Determination of Tetracyclines Residues in Egg, Milk, and Milk Powder by Online Coupling of A Precolumn Packed with Molecular Imprinted Hybrid Composite Materials to RP-HPLC-UV

Abstract

A rapid, specific, and sensitive method was developed for determination of tetracyclines (TCs) in egg, milk, and milk powder samples by online molecularly imprinted solid-phase extraction (MISPE) coupled to a reversed-phase high-performance liquid chromatography (HPLC). A molecularly imprinted polymer hybrid composite material (MIP-HCM) was prepared using TC as the template, methacrylic acid as the functional monomer, tetraethoxysilane as inorganic precursor, and methacryloxypropyltrimethoxysilane as the coupling agent. A new technique of online solid-phase extraction (SPE) coupled with HPLC was established. The conditions of online SPE were optimized. Under the optimal conditions, three TCs residues in egg, milk, and milk powder were separated and detected by the proposed method with better clean-up and recoveries. The recoveries of TCs ranged from 85.3% to 98.3%. The limits of detection and quantitation of the proposed method were in the range of 0.76-1.13 mg=kg and 2.53-3.77 mg=kg, respectively. The MIP-HCM was first used as online SPE packing and the hyphenated technique is promising as a general strategy for direct determination of veterinary drug residues in milk and other biological samples.

Analysis of tetracyclines from milk powder by molecularly imprinted solid‐phase dispersion based on a metal–organic framework followed by ultra high performance liquid chromatography with tandem mass spectrometry

“…Other methods [34][35][36][37][38][39] for detection of TCs were compared and presented in Supporting Information Table S7 to better reflect the performance of this method. Considering all aspects including sample preparation time, the recovery, LOD, and RSD, this method has some advantages over other methods.…”

An overview of the main foodstuff sample preparation technologies for tetracycline residue determination

“…Protein precipitation in milk and egg samples involves the use of organic solvents including acetonitrile [6,10,23,46,51], methanol [52][53][54][55] or acetone [56], as well as the combination of these solvents with acid compounds, such as trichloroacetic acid [46,[57][58][59][60][61], trifluoroacetic acid [62,63], glacial acetic acid [64][65][66], succinic acid [67,68], citric acid [23,69], formic acid [54,70], or perchloric acid [71]. Other authors have used McIlvaine-EDTA [6,[72][73][74][75][76][77][78][79], sodium citrate [10], oxalate [63], sodium succinate [80] and phosphate [81] buffers as deproteinizing agents for the treatment of these samples. Such processes are generally followed by some sample clean-up procedures.…”

“…Although the configuration of the latter is not very common in analytical chemistry, it provides good detection limits because of the avoidance of the dilution phenomenon involved in the elution process [92]. On the other hand, most on-line SPE protocols for the determination of tetracyclines in animal-derived foods consist of SPE columns coupled with one of the following: HPLC systems [76][77][78]100,114], spectrophotometric detectors [74] or chemiluminescence [105] detectors.…”

“…Tetracyclines were determined in egg and honey samples by coupling HPLC with on-line SPE using PLRP-S [114] and C18 [78] columns, respectively. In addition, on-line SPE based on MIP coupled to HPLC-UV has also been used to determine tetracycline antibiotic residues in egg samples [100], and egg, milk, and milk powder samples [77]. All tested sorbents showed sufficient sensitivity for residue detection in the target matrices, achieving good recoveries in each case.…”

Article 31

“…Its extensive use in human disease treatment and animal husbandry is as a result of its high availability, low price and effectiveness. Residues of TC and its derivatives (tetracycline hydrochloride, oxytetracycline, doxycycline and chlortetracycline) have been reported in cattle (Aalipour et al, 2015;Kimera et al, 2015) and poultry (Abdel-Mohsein et al, 2015;Lv et al, 2015) products. Reports of TC toxicity has shown that it can cause growth inhibition of soil and water microorganisms and various stress induced dose-dependent transcriptional responses of organisms (Chang et al, 2015).…”