Polyfluoroalkyl Chain-Based Assemblies for Biomimetic Catalysis

Amphiphobic fluoroalkyl chains are exploited for creating robust and diverse self-assembled biomimetic catalysts. Long terminal perfluoroalkyl chains (CnF2n+1 with n=6, 8, and 10) linked with a short perhydroalkyl chains (CmH2m with m=2 and 3) were used to synthesize several 1,4,7-triazacyclononane (TACN) derivatives, CnF2n+1-CmH2m-TACN. In the presence of an equimolar amount of Zn2+ ions that coordinate the TACN moiety and drive the self-assembly into micelle-like aggregates, the critical aggregation concentration of polyfluorinated CnF2n+1-CmH2m-TACN & sdot;Zn2+ was lowered by similar to 1 order of magnitude compared to the traditional perhyroalkyl counterpart with identical carbon number of alkyl chain. When 2'-hydroxypropyl-4-nitrophenyl phosphate was used as the model phosphate substrate, polyfluorinated CnF2n+1-CmH2m-TACN & sdot;Zn2+ assemblies showed higher affinity and catalytic activity, compared to its perhyroalkyl chain-based counterpart. Coarse-grained molecular dynamic simulations have been introduced to explore the supramolecular assembly of polyfluoroalkyl chains in the presence of Zn2+ ions and to better understand their enhanced catalytic activity. Polyfluoroalkyl chain-based TACN derivatives were developed to lower their CAC in the presence of equimolar amount of Zn2+ ions to drive the self-assembly and afford high catalytic activity towards the hydrolysis reaction of HPNP, demonstrating the robustness of F-chain assemblies, compared with their perhydroalkyl chain counterparts.image

Automated summary

Amphiphobic fluoroalkyl chains are used to create robust and diverse self-assembled biomimetic catalysts. The addition of zinc ions reduces the critical aggregation concentration and enhances the catalytic activity of the catalyst. Molecular dynamic simulations provide insights into the supramolecular assembly and catalytic activity.