Distonic radical anion species in cysteine oxidation processes
Literature Information
Zhengbo Qin, Gao-Lei Hou, Zheng Yang, Marat Valiev, Xue-Bin Wang
Oxidation of cysteine residues constitutes an important regulatory mechanism in the function of biological systems. Much of this behavior is controlled by the specific chemical properties of the thiol side-chain group, where reactions with reactive oxygen species take place. Herein, we investigated the entire cysteine oxidation cycle Cys-SH → Cys-SOnH (n = 1, 2, and 3) using cryogenic negative ion photoelectron spectroscopy and quantum-chemical calculations. The conventional view of the first reversible oxidation step (n = 1) is associated with sulfenate species. Yet our results indicate that an alternative option exists in the form of a novel distonic radical anion, ˙OS–CH2CH(NH2)–COO−, with an unpaired electron on the thiol group and excess negative charge on the carboxylate group. Higher order oxidation states (n = 2 and 3) are thought to be associated with irreversible oxidative damage, and our results show that excess negative charge in those cases migrates to the –SOn− group. Furthermore, these species are stable towards 1e oxidation, as opposed to the n = 1 case that undergoes intra-molecular proton transfer. The molecular level insights reported in this work provide direct spectroscopic evidence of the unique chemical versatility of Cys-sulfenic acid (Cys-SOH) in post-translational modifications of protein systems.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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