title: Anion-π Interactions in Flavoproteins Involve a Substantial Charge-Transfer Component.
abstract: Anion-π interactions have been shown to stabilize flavoproteins and to regulate the redox potential of the flavin cofactor. They are commonly attributed to electrostatic forces. Herein we show that anion-flavin interactions can have a substantial charge-transfer component. Our conclusion emanates from a multi-approach theoretical analysis and is backed by previously reported observations of absorption bands, originating from charge transfer between oxidized flavin and proximate cysteine thiolate groups. This partial covalency of anion-flavin contacts renders classical simulations of flavoproteins questionable.
authors.affiliation: CEITEC-Central European Institute of Technology, Masaryk University, Kamenice 5/A4, 62500, Brno, Czech Republic.|Department of Condensed Matter Physics, Faculty of Science, Masaryk University, Kotlářská 2, 61137, Brno, Czech Republic.
authors.forename: Yevgen P
authors.identifier: http://orcid.org/0000-0003-3925-0384
authors.initials: YP
authors.lastname: Yurenko
authors.affiliation: Center for Free-Electron Laser Science, DESY, Notkestraße 85, 22607, Hamburg, Germany.|Department of Chemistry, University of Hamburg, Grindelallee 117, 20146, Hamburg, Germany.
authors.forename: Sophia
authors.identifier: http://orcid.org/0000-0001-5885-3231
authors.initials: S
authors.lastname: Bazzi
authors.affiliation: CEITEC-Central European Institute of Technology, Masaryk University, Kamenice 5/A4, 62500, Brno, Czech Republic.|National Center for Biomolecular Research, Faculty of Science, Masaryk University, Kamenice 5/A4, 62500, Brno, Czech Republic.
authors.forename: Radek
authors.identifier: http://orcid.org/0000-0002-3668-3523
authors.initials: R
authors.lastname: Marek
authors.affiliation: Department of Condensed Matter Physics, Faculty of Science, Masaryk University, Kotlářská 2, 61137, Brno, Czech Republic.|INSERM, U 1134, DSIMB, 75739, Paris, France.|Université Paris Diderot, Sorbonne Paris Cité, UMRS 1134, 75739, Paris, France.|Institut National de la Transfusion Sanguine (INTS), 75739, Paris, France.|Laboratoire d'Excellence GR-Ex, 75739, Paris, France.
authors.forename: Jiří
authors.identifier: http://orcid.org/0000-0003-0250-1928
authors.initials: J
authors.lastname: Kozelka
mesh_terms: D000838:Anions / Q000737:chemistry; D001665:Binding Sites; D003198:Computer Simulation; D003545:Cysteine / Q000737:chemistry; D005415:Flavins / Q000737:chemistry*; D005420:Flavoproteins / Q000737:chemistry*; D010084:Oxidation-Reduction; D011485:Protein Binding; D011487:Protein Conformation; D055672:Static Electricity; D013438:Sulfhydryl Compounds / Q000737:chemistry
chemical_list: D000838:Anions; D005415:Flavins; D005420:Flavoproteins; D013438:Sulfhydryl Compounds; D003545:Cysteine
keywords: ab initio calculations; anion-π interactions; donor-acceptor systems; energy decomposition analysis; π interactions