Ultrasensitive and visual detection of tetracycline based on dual-recognition units constructed multicolor fluorescent nano-probe

Highlights: • The SiQDs functionalized dual-response ratiometric fluorescent nano-probe was manufactured. • The rich color tunability of the nano-probe makes it highly sensitive and selective in the detection of TC. • The nanoprobe can realize the fast detection through the chromaticity analysis software in smart phones. Ultrasensitive and visual detection of tetracycline antibiotic (TC) residues is of great significance to public health and environmental safety. A novel dual-response ratiometric fluorescent nano-probe (SiQDs-Cit-Eu) has been elaborately tailored for the determination and on-site visual assay of tetracycline, by grafting citric acid and europium (Eu³⁺) ions onto the surface of silicon quantum dots (SiQDs). The blue-emissive SiQDs (λ_em = 455 nm) fabricated by a one-step facile method act as both scaffold for coordination with Eu³⁺ ions and recognition unit for TC owing to the inner filter effect (IFE). The coordinate unsaturated red-fluorescent Eu³⁺ ions (λ_em = 617 nm) bond to the surface of SiQDs, serving as the specific recognition element for TC due to the antenna effect. In the presence of TC, the as-synthesized nano-probe exhibits double (λ_em = 455 and 617 nm) and reverse response signals which are accompanied by a marked color change from blue to purple, and then red, thus achieving ultra-high sensitivity with a detection limit of 7.1 nM and instant visual detection of TC in real samples (milk, honey, lake and river water). Furthermore, smartphone-assisted point-of-care testing platform is also constructed based on nano-probe-immobilized test paper by using the color scanning APP.