Enantioselective Fluorescence Recognition of Free α-Amino Acids by Ion-Type Ammonium Salt-Based Sensors

Optically pure amino acids have extensive applications in pharmaceuticals, pesticides, food, materials, and other fields. Enantiomers recognition of chiral amino acids using optical methods with synthetic chiral sensors has attracted extensive attention. Most reported sensors typically identify guests by covalent or hydrogen bonding or hydrophobic interaction with amino acids and their derivatives. In this paper, a series of ion-type quaternary ammonium salt-based enantioselective fluorescent sensors were synthesized for chiral recognition of free α-amino acids via electrostatic interaction. The fluorescence intensity ratios I_D/I_L (I_D, I_L, fluorescence intensity of sensor when treated with D- or L-amino acid) were up to 2.1 and enantioselective fluorescence enhancement ratios ef (ef=[I_L-I₀]/[I_D-I₀] or [I_D-I₀]/[I_L-I₀]. (I₀, fluorescence intensity of the sensor)) were up to 5.0. Among them, sensor 3 showed best enantioselective recognition performance toward tryptophan (Trp), and L-Trp significantly quenched the fluorescence of sensor 3, but D-Trp greatly enhanced the fluorescence of sensor 3, its I_D/I_L was 2.11 and ef was 1.8. The mechanistic investigation by NMR spectrum revealed that a tight three-point interaction, including electrostatic interaction, hydrogen bond, and π-π stacking, between sensor 3 and D-Trp was formed.