Investigating Electrochemistry in Confined Volumes

我们在电化学领域做出了贡献，这是一个为可再生能源、诊断和腐蚀等一些社会重要问题提供独特解决方案的领域。在电化学中，两种尺度主导着发展：由半无限线性扩散控制的大系统和单一实体电化学。在有限体积中，中间尺度材料的实验和理论框架存在差距，其中质量传递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。该发现计划针对三种类型的受限体积的电化学；1-氧化还原脂质体，2-电化学发光（ECL）纳米球和3-电化学显微镜定义的间隙。1)了解氧化反应脂质体中氧化触发膜分解的机制。我们将首次全面研究氧化反应双分子层中的膜动力学。我们打算制备二茂铁氘化的两种反应性两亲化合物的类似物。为了补充这些结构，商业上可用的材料将与未氘化的二茂铁一起用于制备链渗透两亲体。这些材料将被纳入多层囊泡或脂质体中，用于电化学、固态核磁共振和小角度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。电化学发光纳米微球的研究。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ECL金属中心，生物相容性块和胶束外围的生物识别单元。纳米球相对于拆解的ECL嵌段共聚物的ECL扩增将使用我们的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，我们将使用考虑非均相、均相动力学和质量输运限制效应的动力学模型来分析结果，目的是实时提取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)电化学显微镜中定义的受限体积。我们建议发展超分辨率SECM。为了实现超分辨率，我们必须绕过扩散展宽中SECM图像分辨率的理论极限。我们建议克服过去的限制，利用光学成像方面的突破，利用成像处理来实现超分辨率SECM，其中基于算法的方法已经带来了重大发现，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.