Concentration-tuned diverse response to selective biogenic amines using a reusable fluorophore: monitoring protein-rich food spoilage

Abstract

Maintaining the freshness of food is essential for a healthy and quality life. Nevertheless, it remains a global challenge. Hence, an easy detection and monitoring protocol would be highly desirable. A cyanoacrylic acid (CAA)-based fluorophore is manifested as a reusable platform that responds diversely against different concentrations of selective aliphatic biogenic amines (BAs) in both solution and vapor phases. Slow spoilage of the protein-rich food is progressively monitored through emission shifts visible to the naked eye. This fluorophore provides easy and naked-eye detection of the BA vapor through a change in emission, i.e., red → orange → orange-yellow → cyan → green and quantum yield enhancement, which occur in stepwise increments of vapor concentrations. The probe design includes π-conjugated functionalized fluorescent molecules linked to multiple twisting sites, resulting in both solid and solution-state emission. The attached carboxylic acid responds quickly with selective BAs, mainly putrescine (PUT), cadaverine (CAD), and spermidine (SPM), where the concentration-based emission variation has appeared to be distinct and prominent against PUT [sensitivity (μM): 2 (solution); 3.3 (vapour)]. The selectivity towards diamine can be clarified by the formation of carboxylic acid salts and the consequent proton exchanges between free and protonated amines. In addition, –CN···H interaction is likely to develop within this ammonium carboxylate system, providing extra stability. Such ammonium carboxylate salt formation and gradual change in the molecular arrangement, resulting in symmetry development, are validated by FT-IR and wide-angle X-ray diffraction studies. Besides, this fact is supported by DFT studies that validate intramolecular H-atom exchange between free amine and ammonium salt units. A fluorophore-coated coverslip, filter paper, or silica gel-coated Al-plate is fruitfully utilized to detect the freshness of fish and chicken, which reveals the potential of this probe to prevent food waste and control food safety.