{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Kim H"],"funding":["NIGMS NIH HHS"],"pagination":["5907-5912"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC7920932"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["60(11)"],"pubmed_abstract":["A new end-on low-spin ferric heme peroxide, [(P<sup>Im</sup> )Fe<sup>III</sup> -(O<sub>2</sub> <sup>2-</sup> )]<sup>-</sup> (P<sup>Im</sup> -P), and subsequently formed hydroperoxide species, [(P<sup>Im</sup> )Fe<sup>III</sup> -(OOH)] (P<sup>Im</sup> -HP) are generated utilizing the iron-porphyrinate P<sup>Im</sup> with its tethered axial base imidazolyl group. Measured thermodynamic parameters, the ferric heme superoxide [(P<sup>Im</sup> )Fe<sup>III</sup> -(O<sub>2</sub> <sup>⋅-</sup> )] (P<sup>Im</sup> -S) reduction potential (E°') and the P<sup>Im</sup> -HP pK<sub>a</sub> value, lead to the finding of the OO-H bond-dissociation free energy (BDFE) of P<sup>Im</sup> -HP as 69.5 kcal mol<sup>-1</sup> using a thermodynamic square scheme and Bordwell relationship. The results are validated b"],"journal":["Angewandte Chemie (International ed. in English)"],"pubmed_title":["Ferric Heme Superoxide Reductive Transformations to Ferric Heme (Hydro)Peroxide Species: Spectroscopic Characterization and Thermodynamic Implications for H-Atom Transfer (HAT)."],"pmcid":["PMC7920932"],"funding_grant_id":["R01 GM040392","R01 GM060353"],"pubmed_authors":["Kim H","Rogler PJ","Sharma SK","Solomon EI","Schaefer AW","Karlin KD"],"additional_accession":[]},"is_claimable":false,"name":"Ferric Heme Superoxide Reductive Transformations to Ferric Heme (Hydro)Peroxide Species: Spectroscopic Characterization and Thermodynamic Implications for H-Atom Transfer (HAT).","description":"A new end-on low-spin ferric heme peroxide, [(P<sup>Im</sup> )Fe<sup>III</sup> -(O<sub>2</sub> <sup>2-</sup> )]<sup>-</sup> (P<sup>Im</sup> -P), and subsequently formed hydroperoxide species, [(P<sup>Im</sup> )Fe<sup>III</sup> -(OOH)] (P<sup>Im</sup> -HP) are generated utilizing the iron-porphyrinate P<sup>Im</sup> with its tethered axial base imidazolyl group. Measured thermodynamic parameters, the ferric heme superoxide [(P<sup>Im</sup> )Fe<sup>III</sup> -(O<sub>2</sub> <sup>⋅-</sup> )] (P<sup>Im</sup> -S) reduction potential (E°') and the P<sup>Im</sup> -HP pK<sub>a</sub> value, lead to the finding of the OO-H bond-dissociation free energy (BDFE) of P<sup>Im</sup> -HP as 69.5 kcal mol<sup>-1</sup> using a thermodynamic square scheme and Bordwell relationship. The results are validated b","dates":{"release":"2021-01-01T00:00:00Z","publication":"2021 Mar","modification":"2025-04-04T19:53:39.028Z","creation":"2025-04-04T19:53:39.028Z"},"accession":"S-EPMC7920932","cross_references":{"pubmed":["33348450"],"doi":["10.1002/anie.202013791"]}}