Matches in SemOpenAlex for { <https://semopenalex.org/work/W1999089069> ?p ?o ?g. }
- W1999089069 endingPage "12309" @default.
- W1999089069 startingPage "12299" @default.
- W1999089069 abstract "Indoleamine 2,3-dioxygenase (IDO) and tryptophan 2,3-dioxygenase (TDO) are heme-containing dioxygenases and catalyze oxidative cleavage of the pyrrole ring of l-tryptophan. On the basis of three recent crystal structures of these heme-containing dioxygenases, two new mechanistic pathways were proposed by several groups. Both pathways start with electrophilic addition of the Fe(II)-bound dioxygen concerted with proton transfer (oxygen ene-type reaction), followed by either formation of a dioxetane intermediate or Criegee-type rearrangement. However, density functional theory (DFT) calculations do not support the proposed concerted oxygen ene-type and Criegee-type rearrangement pathways. On the basis of DFT calculations, we propose a new mechanism for dioxygen activation in these heme systems. The mechanism involves (a) direct electrophilic addition of the Fe(II)-bound oxygen to the C2 or C3 position of the indole in a closed-shell singlet state or (b) direct radical addition of the Fe(III)−superoxide to the C2 position of the indole in a triplet (or open-shell singlet) state. Then, a radical-recombination or nearly barrierless charge-recombination step from the resultant diradical or zwitterionic intermediates, respectively, proceeds to afford metastable dioxetane intermediates, followed by ring-opening of the dioxetanes. Alternatively, homolytic O−O bond cleavage from the diradical intermediate followed by oxo attack and facile C2−C3 bond cleavage could compete with the dioxetane formation pathway. Effects of ionization of the imidazole and negatively charged oxyporphyrin complex on the key dioxygen activation process are also studied." @default.
- W1999089069 created "2016-06-24" @default.
- W1999089069 creator A5009377050 @default.
- W1999089069 creator A5020600412 @default.
- W1999089069 creator A5037062657 @default.
- W1999089069 creator A5082152558 @default.
- W1999089069 creator A5087232698 @default.
- W1999089069 date "2008-08-20" @default.
- W1999089069 modified "2023-09-23" @default.
- W1999089069 title "Density Functional Theory Study on a Missing Piece in Understanding of Heme Chemistry: The Reaction Mechanism for Indoleamine 2,3-Dioxygenase and Tryptophan 2,3-Dioxygenase" @default.
- W1999089069 cites W133895625 @default.
- W1999089069 cites W1487436709 @default.
- W1999089069 cites W1491975375 @default.
- W1999089069 cites W1523821465 @default.
- W1999089069 cites W1582908944 @default.
- W1999089069 cites W1607682771 @default.
- W1999089069 cites W172213682 @default.
- W1999089069 cites W1963592955 @default.
- W1999089069 cites W1966182479 @default.
- W1999089069 cites W1966792574 @default.
- W1999089069 cites W1967700647 @default.
- W1999089069 cites W1971690451 @default.
- W1999089069 cites W1973251492 @default.
- W1999089069 cites W1975262546 @default.
- W1999089069 cites W1975929837 @default.
- W1999089069 cites W1976707323 @default.
- W1999089069 cites W1979850841 @default.
- W1999089069 cites W1981368803 @default.
- W1999089069 cites W1981451973 @default.
- W1999089069 cites W1986285274 @default.
- W1999089069 cites W1988768857 @default.
- W1999089069 cites W1990442032 @default.
- W1999089069 cites W1990833174 @default.
- W1999089069 cites W1992486156 @default.
- W1999089069 cites W1995042715 @default.
- W1999089069 cites W1995599900 @default.
- W1999089069 cites W1995794402 @default.
- W1999089069 cites W1996348788 @default.
- W1999089069 cites W1997412769 @default.
- W1999089069 cites W2001900976 @default.
- W1999089069 cites W2005043252 @default.
- W1999089069 cites W2010157405 @default.
- W1999089069 cites W2016708089 @default.
- W1999089069 cites W2017445815 @default.
- W1999089069 cites W2020141438 @default.
- W1999089069 cites W2021406372 @default.
- W1999089069 cites W2021426561 @default.
- W1999089069 cites W2023271753 @default.
- W1999089069 cites W2025105240 @default.
- W1999089069 cites W2030261902 @default.
- W1999089069 cites W2030687437 @default.
- W1999089069 cites W2034796508 @default.
- W1999089069 cites W2034890453 @default.
- W1999089069 cites W2038083805 @default.
- W1999089069 cites W2039485473 @default.
- W1999089069 cites W2041893866 @default.
- W1999089069 cites W2042183419 @default.
- W1999089069 cites W2044961513 @default.
- W1999089069 cites W2045352208 @default.
- W1999089069 cites W2047284988 @default.
- W1999089069 cites W2049079467 @default.
- W1999089069 cites W2049741984 @default.
- W1999089069 cites W2051449483 @default.
- W1999089069 cites W2054340807 @default.
- W1999089069 cites W2054704030 @default.
- W1999089069 cites W2062893953 @default.
- W1999089069 cites W2063060249 @default.
- W1999089069 cites W2070366769 @default.
- W1999089069 cites W2071713207 @default.
- W1999089069 cites W2071848867 @default.
- W1999089069 cites W2071967435 @default.
- W1999089069 cites W2072724034 @default.
- W1999089069 cites W2073144071 @default.
- W1999089069 cites W2077318436 @default.
- W1999089069 cites W2077621515 @default.
- W1999089069 cites W2079202542 @default.
- W1999089069 cites W2079874097 @default.
- W1999089069 cites W2080887013 @default.
- W1999089069 cites W2084902151 @default.
- W1999089069 cites W2086675509 @default.
- W1999089069 cites W2086946343 @default.
- W1999089069 cites W2086957099 @default.
- W1999089069 cites W2097532911 @default.
- W1999089069 cites W2100032379 @default.
- W1999089069 cites W2101003026 @default.
- W1999089069 cites W2101796112 @default.
- W1999089069 cites W2112862672 @default.
- W1999089069 cites W2113248394 @default.
- W1999089069 cites W2113910772 @default.
- W1999089069 cites W2119292856 @default.
- W1999089069 cites W2119992321 @default.
- W1999089069 cites W2127525205 @default.
- W1999089069 cites W2137460896 @default.
- W1999089069 cites W2140158011 @default.
- W1999089069 cites W2141403265 @default.
- W1999089069 cites W2141705345 @default.
- W1999089069 cites W2143981217 @default.
- W1999089069 cites W2147434133 @default.