Identification of a Ubiquinone-Ubiquinol Quinhydrone Complex in Bacterial Photosynthetic Membranes and Isolated Reaction Centers by Time-Resolved Infrared Spectroscopy

Ubiquinone redox chemistry is of fundamental importance in biochemistry, notably in bioenergetics. The bi-electronic reduction of ubiquinone to ubiquinol has been widely studied, including by Fourier transform infrared (FTIR) difference spectroscopy, in several systems. In this paper, we have recorded static and time-resolved FTIR difference spectra reflecting light-induced ubiquinone reduction to ubiquinol in bacterial photosynthetic membranes and in detergent-isolated photosynthetic bacterial reaction centers. We found compelling evidence that in both systems under strong light illumination-and also in detergent-isolated reaction centers after two saturating flashes-a ubiquinone-ubiquinol charge-transfer quinhydrone complex, characterized by a characteristic band at similar to 1565 cm(-1), can be formed. Quantum chemistry calculations confirmed that such a band is due to formation of a quinhydrone complex. We propose that the formation of such a complex takes place when Q and QH(2) are forced, by spatial constraints, to share a common limited space as, for instance, in detergent micelles, or when an incoming quinone from the pool meets, in the channel for quinone/quinol exchange at the Q(B) site, a quinol coming out. This latter situation can take place both in isolated and membrane bound reaction centers Possible consequences of the formation of this charge-transfer complex under physiological conditions are discussed.

Automated summary

This study investigates the formation of a charge-transfer quinhydrone complex in bacterial photosynthetic membranes and detergent-isolated photosynthetic bacterial reaction centers through Fourier transform infrared (FTIR) difference spectroscopy. The results show that under strong light illumination and after two saturating flashes, a characteristic band at approximately 1565 cm(-1) corresponding to the formation of a quinhydrone complex can be observed. Quantum chemistry calculations support this finding. The formation of this complex is believed to occur when ubiquinone and ubiquinol are spatially constrained to share a limited space, such as in detergent micelles, or when a quinol meets a quinone in the channel for quinone/quinol exchange at the Q(B) site.