“Click” Reaction-Mediated Silk Fibroin-Functionalized Thiol-Branched Graphene Oxide Quantum Dots for Smart Sensing of Tetracycline

Abstract

The abuse of tetracycline (TC) antibiotics causes the accumulation of their residue in the environment, which has an irreversible impact on food safety and human health. In light of this, it is vital to offer a portable, quick, efficient, and selective sensing platform to detect TC instantly. Herein, we have successfully developed a sensor using silk fibroin-decorated thiol-branched graphene oxide quantum dots through a well-known thiol-ene click reaction. It is applied to ratiometric fluorescence sensing of TC in real samples in the linear range of 0-90 nM, with the detection limit of 49.69, 47.76, 55.25, 47.90, and 45.78 nM for deionized water, chicken sample, fish sample, human blood serum, and honey sample, respectively. With the gradual addition of TC to the liquid media, the sensor develops a synergetic luminous effect in which the fluorescence intensity of the nanoprobe steadily declines at 413 nm, while the intensity of a newly emerging peak increases at 528 nm, maintaining a ratio that is dependent on the analyte concentration. The increase of luminescence properties in the liquid media is clearly visible by naked eyes in the presence of 365 nm UV light. The result helps us in building a filter paper strip-based portable smart sensor using an electric circuit comprising a 365 nm LED (light-emitting diode) powered by a mobile phone battery which is attached just below the rear camera of a smartphone. The camera of the smartphone captures the color changes that occur throughout the sensing process and translates into readable RGB data. The dependency of color intensity with respect to the concentration of TC was evaluated by deducing a calibration curve from where the limit of detection was calculated and found to be 0.125 μM. These kinds of gadgets are important for the possible real-time, on-the-spot, quick detection of analytes in situations where high-end approaches are not easily accessible.