Highly sensitive enantioselective spectrofluorimetric determination of R-/S-mandelic acid using l-tryptophan-modified amino-functional silica-coated N-doped carbon dots as novel high-throughput chiral nanoprobes

Abstract

Amino-functional silica-coated N-doped carbon dots (NH₂-SiO₂-CDs) were covalently modified by l-tryptophan (chiral selector) by producing an amide bond between carboxyl groups of L-try and amino groups of NH₂-SiO₂-CDs to develop a novel high throughput chiral nanoprobes (L-try-CONH-SiO₂-CDs) for highly sensitive and enantioselective quantification of S-/R-mandelic acid (S-/R-Man). The method showed a great difference between S- and R-isomers (enantioselectivity coefficient = 4.17) due to the ultra-stability of the Meisenheimer complex that was formed between S-isomer and nanoprobe (K_S-Man/K_R-man = 2122.7, where K is the binding-constant). At optimal experimental conditions, two linear ranges of 0.5-25.0 (LOD of 0.05 μM) and 0.5-22.0 μM (LOD of 0.27 μM) for S- and R-Man, respectively, along with an enhanced sensitivity toward S-isomer (about 5.7-fold higher than R-isomer) were attained. High selectivity for the determination of mandelic acid was achieved compared to metal ions, amino acids, and sugars that commonly coexist with it. Intra-day as well as inter-day assays, respectively, showed RSD values of about 3.2 and 3.9%. The mechanistic studies were performed for proving the enantioselective behavior of the developed nanoprobe. The method was then used for S-/R-mandelic acid determination in bio-samples. The figures of merit for the method were found to be better than those already reported for enantioselective detection of R-/S-Man.

Keywords: Amino-functional silica-coated N-Doped carbon dots; Enantioselective sensing; Fluorescent chiral nanoprobes; L-try–CONH–SiO(2)-CDs; R-/S-Mandelic acid.