Electro-enzymatic hydroxylation of ethylbenzene by the evolved unspecific peroxygenase of Agrocybe aegerita

Horst, Andréa; Bormann, Sebastian; Meyer, Johanna; Steinhagen, Max; Ludwig, Roland; Drews, Anja; Ansorge‐Schumacher, Marion B.; Holtmann, Dirk

doi:10.1016/j.molcatb.2016.12.008

Cited by 58 publications

(44 citation statements)

References 29 publications

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“…[161,162] They can be activated by H 2 O 2 to form ac atalytically reactive oxo-ferryl species.H owever,o wing to oxidative degradation of their catalytic heme moiety by concentrated H 2 O 2 ,i nsitu generation of H 2 O 2 is required for the application of peroxygenases. This challenge has been accomplished by in situ generation of H 2 O 2 through partial reduction of molecular O 2 via enzymatic, [163][164][165][166][167] chemical, [168,169] electrochemical, [170][171][172][173][174] photochemical, [175][176][177] or photoelectrochemical [178] methods.P hotochemical H 2 O 2 generation in situ is advantageous in terms of operational stability,a llowing higher substrate conversion compared to the addition of ad iluted H 2 O 2 solution. The Hollmann group developed ap hotochemical in situ H 2 O 2 generation platform using flavins (e.g.,F AD,F MN,o r riboflavin) as ap hotocatalyst.…”

Section: Hemoprotein Activation By Photochemically Generated H 2 Omentioning

confidence: 99%

Photobiocatalysis: Activating Redox Enzymes by Direct or Indirect Transfer of Photoinduced Electrons

et al. 2018

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Biocatalytic transformation has received increasing attention in the green synthesis of chemicals because of the diversity of enzymes, their high catalytic activities and specificities, and mild reaction conditions. The idea of solar energy utilization in chemical synthesis through the combination of photocatalysis and biocatalysis provides an opportunity to make the "green" process greener. Oxidoreductases catalyze redox transformation of substrates by exchanging electrons at the enzyme's active site, often with the aid of electron mediator(s) as a counterpart. Recent progress indicates that photoinduced electron transfer using organic (or inorganic) photosensitizers can activate a wide spectrum of redox enzymes to catalyze fuel-forming reactions (e.g., H evolution, CO reduction) and synthetically useful reductions (e.g., asymmetric reduction, oxygenation, hydroxylation, epoxidation, Baeyer-Villiger oxidation). This Review provides an overview of recent advances in light-driven activation of redox enzymes through direct or indirect transfer of photoinduced electrons.

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Section: Hemoprotein Activation By Photochemically Generated H 2 Omentioning

confidence: 99%

Photobiocatalysis: Activating Redox Enzymes by Direct or Indirect Transfer of Photoinduced Electrons

et al. 2018

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“…Methanol is an attractive electron donor since formaldehyde and formate are oxidized very fast, and therefore gaseous CO 2 is the only significant side product which leaves the reaction mixture and does not further complicate the downstream processing. The enzymatic reaction is studied very well and therefore allows for a good comparison …”

Section: Introductionmentioning

confidence: 98%

“…Many strategies are known for a H 2 O 2 supply in adequate concentrations, especially in situ generation by reduction of molecular oxygen is often applied e. g. via chemical, enzymatic, electrochemical or photochemical approaches to alleviate the instability issue, see Table S4 for a detailed comparison of the methods on the example of Aae UPO catalyzed hydroxylation of ethylbenzene.…”

Section: Introductionmentioning

confidence: 99%

Photoenzymatic Hydroxylation of Ethylbenzene Catalyzed by Unspecific Peroxygenase: Origin of Enzyme Inactivation and the Impact of Light Intensity and Temperature

et al. 2019

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Photoenzymatic cascades can be used for selective oxygenation of C−H‐Bonds under mild conditions circumventing the hydrogen peroxide mediated peroxygenase inactivation via in situ H2O2 generation. Here, we report the “on demand” production of hydrogen peroxide via methanol assisted reduction of molecular oxygen using UV‐illuminated titanium dioxide (Aeroxide P25) combined with the enantioselective hydroxylation of ethylbenzene to (R)‐1‐phenylethanole catalyzed by the Unspecific Peroxygenase from Agrocybe Aegerita. For the application of the system it is important to understand the influence of the reaction parameters to be able to optimize the system. Therefore, we systematically investigated product formation and enzyme inactivation as well as ROS formation (H2O2, .OH and .O2−) applying different light intensities and temperatures. As a result, Turnover Numbers up to 220 000, photonic efficiencies up to 13.6 % and production rates up to 0.9 mM h−1 were achieved.

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“…[54] Bei Bestrahlung mit sichtbarem Licht und einer angelegten Vorspannung von 1.2 Vextrahierte die Peroxygenasen besitzen eine prosthetische Häm-Gruppe, die von einem Cysteinliganden koordiniert ist und eine Vielzahl von Oxyfunktionalisierungen katalysiert. [161,162] [163][164][165][166][167] chemische, [168,169] elektrochemische, [170][171][172][173][174] photochemische [175][176][177] oder photoelektrochemische [178] [183] Durch die räumliche Tr ennung der Kompartimente zur Kofaktor-Regenerierung und zur enzymatischen Synthese, [184] oder durch die Immobilisierung des Elektronenmediators auf Gerüstmaterialien (wie beispielsweise auf Fasern aus Kohlenstoffnanorçhren [185] [190] Aktuelle Fortschritte auf dem Gebiet der synthetischen Biologie aufgrund eines theoretischen De-novo-Designs bieten Perspektiven zur Entwicklung robuster Enzyme mit verbesserter Aktivitätu nd Stabilität und so zu neuen Mçglichkeiten füri ndustrielle Anwendungen.…”

Section: Angewandte Chemieunclassified

Photobiokatalyse: Aktivierung von Redoxenzymen durch direkten oder indirekten Transfer photoinduzierter Elektronen

et al. 2018

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Biokatalytische Umsetzungen rücken aufgrund der Vielfältigkeit der Enzyme, ihrer hohen katalytischen Aktivität und Spezifität und der milden Reaktionsbedingungen zunehmend in den Fokus einer “grünen” Synthesechemie. Der Ansatz, Sonnenenergie durch Kombination von Photokatalyse und Biokatalyse für die chemische Synthese nutzbar zu machen, bietet eine Möglichkeit, diesen “grünen” Prozess noch nachhaltiger zu gestalten. Oxidoreduktasen katalysieren die Umsetzung verschiedener Substrate durch den Austausch von Elektronen am aktiven Zentrum des Enzyms, meist mithilfe von Elektronenmediatoren. Aktuelle Fortschritte auf diesem Gebiet zeigen, dass photoinduzierter Elektronentransfer unter Einsatz organischer (oder anorganischer) Photosensibilisatoren ein breites Spektrum von Redoxenzymen aktivieren kann, welche in Folge wichtige Brennstoffe liefern (z. B. H2‐Bildung, CO2‐Reduktion) oder synthetisch relevante Reduktionen vermitteln (z. B. asymmetrische Reduktionen, Oxygenierungen, Hydroxylierungen, Epoxidierungen, Bayer‐Villiger‐Oxidation). Dieser Aufsatz gibt einen Überblick über aktuelle Entwicklungen auf dem Gebiet der Photoaktivierung von Redoxenzymen mittels direkter oder indirekter Übertragung photoinduzierter Elektronen.

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Electro-enzymatic hydroxylation of ethylbenzene by the evolved unspecific peroxygenase of Agrocybe aegerita

Cited by 58 publications

References 29 publications

Photobiocatalysis: Activating Redox Enzymes by Direct or Indirect Transfer of Photoinduced Electrons

Photobiocatalysis: Activating Redox Enzymes by Direct or Indirect Transfer of Photoinduced Electrons

Photoenzymatic Hydroxylation of Ethylbenzene Catalyzed by Unspecific Peroxygenase: Origin of Enzyme Inactivation and the Impact of Light Intensity and Temperature

Photobiokatalyse: Aktivierung von Redoxenzymen durch direkten oder indirekten Transfer photoinduzierter Elektronen

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