Smart Materials Lab (SML), New York University Abu Dhabi, Abu Dhabi, United Arab Emirates.
Merck KGaA, Frankfurter Strasse 250, 64293 Darmstadt, Germany.
Chem Rev. 2022 Aug 24;122(16):13207-13234. doi: 10.1021/acs.chemrev.1c01047. Epub 2022 Aug 4.
The chemical reactions underlying the emission of light in fireflies and other bioluminescent beetles are some of the most thoroughly studied processes by scientists worldwide. Despite these remarkable efforts, fierce academic arguments continue around even some of the most fundamental aspects of the reaction mechanism behind the beetle bioluminescence. In an attempt to reach a consensus, we made an exhaustive search of the available literature and compiled the key discoveries on the fluorescence and chemiluminescence spectrochemistry of the emitting molecule, the firefly oxyluciferin, and its chemical analogues reported over the past 50+ years. The factors that affect the light emission, including intermolecular interactions, solvent polarity, and electronic effects, were analyzed in the context of both the reaction mechanism and the different colors of light emitted by different luciferases. The collective data points toward a combined emission of multiple coexistent forms of oxyluciferin as the most probable explanation for the variation in color of the emitted light. We also highlight realistic research directions to eventually address some of the remaining questions related to firefly bioluminescence. It is our hope that this extensive compilation of data and detailed analysis will not only consolidate the existing body of knowledge on this important phenomenon but will also aid in reaching a wider consensus on some of the mechanistic details of firefly bioluminescence.
萤火虫和其他生物发光甲虫发光背后的化学反应是全球科学家研究最透彻的过程之一。尽管这些研究非常出色，但围绕着甲虫生物发光的反应机制的一些最基本方面，激烈的学术争论仍在继续。为了达成共识，我们对现有文献进行了详尽的搜索，并编译了过去 50 多年来关于发光分子萤火虫荧光素及其化学类似物的荧光和化学发光光谱化学的关键发现。我们分析了影响发光的因素，包括分子间相互作用、溶剂极性和电子效应，同时考虑了反应机制和不同荧光酶发出的不同颜色的光。综合数据表明，多种共存形式的氧化荧光素的联合发射是解释发光颜色变化的最可能原因。我们还强调了现实的研究方向，以最终解决与萤火虫生物发光相关的一些剩余问题。我们希望，这一广泛的数据汇编和详细分析不仅将巩固这一重要现象的现有知识体系，还将有助于就萤火虫生物发光的一些机制细节达成更广泛的共识。
