title: Challenging Density Functional Theory Calculations with Hemes and Porphyrins.
abstract: In this paper we review recent advances in computational chemistry and specifically focus on the chemical description of heme proteins and synthetic porphyrins that act as both mimics of natural processes and technological uses. These are challenging biochemical systems involved in electron transfer as well as biocatalysis processes. In recent years computational tools have improved considerably and now can reproduce experimental spectroscopic and reactivity studies within a reasonable error margin (several kcal·mol(-1)). This paper gives recent examples from our groups, where we investigated heme and synthetic metal-porphyrin systems. The four case studies highlight how computational modelling can correctly reproduce experimental product distributions, predicted reactivity trends and guide interpretation of electronic structures of complex systems. The case studies focus on the calculations of a variety of spectroscopic features of porphyrins and show how computational modelling gives important insight that explains the experimental spectra and can lead to the design of porphyrins with tuned properties.
authors.affiliation: Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, the University of Manchester, 131 Princess Street, Manchester M1 7DN, UK. sam.devisser@manchester.ac.uk.
authors.forename: Sam P
authors.initials: SP
authors.lastname: de Visser
authors.affiliation: Department of Chemistry, The University of Western Ontario, London, ON N6A 5B7, Canada. martin.stillman@uwo.ca.
authors.forename: Martin J
authors.initials: MJ
authors.lastname: Stillman
mesh_terms: D000818:Animals; D003577:Cytochrome P-450 Enzyme System / Q000737:chemistry; D003578:Cytochrome-c Peroxidase / Q000737:chemistry; D003576:Electron Transport Complex IV / Q000737:chemistry; D004583:Electrons; D006418:Heme / Q000737:chemistry*; D006420:Hemeproteins / Q000737:chemistry; D006441:Hemoglobin A / Q000737:chemistry; D006801:Humans; D008665:Metalloporphyrins / Q000737:chemistry; D008958:Models, Molecular; D011166:Porphyrins / Q000737:chemistry*; D011487:Protein Conformation; D011789:Quantum Theory
chemical_list: D006420:Hemeproteins; D008665:Metalloporphyrins; D011166:Porphyrins; D006418:Heme; D006441:Hemoglobin A; D003577:Cytochrome P-450 Enzyme System; D003578:Cytochrome-c Peroxidase; D003576:Electron Transport Complex IV
keywords: DFT; Ga(III)PPIX; MCD spectroscopy; chlorophylls; enzyme mechanism