Demchenko Alexander P
Yuriy Fedkovych National University, Kotsubynskoho 2, Chernivtsi, 58012, Ukraine.
Palladin Institute of Biochemistry, Leontovicha 9, Kyiv, 01030, Ukraine.
BBA Adv. 2023 Mar 9;3:100085. doi: 10.1016/j.bbadva.2023.100085. eCollection 2023.
The present Review is an attempt by projecting the basic knowledge on photochemical proton transfer to achieve consistent understanding of proton motions in biocatalysis, photobiocatalysis, operation of selective proton channels and systems of photosynthesis and cellular respiration. The basic mechanisms of proton transfer are in active research in the electronic excited states of organic molecules. This allows observing the reactions directly in real time, providing their dynamic and thermodynamic description and coupling with structural and energetic variables. These achievements lay the background for understanding the proton transfers in biochemical reactions, where such ultrafast events are not only 'optically silent' but are hidden under much slower rate-limiting steps, such as protein conformational changes, substrate binding and product release. The mechanistic description of biocatalytic and transmembrane proton transport is shown as a multi-step proton migration that is available for modeling in photochemical reactions. For explaining the formation of transmembrane proton gradients, a simple 'proton lift' concept is presented that may be the basis of further research and analysis.
本综述试图通过阐述光化质子转移的基础知识，来实现对生物催化、光生物催化、选择性质子通道的运作以及光合作用和细胞呼吸系统中质子运动的一致理解。质子转移的基本机制是有机分子电子激发态的活跃研究领域。这使得能够直接实时观察反应，提供其动力学和热力学描述，并与结构和能量变量相联系。这些成果为理解生化反应中的质子转移奠定了基础，在生化反应中，此类超快事件不仅“光学上无信号”，而且隐藏在诸如蛋白质构象变化、底物结合和产物释放等慢得多的限速步骤之下。生物催化和跨膜质子传输的机制描述显示为多步质子迁移，可用于光化学反应建模。为了解释跨膜质子梯度的形成，提出了一个简单的“质子提升”概念，这可能是进一步研究和分析的基础。
