Tetraphenylethene-based fluorescent probe with aggregation-induced emission behavior for Hg2+ detection and its application

Abstract

A tetraphenylethene (TPE) derivative was designed and synthesized upon conjugation with bis(thiophen-2-ylmethyl) amine (BTA) containing a mercury-binding moiety and further characterized by using Nuclear magnetic resonance (NMR), LC-MS, UV-Vis, and fluorescence spectroscopic methods. The resulting TPE-BTA exhibited comprehensive aggregation-induced emission while expressing a high quantum yield and emission intensity at 70% water fraction. The probe exhibited a good photochromic effect with a Stokes shift of 178 nm, and the emission intensity at 550 nm increased considerably with the color turning from dark green to bright green under a UV lamp upon the addition of 5 μM Hg²⁺. The lowest-energy conformation of the probe showed that two thiophene rings were perpendicular to the phenyl ring, while two BTA molecules were situated in a staggered form to each other. The sulfur and nitrogen atoms present in TPE-BTA were coordinated to the Hg²⁺ ion, and these binding sites were confirmed by the NMR parameters, X-ray photoelectron spectroscopy signals, and structural calculations. The binding of Hg²⁺ to TPE-BTA was believed to restrict the intramolecular motion of TPE-BTA, thus inducing it to shine brighter according to the unique aggregation-induced emission effect. The concentration of Hg²⁺ was determined based on the enhancement of the emission intensity, and the present probe showed an extremely high sensitivity with a limit of detection of 10.5 nM. Furthermore, TPE-BTA enabled selective detection of Hg²⁺ even in the presence of a 1000-fold excess of other interfering metal ions. The proposed method was successfully employed to determine Hg²⁺ in living HeLa cells and real water samples.

Keywords: Aggregation-induced emission; Bioimaging; Bis(thiophen-2-ylmethyl)amine; Density functional theory; Fluorescent Hg(2+) probe; Tetraphenylethene.