Biomimetic Catalytic and Sensing Cascades Built with Two Designer Bolaamphiphilic Self-Assemblies

A system performing both a catalytic hydrolysis reaction and the direct optical monitoring of the product was created by the combination of two bolaamphiphile self-assemblies. Two bolaamphiphilic self-assemblies were applied as a biomimetic catalyst of p-nitrophenyl acetate (p-NPA) hydrolysis and an optical sensor probe that detects p-NPA hydrolysis through photoluminescence quenching by p-nitrophenol (p-NP), the product of p-NPA hydrolysis. One bolaamphiphilic self-assembly with a histidine moiety catalytically hydrolyzed the p-NPA substrate, and the other self-assembly of tyrosyl bolaamphiphile monitored the product of p-NP by photoluminescence quenching. The progression of the reaction and quenching degree were adjusted by controlling the quantity of histidyl and tyrosyl self-assemblies, respectively. The reaction and subsequent sensing cascade could be interrupted by a reducing agent. The addition of NaBH4 induced the chemical conversion of p-NP to p-aminophenol, which retarded photoluminescence quenching. Thus, it was demonstrated that hydrolysis of an organic substrate and subsequent monitoring of the hydrolysis reaction could be achieved through a combination of independent bolaamphiphilic self-assemblies. This study demonstrated the construction of a catalytic reaction and detection system incorporating designer biomimetic self-assemblies whose functionalities were devised to realize deliberate functions.