Synthesis of a magnetic micro-eutectogel based on a deep eutectic solvent gel immobilized in calcium alginate: Application for green analysis of melamine in milk and dairy products

Abstract

A new three-component magnetic eutectogel composed of a crosslinked copolymeric deep eutectic solvent (DES) and polyvinylpyrrolidone-coated Fe3O4 nano-powder impregnated in calcium alginate gel was synthesized and applied as a sorbent material in a green alternative micro solid-phase extraction of melamine in milk and dairy products. The analyses were performed using the HPLC-UV technique. The copolymeric DES was prepared through thermally-induced free-radical polymerization of [2-hydroxyethyl methacrylate]:[thymol] DES (1:1 mol ratio) as functional monomer, azobisisobutyronitrile (as initiator), and ethylene glycol dimethacrylate (as crosslinker). The sorbent was characterized using ATR-FTIR, 1H &13C FT-NMR, SEM, VSM, and BET techniques. The stability of the eutectogel in water and its effect on the pH of the aqueous solution was studied. A one-at-a-time approach was applied to optimize the impact of significant factors influencing sample preparation efficiency (sorbent mass, desorption conditions, adsorption time, pH, and ionic strength). The method validation was performed by evaluating matrix-matched calibration linearity (2–300 μg kg−1, r2 = 0.9902), precision, system suitability, specificity, enrichment factor, and matrix effect. The obtained limit of quantification (0.38 μg kg−1) was lower than the established maximum level for melamine by Food and Drug Administration (FDA) (0.25 mg kg−1), Food and Agriculture Organization (FAO) (0.5 & 2.5 mg kg−1), and The European Union (EU) (2.5 mg kg−1) in milk and dairy products. The optimized procedure was applied for the analysis of melamine in bovine milk, yogurt, cream, cheese, and ice cream. The obtained normalized recoveries of 77.4–105.3% (RSD% <7.0%) were acceptable regarding the practical default range set by the European Commission (70–120%, RSD≤20%). The sustainability and green aspects of the procedure were evaluated by the Analytical Greenness Metric Approach (0.6/1.0) and the Analytical Eco-Scale tool (73/100). This paper presents the first-time synthesis and application of this micro-eutectogel for the analysis of melamine in milk and milk-based dairy products.