Analytical electrochemistry at supramolecular interfaces: structural probing and dynamic sensing

电化学在过去二十年中重新流行起来，这不仅是因为设计清洁和可再生能源转换设备（例如，现代电池，燃料电池和太阳能电池板）的需求不断增长，而且还因为开发即时电化学生物传感器（超越手持式血糖仪）的动机。我们感兴趣的是适应电化学原理和技术来评估分子界面，以研究分子如何在固液界面组装和相互作用。提出的研究计划的目标是扩大分析电化学的能力，使其成为探测和调节带电界面分子环境的常规和强大工具。******考虑到这项任务的多学科性质，创造高性能的电化学设备是具有挑战性的，特别是构建理想的电极-电解质界面，将催化或传感分子组装在一起，优化覆盖范围、分布和方向。作为基于先进仪器的显微成像技术的补充，我们的方法是将超分子化学用于构建和检查带电分子界面。最近合成了一类南瓜形状、纳米大小的宿主分子，并发现它们通过非共价、可逆的结合，以超高亲和力（优于抗体-抗原相互作用）识别电活性客体分子。这些相当大的宿主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感知，并提供对表面可用空间和位置的精确测量。随后，我们将研究如何调节超分子包合物的界面形成，以便为不限于生物传感的应用创建动态表面。******拟议的研究为培训高素质人员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在考虑基础科学和潜在应用的情况下一起工作。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及其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. *****