Benchmarking Cationic Monolayer Protected Nanoparticles and Micelles for Phosphate‐Mediated and Nucleotide‐Selective Proton Transfer Catalysis

Abstract

Both micelles and self‐assembled monolayer (SAM)‐protected nanoparticles are capable of efficiently hosting water‐immiscible substrates to carry out organic reactions in aqueous media. Herein, we have analyzed the different catalytic effect of SAM‐protected cationic nanoparticles and cationic surfactants of varying chain length towards base‐catalyzed proton transfer mediated ring‐opening reaction of 5‐nitrobenzisoxazole (NBI) (also known as Kemp Elimination (KE) reaction). We use inorganic phosphate ion or different nucleotide (phosphate‐ligated different nucleoside) as base to promote the reaction on micellar or nanoparticle interface. We find almost 2–3 orders of magnitude higher concentration of surfactants of comparable hydrophobicity required to reach the similar activity which attained by low cationic head group concentration bound on nanoparticle. Additionally, at low concentration of nanoparticle‐bound surfactant or with high surfactant in micellar form, nucleotide‐selectivity has been observed in activating KE reaction unlike free surfactant at low concentration. Finally, we showed enzyme‐mediated nucleotide hydrolysis to generate phosphate ion which in situ upregulate the KE activity much more in GNP‐based system compared to CTAB. Notably, we show a reasonable superiority of SAM‐protected nanoparticles in activating chemical reaction in micromolar concentration of headgroup which certainly boost up application of SAM‐based nanoparticles not only for selective recognition but also as eco‐friendly catalyst.