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、诊断和腐蚀方面的一些社会重要问题提供了独特的解决方案。 在电化学中，有两个尺度主导着发展：半无限线性扩散的大系统和单实体电化学。对于受限体积的中等尺度材料，存在实验和理论框架缺口，其中质量传输过程和动力学之间的平衡被改变，产生意想不到的电化学行为。这一发现计划以三种受限体积的电化学为目标：1-氧化还原脂质体、2-电化学发光(ECL)纳米球和在电化学显微镜下定义的3-间隙。 1)了解氧化还原响应型脂质体中氧化引发膜解离的机理。 我们将开展氧化响应性双层膜动力学的首次全面研究。 我们打算制备我们以前使用过的两个响应性两亲分子的二茂铁-氚类似物。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用于制备链式过氚两亲化合物。这些材料将被结合到多层囊泡或脂质体中，用于电化学、固态核磁共振和小角X射线散射研究。我们的目标是实时提取氧化反应膜分解过程的动态信息。 2)电化学发光纳米球的研究。 我们将建立一个实验和理论框架，以了解新发现的聚合物纳米球中电致化学发光响应放大的基本基础。 胶束结构通常包括疏水核心、高密度的ECL金属中心、生物相容块和位于胶束外围的生物识别单元。纳米球相对于分解的ECL嵌段共聚物的ECL放大将使用我们的ECL检测系统进行测量，该系统能够同时定量获取电化学和ECL数据。然后，我们将使用动力学模型来分析结果，该模型考虑了非均相、均相动力学和质量传输限制效应，目的是实时提取关于自组装聚合物纳米球中共反应物电化学发光的动态信息。 3)在电化学显微镜下定义的限制体积。 我们建议发展超分辨SECM。为了达到超分辨率，我们必须在扩散加宽的SECM图像分辨率的理论极限附近工作。我们建议克服过去的限制，利用光学成像方面的突破，使用成像处理来实现超分辨率SECM，在这些突破中，基于算法的方法已导致重大发现，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.