Investigating Electrochemistry in Confined Volumes

研究有限体积内的电化学

• 批准号: RGPIN-2020-04609
• 负责人: Mauzeroll, Janine
• 金额: $ 4.66万
• 依托单位: McGill University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2021
• 资助国家: 加拿大
• 起止时间: 2021-01-01 至 2022-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=739704
• 关键词: Investigating; Electrochemistry; Confined; Volumes

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.

我们正在为电化学做出贡献，该领域为社会可再生能量，诊断和腐蚀方面的某些重要问题提供了独特的解决方案。在电化学中，有两个量表主导了发展：由半无限线性扩散和单一实体电化学控制的大型系统。有一个实验性和理论框架差距，用于中等规模的材料，其中大容量和动力学之间的平衡会改变，从而产生意外的电化学行为。该发现计划以三种类型的限量为目标。 1-雷克斯脂质体，2电化学发光（ECL）纳米球和在电化学显微镜过程中定义的3粒。 1）了解氧化还原响应性脂质体中氧化触发的膜拆解的机制。我们将在氧化响应式双层中对膜动力学进行首次全面研究。我们打算准备我们以前雇用过的两个反应式两亲物的二元化类似物。为了完成这些结构，将与非浇注的铁芯一起使用市售的材料，以制备链式渗透性的两亲物。这些材料将纳入用于电化学，固态NMR和小角度X射线散射研究的多层蔬菜或脂质体中。我们的目标是提取有关实时氧化响应膜拆卸过程的动态信息。 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化化学发光反应的新发现的基本基础。胶束结构通常涉及疏水核，高密度的ECL金属中心，生物相容性块和胶束外围的生物识别单元。纳米球相对于拆卸的ECL块共聚物的ECL扩增将使用我们的ECL检测系统来测量能够定量对电化学和ECL数据的简单获取。然后，我们将使用动力学建模分析结果，该模型考虑了异质，同质动力学和质量传输限制效应，以实时提取有关自组装聚合物纳米圈中共同反应电化学发光的动态信息。 3）在电化学显微镜过程中定义的限量。我们建议开发超分辨率SECM。为了实现超分辨率，我们必须围绕以弥漫性扩展为SECM图像分辨率的理论限制。我们提议克服过去的局限性，并使用成像处理使用光学成像中的突破来实现超分辨率SECM，在这些突破中，基于算法的方法导致了重大发现，包括2014年的诺贝尔奖。