Optofluidic microreactors for exploration of novel enzyme mimics

天然酶特别适合于帮助制造高价值产品。然而，它们的应用仅限于几种类型的酶，以及它们催化的少数化学过程。在酶设计的一般限制中，一个重要的限制是对酶活性的探索和验证。基于黄素的酶的使用已经被探索用来启发新型复合光催化剂的设计，这些光催化剂可用于制造工艺，特别是合成新型染料和药物化合物。光催化体系的研究在可再生燃料领域也引起了极大的兴趣。太阳能可以通过人工光合作用系统转化为化学燃料，其中光敏剂起着关键作用。常用的光敏剂包括分子染料、纳米二氧化钛和半导体，如硫化镉和硫化镉。然而，染料通常价格昂贵且难以制备，二氧化钛纳米颗粒的水分散性差，基于镉的体系有毒，元素丰度低[8]。这导致了碳纳米点(CND)作为有吸引力的光敏剂替代品的出现。它们具有成本低、无毒、易化学修饰、易溶于水、稳定性好等特点。该项目的目标是克服在模拟酶的光催化剂和碳纳米点(CND)光敏剂领域取得进展的主要障碍之一：缺乏对小反应体积的原位定量分析方法。使用光流控微反应器将能够快速筛选各种光催化反应，从而更好地了解所涉及的潜在机制。空芯光子晶体纤维(HC-PCF)将通过各种不同的固定化策略被黄素催化剂或CND固定化，以创建新型的光催化微反应器。这些微反应器将用于小反应体积内的超灵敏光谱，包括UV-Vis、拉曼和荧光光谱等方法。这将使光催化反应动力学、稳态反应条件以及反应中间体和产物的鉴定成为可能。推进最先进的技术将对绿色催化、可持续制造和绿色太阳能燃料生产产生巨大影响。通过创建研究光驱动催化的光纤微反应器，该项目与催化、分析科学以及传感器和仪器EPSRC的研究领域紧密结合。

Natural enzymes are exceptionally well-suited to aid the manufacturing of high value products. However, their applications have been limited to few types of enzymes and only a handful of chemical processes they catalyse. Among the general limitations of the enzyme design, one significant limitation is the exploration and validation of the enzyme activity. The use of flavin-based enzymes has been explored to inspire the design of new types of hybrid photocatalysts useful for manufacturing processes, in particular synthesis of novel dyes and pharmaceutical compounds. The study of photocatalytic systems is also of great interest in the field of renewable fuel sources. Solar energy can be converted to chemical fuels through artificial photosynthesis systems, in which photosensitizers play a key role. Commonly used photosensitizers include molecular dyes, TiO2 nanoparticles and semiconductors such as CdSe and CdS. However, dyes are often expensive and difficult to prepare, TiO2 nanoparticles have poor aqueous dispersibility and Cd based systems are toxic and suffer from low elemental abundance[8]. This has led to the emergence of carbon-nanodots (CND) as attractive photosensitizer alternatives. They are low-cost, non-toxic, simple to chemically modify, water soluble and stable. This project will aim to overcome one of the main barriers to advancing the fields of enzyme-mimetic photocatalysts and carbon nanodot (CND) photosensitizers: the lack of quantitative in-situ analysis methods for small reaction volumes. The use of optofluidic microreactors will allow rapid screening of various photocatalytic reactions, acting to develop a greater understanding of the underlying mechanisms involved. Hollow-core photonic crystal fibres (HC-PCF) will be immobilised with either flavin catalysts or CND through various different immobilisation strategies to create novel photocatalytic microreactors. These microreactors will be used for ultrasensitive spectroscopy within small reaction volumes, including methodologies such as UV-vis, Raman and fluorescent spectroscopy. This will allow robust characterisation of photocatalytic reaction dynamics, steady-state reaction conditions and identification of reaction intermediates and products. Advancing the state of the art will have huge implications for green catalysis, sustainable manufacturing and green solar fuel production. By creating an optical fibre microreactor to study light-driven catalysis, this project closely aligns with the catalysis, analytical science and sensors and instrumentation EPSRC research areas.