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

机器和设备的工业批量生产依赖于以最快、最高效的方式以特定顺序组装不同的部件。然而，当我们考虑连接元件来制造纳米设备时，在日常长度尺度上的例行公事就变得更加困难和耗时。当人们希望创建特定的分子-纳米结构结构时，情况尤其如此。利用合成化学工具和纳米制造技术(如纳米压痕和注射成型)，可以批量生产单个组分分子和复杂的纳米结构结构。然而，现有的以特定方式组合这些单独元素的技术速度很慢(例如，浸渍笔纳米光刻需要数十个小时才能使cm2样品功能化)，因此产量较低(即与大规模生产不兼容)。因此，创造相对复杂的分子-纳米混杂材料相当于手工制作一辆宾利，而不是大众高尔夫的装配线批量生产。我们提出了一种创新的方法，用于对(等离子体)纳米结构的化学功能化进行纳米尺度的空间控制，该方法既具有约20 nm的纳米级分辨率，又简单快速。这个概念，我们称之为“超化学”，涉及到使用脉冲激光在纳米结构周围的特定区域局部加热溶剂。然后，可以利用这些纳米级的温度梯度来以空间选择性的方式驱动化学。在该提案中，我们将对纳米结构周围的液体中如何产生和传输热量有一个基本的了解，从而为最佳空间控制提供基础。同样关键的是，我们将合成热响应性聚合物，这些聚合物将在局部加热的溶剂中转化，产生纳米结构域，随后可以进行化学功能化。利用元化学概念，纳米结构衬底的cm2可以在不到60秒的时间内被空间和选择性地化学修饰，为随后的化学功能化做准备。这项提议处于化学、物理和工程的尖端，它将发现新的基础科学，从长远来看，这可能是纳米科学工具箱强大而灵活的技术的基础。

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.