Harnessing Bioluminescent Bacteria to Power Photochemical Transformations

利用光能促进化学反应是当前研究中最具活力和最多功能的领域之一。特别是，可见光激发允许特定分子的选择性激发，然后能够与试剂进行能量或电子转移。这是一种强有力的策略，以高选择性的方式形成催化量的高活性中间体，如自由基或卡宾。使用这种方法已经产生了大量的新反应和新分子。然而，尽管它在学术和工业实验室中广泛使用，但其在大规模多吨反应中的应用尚未实现。这可以通过许多光化学方法的可扩展性差来合理化。其主要原因是由比尔-朗伯定律描述的光的衰减。简单地增加反应的规模将大大减少其表面积，并且随着光强度在容器内呈指数下降，大部分能量被浪费。在这个项目中，我们试图利用生物发光细菌作为光子源进行光化学转化。重要的是，一系列荧光蛋白，发光海洋和土壤微生物是现成的;因此，提供了各种波长的可见光。初步研究将侧重于使用化学光氧化还原反应获得概念验证，重点是生物相容性。我们将评估生物体对光化学中间体的存在的生物反应（通过转录组学），除了使用现代合成生物学方法来调整生物发光的强度和波长，以创建一个模块化的遗传方法来细胞产生光，用于一系列光化学反应。总的来说，这一战略的成功实施将提供一种新的方法，在没有高功率光源的情况下为光化学转化提供动力。这种能源密集度较低的方法将有助于通过降低成本和有害排放来在制造规模上采用这些反应。

The use of light energy to promote chemical reactions is one of the most vibrant and versatile areas of current research. In particular, visible light photocatalysis allows for the selective excitation of a specific molecule, which is then able to undergo energy or electron transfer with a reagent. This is a powerful strategy to form catalytic quantities of highly reactive intermediates, such as radicals or carbenes, in a highly selective manner. A vast array of novel reactions and new molecules have been generated using this approach. However, despite its widespread use in academic and industrial labs its application in large-scale multi-tonne reactions has not been realised. This can be rationalised by the poor scalability of many photochemical methods. The main factor attributed to this is the attenuation of light as described by the Beer-Lambert law. Simply increasing the scale of a reaction will drastically reduce its surface area and with light intensity decreasing exponentially within the vessel much of this energy is wasted. In this project, we seek to utilise bioluminescent bacteria as a photon source to conduct photochemical transformations. Importantly, a range of fluorescent proteins, luminescent marine and soil microorganisms are readily available; therefore, providing access to a variety of wavelengths of visible light. Initial studies will focus on obtaining proof-of-concept using a chemical photoredox reaction with a focus on biocompatibility. We will assess the biological response of the organism to the presence of photochemical intermediates (via transcriptomics) in addition to using modern synthetic biology approaches to tune the intensity and wavelength of the bioluminescence to create a modular, genetic approach to the cellular generation of light for a range of photochemical reactions. Overall, the successful implementation of this strategy will offer a new method for powering photochemical transformations without a high-powered light source. This less energy intensive approach will assist the adoption of these reactions on manufacturing scales by cutting both costs and harmful emissions.