Remote electrochemical modulation of pKa in a rotaxane by co-conformational allostery.
Allosteric control, one of Nature's most effective ways to regulate functions in biomolecular machinery, involves the transfer of information between distant sites. The mechanistic details of such a transfer are still an object of intensive investigation and debate, and the idea that intramolecular communication could be enabled by dynamic processes is gaining attention as a complement to traditional explanations. Mechanically interlocked molecules, owing to the particular kind of connection between their components and the resulting dynamic behavior, are attractive systems to investigate allosteric mechanisms and exploit them to develop functionalities with artificial species. We show that the pKa of an ammonium site located on the axle component of a [2]rotaxane can be reversibly modulated by changing the affinity of a remote recognition site for the interlocked crown ether ring through electrochemical stimulation. The use of a reversible ternary redox switch enables us to set the pKa to three different values, encompassing more than seven units. Our results demonstrate that in the axle the two sites do not communicate, and that in the rotaxane the transfer of information between them is made possible by the shuttling of the ring, that is, by a dynamic intramolecular process. The investigated coupling of electron- and proton-transfer reactions is reminiscent of the operation of the protein complex I of the respiratory chain.
['Ragazzon|Giulio|G|', 'Schäfer|Christian|C|', 'Franchi|Paola|P|', 'Silvi|Serena|S|', 'Colasson|Benoit|B|', 'Lucarini|Marco|M|', 'Credi|Alberto|A|0000-0003-2546-9801']
D001665:Binding Sites D004558:Electric Stimulation D055664:Electrochemical Techniques D004579:Electron Transport D004735:Energy Transfer D008956:Models, Chemical D008968:Molecular Conformation D015394:Molecular Structure D011522:Protons D043862:Rotaxanes
acid–base processes electrochemistry free energy change molecular machine molecular switch