Organocatalytic Microfluidic Double‐Layer Capacitors

Article Article scientifique Article Organocatalytic Microfluidic Double‐Layer Capacitors eng 2025-09-21 2025-11-03 author Guo Shenyi Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.,National Centre of Competence in Research (NCCR) Molecular Systems Engineering, Basel, Switzerland. 416404 Chimie organique (groupe 1) (CHOR1) author Paraja Miguel Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.,National Centre of Competence in Research (NCCR) Molecular Systems Engineering, Basel, Switzerland. 909609 Chimie organique (groupe 1) (CHOR1) author Jozeliunaite Augustina Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.,National Centre of Competence in Research (NCCR) Molecular Systems Engineering, Basel, Switzerland. 405376 author Gallardo Villagran Manuel Angel Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.,National Centre of Competence in Research (NCCR) Molecular Systems Engineering, Basel, Switzerland. 419526 author Zhang Qingxia Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.,National Centre of Competence in Research (NCCR) Molecular Systems Engineering, Basel, Switzerland. 416770 Chimie organique (groupe 1) (CHOR1) author Marsalek Alenka Ludmila Marie Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.,National Centre of Competence in Research (NCCR) Molecular Systems Engineering, Basel, Switzerland. 897641 Chimie organique (groupe 1) (CHOR1) author Sakai Naomi 0000-0002-9460-1944 Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.,National Centre of Competence in Research (NCCR) Molecular Systems Engineering, Basel, Switzerland. 131140 Département de chimie organique (CHIOR) author Matile Stefan 0000-0002-8537-8349 Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.,National Centre of Competence in Research (NCCR) Molecular Systems Engineering, Basel, Switzerland. 129654 Département de chimie organique (CHIOR) e202517078 10.1002/anie.202517078 40977072 1433-7851 PMC12582001 https://onlinelibrary.wiley.com/doi/10.1002/anie.202517078 Ideas to use external electric fields to enable, accelerate and direct the movement of electrons during chemical reactions are not new. Theory and experiments under special conditions predict that electric-field catalysis (EFC) from externally applied fields could change the way we make molecules. The challenge is the incompatibility with organic synthesis under scalable bulk conditions. Access to applied electric fields (AEFs) > 1 V nm<sup>-1</sup> , predicted as necessary for direct transition-state stabilization, is not possible even with electromicrofluidic systems, where the distance between the plate electrodes is minimized. Therefore, we decided to shift our attention from the applied fields to their consequences. We consider electrical double layers (EDLs) that form within a few nanometers from the plate electrodes as engineerable supramolecular electrodes. Applying lessons from cell-penetrating peptides (CPPs), we report supramolecular electrodes with effective electric fields (EEFs) that exceed applied fields by more than five million. According to a proline-catalyzed aldol condensation installed as benchmark reaction, those engineered from polyarginine and pyrenebutyrate are most active for EFC, exactly as in cellular uptake. With the best supramolecular electrodes, EFC triples the yield of one of the most optimized reactions in organocatalysis. New methods to access scalable EFC open up broad perspectives in organic synthesis and beyond. Arginine Electrical double layer Electric‐field catalysis Enamine chemistry Flow chemistry Organocatalysis Polyarginine Dewey 540 Swiss National Science Foundation Translational Dynamic Covalent Exchange Cascades (TIMEUP) 209190 CH Swiss National Science Foundation NCCR MSE: Molecular Systems Engineering (phase III) 205608 CH Swiss National Science Foundation Synthetic Supramolecular Systems at Work 204175 CH 36 Département de chimie organique 141 false 761 Groupe Matile https://doi.org/10.5281/zenodo.17052869 Angewandte Chemie 64 45 4d269653-16f5-45da-93dc-aca00f1eeb1d Article (Published version) Public file.pdf 1893035 application/pdf CC BY-4.0 7cb7f35ea2c171cefe47f60728903231807dabbf22f7461aced3e300e21f5ce9 openAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie organique

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Organocatalytic Microfluidic Double‐Layer Capacitors	Angewandte Chemie			2025	38	50

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Gallardo Villagran, Manuel Angel