Investigating Electrochemistry in Confined Volumes

我们在电化学领域做出了贡献，该领域为可再生能源，诊断和腐蚀等社会重要问题提供了独特的解决方案。在电化学中，两个尺度主导了发展：由半无限线性扩散和单一实体电化学控制的大系统。对于受限体积中的中等规模材料，存在实验和理论框架差距，其中质量传递过程和动力学之间的平衡被改变，从而产生意想不到的电化学行为。该发现计划针对三种类型的封闭体积中的电化学; 1-氧化还原脂质体，2-电化学发光（ECL）纳米球和3-电化学显微镜期间定义的间隙。1)了解氧化还原反应脂质体中氧化触发膜解体的机制。我们将进行第一次全面的研究膜动力学的氧化反应双层。我们打算制备二茂铁氘代类似物的两个响应的两亲物，我们以前雇用。为了补充这些结构，商业上可获得的材料将与非氘代二茂铁一起使用以制备链全氘代两亲物。这些材料将被纳入多层囊泡或脂质体的电化学，固态NMR和小角X射线散射研究。我们的目标是在真实的时间提取动态信息的氧化响应膜拆卸过程。2)电化学发光奈米微球之研究。 我们将建立一个实验和理论框架，以了解新发现的放大聚合物纳米球中的电致化学发光响应的基本基础。 胶束结构通常包括疏水核心、高密度ECL金属中心、生物相容性嵌段和胶束外围的生物识别单元。将使用我们的ECL检测系统测量纳米球相对于分解的ECL嵌段共聚物的ECL放大，该系统能够定量同时采集电化学和ECL数据。然后，我们将使用动力学建模，考虑异构，均相动力学和传质限制效应的结果进行分析，其目的是提取动态信息的共反应物的电化学发光在自组装聚合物纳米球在真实的时间。3)电化学显微镜检查期间定义的限制体积。 我们建议发展超分辨率SECM。为了实现超分辨率，我们必须围绕扩散增宽中SECM图像分辨率的理论极限进行工作。我们建议克服过去的局限性，使用成像处理来实现超分辨率SECM，利用光学成像的突破，其中基于算法的方法导致了重大发现，包括2014年的诺贝尔奖。

We are making contributions in Electrochemistry, a field offering unique solutions to some of society's important problems in renewable energies, diagnostics, and corrosion. In electrochemistry, two scales have dominated developments: large systems governed by semi-infinite linear diffusion and single entity electrochemistry. There is an experimental and theoretical framework gap for intermediate scale materials in confined volumes, where the balance between mass transport processes and kinetics is altered yielding unexpected electrochemical behavior. This discovery program targets electrochemistry in three types of confined volumes; 1-redox liposomes, 2-electrochemically luminescent (ECL) nanospheres and 3-gaps defined during electrochemical microscopy. 1)Understanding the mechanism of oxidatively-triggered membrane disassembly in redox-responsive liposomes. We will carry out the first comprehensive study of membrane dynamics in an oxidatively responsive bilayer. We intend to prepare ferrocene-deuterated analogues of the two responsive amphiphiles we have employed previously. To complement these structures, commercially available materials will be used with non-deuterated ferrocenes to prepare chain-perdeuterated amphiphiles. These materials will be incorporated into multilamellar vesicles or liposomes for electrochemical, solid state NMR and small-angle X-ray scattering studies. Our objective is to extract dynamic information about the oxidatively responsive membrane disassembly process in real time. 2) Studies of electrochemically luminescent nanospheres.  We will establish an experimental and theoretical framework to understand the fundamental basis for the newly discovered amplification of the electrogenerated chemiluminescence response in polymeric nanospheres. The micelle architecture will generally involve a hydrophobic core, a high density of ECL metal centers, a biocompatible block and a biological recognition unit at the periphery of the micelle. The ECL amplification of the nanospheres relative to the disassembled ECL block copolymer will be measured using our ECL Detection System capable of quantitative simultaneous acquisition of electrochemical and ECL data. We will then analyze the results using kinetic modelling that considers heterogeneous, homogenous kinetics and mass transport confinement effects, with the aim of extracting dynamic information about the co-reactant electrochemical luminescence in self-assembled polymeric nanospheres in real time. 3) Confined Volume defined during electrochemical microscopy. We propose to develop super-resolution SECM. To achieve super-resolution, we must work around the theoretical limit on SECM image resolution routed in diffusional broadening. We are proposing to overcome past limitations and use imaging processing to achieve super-resolution SECM using breakthroughs in optical imaging where algorithm-based approaches have led to major discoveries, including the Nobel Prize in 2014.