Electrosynthesis of Mussel-inspired Adhesive Polymers as a Novel Class of Transient Enzyme Stabilizers

Tilmann J Neubert; Maximilian M Hielscher; Keven Walter; Carolin M Schröter; Marion Stage; Ruben R Rosencrantz; Felix Panis; Annette Rompel; Kannan Balasubramanian; Siegfried R Waldvogel; Hans G Börner

doi:10.1002/anie.202419684

Electrosynthesis of Mussel-inspired Adhesive Polymers as a Novel Class of Transient Enzyme Stabilizers

Angew Chem Int Ed Engl. 2025 Jan 2:e202419684. doi: 10.1002/anie.202419684. Online ahead of print.

Authors

Tilmann J Neubert^{1

2}, Maximilian M Hielscher³, Keven Walter¹, Carolin M Schröter¹, Marion Stage⁴, Ruben R Rosencrantz^{4

5}, Felix Panis⁶, Annette Rompel⁶, Kannan Balasubramanian^{1

2}, Siegfried R Waldvogel^{3

7

8}, Hans G Börner¹

Affiliations

¹ Humboldt-Universität zu Berlin, Department of Chemistry, Unter den Linden 6, 10117, Berlin, Germany.
² Humboldt-Universität zu Berlin, School of Analytical Sciences Adlershof (SALSA) & IRIS Adlershof, Unter den Linden 6, 10117, Berlin, Germany.
³ Johannes Gutenberg University Mainz, Department of Chemistry, Duesbergweg 10-14, 55128, Mainz, Germany.
⁴ Fraunhofer Institute for Applied Polymer Research IAP, Life Science & Bioprocesses, Geiselbergstraße 69, 14476, Potsdam-Golm, Germany.
⁵ Brandenburg University of Technology BTU, Institute for Materials Chemistry, Chair of Biofunctional Polymermaterials, Universitätsplatz 1, 01968, Senftenberg, Germany.
⁶ Universität Wien, Fakultät für Chemie, Institut für Biophysikalische Chemie, Josef-Holaubek-Platz 2, 1090, Wien, Austria.
⁷ Max-Planck-Institute for Chemical Energy Conversion, Stiftstraße 34-36, 45470, Mülheim an der Ruhr, Germany.
⁸ Karlsruhe Institute of Technology (KIT), Institute of Biological and Chemical Systems-Functional Molecular Systems (IBCS-FMS), Kaiserstraße 12, 76131, Karlsruhe, Germany.

PMID: 39743873
DOI: 10.1002/anie.202419684

Abstract

Multifunctional ortho-quinones are required for the formation of thiol-catechol-connectivities (TCC) but can be delicate to handle. We present the electrochemical oxidation of the dipeptide DiDOPA, achieving up to 92 % conversion efficiency of the catechols to ortho-quinones. Graphite and stainless steel could be employed as cost-efficient electrodes. The electrochemical activation yields quinone-solutions, which are free of undesired reactive compounds and eliminates the challenging step of isolating the reactive quinones. The DiDOPA quinones were employed in polyaddition reactions with multi-thiols, forming oligomers that functioned as transient enzyme stabilizers (TES). These TCC-TES-additives improved the thermal stability and the activity of tyrosinase in heat stress assays.

Keywords: PEGylation; electrosynthesis; green chemistry; peptide adhesive; protein engineering.

Abstract

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