Mediated electron transfer with monooxygenases—Insight in interactions between reduced mediators and the co-substrate oxygen

Tosstorff, Andreas; Dennig, Alexander; Ruff, Anna Joëlle; Schwaneberg, Ulrich; Sieber, Volker; Mangold, Klaus‐Michael; Schrader, Jens; Holtmann, Dirk

doi:10.1016/j.molcatb.2014.06.011

Cited by 24 publications

(23 citation statements)

References 43 publications

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“…Another possible handle could be the choice of electrode material. A recent study, for example, demonstrated that glassy carbon exhibited significantly higher reduction rates with Co sepulchrate than Pt electrodes, together with reduced O 2 reduction rates …”

Section: Ways To Deal With the Oxygen Dilemmamentioning

confidence: 99%

The Oxygen Dilemma: A Severe Challenge for the Application of Monooxygenases?

2016

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Monooxygenases are promising catalysts because they in principle enable the organic chemist to perform highly selective oxyfunctionalisation reactions that are otherwise difficult to achieve. For this, monooxygenases require reducing equivalents, to allow reductive activation of molecular oxygen at the enzymes' active sites. However, these reducing equivalents are often delivered to O2 either directly or via a reduced intermediate (uncoupling), yielding hazardous reactive oxygen species and wasting valuable reducing equivalents. The oxygen dilemma arises from monooxygenases' dependency on O2 and the undesired uncoupling reaction. With this contribution we hope to generate a general awareness of the oxygen dilemma and to discuss its nature and some promising solutions.

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Section: Ways To Deal With the Oxygen Dilemmamentioning

confidence: 99%

The Oxygen Dilemma: A Severe Challenge for the Application of Monooxygenases?

2016

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“…In order to achieve a high productivity in electro-enzymatic processes, ET from mediator to enzyme redox center is one of the most important parameters to achieve the overall goal of high product formation. 69 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 Finally, the presented study evidences how MD simulation is an important tool for a rational process development of electro-enzymatic processes. 70 The more knowledge gained about the process on a molecular level, the more accurate models can be developed, and thereby improved predictions for future designs are possible.…”

Section: Resultsmentioning

confidence: 54%

Unraveling Binding Effects of Cobalt(II) Sepulchrate with the Monooxygenase P450 BM-3 Heme Domain Using Molecular Dynamics Simulations

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Schwaneberg

Holtmann

et al. 2015

J. Chem. Theory Comput.

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One of the major limitations to exploit enzymes in industrial processes is their dependence on expensive reduction equivalents like NADPH to drive their catalytic cycle. Soluble electron transfer (ET) mediators like Cobalt(II)Sepulchrate have been proposed as a cost-effective alternative to shuttle electrons between an inexpensive electron source and enzyme redox center.The interactions of these molecules with enzymes are not elucidated at molecular level yet.

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“…Note that evidences of chemical bonding versus simple adsorption were already reported in this previous work, with using the same batch of enzyme. All the electrochemical characterizations have been performed in the absence of oxygen to avoid any effect on the electrocatalytic reaction …”

Section: Resultsmentioning

confidence: 99%

Molecular and Biological Catalysts Coimmobilization on Electrode by Combining Diazonium Electrografting and Sequential Click Chemistry

et al. 2018

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A generic approach has been developed for sequential heterogeneous surface modification of electrodes. The strategy, which is applicable for a wide range of functional groups, involves two main steps. In the first one, azide‐alkene bifunctionalized electrodes are obtained by electrochemical reduction of a mixture of diazonium salts generated in situ from the corresponding 4‐azidoaniline and 4‐vinylaniline. In that way, we provide reactive sites that are available for further selective functionalization in a sequential process based on ‘click reactions’, in which subsequent immobilization of the targeted molecules is achieved by the azide‐alkyne cycloaddition Huisgen reaction and alkene‐thiol coupling. Feasibility of the method has been first demonstrated for the coimmobilization of two distinct redox moieties (cobaltocenium and ferrocene) as evidenced by cyclic voltammetry and X‐ray photoelectron spectroscopy measurements. The versatility of the sequential method has then been exploited for the coimmobilization of a molecular electrocatalyst [Cp*Rh(bpy) Cl]+ and a biological catalyst, a NAD‐dependent dehydrogenase, that were proved to act in cascade in the electroenzymatic reduction of D‐fructose to D‐sorbitol. Such simple combination of diazonium chemistry and robust chemical reactions (‘click chemistry’) is promising for the environmentally friendly heterogeneous modification of electrodes with multiple chemical and biological catalysts.

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Mediated electron transfer with monooxygenases—Insight in interactions between reduced mediators and the co-substrate oxygen

Cited by 24 publications

References 43 publications

The Oxygen Dilemma: A Severe Challenge for the Application of Monooxygenases?

The Oxygen Dilemma: A Severe Challenge for the Application of Monooxygenases?

Unraveling Binding Effects of Cobalt(II) Sepulchrate with the Monooxygenase P450 BM-3 Heme Domain Using Molecular Dynamics Simulations

Molecular and Biological Catalysts Coimmobilization on Electrode by Combining Diazonium Electrografting and Sequential Click Chemistry

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