2022
DOI: 10.1002/asia.202200490
|View full text |Cite
|
Sign up to set email alerts
|

QM/MM Calculations Suggest Concerted O−O Bond Cleavage and Substrate Oxidation by Nonheme Diiron Toluene/o‐Xylene Monooxygenase

Abstract: The nonheme diiron toluene/o-xylene monooxygenase (ToMO) is the most studied toluene monooxygenase that mediates an aromatic hydroxylation reaction. In this work, QM/MM calculations were performed to understand the reaction mechanism. It is revealed that the μ-η 2 :η 2 peroxodiferric species is the reactive intermediate after the binding of the O 2 molecule to the reduced diferrous center. Subsequently, both a stepwise and a concerted mechanism involving the critical OÀ O bond cleavage and CÀ O bond formation … Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
2
1
1
1

Citation Types

1
9
0

Year Published

2023
2023
2024
2024

Publication Types

Select...
6

Relationship

1
5

Authors

Journals

citations
Cited by 7 publications
(10 citation statements)
references
References 147 publications
1
9
0
Order By: Relevance
“…First, QM model calculations have been performed to identify the most likely structures of P. Figure 2 shows three candidate structures of P. It is seen that P1 with the side-on peroxo binding to both irons has the lowest energy. Such butterfly-like structure of P1 is analogous to those proposed in sMMO, 5,94 epoxidase BoxB, 25,50 ToMo, 51,95 CmlA, 52 and AurF. 49 For the end-on binding Z-like P2, its energy is 1.8 kcal/mol higher than that of P1.…”
Section: Possible Structures Of P In Sznfsupporting
confidence: 69%
See 2 more Smart Citations
“…First, QM model calculations have been performed to identify the most likely structures of P. Figure 2 shows three candidate structures of P. It is seen that P1 with the side-on peroxo binding to both irons has the lowest energy. Such butterfly-like structure of P1 is analogous to those proposed in sMMO, 5,94 epoxidase BoxB, 25,50 ToMo, 51,95 CmlA, 52 and AurF. 49 For the end-on binding Z-like P2, its energy is 1.8 kcal/mol higher than that of P1.…”
Section: Possible Structures Of P In Sznfsupporting
confidence: 69%
“…In addition to the above two mechanistic pathways, one plausible mechanism involves the electrophilic attack of peroxo species onto the N site of guanidium, which may trigger the heterolytic cleavage of the O–O bond, leading to l -HMA (Scheme c). Such a mechanism in Scheme c is reminiscent of O 2 activation mechanisms by the diiron enzymes AurF, BoxB, ToMo, and CmlA …”
Section: Introductionmentioning
confidence: 99%
See 1 more Smart Citation
“…The presence of these hydrogen bonds in React OR , along with the hydroxo-bridge between two iron ions, inclines the O 2 moiety to bind with the two irons in a side-on symmetric manner: oxyl fragment coordinates as a bridge between two iron ions in the μ-η 1 :η 1 mode (see Figure S4). 2,83 This binding mode is similar to the peroxo-diiron(III) species found in other nonheme diiron enzymes, like cyanobacterial aldehyde-deformylating oxygenase 90 and acyl carrier protein Δ 9 -desaturase. 91 Other possible candidates for React OR were also explored.…”
Section: Resultsmentioning
confidence: 99%
“…Several recent studies have investigated reactivity of non-haem diiron enzymes. [88][89][90][91] Song et al used ChemShell to model PhnZ, a mixed-valence diiron oxygenase, which catalyses the conversion of organophosphonic acids to inorganic phosphate via a mechanism involving the substrate bonding to one Fe(III) site and oxygen to the other. 92 [NiFe]-hydrogenases have also been explored, 93,94 which are of great interest in the development of the hydrogen economy due to their ability to catalyse H 2 oxidation at ambient conditions.…”
Section: Qm/mm Simulations Of Biomoleculesmentioning
confidence: 99%