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Artificial photosynthesis: Hybrid systems

Ni, Y. (author), Hollmann, F. (author)

Oxidoreductases are promising catalysts for organic synthesis. To sustain their catalytic cycles they require efficient supply with redox equivalents. Today classical biomimetic approaches utilizing natural electron supply chains prevail but artificial regeneration approaches bear the promise of simpler and more robust reaction schemes....

book chapter 2016

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Natural deep eutectic solvents as performance additives for biocatalysis

Erol, Özlem (author), Hollmann, F. (author)

Following ionic liquids, (natural) deep eutectic solvents ((NA)DES) are receiving significant attention as performance additives for biocatalytic reactions. (NA)DES are increasingly evaluated as solvents to replace water in hydrolase-catalyzed esterification reactions thereby shifting the reaction equilibrium. They also frequently outperform...

book chapter 2021

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Synthesis of vinyl polymers via enzymatic oxidative polymerisation

Zhang, W. (author), Hollmann, F. (author)

Enzymatic methods for the polymerisation of vinyl monomers are presented and critically discussed. Vinyl monomers can be polymerised initiated by enzyme-catalysed radical formation. The most widely used initiators for this purpose are β-diketo compounds, which can be transformed into the corresponding radicals via peroxidase- or laccase...

book chapter 2019

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Protection strategies for biocatalytic proteins under plasma treatment

Yayci, Abdulkadir (author), Dirks, Tim (author), Kogelheide, Friederike (author), Alcalde, Miguel (author), Hollmann, F. (author), Awakowicz, Peter (author), Bandow, Julia E. (author)

In plasma-driven biocatalysis, enzymes are employed to carry out reactions using species generated by non-thermal plasmas as the precursors. We have previously demonstrated that this is feasible in principle, but that the approach suffers from the short lifetime of the biocatalyst under operating conditions. In this work, protection...

journal article 2020

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Pilot-scale production of peroxygenase from agrocybe aegerita

Tonin, F. (author), Tieves, F. (author), Willot, S.J. (author), Van Troost, Anouska (author), van Oosten, R.J.C. (author), Breestraat, Stefaan (author), Van Pelt, Sander (author), Alcalde, Miguel (author), Hollmann, F. (author)

The pilot-scale production of the peroxygenase from Agrocybe aegerita (rAaeUPO) is demonstrated. In a fed-batch fermentation of the recombinant Pichia pastoris, the enzyme was secreted into the culture medium to a final concentration of 0.29 g L-1 corresponding to 735 g of the peroxygenase in 2500 L of the fermentation broth after 6 days. Due...

journal article 2021

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Optimization and Engineering of Fatty Acid Photodecarboxylase for Substrate Specificity

Santner, Paul (author), Szabó, László Krisztián (author), Chanquia, Santiago Nahuel (author), Merrild, Aske Høj (author), Hollmann, F. (author), Kara, S. (author), Eser, Bekir Engin (author)

Fatty acid photodecarboxylase (FAP) is one of the few photoenzymes in nature. The ability of FAP to convert fatty acids into alka(e)nes without the need for reducing equivalents put this enzyme into spotlight for biocatalytic applications. Although it has been discovered only a few years ago, many studies already emerged demonstrating its...

journal article 2021

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Two (Chemo)-enzymatic cascades for the production of opposite enantiomers of chiral azidoalcohols

Calderini, Elia (author), Süss, Philipp (author), Hollmann, F. (author), Wardenga, Rainer (author), Schallmey, Anett (author)

Multi-step cascade reactions have gained increasing attention in the biocatalysis field in recent years. In particular, multi-enzymatic cascades can achieve high molecular complexity without workup of reaction intermediates thanks to the enzymes’ intrinsic selectivity; and where enzymes fall short, organo-or metal catalysts can further expand...

journal article 2021

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Enzyme engineering for biocatalysis

Paul, C.E. (author), Hanefeld, U. (author), Hollmann, F. (author), Qu, Ge (author), Yuan, Bo (author), Sun, Zhoutong (author)

Contemporary Biocatalysis heavily relies on enzyme engineering as natural enzymes frequently lack the requisite attributes for effective organic synthesis. The inherent limitations in stability, catalytic activity, and selectivity of wild-type enzymes often hinder their suitability for chemical synthesis. Over the past 25 years, there has...

journal article 2024

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Peroxygenase-Catalysed Selective Oxidation of Silanes to Silanols

Xu, X. (author), van Hengst, J.M.A. (author), Mao, Yejia (author), Martinez, Mireia (author), Roda, Sergi (author), Floor, Martin (author), Guallar, Victor (author), Paul, C.E. (author), Alcalde, Miguel (author), Hollmann, F. (author)

A peroxygenase-catalysed hydroxylation of organosilanes is reported. The recombinant peroxygenase from Agrocybe aegerita (AaeUPO) enabled efficient conversion of a broad range of silane starting materials in attractive productivities (up to 300 mM h⁻¹), catalyst performance (up to 84 s⁻¹ and more than 120 000 catalytic...

journal article 2023

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Photoelectrocatalytic N₂ fixation and C-H oxyfunctionalization driven by H₂O oxidation

Kim, Chang Hyun (author), Kim, Jinhyun (author), Hollmann, F. (author), Park, Chan Beum (author)

Solar-driven N₂ fixation offers a green alternative to the highly energy-intensive Haber-Bosch process that releases more than 300 million metric tons of CO₂ annually to form NH₃. However, N₂-reducing photoelectrochemical (PEC) studies have not elucidated how an oxidation reaction affects the N<sub...

journal article 2023

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Towards preparative peroxygenase-catalyzed oxyfunctionalization reactions in organic media

Fernandez Fueyo, E. (author), Ni, Y. (author), Gomez Baraibar, A. (author), Alcalde, Miguel (author), van Langen, L.M. (author), Hollmann, F. (author)

The peroxygenase from Agrocybe aegerita (AaeUPO) has been evaluated for stereoselective oxyfunctionalization chemistry under non-aqueous reaction conditions. The stereoselective hydroxylation of ethylbenzene to (R)-1-phenylethanol was performed in neat substrate as reaction medium together with the immobilized biocatalyst and <sup>tert</sup...

journal article 2016

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A survey of synthetic nicotinamide cofactors in enzymatic processes

Paul, C.E. (author), Hollmann, F. (author)

Synthetic nicotinamide cofactors are analogues of the natural cofactors used by oxidoreductases as redox intermediates. Their ability to be fine-tuned makes these biomimetics an attractive alternative to the natural cofactors in terms of stability, reactivity, and cost. The following mini-review focuses on the current state of the art of...

journal article 2016

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Light-driven enzymatic decarboxylation

Köninger, Katharina (author), Grote, Marius (author), Zachos, Ioannis (author), Hollmann, F. (author), Kourist, Robert (author)

Oxidoreductases belong to the most-applied industrial enzymes. Nevertheless, they need external electrons whose supply is often costly and challenging. Recycling of the electron donors NADH or NADPH requires the use of additional enzymes and sacrificial substrates. Interestingly, several oxidoreductases accept hydrogen peroxide as electron...

journal article 2016

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Continuous-flow CvFAP photodecarboxylation of palmitic acid under environmentally friendly conditions

Benincá, Luiza A.D. (author), França, Alexandre S. (author), Brêda, Gabriela C. (author), Leão, Raquel A.C. (author), Almeida, Rodrigo V. (author), Hollmann, F. (author), de Souza, Rodrigo O.M.A. (author)

The fatty acid photodecarboxylase from Chlorella variabilis NC64A (CvFAP) promotes the elimination of CO₂ from fatty acids (C_n) producing the corresponding hydrocarbon (_Cn-1). Therefore, this enzyme is of great biotechnological interest since it can be used in alternative biofuel production routes matching the...

journal article 2022

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Deazaflavins as photocatalysts for the direct reductive regeneration of flavoenzymes

van Schie, M.M.C.H. (author), Younes, S.H.H. (author), Rauch, M.C.R. (author), Pesic, M. (author), Paul, C.E. (author), Arends, I.W.C.E. (author), Hollmann, F. (author)

Deazaflavins are potentially useful redox mediators for the direct, nicotinamide-independent regeneration of oxidoreductases. Especially the O₂-stability of their reduced forms have attracted significant interest for the regeneration of monooxygenases. In this contribution we further investigate the photochemical properties of...

journal article 2018

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Mirror, mirror on the wall which is the greenest of them all? A critical comparison of chemo- and biocatalytic oxyfunctionalisation reactions

Wu, Y. (author), Paul, C.E. (author), Hollmann, F. (author)

This review article critically compares two widely used types of catalysis, chemo- and biocatalysis, and provides insights on their greenness according to specified parameters. A comparative analysis of the environmental impact of chemo- and biocatalytic oxyfunctionalisation reactions based on published experimental data reveals that both...

journal article 2023

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Selective Oxyfunctionalisation Reactions Driven by Sulfite Oxidase-Catalysed In Situ Generation of H₂O₂

van Schie, M.M.C.H. (author), Kaczmarek, Alexander T. (author), Tieves, F. (author), Gomez de Santos, Patricia (author), Paul, C.E. (author), Arends, I.W.C.E. (author), Alcalde, Miguel (author), Schwarz, Günter (author), Hollmann, F. (author)

H₂O₂ can be accepted by several peroxygenases as a clean oxidant, able to supply both the necessary electrons and oxygen atom at the same time. The biocatalysts, in turn, are able to catalyse an array of interesting oxygen insertion reactions at enantio- and regio-selectivities hard to attain with classical chemical...

journal article 2020

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Whole-Cell Photoenzymatic Cascades to Synthesize Long-Chain Aliphatic Amines and Esters from Renewable Fatty Acids

Cha, Hee Jeong (author), Hwang, Se Yeun (author), Lee, Da Som (author), Kumar, Akula Ravi (author), Kwon, Yong Uk (author), Voß, Moritz (author), Schuiten, Eva (author), Bornscheuer, Uwe T. (author), Hollmann, F. (author)

Long-chain aliphatic amines such as (S,Z)-heptadec-9-en-7-amine and 9-aminoheptadecane were synthesized from ricinoleic acid and oleic acid, respectively, by whole-cell cascade reactions using the combination of an alcohol dehydrogenase (ADH) from Micrococcus luteus, an engineered amine transaminase from Vibrio fluvialis (Vf-ATA), and a...

journal article 2020

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FOx News: Towards Methanol-driven Biocatalytic Oxyfunctionalisation Reactions

Willot, S.J. (author), Hoang, Manh Dat (author), Paul, C.E. (author), Alcalde, Miguel (author), Arends, I.W.C.E. (author), Bommarius, Andreas S. (author), Bommarius, Bettina (author), Hollmann, F. (author)

The novel formate oxidase from Aspergillus oryzae (AoFOx) is a useful catalyst to promote H₂O₂-dependent oxyfunctionalisation reactions. In this contribution we exploit the substrate promiscuity of AoFOx to fully oxidise methanol and formaldehyde to CO₂ and drive peroxygenase-catalysed stereoselective...

journal article 2020

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Stereoselective double reduction of 3-methyl-2-cyclohexenone by use of palladium and platinum nanoparticles in tandem with alcohol dehydrogenase

Coccia, F. (author), Tonucci, Lucia (author), Del Boccio, Piero (author), Caporali, Stefano (author), Hollmann, F. (author), D’Alessandro, Nicola (author)

The combination of metal nanoparticles (Pd or Pt NPs) with NAD-dependent thermostable alcohol dehydrogenase (TADH) resulted in the one-flask catalytic double reduction of 3-methyl-2-cyclohexenone to 3-(1S,3S)-methylcyclohexanol. In this article some assumptions about the interactions between a chemocatalyst and a biocatalyst have been...

journal article 2018