2-(4-Boronophenyl)quinoline-4-carboxylic acid derivatives: Design and synthesis, aggregation-induced emission characteristics, and binding activity studies for D-ribose with long-wavelength emission

Abstract

Long-wavelength fluorescent sensors with large Stokes shifts show useful applications in chemical biology and clinical laboratory diagnosis. We have recently reported [4-(4-{[3-(4-boronobenzamido)propyl]carbamoyl}quinolin-2-yl)phenyl]boronic acid that can selectively recognize d-ribose in a buffer solution of pH 7.4. However, the short emission wavelength (395 nm) and aggregation-caused quenching effect are not conducive to applications as a sensor. Novel diboronic acid compounds are synthesized using 2-(4-boronophenyl)quinoline-4-carboxylic acid as the building block and p-phenylenediamine as the linker. These compounds show aggregation-induced emission and fluorescence emission at about 500 nm. In addition, after binding to most carbohydrates, the aggregated state of the boronic acid–containing compounds is dissociated, resulting in fluorescence quenching. Using [4-(4-{[4-(3-borono-5-methoxybenzamido)phenyl]carbamoyl}quinoline-2-yl)phenyl]boronic acid as an example, addition of 55 mM of d-ribose resulted in the strongest quenching of 83% for all the tested carbohydrates, indicating selectively recognizing d-ribose. The reciprocal of the fluorescence intensity change showed a good linear relationship with the reciprocal of d-ribose concentration ( R2 ⩾ 0.99), indicating sensor binding to d-ribose in a ratio of 1:1 to form an inclusion complex. The fluorescence emission is red-shifted compared to 2-(4-boronophenyl)quinoline-4-carboxylic acid and its common derivatives, which provides a new method for the development of long-wavelength fluorescent sensors.