Controlled oxidation of aliphatic CH bonds in metallo-monooxygenases: Mechanistic insights derived from studies on deuterated and fluorinated hydrocarbons

Chen, Yaosheng; Luo, Wen-I; Yang, Chung-Ling; Tu, Yi‐Jung; Chang, Cheng-Chun; Chiang, Chih-Hsiang; Chang, Chi-Yao; Chan, Sunney I.; Yu, Steve S.‐F.

doi:10.1016/j.jinorgbio.2014.02.005

Cited by 11 publications

(6 citation statements)

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“…The EPR spectrum of copper oxide nanoparticles at 298 K indicated an isotropic signal, reminiscent of a previous study of pMMO with trinuclear copper cluster feature (Nguyen et al, 1994), which was significantly broadened and presented relatively poor signal-to-noise ratio than the one at 77 K ( Figure 3B) (Wanna et al, 2019b). The result here reveals substantial dynamic motions around the metal centers, which are behaving like metal active sites in the metallo-monooxygenases (Chen et al, 2014;Wang et al, 2017;Yang et al, 2017). In addition, the corresponding EXAFS data fittings (k 3 -weighted) using two structural models of copper oxide and trinuclear copper cluster model (Cu 2.8 O 4.6 ), respectively, can both give reasonable fits of R fit = 0.027 and 0.15%, respectively (Wanna et al, 2019b), which indicated that a trinuclear copper cluster feature is manifested from the obtained oxide materials (Figure 3).…”

Section: Highly Selective Oxidation Of Benzene To P-benzoquinone (P-bsupporting

confidence: 81%

Selective Oxidation of Simple Aromatics Catalyzed by Nano-Biomimetic Metal Oxide Catalysts: A Mini Review

et al. 2020

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The process of selective oxy-functionalization of hydrocarbons using peroxide, O 3 , H 2 O 2 , O 2 , and transition metals can be carried out by the reactive oxygen species such as hydroxyl/hydroperoxyl radical and/or metal oxygenated species generated in the catalytic reaction. Thus, a variety of mechanisms have been proposed for the selective catalytic oxidation of various hydrocarbons including light alkanes, olefins, and simple aromatics by the biological metalloproteins and their biomimetics either in their homogeneous or heterogeneous platforms. Most studies involving these metalloproteins are Fe or Cu monooxygenases. The pathways carried out by these metalloenzymes in the oxidation of C-H bonds invoke either radical reaction mechanisms including Fenton's chemistry and hydrogen atom transfer followed by radical rebound reaction mechanism or electrophilic oxygenation/O-atom transfer by metal-oxygen species. In this review, we discuss the metal oxide nano-catalysts obtained from metal salts/molecular precursors (M = Cu, Fe, and V) that can easily form in situ through the oxidation of substrates using H 2 O 2(aq) in CH 3 CN, and be facilely separated from the reaction mixtures as well as recycled for several times with comparable catalytic efficiency for the highly selective conversion from hydrocarbons including aromatics to oxygenates. The mechanistic insights revealed from the oxy-functionalization of simple aromatics mediated by the novel biomimetic metal oxide materials can pave the way toward developing facile, cost-effective, and highly efficient nano-catalysts for the selective partial oxidation of simple aromatics.

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Section: Highly Selective Oxidation Of Benzene To P-benzoquinone (P-bsupporting

confidence: 81%

Selective Oxidation of Simple Aromatics Catalyzed by Nano-Biomimetic Metal Oxide Catalysts: A Mini Review

et al. 2020

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“…To emphasize that CH/π interactions with the aromatic side chains might make a significant contribution to stabilizing the binding of the hydrocarbon in addition to hydrophobic forces, this binding site has been referred to as the "aromatic box". 43,127,129 In addition to the substrate binding pockets highlighted above, other hydrocarbon binding sites for different substrates have been suggested. 89,123…”

Section: Hydrocarbon Binding Site and The Aromatic Boxmentioning

confidence: 99%

“…These amino acids are also highly conserved (Figure ), just like the ones that have been used to model and construct the tricopper cluster site at the D site. To emphasize that CH/π interactions with the aromatic side chains might make a significant contribution to stabilizing the binding of the hydrocarbon in addition to hydrophobic forces, this binding site has been referred to as the “aromatic box”. ,, …”

Section: Particulate Methane Monooxygenase: Protein Structure Active ...mentioning

confidence: 99%

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Alkane Oxidation: Methane Monooxygenases, Related Enzymes, and Their Biomimetics

et al. 2017

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Methane monooxygenases (MMOs) mediate the facile conversion of methane into methanol in methanotrophic bacteria with high efficiency under ambient conditions. Because the selective oxidation of methane is extremely challenging, there is considerable interest in understanding how these enzymes carry out this difficult chemistry. The impetus of these efforts is to learn from the microbes to develop a biomimetic catalyst to accomplish the same chemical transformation. Here, we review the progress made over the past two to three decades toward delineating the structures and functions of the catalytic sites in two MMOs: soluble methane monooxygenase (sMMO) and particulate methane monooxygenase (pMMO). sMMO is a water-soluble three-component protein complex consisting of a hydroxylase with a nonheme diiron catalytic site; pMMO is a membrane-bound metalloenzyme with a unique tricopper cluster as the site of hydroxylation. The metal cluster in each of these MMOs harnesses O to functionalize the C-H bond using different chemistry. We highlight some of the common basic principles that they share. Finally, the development of functional models of the catalytic sites of MMOs is described. These efforts have culminated in the first successful biomimetic catalyst capable of efficient methane oxidation without overoxidation at room temperature.

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“…Given the attractive features of P450 BM3, the enzyme has garnered significant attention and has been the subject of numerous reviews highlighting its exceptional properties and characteristics. Reviews have been conducted on various aspects of P450 BM3, including structural and mechanistic details, − hydroxylation, ,,− pharmaceutical compound hydroxylation, ,− epoxidation, ,,, and carbene/nitrene transfer. ,,,,,,− Additionally, studies have explored the use of decoy molecules to improve enzymatic activity, ,,,,,,− as well as P450 BM3-inorganic complexes. − Reviews of P450 BM3 frequently place it within a broader context of other P450 enzymes, resulting in a lack of focus. Though some reviews do describe reactions catalyzed by P450 BM3 variants, they are typically limited to discussion of the “best” variants for a given reaction and do not offer a comprehensive review of reported variants.…”

Section: P450 Bm3: Properties and Limitationsmentioning

confidence: 99%

Choose Your Own Adventure: A Comprehensive Database of Reactions Catalyzed by Cytochrome P450 BM3 Variants

Fansher,

Besna,

Fendri

et al. 2024

ACS Catal.

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Cytochrome P450 BM3 monooxygenase is the topic of extensive research as many researchers have evolved this enzyme to generate a variety of products. However, the abundance of information on increasingly diversified variants of P450 BM3 that catalyze a broad array of chemistry is not in a format that enables easy extraction and interpretation. We present a database that categorizes variants by their catalyzed reactions and includes details about substrates to provide reaction context. This database of >1500 P450 BM3 variants is downloadable and machine-readable and includes instructions to maximize ease of gathering information. The database allows rapid identification of commonly reported substitutions, aiding researchers who are unfamiliar with the enzyme in identifying starting points for enzyme engineering. For those actively engaged in engineering P450 BM3, the database, along with this review, provides a powerful and user-friendly platform to understand, predict, and identify the attributes of P450 BM3 variants, encouraging the further engineering of this enzyme.

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Controlled oxidation of aliphatic CH bonds in metallo-monooxygenases: Mechanistic insights derived from studies on deuterated and fluorinated hydrocarbons

Cited by 11 publications

References 148 publications

Selective Oxidation of Simple Aromatics Catalyzed by Nano-Biomimetic Metal Oxide Catalysts: A Mini Review

Selective Oxidation of Simple Aromatics Catalyzed by Nano-Biomimetic Metal Oxide Catalysts: A Mini Review

Alkane Oxidation: Methane Monooxygenases, Related Enzymes, and Their Biomimetics

Choose Your Own Adventure: A Comprehensive Database of Reactions Catalyzed by Cytochrome P450 BM3 Variants

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