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Exploration and exploitation of alloelectronic catalysis

Project description

Mimicking biology’s energy-driven chemistry with ‘alloelectronic’ catalysis

Living systems routinely perform chemical reactions whose kinetic and thermodynamic conditions make them difficult to replicate synthetically. Nature couples these reactions to energy-carrier molecules via allostery – ligand binding adjacent to an active site that modifies the enzyme’s conformation to increase catalytic activity. Realising this capability in synthetic chemistry would be transformative. With the support of the Marie Skłodowska-Curie Actions programme, the AlloElectro project aims to develop an analogous strategy for synthetic metal catalysts, exploiting controlled remote electronic perturbations to dynamically adapt catalytic activity without direct modification of the active site. This ‘alloelectronic’ approach could enable uphill, programmable synthesis using established catalysts and methods.

Objective

The kinetic and thermodynamic rules that govern synthetic chemistry should be considered limitations to overcome. Thermodynamically, spontaneous chemical reactions must proceed energetically downhill. Kinetically, the rate of a reaction is constrained by the slowest chemical step, which limits the extent to which a reaction can accelerated by catalysis. Biology overcomes these limitations by expending energy, coupling the reactions of ‘energy carrier’ molecules to thermodynamically or kinetically unfavourable processes, enabling nitrogen fixation under mild conditions (driven catalysis), ‘uphill’ adenosine triphosphate (ATP) synthesis (endergonic synthesis), and high-fidelity sequence-specific polymerization (programmable synthesis) by the ribosome. Replicating this strategy would be transformative in synthetic chemistry, changing the way that chemists think about and perform synthesis. Crucial to biology’s driven reactivity is allostery, where ligand binding adjacent to an enzyme active site induces a conformational change that modulates catalytic activity. When these conformational changes are driven by the reaction of ‘energy carrier’ molecules at the allosteric site, energy can be transduced to the catalysed reaction to permit nonequilibrium control. Instead of complex conformational changes, the aim of this proposal is to develop and explore alloelectronic catalysis. AlloElectro aims to exploit simple and controlled electronic changes in the ligand field (i.e. at an ‘alloelectronic’ site) of common metal catalysts. Reversible changes in the electronic environment of the ‘active site’ will enable a metal catalyst to adapt to individual elementary steps and overcome them, with the energy input capable of being transduced to drive the catalysed reaction uphill. The alloelectronic effect therefore results in new opportunities for ‘contra-thermodynamic’ reactivity, driven catalysis and programmable synthesis using established catalysts, ligands and methods.

Fields of science (EuroSciVoc)

Keywords

Programme(s)

Topic(s)

Funding Scheme

HORIZON-TMA-MSCA-PF-GF - HORIZON TMA MSCA Postdoctoral Fellowships - Global Fellowships

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Call for proposal

(opens in new window) HORIZON-MSCA-2025-PF

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Coordinator

THE CHANCELLOR MASTERS AND SCHOLARS OF THE UNIVERSITY OF CAMBRIDGE
Net EU contribution
€ 296 098,68
Address
TRINITY LANE THE OLD SCHOOLS
CB2 1TN CAMBRIDGE
United Kingdom
Region
East of England East Anglia Cambridgeshire CC
Activity type
Higher or Secondary Education Establishments
Links
Total cost
No data

Partners (1)