"Meta-chemistry": Nanoscale chemical control using spatially localised solvent heating

机器和设备的工业大规模生产依赖于以最快速和有效的方式按照特定的顺序组装不同的部件。然而，当我们考虑连接组件以创建纳米设备时，日常长度尺度上的常规操作将变得更加困难和耗时。当人们希望创建一个特定的分子-纳米结构结构时，情况尤其如此。单个成分分子和复杂的纳米结构结构可以使用合成化学和纳米制造技术（例如纳米压印和注射成型）的工具大规模生产。然而，以特定方式组合这些单个元素的现有技术速度很慢（例如，浸笔纳米光刻需要数十小时才能使cm2样品功能化），因此吞吐量低（即与大规模生产不兼容）。因此，制造相对复杂的分子纳米混合材料，相当于手工制作一辆宾利，而不是大众高尔夫的流水线批量生产。我们提出了一种创新的（等离子体）纳米结构化学功能化的纳米尺度空间控制方法，该方法具有约20 nm的纳米尺度分辨率，并且简单快速。这个概念，我们称之为“元化学”，包括使用脉冲激光局部加热纳米结构周围特定区域的溶剂。然后可以利用这些纳米级的热梯度以空间选择性的方式驱动化学反应。在提案中，我们将对围绕纳米结构的液体如何产生和传输热量进行基本理解，从而为最佳空间控制提供基础。同样重要的是，我们将合成热响应聚合物，这些聚合物将在局部加热的溶剂中转化，创造出随后可以化学功能化的纳米结构域。利用元化学概念，cm2的纳米结构衬底可以在不到60秒的时间内进行空间和选择性的化学修饰，为后续的化学功能化做准备。该提案处于化学物理和工程的尖端，它将发现新的基础科学，从长远来看，它可能成为纳米科学工具箱中强大灵活技术的基础。

The industrial mass production of machines and devices relies on the assembly of different components in a specific order in the most rapid and efficient way. However what is routine at everyday length scales is infinitely more difficult and time consuming when we consider linking components to create nano-devices. This is particularly the case when one wishes to create a specific molecule-nanostructure construct. The individual component molecules and complex nanostructure architectures can be mass produced using tools of synthetic chemistry and nanofabrication techniques (e.g. nano-imprint and injection moulding). However, established technologies for combining these individual elements in a specific way are slow (e.g. dip pen nanolithography takes tens of hours to functionalise cm2 samples) and hence low throughput (i.e. incompatible with mass production). Therfore, creating relative complex hybrid molecular-nanofabricated materials is comparable to handcrafting a Bentley rather than the assembly line mass production of Volkswagen Golfs. We propose an innovative approach for nanoscale spatial control of chemical functionalisation of (plasmonic) nanostructures which has both nanoscale resolution ca. 20 nm and is simple and rapid. The concept, which we call "Meta-chemistry", involves using a pulsed laser to locally heat the solvent in specific regions surrounding a nanostructure. These nanoscale thermal gradients can then be exploited to drive chemistry in a spatially selective manner. In the proposal we will develop a fundamental understanding of how heat is generated and transported in a liquid surrounding a nanostructure, thus providing the foundation for optimal spatial control. Also crucially, we will synthesise thermally responsive polymers which will be transformed in the locally heated solvent, creating nano-domains which can be subsequently chemically functionalised. Using the meta-chemistry concept cm2 of a nanostructured substrate can be both spatially and selectively chemically modified, in preparation for subsequent chemical functionalisation, in less than 60 seconds. The proposal is at the cusp of chemistry physics and engineering, it will discover novel fundamental science which in the longer term could be the foundation of a powerful flexible technology for the nanoscience toolbox.