Collaborative compounding of metal–organic frameworks for dispersive solid-phase extraction HPLC–MS/MS determination of tetracyclines in honey
Introduction
Bees are prone to bacterial diseases and are often fed antibacterial drugs. Tetracyclines (TCs), a group of low-cost and broad-spectrum antibiotics, are widely used as veterinary medicines for their antibacterial activity against both gram-positive and gram-negative bacteria (Koesukwiwat, Jayanta, & Leepipatpiboon, 2007). Commercial beekeepers have traditionally used antibacterial drugs for the control of bee diseases. In particularly, TCs are abused as a treatment or preventive measure for infectious American and European foulbrood (Reybroeck, Ooghe, Brabander, & Daeseleire, 2007). Therefore, TCs may accumulate in the bee and become a harmful contaminant in honey. Excessive exposure to TCs may cause allergic reactions, gastrointestinal disturbances and tetracycline teeth pigmentation in humans (HAKUTA et al., 2009, Pastor-Navarro et al., 2009).
The determination and control of TCs residual in honey is of great significance. Many countries and regions have stipulated maximum residue limits (MRL) of TCs in honey, such as 50 μg/kg in China, 20 μg/kg in the European Union, and 10 μg/kg in the United States (Khong et al., 2005, Xu et al., 2008). In Switzerland, TCs are banned in honey products (Zhang, Li, Li, Zhang, Gao, & Li, 2019). In order to detect TC residues in honey, it is urgent to establish a convenient and effective method.
High-performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS) has good selectivity and sensitivity for trace organic contaminants, such as pesticide and veterinary drug residues including TCs (Bogialli and Corcia, 2009, Huang et al., 2019, Tuzimski and Petruczynik, 2020). Indeed, this technique requires sample pretreatment, including clean-up samples, isolating and enrich analytes from sample matrix. The extraction of TCs from honey is a key step for determination by HPLC–MS/MS. In recent years, the pretreatment methods of TCs include dispersive liquid–liquid microextraction, solid-phase extraction and magnetic solid-phase extraction (Gao et al., 2017, He et al., 2019, Kaewsuwan et al., 2017). However, little attention has been devoted to dispersive solid-phase extraction (d-SPE). d-SPE can be easily modified, and its steps are all relatively straightforward, making it simple, fast, effective and user-friendly. Extraction of hundreds of pesticides with high recovery rate from various food products has been consistently achieved by d-SPE (Kim et al., 2019, Tuzimski and Rejczak, 2016). In principle, the extraction efficiency of d-SPE mainly depends on the type of adsorbent. Currently, polymer (Koseoglu, Ulusoy, Yilmaz, & Soylak, 2020), silica (Islas, Ibarra, Hernandez, Miranda, & Cepeda, 2017), carbon-base materials (Zacs, Rozentale, Reinholds, & Bartkevics, 2018), zirconium dioxide-based materials (Tuzimski & Rejczak, 2017) and magnetic composites (Giakisikli & Anthemidis, 2013) are used as d-SPE adsorbents. Alternatively, metal–organic frameworks (MOFs), porous polymers formed by self-assembly of numerous metal ions and organic ligands with various properties, provide a tremendous advantage in d-SPE, due to their diversity and excellent performance (Gu et al., 2012, Wang et al., 2018).
There are a range of choices of MOFs for screening and compounding suitable adsorbents for targets. Messner et al. (2013) first presented Er-MOF as a d-SPE sorbent for the enrichment of phosphopeptides based on immobilized metal ion affinity chromatography methodology in 2013. After comparing five kinds of MOFs, Rocío-Bautista et al. (2018) found that MIL-53 (Al) as adsorbent of d-SPE can successfully adsorb pollutants with completely different properties, such as hormones in sewage.
Most d-SPE phases in food samples are pretreated utilizing single MOF. Due to the difference of interaction between the targets and the adsorbents, the extraction and recovery of several analytes simultaneously cannot be guaranteed (Islas, Ibarra, Hernandez, Miranda, & Cepeda, 2017). Compounding adsorbents with different adsorption properties can complement each other and further comprehensively improve the extraction and recoveries of the targets. To the best of our knowledge, compounding of MOFs as adsorbents has not been reported for d-SPE in food.
TCs have a common chemical structure with several modifiable sites and a conjugated system (Ibarra, Rodriguez, Miranda, Vega, & Barrado, 2011). Herein, 3 MOFs abundant in π system, MIL-101 (Cr), MIL-100 (Fe) and MIL-53 (Al), were compounded for d-SPE of 4 TCs: oxytetracycline (OTC), tetracycline (TC), chlortetracycline (CTC) and doxycycline (DC). The aim of this work was to explore a efficient method for d-SPE of TCs in honey with compounding of MOFs to establish a more sensitive TCs determination method.
Section snippets
Reagents and chemicals
All chemicals were at least of analytical grade. The standards of OTC (96%), TC (97.7%), CTC (99.5%), DC (98.7%) were purchased from Dr. Ehrenstorfer GmbH (Augsburg, Germany), Cr(NO3)3·9H2O was purchased from Shanghai Macklin Biochemical Co., Ltd. (Shanghai, China), Al(NO3)3·9H2O, terephthalic acid, and reduced iron powder were purchased from Shanghai Aladdin Bio-Chem Technology Co., Ltd. (Shanghai, China). Hydrofluoric acid, trimesic acid, N,N-dimethylformamide (DMF), nitric acid, ethanol,
Compounding MOFs for d-SPE
Fig. 1 shows the compounding 3 MOFs as a d-SPE adsorbent to extract and detect 4 TCs in honey. TCs are a group of analogs with similar chemical structures, which have several modifiable sites and a conjugated system. The maximum molecular length of the 4 TCs is about 12.2 Å.
MIL-101 (Cr), MIL-100 (Fe) and MIL-53 (Al) are the same MOF series; however, they have different ligand, crystal structure and pore size, resulting in different adsorption properties. MIL-101 (Cr) is built up from a hybrid
Conclusion
In summary, we developed a reliable d-SPE method based on the collaborative compounding of MIL-101 (Cr), MIL-100 (Fe) and MIL-53 (Al), and combined it with HPLC–MS/MS to determine four TCs in honey. The compounding MOFs adsorbent can improve the detection accuracy and reduce the LOD and LOQ, which provides a methodological basis for using other kinds of compounding MOFs as d-SPE adsorbents in the future. Overall, the proposed method is expected to be applied to the routine extraction and
CRediT authorship contribution statement
Yue-Hong Pang: Conceptualization, Resources, Writing - review & editing, Project administration, Funding acquisition. Zhi-Yang Lv: Conceptualization, Methodology, Formal analysis, Investigation, Writing - original draft. Ji-Cheng Sun: Validation, Investigation, Data curation. Cheng Yang: Conceptualization, Methodology, Investigation. Xiao-Fang Shen: Methodology, Formal analysis, Validation, Investigation, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
This work was supported by the National Key R&D Program of China (2018YFC1602300), the National Natural Science Foundation of China (21976070, 22076067), and the Fundamental Research Funds for the Central Universities (JUSRP22003).
References (31)
- et al.
Magnetic materials as sorbents for metal/metalloid preconcentration and/or separation. A review
Analytica Chimica Acta
(2013) - et al.
Determination of multi-pesticide residues in green tea with a modified QuEChERS protocol coupled to HPLC-MS/MS
Food Chemistry
(2019) - et al.
Magnetic solid phase extraction based on phenyl silica adsorbent for the determination of tetracyclines in milk samples by capillary electrophoresis
Journal of Chromatography A
(2011) - et al.
Review of the QuEChERS method for the analysis of organic pollutants: Persistent organic pollutants, polycyclic aromatic hydrocarbons, and pharmaceuticals
Trends in Environmental Analytical Chemistry
(2019) - et al.
Solid-phase extraction for multiresidue determination of sulfonamides, tetracyclines, and pyrimethamine in Bovine’s milk
Journal of Chromatography A
(2007) - et al.
Insights in the analytical performance of neat metal-organic frameworks in the determination of pollutants of different nature from waters using dispersive miniaturized solid-phase extraction and liquid chromatography
Talanta
(2018) - et al.
Application of HPLC-DAD after SPE/QuEChERS with ZrO2-based sorbent in d-SPE clean-up step for pesticide analysis in edible oils
Food Chemistry
(2016) - et al.
Analysis of tetracycline residues in royal jelly by liquid chromatography–tandem mass spectrometry
Journal of Chromatography B
(2008) - et al.
Antibiotic residues in honey: A review on analytical methods by liquid chromatography tandem mass spectrometry
Trac Trends in Analytical Chemistry
(2019) - et al.
Recent applications of liquid chromatography–mass spectrometry to residue analysis of antimicrobials in food of animal origin
Analytical and Bioanalytical Chemistry
(2009)
Adsorption behaviors of organic micropollutants on zirconium metal–organic framework UiO-66: Analysis of surface interactions
ACS Applied Materials & Interfaces
Hydrogen adsorption in the nanoporous metal-benzenedicarboxylate M (OH) (O2C–C6H4–CO2) (M= Al3+, Cr3+), MIL-53
Chemical Communications
A chromium terephthalate-based solid with unusually large pore volumes and surface area
Science
Control of the Coordination Status of the Open Metal Sites in Metal-Organic Frameworks for High Performance Separation of Polar Compounds
Langmuir
Salting-out-enhanced ionic liquid microextraction with a dual-role solvent for simultaneous determination of trace pollutants with a wide polarity range in aqueous samples
Analytical and Bioanalytical Chemistry
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