Mechanistically-driven Approaches to Design and Engineer Artificial Metalloenzymes for Sustainable Catalysis
Asst. Prof. Patricia Rodriguez Macia
University of Leicester
Designing efficient catalysts for energy-conversion reactions (e.g., reduction of CO2 into simple carbon-building blocks, reduction of N2 to ammonia and production or oxidation of H2) is essential to solve many major environmental and energy-related problems confronting our planet. In this respect, small-molecule activation (SMA) reactions are crucial for energy sustainability but the chemistry of these reactions is extremely complex and represents huge challenges for industry.1 Metalloenzymes have evolved in nature for billions of years to be able to activate small molecules such as CO2, H2 and N2 with spectacular efficiency and selectivity, only by using earth-abundant metals in their active sites.2 However, their large size, tedious and high cost of preparation hinder their widespread use in biotechnology. Semi-synthetic and artificial metalloenzymes (ArMs) combine the best of two worlds: state-of-the-art transition-metal catalysis with the selectivity and efficiency of natural metalloenzymes, offering an attractive means to develop sustainable biohybrid catalysts for energy-relevant reactions. However, the design and engineering of ArMs is complex.3 Therefore, approaches providing mechanistic insight to inform design of enhanced ArMs are needed. For example, direct electrochemistry tools, such as protein film electrochemistry (PFE), offer valuable insight into the redox properties of metalloenzymes. However, such detailed characterisation approaches remain scarce in ArM design campaigns. In this talk, I will show how a suite of structural, spectroscopic and electrochemical techniques has been used to mechanistically characterise newly developed semi-synthetic and artificial metalloenzymes, and how the acquired mechanistic information has been fed into the development of design criteria for the generation of tailored ArMs with target applications in electrocatalysis. Overall, this work provides a tool-box of mechanistically-driven approaches for design of biohybrid catalysts for energy relevant transformations
References
- A. A. Salamatian, K. L. Bren, FEBS Letters 2023, 597, 174-190
- J. M.Le, K. L. Bren, ACS Energy Letters 2019, 4, 2168-2180
- C. Van Stappen, Y. Deng, Y. Liu, H. Heidari, J.-X. Wang, Y. Zhou, A. P. Ledray, Y. Lu, Chem. Rev. 2022, 122, 11974-12045