Amphiphilic Emulgels Loaded with Pomegranate Carbon Dots and Rosemary Oil for Metabolic pH Monitoring
Hebat-Allah S. Tohamy, Ilaria CacciottiThe development of sustainable, smart food packaging materials that simultaneously provide antimicrobial protection and real-time monitoring of food quality is a critical frontier in food safety. This study reports the fabrication of a multifunctional amphiphilic emulgel designed for the detection of pathogen-induced metabolic pH changes in food systems. The system utilizes Pomegranate-derived nitrogen-doped quasi-spherical carbon dots (QS-CDs) as fluorescent nanoprobes and Rosemary Essential Oil (REO) as a natural antimicrobial agent, both encapsulated within a polyelectrolyte complex of chitosan and sugarcane bagasse-derived carboxymethyl cellulose (CMC). A low degree of substitution (DS = 0.4) was specifically engineered for the CMC to ensure an amphiphilic character, enabling nanocomposite complex stabilization of the REO droplets without synthetic surfactants. Structural characterization via Transmission Electron Microscopy (TEM) revealed well-dispersed QS-CDs (4.71–6.62 nm) and stable oil droplets (~605.49 nm) anchored within a zipped polymer network. Thermal analysis (TGA/DSC) using the Coats–Redfern model revealed a significant synergistic effect: the smart-emulgel exhibits a distinct two-stage degradation profile, with the high-temperature stage requiring an activation energy (Ea) of 95.19 kJ/mol, a substantial increase over the corresponding stage in the CD-emulgel baseline (18.69 kJ/mol). This enhanced stability is complemented by a slight increase in crystallinity (Xc from 0.11 to 0.14). While the smart-emulgel remains predominantly amorphous, this shift suggests that the integration of REO and QS-CDs into the polymer network promotes the formation of localized, more ordered domains, contributing to a more robust and structurally integrated matrix. The emulgel demonstrated a dual-mode optical response (colorimetric and fluorometric) sensitive to the metabolic byproducts (e.g., organic acids, amines, other alkaline compounds) produced by Escherichia coli and Staphylococcus aureus. These findings were corroborated by Density Functional Theory (DFT) calculations, which confirmed the thermodynamic stability and optimized electronic energy gaps for pH-responsive sensing. This research provides a green, high-performance platform for the real-time monitoring of food freshness and the prevention of foodborne illnesses.