title: Mechanisms of metalloenzymes studied by quantum chemical methods.
abstract: The study of metalloenzymes using quantum chemical methods of high accuracy is a relatively new field. During the past five years a quite good understanding has been reached concerning the methods and models to be used for these systems. For systems containing transition metals hybrid density functional methods have proven both accurate and computationally efficient. A background on these methods and the accuracy achieved in benchmark tests are given first in this review. The rest of the review describes examples of studies on different metalloenzymes. Most of these examples describe mechanisms where dioxygen is either formed, as in photosystem II, or cleaved as in many other enzymes like cytochrome c oxidase, ribonucleotide reductase, methane mono-oxygenase and tyrosinase. In the descriptions below high emphasis is put on the actual determination of the transition states, which are the key points determining the mechanisms.
authors.affiliation: Department of Physics, Stockholm Centre for Physics, Astronomy and Biotechnology (SCFAB), Stockholm University, S-106 91 Stockholm, Sweden.
authors.forename: Per E M
authors.initials: PE
authors.lastname: Siegbahn
mesh_terms: D006631:Amine Oxidase (Copper-Containing) / Q000737:chemistry; D001703:Biophysics / Q000379:methods; D002374:Catalase / Q000737:chemistry; D004156:Catechol Oxidase / Q000737:chemistry; D003578:Cytochrome-c Peroxidase / Q000737:chemistry; D003576:Electron Transport Complex IV / Q000737:chemistry; D004798:Enzymes / Q000737:chemistry*; D005692:Galactose Oxidase / Q000737:chemistry; D006899:Mixed Function Oxygenases / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D014442:Monophenol Monooxygenase / Q000737:chemistry; D010088:Oxidoreductases / Q000737:chemistry; D010105:Oxygenases / Q000737:chemistry; D045322:Photosynthetic Reaction Center Complex Proteins; D045332:Photosystem II Protein Complex; D012264:Ribonucleotide Reductases / Q000737:chemistry
chemical_list: D004798:Enzymes; D045322:Photosynthetic Reaction Center Complex Proteins; D045332:Photosystem II Protein Complex; D006899:Mixed Function Oxygenases; D010088:Oxidoreductases; D005692:Galactose Oxidase; D004156:Catechol Oxidase; D003578:Cytochrome-c Peroxidase; D002374:Catalase; D010105:Oxygenases; C021555:methane monooxygenase; D014442:Monophenol Monooxygenase; D012264:Ribonucleotide Reductases; C038370:isopenicillin N synthetase; D006631:Amine Oxidase (Copper-Containing); D003576:Electron Transport Complex IV; C021572:methyl coenzyme M reductase