Analytical electrochemistry at supramolecular interfaces: structural probing and dynamic sensing

在过去的二十年里，电化学重新流行起来，不仅是因为对设计清洁和可再生能源转换设备(如现代电池、燃料电池和太阳能电池板)的需求不断增长，而且随着开发护理点式电化学生物传感器的动机(超越手持血糖仪)。我们感兴趣的是采用电化学原理和技术来评估分子界面，以便研究分子如何在固-液界面上组装和相互作用。该研究计划的目标是扩大分析电化学作为探测和调节带电界面分子环境的常规和强大工具的能力。考虑到这项任务的多学科性质，特别是构建具有最佳覆盖、分布和取向的催化或传感分子的理想电极-电解液界面，创造高性能的电化学设备是具有挑战性的。作为基于先进仪器的显微成像技术的补充，我们的方法是采用超分子化学来建立和检查带电的分子界面。最近合成了一类南瓜形状的纳米主体分子，并发现它们通过非共价、可逆的超高亲和力(优于抗体-抗原相互作用)识别电活性客体分子。这些相当大的主体分子在与客体配体连接的表面上的组装可以通过传统的电化学测量来检测，并提供对表面可用空间和位置的准确测量。随后，我们将研究如何调节超分子包合物的界面形成，以创造动态的表面应用，而不仅仅限于生物传感。*拟议的研究为培养高素质人才提供了一个跨学科的平台；电化学家、分析化学家、生物化学家和合成化学家将结合基础科学和潜在的应用进行合作。拟议研究的成功将使加拿大在将超分子化学应用于分析电化学研究和应用方面处于领先地位。*****

Electrochemistry has regained popularity in the last two decades, not only with the ever-growing demand of designing clean and renewable energy conversion devices (e.g., modern batteries, fuel cells, and solar panels), but also with the motivation of developing point-of-care electrochemical biosensors (beyond hand-held glucose meters). We are interested in adapting electrochemical principles and techniques to evaluate molecular interfaces in order to investigate how molecules assemble and interact at solid-liquid interfaces. The goal of the proposed research program is to expand the capabilities of analytical electrochemistry as a routine and powerful tool for probing and modulating the molecular environment at electrified interfaces.******It is challenging to create high performance electrochemical devices given the multidisciplinary nature of this task, particularly the construction of ideal electrode-electrolyte interfaces with catalytic or sensing molecules assembled with optimized coverage, distribution, and orientation. In complement to microscopic imaging techniques based on advanced instrumentation, our approach is to adapt supramolecular chemistry for building and examining electrified molecular interfaces. A class of pumpkin-shape, nanometer-size host molecules have been recently synthesized and found to recognize electroactive guest molecules through noncovalent, reversible binding with ultrahigh affinity (superior to antibody-antigen interaction). The assembly of these rather large host molecules on the surface tethered with guest ligands can be sensed by conventional electrochemical measurements, and provide accurate measures of available space and locations of the surface. Subsequently, we will study how to modulate the interfacial formation of supramolecular inclusion complex, in order to create dynamic surfaces for applications not limited to biosensing.******The proposed research offers an interdisciplinary platform for the training of highly qualified personnel; electrochemists, analytical chemists, biochemists, and synthetic chemists will work together with both the fundamental science and potential applications in mind. The success of the proposed research will put Canada in a leading position in adapting supramolecular chemistry for analytical electrochemistry studies and applications thereof. *****