2017
DOI: 10.1002/cphc.201701128
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Role of the Chalcogen (S, Se, Te) in the Oxidation Mechanism of the Glutathione Peroxidase Active Site

Abstract: The front cover artwork is provided by the groups of Prof. Dr. F. Matthias Bickelhaupt (VU Amsterdam, The Netherlands) and Prof. Dr. Laura Orian (Università degli Studi di Padova, Italy). The GPx active sites resemble lightning bolts during a thunderstorm (S and Te mutants), and during a clear night for Sec‐GPx, associating its much higher anti‐oxidant power to the tremendously powerful positive lightning bolts. Read the full text of the article at 10.1002/cphc.201700743.

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“…[64] The mechanism of oxidation of the tellurium mutant of human GPx4 (Tec-GPx) has been in silico investigated and compared with that of Sec-GPx and Cys-GPx in order to establish the role of the chalcogen atom. [65] For Cys-and Sec-containing enzymes the study validates a mechanism proceeding through charge-separated intermediates with a thiolate or a selenolate center, respectively. Conversely, because of the fact that the tellurium hydrogen bond is not polarised, Tec-GPx the study suggests a catalytic path involving the direct oxidation of the tellurol moiety, leading to a telluroxide intermediate.…”
Section: Telluroproteinsmentioning
confidence: 63%
“…[64] The mechanism of oxidation of the tellurium mutant of human GPx4 (Tec-GPx) has been in silico investigated and compared with that of Sec-GPx and Cys-GPx in order to establish the role of the chalcogen atom. [65] For Cys-and Sec-containing enzymes the study validates a mechanism proceeding through charge-separated intermediates with a thiolate or a selenolate center, respectively. Conversely, because of the fact that the tellurium hydrogen bond is not polarised, Tec-GPx the study suggests a catalytic path involving the direct oxidation of the tellurol moiety, leading to a telluroxide intermediate.…”
Section: Telluroproteinsmentioning
confidence: 63%