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Photochem Photobiol Sci ; 23(5): 839-851, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38615307

RESUMEN

Photolabile (µ-peroxo)(µ-hydroxo)bis[bis(bipyridyl)-cobalt-based caged oxygen compounds have been synthesized and characterized by optical absorbance spectroscopy, X-ray crystallography. and the quantum yield and redox stability were investigated. Furthermore, conditions were established where redox incompatibilities encountered between caged oxygen compounds and oxygen-dependant cytochrome c oxidase (CcO) could be circumvented. Herein, we demonstrate that millimolar concentrations of molecular oxygen can be released from a caged oxygen compound with spatio-temporal control upon laser excitation, triggering enzymatic turnover in cytochrome c oxidase. Spectroscopic evidence confirms the attainment of a homogeneous reaction initiation at concentrations and conditions relevant for further crystallography studies. This was demonstrated by the oxidizing microcrystals of reduced CcO by liberation of millimolar concentrations of molecular oxygen from a caged oxygen compound. We believe this will expand the scope of available techniques for the detailed investigation of oxygen-dependant enzymes with its native substrate and facilitate further time-resolved X-ray based studies such as wide/small angle X-ray scattering and serial femtosecond crystallography.


Asunto(s)
Complejo IV de Transporte de Electrones , Oxígeno , Complejo IV de Transporte de Electrones/química , Complejo IV de Transporte de Electrones/metabolismo , Oxígeno/química , Cristalografía por Rayos X , Oxidación-Reducción , Cobalto/química , Complejos de Coordinación/química , Complejos de Coordinación/síntesis química , Factores de Tiempo , Estructura Molecular , Modelos Moleculares
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