Chiral Supramolecular Helical Nanozymes with Tunable Screw Pitch and Catalytic Enantioselectivity
Supramolecular helical architectures hold promise for enantioselective catalysis, yet the influence of screw pitch on catalytic performance remains underexplored. Here, we report the construction of right-/left-handed helical nanoribbons (P/M-DAIPA) based on 5-aminoisophthalic acid dimer (DAIPA). Through an alcohol-mediated self-assembly strategy, the average screw pitch was tuned from 360 to 3152 nm. Mechanistic studies revealed that hydrogen-bonding interactions between DAIPA, modulated by alcohol identity and alcohol/water ratios, dictate helical morphology and pitch. Encapsulation of Fe3O4 nanoparticles yielded P-DAIPA-Fe3O4 and M-DAIPA-Fe3O4 nanozymes, which exhibited higher catalytic efficiency toward S-3,4-dihydroxyphenylalanine (DOPA) and R-DOPA, respectively. Notably, catalytic enantioselectivity inversely correlated with screw pitch, achieving selectivity factors from 1.52 to 2.01. Experimental evidence demonstrated that shorter screw pitch enhances adsorption enantioselectivity of R/S-DOPA on the nanozymes, providing mechanistic insight into pitch-dependent asymmetric catalysis. This work deciphers solvent-driven control of supramolecular screw pitch and establishes a framework for engineering chiral nanozymes with tunable enantioselectivity, advancing enantioselective synthesis.