Photoenzymatic cascade reactions: Coupling photocatalytic in-situ generation of hydrogen peroxide with peroxidase-based enzymatic reactions

• Applicant: Dr. Jonathan Bloh
• Subject Area: Biological Process Engineering ; Technical Chemistry
• Term: from 2015 to 2023
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 277634680

• Final Report Year: 2023

Final Report Abstract

The aim of this project was the study of photoenzymatic processes wherein a photocatalyst like TiO2 is combined with a peroxygenase like AaeUPO. Here, the photocatalyst produces H2O2 in-situ, which is then consumed by the enzyme. For the optimization of this hybrid system, first the kinetics of the individual components (photocatalyst and enzyme) have been studied in detail in dependence of various reaction conditions und described with a kinetic model. Additionally, different photocatalyst materials have been evaluated concerning their suitability for this system. In particular, polymeric carbon nitride materials with phosphate modification as well as antraquinone-loaded titanium dioxide were found to be excellent candidates for this purpose. The enzyme was also improved in its stability by immobilization. With these optimized components and the kinetic model, the process could be vastly optimized, so that the relevant indicators photonic efficiency, product formation rate and turnover number of the enzyme were each improved by orders of magnitude. This project has also developed the tools needed to optimize other processes in a similar manner.

Publications

• Formation of hydrogen peroxide via heterogeneous photocatalysis, IPS-21 Conference, 2016, St. Petersburg (Russland).
  Burek, B. O.; Bahnemann, D. W. & Bloh, J. Z.
  
• Photocatalytic in-situ formation of hydrogen peroxide for enzymatic reactions, IPS-21 Conference, 2016, St. Petersburg (Russland).
  Burek, B. O. & Bloh, J.Z.
  
• Photocatalytic In-situ Formation of Hydrogen Peroxide for Peroxidase Enzymes. SPEA9 Conference, 2016, Strasbourg (Frankreich).
  Burek, B.O. & Bloh, J. Z.
  
• Coated Wireless Light Emitters for Efficient Up Scaling of Photocatalytic Processes, ACA VI Conference, 2017, Belgrad (Serbien).
  Burek, B. O., Bahnemann, D. W. & Bloh, J. Z.
  
• Coated Wireless Light Emitters for Efficient Up Scaling of Photocatalytic Processes. SP-6 Conference, 2017, Oldenburg.
  Burek, B. O.; Bahnemann, D. W. & Bloh, J. Z.
  
• Completely integrated wirelessly-powered photocatalyst-coated spheres as a novel means to perform heterogeneous photocatalytic reactions. Catal. Sci. Technol., 7(21), 4977-4983.
  Burek, B. O.; Sutor, A.; Bahnemann, D. W. & Bloh, J. Z.
  
• Drahtlos betreibbare Leuchte zur Anregung lichtgetriebener chemischer Reaktionen in einem Reaktionsgefäß, Verfahren zu deren Herstellung und Vorrichtung mit einer solchen Leuchte, DE102017109687, 2017.
  Burek, B. O. & Bloh, J. Z.
  
• Photocatalytic in situ Hydrogen Peroxide Production for Biocatalysis based on Peroxidases, SP-6 Conference, 2017, Oldenburg.
  Burek, B. O.; Bahnemann, D. W. & Bloh, J. Z.
  
• Selective Activation of C−H Bonds in a Cascade Process Combining Photochemistry and Biocatalysis. Angewandte Chemie International Edition, 56(48), 15451-15455.
  Zhang, Wuyuan; Burek, Bastien O.; Fernández‐Fueyo, Elena; Alcalde, Miguel; Bloh, Jonathan Z. & Hollmann, Frank
  
• Using heterogeneous photocatalysis for cofactor regeneration of coupled enzymatic reactions, EMN Catalysis, 2017, Dubrovnik (Kroatien).
  Burek, B. O., Bahnemann, D. W. & Bloh, J. Z.
  
• Coupling Peroxidase Enzymes with Photocatalytic Hydrogen Peroxide Production, CIMTEC 2018, Perugia (Italien).
  Burek, B. O., Bahnemann, D. W. & Bloh, J. Z.
  
• Modeling and Optimization of the Photocatalytic Reduction of Molecular Oxygen to Hydrogen Peroxide over Titanium Dioxide. ACS Catalysis, 9(1), 25-37.
  Burek, Bastien O.; Bahnemann, Detlef W. & Bloh, Jonathan Z.
  
• Photocatalyst-Coated Wireless Light Emitters for Efficient Up-Scaling of Photocatalytic Processes. Reaktionstechnik Jahrestagung 2018, Würzburg.
  Burek, B. O.; Sutor, A. & Bloh, J. Z.
  
• Selective Activation of C-H Bonds in a Combined Photo-Enzymatic Process. IPS-22 Conference, 2018, Hefei (China).
  Burek, B. O., Bahnemann, D. W. & Bloh, J. Z.
  
• A Holistic Approach to Model the Kinetics of Photocatalytic Reactions. Frontiers in Chemistry, 7.
  Bloh, Jonathan Z.
  
• A holistic approach to model the kinetics of photocatalytic reactions. SP-7 Conference, 2019, Mailand (Italien).
  Bloh, J. Z.
  
• Hydrogen peroxide driven biocatalysis. Green Chemistry, 21(12), 3232-3249.
  Burek, B. O.; Bormann, S.; Hollmann, F.; Bloh, J. Z. & Holtmann, D.
  
• Kinetic effects and oxidation pathways of sacrificial electron donors on the example of the photocatalytic reduction of molecular oxygen to hydrogen peroxide over illuminated titanium dioxide. Catalysis Today, 335, 354-364.
  Burek, Bastien O.; Timm, Jana; Bahnemann, Detlef W. & Bloh, Jonathan Z.
  
• Photoenzymatic Hydroxylation of Ethylbenzene Catalyzed by Unspecific Peroxygenase: Origin of Enzyme Inactivation and the Impact of Light Intensity and Temperature. ChemCatChem, 11(13), 3093-3100.
  Burek, Bastien O.; de Boer, Sabrina R.; Tieves, Florian; Zhang, Wuyuan; van Schie, Morten; Bormann, Sebastian; Alcalde, Miguel; Holtmann, Dirk; Hollmann, Frank; Bahnemann, Detlef W. & Bloh, Jonathan Z.
  
• Photoenzymatic Cascade Reactions: Photocatalytic in situ Hydrogen Peroxide Production for Biocatalysis based on Peroxidases, SPEA11, 2022, Turin (Italien).
  Wegstein, D., Burek, B. O. & Bloh, J.Z.
  
• Strategies to overcome efficiency loss of photocatalytic reactions at high light intensity using kinetic analysis and optimized reactor concepts. SPASEC-22, 2022, Rostock.
  Bloh, J. Z.
  
• Photocatalytic Synthesis of Hydrogen Peroxide from Molecular Oxygen and Water. Topics in Current Chemistry, 381(4).
  Garcia-Munoz, Patricia; Valenzuela, Laura; Wegstein, Deborah; Schanz, Tobias; Lopez, Girlie Eunice; Ruppert, Agnieszka M.; Remita, Hynd; Bloh, Jonathan Z. & Keller, Nicolas
  
• Robust Light Driven Enzymatic Oxyfunctionalization via Immobilization of Unspecific Peroxygenase. ChemSusChem, 16(23).
  De Santis, Piera; Wegstein, Deborah; Burek, Bastien O.; Patzsch, Jacqueline; Alcalde, Miguel; Kroutil, Wolfgang; Bloh, Jonathan Z. & Kara, Selin
  
• The Importance of Precise Reaction Condition Control for the Comparison of Photocatalyst Materials on the Example of Hydrogen Peroxide Formation over Polymeric Carbon Nitrides. ChemPhotoChem, 7(11).
  Wegstein, Deborah; Zaim, Abdelkarim; Burek, Bastien O. & Bloh, Jonathan Z.