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.

我们正在电化学领域做出贡献，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独特的解决方案。在电化学领域，两种规模主导了发展：由半无限线性扩散和单一实体电化学控制的大型系统。受限体积内的中等尺度材料存在实验和理论框架差距，其中传质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。电化学显微镜中定义的 1-氧化还原脂质体、2-电化学发光 (ECL) 纳米球和 3-间隙 1)了解氧化还原响应脂质体中氧化触发的膜分解机制我们将首次对膜动力学进行全面研究。我们打算制备这两种物质的二茂铁氘化类似物。为了补充这些结构，市售材料将与非氘代二茂铁一起制备链全氘化两亲物，这些材料将被掺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分析。 X 射线散射研究。我们的目标是实时提取有关氧化响应膜分解过程的动态信息 2) 电化学研究。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。胶束结构通常涉及疏水核、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相对于分解的 ECL 嵌段共聚物的纳米球的 ECL 放大将是使用我们的 ECL 检测系统进行测量，该系统能够同时定量采集电化学和 ECL 数据，然后我们将使用考虑异质、均质动力学和质量传输限制效应的动力学模型来分析结果，目的是提取有关共反应物的动态信息。实时自组装聚合物纳米球中的电化学发光3）我们建议开发超分辨率SECM。超分辨率，我们必须解决扩散展宽中 SECM 图像分辨率的理论限制，我们建议克服过去的限制，并利用基于算法的方法在光学成像方面取得的突破，利用成像处理来实现超分辨率 SECM。重大发现，包括2014年诺贝尔奖。