Advancing Design and Application of Porous Polymeric Sorptive Phases for Direct Introduction Mass Spectrometry

该项目旨在创造一种新的方法，使用依赖于多孔聚合物薄涂层的设备来有效地从复杂的样品溶液中抓取分子。这些涂层将针对水和生物样品中的环境污染物、药物和非法药物而量身定制。新材料将被纳入创新的设备，可以直接耦合到超灵敏的分析仪器，用于快速自动化样品制备和在线分析。我们将创造一种新的方法，利用基于基础科学的预测数学和化学模型来进行理性设计，这些基础科学涉及这些材料是如何形成的，以及它们识别分子的过程。本研究立足于绿色分析化学的原则，关注试剂的经济使用（即，使用的大多数原子最终在材料中几乎没有浪费），减少有害化学物质的使用，并意识到分析设备的生命周期，以减少环境足迹，同时允许扩大筛选能力（即，增加时间或空间测量）。为了实现这些目标，我的研究将集中在四个目标上。1)开发新的工具来快速表征薄多孔聚合物薄膜中的聚合物特性（例如孔隙度和吸附行为）。在这项工作中，我们将利用固态核磁共振、差示扫描量热法和直接引入质谱法（即解吸电喷雾电离、叶片喷雾等）提出表征多孔聚合物涂层的新方法。2)开发一种新的预测模型，研究这些聚合物如何在固体器件表面形成多孔涂层。在这里，我们将建立在聚合物如何形成的现有模型上，以结合因素来解释聚合物组分首次混合（平衡）时发生的更复杂的过程，然后这些因素如何随着聚合进行而变化。3)建立孔隙率和吸附模型，以了解引入功能以排除或捕获基质成分如何影响聚合物的形态和性能，特别是了解采样的选择性。4)利用这些发现构建用于直接采样的设备，并为临床和环境应用引入质谱。相分离、孔隙率和表面化学的新模型将为科学家们提供更好的工具来预测和控制多孔吸附剂涂层的物理和化学性质。这有可能彻底改变新分析设备的开发，同时减少反复试验所消耗的时间和资源。通过开发多孔聚合物涂层制造和功能的综合模型，可以在尽可能少的浪费的情况下保证性能，使这些环保分析方法更加环保。

This program aims to create a fresh approach to small-volume sample analysis using devices that rely on thin coatings of porous polymer to effectively grab molecules from complex sample solutions. These coatings will be tailor-made to target environmental contaminants, pharmaceuticals, and illicit drugs in water and biological samples. The novel materials will be incorporated into innovative devices that can be coupled directly to ultra-sensitive analytical instruments for fast automatable sample preparation and online analysis. We will create a new approach to rational design using predictive mathematical and chemical models based on fundamental science involved in how these materials are formed and the processes by which they recognize molecules. This research stands on the principles of green analytical chemistry, with attention given to economical use of reagents (i.e., most of the atoms used end up in the material with little waste), reduced use of harmful chemicals, and awareness of the life cycle of analytical devices to reduce environmental footprint while allowing for expanded screening capacity (i.e., increased temporal or spatial measurements). To achieve these goals my research will focus on four goals. 1) Develop new tools for fast characterization of polymer properties (e.g., porosity and adsorption behavior) in thin porous polymer films. In this work, we will advance novel ways to characterize porous polymer coatings using solid state nuclear magnetic resonance, differential scanning calorimetry, and direct introduction mass spectrometry (i.e., desorption electrospray ionization, blade spray, etc.). 2) Develop a new predictive model of how these polymers form porous coatings on solid devices surfaces. Here we will build on existing models of how polymers form to incorporate factors to account for more complex processes that occur when the polymer components are first mixed (equilibria), and then how these factors change as the polymerization proceeds. 3) Build on the porosity and adsorption models to understand how introduction of functionalities to exclude or trap matrix components influence polymer morphology and performance, particularly to understand the selectivity in sampling. 4) Use these discoveries to build devices for direct sampling and introduction to mass spectrometry for clinical and environmental applications. The new model of phase separation, porosity, and surface chemistry will equip scientists with dramatically better tools to predict and control the physical and chemical properties of porous sorbent coatings. This has the potential to revolutionize the development of new analytical devices while reducing the time and resources consumed by trial-and-error refinement. By developing a comprehensive model for porous polymer coatings fabrication and function, performance can be assured with as little waste as possible, making these environmentally-friendly analytical methods even greener.