{"doi":"10.1002/ange.202012673","title":"The pH‐Induced Selectivity Between Cysteine or Histidine Coordinated Heme in an Artificial α‐Helical Metalloprotein","abstract":"Abstract De Novo metalloprotein design assesses the relationship between metal active site architecture and catalytic reactivity. Herein, we use an α‐helical scaffold to control the iron coordination geometry when a heme cofactor is allowed to bind to either histidine or cysteine ligands, within a single artificial protein. Consequently, we uncovered a reversible pH‐induced switch of the heme axial ligation within this simplified scaffold. Characterization of the specific heme coordination modes was done by using UV/Vis and Electron Paramagnetic Resonance spectroscopies. The penta‐ or hexa‐coordinate thiolate heme (9≤pH≤11) and the penta‐coordinate imidazole heme (6≤pH≤8.5) reproduces well the heme ligation in chloroperoxidases or cyt P450 monooxygenases and peroxidases, respectively. The stability of heme coordination upon ferric/ferrous redox cycling is a crucial property of the construct. At basic pHs, the thiolate mini‐heme protein can catalyze O 2 reduction when adsorbed onto a pyrolytic graphite electrode.","journal":"Angewandte Chemie","year":2020,"id":117178,"datarank":0.0,"base_score":0.0,"endowment":0.0,"self_citation_contribution":0.0,"citation_network_contribution":0.0,"self_endowment_contribution":0.0,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":1,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9486,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2020-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":399431,"name":"Toni Kühl","orcid":"0000-0002-6822-1585","position":1,"is_corresponding":false},{"id":399432,"name":"Élisabeth Lojou","orcid":"0000-0003-2593-4670","position":2,"is_corresponding":false},{"id":399433,"name":"Borries Demeler","orcid":"0000-0002-2414-9518","position":3,"is_corresponding":false},{"id":399434,"name":"Barbara Schoepp‐Cothenet","orcid":"0000-0002-6820-4478","position":4,"is_corresponding":false},{"id":399435,"name":"Olga Iranzo","orcid":"0000-0001-8542-2429","position":5,"is_corresponding":false},{"id":399436,"name":"Vincent L. Pecoraro","orcid":"0000-0002-1540-5735","position":6,"is_corresponding":false},{"id":399437,"name":"Anabella Ivancich","orcid":"0000-0002-4275-0980","position":7,"is_corresponding":false},{"id":399430,"name":"Karl J. Koebke","orcid":"0000-0003-2198-2667","position":0,"is_corresponding":true}],"reference_count":31,"raw_metadata":null,"created_at":"2026-07-18T23:13:51.309289Z","pmid":null,"pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}