Online fully automated SPE‐HPLC‐MS/MS determination of ceftiofur in bovine milk samples employing a silica‐anchored ionic liquid as sorbent

Abstract

Solid-phase extraction coupled online with high performance liquid chromatography and tandem mass spectrometry was successfully applied to determine low concentrations of ceftiofur antibiotic in bovine milk samples. A silica-anchored ionic liquid was applied as sorbent material to be used as extraction phase in the proposed online system. The material was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. In order to improve the system reproducibility, the following experimental parameters were optimized: organic solvent percentage, time and sample loading flow rate. Subsequently, the method was validated presenting satisfactory results as adequate selectivity, good linearity and correlation coefficient higher than 0.98. The limit of detection and quantification were 0.1 and 0.7 μg/L, respectively. The precision of the methodology was evaluated as repeatability and intermediate precision, with relative standard deviation values lower than 15%. The accuracy of the method ranged from 72.8 to 137% and the minimum and maximum recovery values were 73.4 and 111.3%, respectively. After the validation, seven milk samples were analyzed and although ceftiofur was not detected in any of them the method was demonstrated to be efficient when applied to the analysis of milk samples fortified with the pollutant of interest.

High‐throughput microscale extraction using ionic liquids and derivatives: A review

“…Significant increase in the sample throughput of IL‐SPE is achieved when using online FI systems [32]. Representative applications using online IL‐μ‐SPE protocols are summarized in Table 1 [32–41]. For example, in a semi‐automatic flow system used for the extraction of a group of dyes in a remediation protocol, a nanocomposite composed by β‐cyclodextrin‐functionalized carbon nanotubes (CNTs) containing also TiO 2 nanoparticles (NPs), and ultimately modified with the 1‐octyl‐3‐methylimidazolium hexaflurophosphate ([C 8 MIM + ][PF 6 − ]) IL, was employed.…”

“…ILs and PILs have also been employed in in‐tube SPME mode [7,10]. In particular, a relatively large number of these applications performed the extraction/elution procedure online using a switchable six‐port injection valve directly connected to the analytical detection technique [35–40], as summarized in Table 1 [35–41]. In these cases, the sample loop of the valve was substituted for the in‐tube capillary containing the IL‐ or PIL‐sorbent material as shown in Figure 2B [38].…”

“…With this configuration, all the steps of the extraction procedure, including liquid desorption with organic solvents and eluate transport to the subsequent analytical detection technique, were undertaken automatically with the aid of the FI‐system. This type of configuration facilitated the combination of the in‐tube SPME method with HPLC [35–39]. In several of these applications, the HPLC mobile phase also served for the elution of the analytes from the capillary, and thus resulting in a simpler system configuration [35,37–39].…”

Spectrophotometric Methods for the Determination of Ceftiofur and Tulathromycin in Bulk and Dosage Forms

“…Compared with the reported methods the proposed methods have some distinct advantages; the reported spectrophotometric methods [10][11][12][13] were less sensitive. Although the reported HPLC and LC/MS methods [3][4][5][6][7][8][17][18][19][20][21][22] are sensitive enough, they are precluded due to higher cost and non-availability of such instruments in each laboratory in developing countries. No reported spectrophotometric methods were reported for determination of TULA in its dosage form.…”

“…CEFT is broad-spectrum antibiotic has been used for bovine and swine respiratory disease, foot rot and metritis infections in cattle [2]. A number of HPLC [3][4][5], LC/MS [6][7][8], capillary electrophoresis [9], UV-Vis spectrophotometric [10][11][12][13] and voltametric [14,15] methods were reported for the quantification of CEFT in dosage forms and or biological samples.…”