该方法还可以很好地分析极性分子，并且与 FID 兼容，因此可能非常有用。我们的工作将极大地推进这种方法及其能力，并使其能够分析当前有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，这对于药物发现非常重要。如果可能的话，它将开辟一条定制药物分离的新途径。通过改变水相的 pH 值，还可以努力分离可电离的分析物。这可以对有机酸和有机碱进行许多重要的分析，这受到制药、石化和其他行业的广泛关注。在并行方法中，我们将进行非常规尝试，在分离过程中动态改变水固定相 pH 值，以控制分析物保留。如果它有效，它可以实现分离的最终控制，可以根据需要洗脱分析物。这一进步可能会对分析大型复杂基质中的目标物质（例如重油中的环烷酸）的能力产生巨大影响。在其他工作中，我们将研究是否也可以分析硫物质以及分析到什么程度。如果是这样，我们会将水相与硫专用检测器配对，并创建可用的最具选择性的硫分析方法之一。我们发明的一种强大的新型硫探测器也将通过相关方法进行检验。这些努力将大大简化原油等复杂样品中硫化合物的分析，并将为石化用户带来竞争优势。