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Analysis of estrogens in milk samples using ionic liquid-modified covalent organic framework and stable isotope labeling technique

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Abstract

Estrogens in milk samples were extracted by a new ionic liquid (IL)-modified covalent organic framework (COF), and then analyzed by stable isotope labeling (SIL) method using dansyl chloride (DNS-Cl) and d6-dansyl chloride (d6-DNS-Cl) as SIL agents. The IL-modified COF (TpPa-Ct@Mi) was synthesized by chemically bonding methylimidazole on to the surface of normal COF to make full use of the high surface area and big conjugated structure of COF, and the abundant charge of IL, which are of crucial importance for adsorption. The synthesized COF can form π–π interactions and hydrophobic effect with estrogens, while the IL can form electrostatic interactions with the analytes. It was applied to the dispersive solid-phase extraction (DSPE) of estrogens in milk samples. The extracted estrogen samples were heavy labeled by d6-DNS-Cl, and then mixed with the light labeled standard. Samples and standards were mixed and analyzed in a single run, and thus the matrix effect was greatly minimized. The optimized extraction conditions were adsorbent amount, 20 mg; desorption solvent and volume of desorption solvent, 2 mL acetonitrile; NaCl concentration, 0 g/L; sample pH 7. The limits of detection were in the range of 9–13 ng/L, and the limits of quantitation were in the range of 29–40 ng/L. Recoveries and matrix effect were in the range of 89.6–95.5% and 96.1–98.9%, respectively, with relative standard deviations of less than 6.2%.

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References

  1. Murphy E (2011) Estrogen signaling and cardiovascular disease. Circ Res 109(6):687–696. https://doi.org/10.1161/CIRCRESAHA.110.236687

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  2. Gunatilake SR, Munasinghe VK, Ranaweera R, Mlsna TE, **a K (2016) Recent advancements in analytical methods for the determination of steroidal estrogen residues in environmental and food matrices. Anal Methods 8(28):5556–5568. https://doi.org/10.1039/c6ay01422d

    Article  CAS  Google Scholar 

  3. Wang S, Huang W, Fang G, Zhang Y, Qiao H (2008) Analysis of steroidal estrogen residues in food and environmental samples. Int J Environ Anal Chem 88(1):1–25. https://doi.org/10.1080/03067310701597293

    Article  CAS  Google Scholar 

  4. Wu R, Chen J, Zhang L, Wang X, Yang Y, Ren X (2021) LC/MS-based metabolomics to evaluate the milk composition of human, horse, goat and cow from China. Eur Food Res Technol 247(3):663–675. https://doi.org/10.1007/s00217-020-03654-1

    Article  CAS  Google Scholar 

  5. D’Orazio G, Hernandez-Borges J, Vicente Herrera-Herrera A, Fanali S, Angel Rodriguez-Delgado M (2016) Determination of estrogenic compounds in milk and yogurt samples by hollow-fibre liquid-phase microextraction-gas chromatography-triple quadrupole mass spectrometry. Anal Bioanal Chem 408(26):7447–7459. https://doi.org/10.1007/s00216-016-9833-0

    Article  CAS  PubMed  Google Scholar 

  6. Snoj T, Majdic G (2018) MECHANISMS IN ENDOCRINOLOGY: Estrogens in consumer milk: is there a risk to human reproductive health? Eur J Endocrinol 179(6):R275–R286. https://doi.org/10.1530/eje-18-0591

  7. Lu H, Xu S (2017) Hollow mesoporous structured molecularly imprinted polymers for highly sensitive and selective detection of estrogens from food samples. J Chromatogr A 1501:10–17. https://doi.org/10.1016/j.chroma.2017.04.050

    Article  CAS  PubMed  Google Scholar 

  8. Omar TFT, Ahmad A, Aris AZ, Yusoff FM (2016) Endocrine disrupting compounds (EDCs) in environmental matrices: review of analytical strategies for pharmaceuticals, estrogenic hormones, and alkylphenol compounds. Trac-Trend Anal Chem 85:241–259. https://doi.org/10.1016/j.trac.2016.08.004

    Article  CAS  Google Scholar 

  9. Sun R, Yang W, Li Y, Sun C (2021) Multi-residue analytical methods for pesticides in teas: a review. Eur Food Res Technol. https://doi.org/10.1007/s00217-021-03765-3

    Article  Google Scholar 

  10. **n J, Wang X, Li N, Liu L, Lian Y, Wang M, Zhao R-S (2020) Recent applications of covalent organic frameworks and their multifunctional composites for food contaminant analysis. Food Chem. https://doi.org/10.1016/j.foodchem.2020.127255

    Article  PubMed  Google Scholar 

  11. Hu K, Cheng J, Zhang W, Pang T, Wu X, Zhang Z, Huang Y, Zhao W, Zhang S (2020) Simultaneous extraction of diverse organic pollutants from environmental water using a magnetic covalent organic framework composite. Anal Chim Acta 1140:132–144. https://doi.org/10.1016/j.aca.2020.10.019

    Article  CAS  PubMed  Google Scholar 

  12. Zhang W, Lan C, Zhang H, Zhang Y, Zhang W, Zhao W, Johnson C, Hu K, **e F, Zhang S (2019) Facile preparation of dual-shell novel covalent-organic framework functionalized magnetic nanospheres used for the simultaneous determination of fourteen trace heterocyclic aromatic amines in nonsmokers and smokers of cigarettes with different tar yields based on UPLC-MS/MS. J Agr Food Chem 67(13):3733–3743. https://doi.org/10.1021/acs.jafc.8b06372

    Article  CAS  Google Scholar 

  13. Zhang W, Zhang Y, Zhang G, Liu J, Zhao W, Zhang W, Hu K, **e F, Zhang S (2019) Facile preparation of a cationic COF functionalized magnetic nanoparticle and its use for the determination of nine hydroxylated polycyclic aromatic hydrocarbons in smokers’ urine. Analyst 144(19):5829–5841. https://doi.org/10.1039/c9an01188a

    Article  CAS  PubMed  Google Scholar 

  14. Zhang L, Chen J, Lv JX, Wang SF, Cui Y (2013) Progress and development of capture for CO2 by ionic Liquids. Asian J Chem 25(5):2355–2358. https://doi.org/10.14233/ajchem.2013.13552

    Article  CAS  Google Scholar 

  15. Fu M-l, Liu J, Dong Y-c, Feng Y, Fang R-s, Chen Q-h, Liu X-j (2011) Effect of ionic liquid-containing system on betulinic acid production from betulin biotransformation by cultured Armillaria luteo-virens Sacc cells. Eur Food Res Technol 233(3):507–515. https://doi.org/10.1007/s00217-011-1549-y

    Article  CAS  Google Scholar 

  16. Zitka J, Pientka Z (2017) Ionic liquids and their polymeric analogues: new membrane materials. Chem Listy 111(3):192–196

    CAS  Google Scholar 

  17. Ding L-G, Yao B-J, Li F, Shi S-C, Huang N, Yin H-B, Guan Q, Dong Y-B (2019) Ionic liquid-decorated COF and its covalent composite aerogel for selective CO2 adsorption and catalytic conversion. J Mater Chem A 7(9):4689–4698. https://doi.org/10.1039/c8ta12046c

    Article  CAS  Google Scholar 

  18. Zhang S, Ji Z, Sun Z, Li M, Sheng C, Yue M, Yu Y, Chen G, You J (2017) Stable isotope labeling assisted liquid chromatography-tandem mass spectrometry for the analysis of perfluorinated carboxylic acids in serum samples. Talanta 166:255–261. https://doi.org/10.1016/j.talanta.2017.01.069

    Article  CAS  PubMed  Google Scholar 

  19. Zhang S, Shi J, Shan C, Huang C, Wu Y, Ding R, Xue Y, Liu W, Zhou Q, Zhao Y, Xu P, Gao X (2017) Stable isotope N-phosphoryl amino acids labeling for quantitative profiling of amine-containing metabolites using liquid chromatography mass spectrometry. Anal Chim Acta 978:24–34. https://doi.org/10.1016/j.aca.2017.04.025

    Article  CAS  PubMed  Google Scholar 

  20. Zhang S, You J, Ning S, Song C, Suo Y-R (2013) Analysis of estrogenic compounds in environmental and biological samples by liquid chromatography–tandem mass spectrometry with stable isotope-coded ionization-enhancing reagent. J Chromatogr A 1280:84–91. https://doi.org/10.1016/j.chroma.2013.01.045

    Article  CAS  PubMed  Google Scholar 

  21. Ma C, Zhang S, Wu X, You J (2020) Permanently positively charged stable isotope labeling agents and its application in the accurate quantitation of alkylphenols migrated from plastics to edible oils. J Agr Food Chem 68(33):9024–9031. https://doi.org/10.1021/acs.jafc.0c03413

    Article  CAS  Google Scholar 

  22. Kandambeth S, Mallick A, Lukose B, Mane MV, Heine T, Banerjee R (2012) Construction of crystalline 2D covalent organic frameworks with remarkable chemical (acid/base) stability via a combined reversible and irreversible route. J Am Chem Soc 134(48):19524–19527. https://doi.org/10.1021/ja308278w

    Article  CAS  PubMed  Google Scholar 

  23. Yang W-C, Adamec J, Regnier FE (2007) Enhancement of the LC/MS analysis of fatty acids through derivatization and stable isotope coding. Anal Chem 79(14):5150–5157. https://doi.org/10.1021/ac070311t

    Article  CAS  PubMed  Google Scholar 

  24. Sun Z, Wang X, Cai Y, Fu J, You J (2014) Development of a pair of differential H/D isotope-coded derivatization reagents d(0)/d(3)-4-(1-methyl-1H-phenanthro 9,10-d imidazol-2-yl) phenlamine and its application for determination of aldehydes in selected aquatic products by liquid chromatography-tandem mass spectrometry. Talanta 120:84–93. https://doi.org/10.1016/j.talanta.2013.11.064

    Article  CAS  PubMed  Google Scholar 

  25. Joint FAO/WHO Expert Committee on Food Additives (JECFA) (2000) Toxicological evaluation of certain veterinary drug residues in food. Who Food Addit 21(4):558-559

  26. Perez RL, Escandar GM (2014) Liquid chromatography with diode array detection and multivariate curve resolution for the selective and sensitive quantification of estrogens in natural waters. Anal Chim Acta 835:19–28. https://doi.org/10.1016/j.aca.2014.05.015

    Article  CAS  PubMed  Google Scholar 

  27. Mezzullo M, Pelusi C, Fazzini A, Repaci A, Di Dalmazi G, Gambineri A, Pagotto U, Fanelli F (2020) Female and male serum reference intervals for challenging sex and precursor steroids by liquid chromatography–tandem mass spectrometry. J Steroid Biochem. https://doi.org/10.1016/j.jsbmb.2019.105538

    Article  Google Scholar 

  28. Tso J, Aga DS (2010) A systematic investigation to optimize simultaneous extraction and liquid chromatography tandem mass spectrometry analysis of estrogens and their conjugated metabolites in milk. J Chromatogr A 1217(29):4784–4795. https://doi.org/10.1016/j.chroma.2010.05.024

    Article  CAS  PubMed  Google Scholar 

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Author notes

  1. Chong Ma and Rui Chang contributed equally to this work.

Authors and Affiliations

  1. Shandong Province Key Laboratory of Life-Organic Analysis, Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine, School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, People’s Republic of China

    Rui Chang, Chong Ma, Chao Yu, Qiang Zhang, Yanxin Li, **mao You & Shijuan Zhang

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  1. Rui Chang
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  2. Chong Ma
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Correspondence to Yanxin Li, **mao You or Shijuan Zhang.

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Chang, R., Ma, C., Yu, C. et al. Analysis of estrogens in milk samples using ionic liquid-modified covalent organic framework and stable isotope labeling technique. Eur Food Res Technol 247, 2729–2738 (2021). https://doi.org/10.1007/s00217-021-03830-x

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