Precision synthesis using nanoscale electrochemistry

纳米科学和技术的出现被认为是一场现代工业革命，刺激了重大的科学、经济和社会发展。这场革命是由功能纳米材料的制造推动的，这些材料在至少一个横向维度上具有十亿分之一米(1-100 nm=10-9-10-7米)的长度尺度。在表面/界面，这些通常是使用基于探头的方法以2D/3D打印材料来实现的。然而，在医疗保健(如药物输送、诊断等)和与能源相关的技术(锂离子电池、超级电容器等)等优先研究领域，对更小尺寸、更高分辨率和更好性能的持续需求，将通过在表面进行探针导向的有机、高分子和超分子合成来满足。当化学反应进行时，试剂/反应物之间的电子交换，即氧化和还原，可以使用电化学刺激来控制反应进程，即通过施加电压或电流来开启和关闭反应。电化学纳米探针已经被开发出来，它可以通过监测电化学信号和表面活性的扰动来精确地控制它们相对于表面的位置。此外，它们可以装载分子，其流量可以通过电场精确控制。在这个项目中，我们将通过研究电化学纳米探针作为反应容器的使用来同时控制从导电(电极)到生物(细胞)底物表面的特定反应的位置和进程，从而启动这一电化学前沿与合成前沿(纳米尺度、空间和时间控制、外部刺激)的结合。具体地说，有利于在宏观尺度上进行电化学控制的化学反应，如电化学介导/触发的自由基、阳离子和开环聚合，将转化为纳米尺度。控制3D表面形貌的概念将通过将电化学中介合成与电化学辅助自组装(EASA)相结合来阐述，当被限制在SECCM纳米管的半月面时，将能够精确地控制表面形貌和形貌。与现有技术相比，这将提高3D分辨率，并扩大可访问纳米材料的结构、形态和功能多样性。从长远来看，这项研究的结果将惠及广泛的科学、工业和社会经济受众，并在纳米技术和医疗保健等领域产生影响。纳米尺度、高分辨率和广泛的化学/功能范围暗示了一种可能的自下而上、直接写入纳米光刻的方法，这种方法广泛用于制造微纳电子元件，为主导我们日常生活的电子设备提供动力。同时，在医疗保健方面，微/纳米阵列诊断、个性化可穿戴技术、组织工程和细胞治疗都有潜在的应用。预计这些申请将使研究方案长期持续下去，远远超过这一研究金的任期。

The emergence of nanoscience and technology is regarded as a modern day industrial revolution, stimulating significant scientific, economic, and social development. The revolution is driven by the fabrication of functional nanomaterials which are materials with length scales on the order of billionths of a metre (1 - 100 nm = 10-9 - 10-7 m) in at least one lateral dimension. At surfaces/interfaces, these are typically achieved using probe-based methods to print materials in 2D/3D. However, in priority research areas such as healthcare (e.g. drug delivery, diagnostics, etc.), and energy-related technologies (Li-ion batteries, supercapacitors, etc), there is sustained demand for smaller dimensions, higher resolution and better properties, which will be met through the development of probe-directed organic, macromolecular and supramolecular synthesis at surfaces. When chemical reactions proceed with the exchange of electrons between reagents/reactants, i.e. oxidation and reduction, the reaction progress can be controlled using an electrochemical stimulus i.e. by applying a voltage or current to switch reactions on and off. Electrochemical nanoprobes have been developed that can precisely control their position relative to a surface by monitoring perturbations in electrochemical signals and surface activity. Furthermore, they can be loaded with molecules the flux of which can be precisely controlled using an electric field. In this project we will initiate the combination of this frontier in the electrochemistry with frontiers in synthesis (nanoscale, spatial and temporal control, external stimulus) by investigating the use of electrochemical nanoprobes as reaction vessels to simultaneously control the location and progress of specific reactions at surfaces ranging from conducting (electrodes) to biological (cells) substrates. Specifically, chemical reactions that lend themselves to electrochemical control on a macroscopic scale such as electrochemically mediated/triggered radical, cationic and ring-opening polymerisation will be translated to the nanoscale. The concept of controlling 3D surface topography will be elaborated by combining electrochemically mediated synthesis with electrochemically assisted self-assembly (EASA), which when confined to the meniscus of an SECCM nanopipette will enable precise control over surface morphology and topography. Compared to existing technologies this will enhance 3D resolution and expand the structural, morphological and functional diversity of accessible nanomaterials. Long-term, the outcomes of this research will reach a broad scientific, industrial and socio-economic audience finding impact in areas such as nanotechnology and healthcare. The nanoscale dimensions, high resolution and broad chemical/functional scope allude to a possible bottom-up, direct-write approach to nanolithography, a method widely used to fabricate micro- and nano-electronic components that power the electronic devices that dominate our daily lives. Whilst, in healthcare there are potential applications in micro-/nano-array diagnostics, personalised wearable technologies, tissue engineering and cell therapy. It is expected that these applications will sustain the programme of research in the long-term, well beyond the tenure of this fellowship.