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Preparation of citrinin-selective molecularly imprinted polymer and its use for on-line solid-phase extraction coupled to liquid chromatography

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Abstract

A new selective molecularly imprinted polymer has been prepared and used for extraction in on-line SPE-HPLC to achieve the selective determination of citrinin. Four different imprinted polymers varying in combinations of components were prepared by bulk polymerization and evaluated in terms of binding capacity and selectivity. Imprinted polymer prepared from a mixture comprising 1-hydoxy-2-naphtoic acid as the template molecule, acrylamide as the structural monomer, ethylene dimethacrylate as the cross-linker (in a molar ratio of 1:4:16), and acetonitrile as the porogenic solvent exhibited the best properties. The selectivity of this sorbent was confirmed by comparison with the non-imprinted counterpart prepared using the same polymerization carried out in the absence of template. Imprinted polymer was packed in a 20 × 3 mm i.d. steel cartridge and coupled to the on-line SPE-HPLC system through a six-port switching valve. The method for determination of citrinin including the on-line extraction step was then developed and validated. The sample in the form of methanolic extract was loaded, cleaned, and preconcentrated in the imprinted SPE cartridge. Subsequent separation of citrinin from residual interferences was achieved using the analytical column Kinetex Biphenyl 100 × 4.6 mm i.d., 5 μm particle size, and fluorescence detection (Ex 335, Em 500 nm). The total analysis time was only 9.50 min. Our fully validated method was also applied to analysis of food supplements based on red yeast rice extracts, the control of which is implemented in European legislation. Only minor yet acceptable contamination was found in tested samples.

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References

  1. Halbert SC, et al. Tolerability of red yeast rice (2,400 mg twice daily) versus pravastatin (20 mg twice daily) in patients with previous statin intolerance. Am J Cardiol. 2010;105:198–204.

    Article  CAS  PubMed  Google Scholar 

  2. Nguyen T, Karl M, Santini A. Red yeast rice. Foods. 2017;6:19.

    Article  CAS  PubMed Central  Google Scholar 

  3. Childress L, Gay A, Zargar A, Ito MK. Reviews of red yeast rice content and current Food and Drug Administration oversight. J Clin Lipidol. 2013;7:117–22.

    Article  PubMed  Google Scholar 

  4. Huiqin W, Shufen Z, Taifeng L, Dawei Z. Introduction and safety evaluation of citrinin in foods. J Food Nutr Sci. 2017;5:179–83.

    Google Scholar 

  5. Ostrý V, Malíř F, Ruprich J. Producers and important dietary sources of ochratoxin A and citrinin. Toxins. 2013;5:1574–86.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  6. Phillips RD, Hayes AW, Berndt WO, Williams WL. Effects of citrinin on renal function and structure. Toxicology. 1980;16:123–37.

    Article  CAS  PubMed  Google Scholar 

  7. Flajs D, Peraica M. Toxicological properties of citrinin. Arh Hig Rada Toksikol. 2009;60:457–64.

    Article  CAS  PubMed  Google Scholar 

  8. Salah A, Bouaziz C, Prola A, Da Silva JP, Bacha H, Abid-Essefi S, et al. Citrinin induces apoptosis in human HCT116 colon cancer cells through endoplasmic reticulum stress. J Toxicol Environ Health A. 2017;80:1230–41.

    Article  CAS  PubMed  Google Scholar 

  9. Wu Y, Zhang N, Li Y, Zhao L, Yang M, Jin Y, et al. Citrinin exposure affects oocyte maturation and embryo development by inducing oxidative stress-mediated apoptosis. Oncotarget. 2017;8:34525–33.

    PubMed  PubMed Central  Google Scholar 

  10. Ribeiro SMR, Chagas GM, Campello AP, Kluppel MLW. Mechanism of citrinin-induced dysfunction of mitochondria. V. Effect on the homeostasis of the reactive oxygen species. Cell Biochem Funct. 1998;15:203–9.

    Article  Google Scholar 

  11. Johannessen LN, Nilsen AM, Løvik M. Mycotoxin-induced depletion of intracellular glutathione and altered cytokine production in the human alveolar epithelial cell line A549. Toxicol Lett. 2007;168:103–12.

    Article  CAS  PubMed  Google Scholar 

  12. Maté G, Gazdag Z, Mike N, Papp G, Pócsi I, Pesti M. Regulation of oxidative stress-induced cytotoxic processes of citrinin in the fission yeast Schizosaccharomyces pombe. Toxicon. 2014;90:155–66.

    Article  CAS  PubMed  Google Scholar 

  13. de Oliveira Filho JWG, et al. A comprehensive review on biological properties of citrinin. Food Chem Toxicol. 2017;110:130–41.

    Article  CAS  PubMed  Google Scholar 

  14. Trivedi AB, Hirota M, Doi E, Kitabatake N. Formation of a new toxic compound, citrinin H1, from citrinin on mild heating in water. J Chem Soc Perkin Trans. 1993;1:2167–71.

    Article  Google Scholar 

  15. European Commission. Commission Regulation (EU) No. 212/2014 amending Regulation (EC) 1881/2006 as regards maximum levels of the contaminant citrinin in food supplements based on rice fermented with red yeast Monascus purpureus. Off J Eur Union. 2014;L67:3–4.

    Google Scholar 

  16. Poór M, Matisz G, Kunsági-Máté S, Derdák D, Szente L, Lemli B. Fluorescence spectroscopic investigation of the interaction of citrinin with native and chemically modified cyclodextrins. J Lumin. 2016;172:23–8.

    Article  CAS  Google Scholar 

  17. Vázquez BI, Fente C, Franco CM, Quinto E, Cepeda A, Prognon P. Rapid semi-quantitative fluorimetric determination of citrinin in fungal cultures isolated from cheese and cheese factories. Lett Appl Microbiol. 1997;24:397–400.

    Article  PubMed  Google Scholar 

  18. Ton X, Acha V, Bonomi P, Tse Sum Bui B, Haupt K. A disposable evanescent wave fiber optic sensor coated with a molecularly imprinted polymer as a selective fluorescence probe. Biosens Bioelectron. 2015;64:359–66.

    Article  CAS  PubMed  Google Scholar 

  19. Sadi BS, Bayat M, Tajik P, Hashemi SJ. Citrinin detection by intensified fluorescence signal of a FRET-based immunosensor using magnetic/silica core-shell. Saudi J Biol Sci. 2018;25:171–7.

    Article  CAS  Google Scholar 

  20. Momar A, Sertić M, Nigović B. Development of a rapid LC/DAD/FLD/MSn method for the simultaneous determination of monacolins and citrinin in red fermented rice products. J Agric Food Chem. 2013;61:1072–80.

    Article  CAS  Google Scholar 

  21. Huertas-Pérez JF, Arroyo-Manzanares N, García-Campaña AM, Gámiz-Gracia L. High-throughput determination of citrinin in rice by ultra-high-performance liquid-chromatography and fluorescence detection (UHPLC-FL). Food Addit Contam Part A Chem Anal Control Expo Risk Assess. 2015;32:1352–7.

    Article  CAS  PubMed  Google Scholar 

  22. Elaine M, Phyllis B, Dave L, Carol D. Analysis of citrinin in cereals, red yeast rice dietary supplement, and animal feed by immunoaffinity column cleanup and LC with fluorescence detection. J AOAC Int. 2016;99:1025–31.

    Article  CAS  Google Scholar 

  23. Appell M, Jackson MA, Wang LC, Bosma WB. Determination of citrinin using molecularly imprinted solid phase extraction purification, HPLC separation, and fluorescence detection. J Liq Chromatogr Relat Technol. 2015;38:1815–9.

    Article  CAS  Google Scholar 

  24. Liu Y, Wang H, Yao S, Zhu P. Detection of trace amounts of citrinin in dried orange peel by using an optimized extraction method coupled with ultra-performance liquid-chromatography-tandem mass spectrometry. Biomed Chromatogr. 2018. https://doi.org/10.1002/bmc.4237.

  25. Ji X, Xu J, Wang X, Qi P, Wei W, Chen X, et al. Citrinin determination in red fermented rice products by optimized extraction method coupled to liquid chromatography tandem mass spectrometry (LC-MS/MS). J Food Sci. 2015;80:T1438–T144.

    Article  CAS  PubMed  Google Scholar 

  26. Wang M, Jiang N, Xian H, Wei D, Shi L, Feng X. A single-step solid phase extraction for the simultaneous determination of 8 mycotoxins in fruits by ultra-high performance liquid chromatography tandem mass spectrometry. J Chromatogr A. 2016;1429:22–9.

    Article  CAS  PubMed  Google Scholar 

  27. Nigović B, Sertić M, Mornar A. Simultaneous determination of lovastatin and citrinin in red yeast rice supplements by micellar electrokinetic capillary chromatography. Food Chem. 2013;138:531–8.

    Article  CAS  PubMed  Google Scholar 

  28. Wang W, Chen Q, Zhang X, Zhang H, Huang Q, Li D, et al. Comparison of extraction methods for analysis of citrinin in red fermented rice. Food Chem. 2014;157:408–12.

    Article  CAS  PubMed  Google Scholar 

  29. Appell M, Mueller A. Mycotoxin analysis using imprinted materials technology: recent developments. J AOAC Int. 2016;99:861–4.

    Article  CAS  PubMed  Google Scholar 

  30. Akyıldırım O, Kardaş F, Beytur M, Yüksek H, Atar N, Yola ML. Palladium nanoparticles functionalized graphene quantum dots with molecularly imprinted polymer for electrochemical analysis of citrinin. J Mol Liq. 2017;243:677–81.

    Article  CAS  Google Scholar 

  31. Fang G, Liu G, Yang Y, Wang S. Quartz crystal microbalance sensor based on molecularly imprinted polymer membrane and three-dimensional Au nanoparticles@mesoporous carbon CMK-3 functional composite for ultrasensitive and specific determination of citrinin. Sensors Actuators B Chem. 2016;230:272–80.

    Article  CAS  Google Scholar 

  32. Guo B, Wang S, Ren B, Li X, Qin F, Li J. Citrinin selective molecularly imprinted polymers for SPE. J Sep Sci. 2010;33:1156–60.

    CAS  PubMed  Google Scholar 

  33. Urraca JL, Huertas-Pérez JF, Cazorla GA, Gracia-Mora J, García-Campaña AM, Moreno-Bondi MC. Development of magnetic molecularly imprinted polymers for selective extraction: determination of citrinin in rice samples by liquid chromatography with UV diode array detection. Anal Bioanal Chem. 2016;408:3033–42.

    Article  CAS  PubMed  Google Scholar 

  34. Campone L, Piccinelli AL, Celano R, Russo M, Valdés A, Ibáñez C, et al. A fully automated method for simultaneous determination of aflatoxins and ochratoxin A in dried fruits by pressurized liquid extraction and on-line solid-phase extraction cleanup coupled to ultra-high-pressure liquid chromatography-tandem mass spectrometry. Anal Bioanal Chem. 2015;407:2899–911.

    Article  CAS  PubMed  Google Scholar 

  35. Drzymala SS, Weiz S, Heinze J, Marten S, Prinz C, Zimathies A, et al. Automated solid-phase extraction coupled online with HPLC-FLD for the quantification of zearalenone in edible oil. Anal Bioanal Chem. 2015;407:3489–97.

    Article  CAS  PubMed  Google Scholar 

  36. Lhotská I, Šatínský D, Havlíková L, Solich P. A fully automated and fast method using direct sample injection combined with fused-core column on-line SPE-HPLC for determination of ochratoxin A and citrinin in lager beers. Anal Bioanal Chem. 2016;408:3319–29.

    Article  CAS  PubMed  Google Scholar 

  37. He C, Long Y, Pan J, Li K, Liu F. Application of molecularly imprinted polymers to solid-phase extraction of analytes from real samples. J Biochem Biophys Methods. 2007;70:133–50.

    Article  CAS  PubMed  Google Scholar 

  38. Vidal JC, Duato P, Bonel L, Castillo JR. Molecularly imprinted on-line solid-phase extraction coupled with fluorescence detection for the determination of ochratoxin A in wheat samples. Anal Lett. 2012;45:51–62.

    Article  CAS  Google Scholar 

  39. Bjarnason B, Chimuka L, Ramström O. On-line solid-phase extraction of triazine herbicides using a molecularly imprinted polymer for selective sample enrichment. Anal Chem. 1999;71:2152–6.

    Article  CAS  PubMed  Google Scholar 

  40. Machyňáková A, Hroboňová K. Synthesis and evaluation of molecularly imprinted polymers as sorbents for selective extraction of coumarins. Chromatographia. 2017;80:1015–24.

    Article  CAS  Google Scholar 

  41. Zhou J, He X, Li Y. An acrylamide-based molecularly imprinted polymer for the efficient recognition of optical amino acid hydantoins. Anal Commun. 1999;36:243–6.

    Article  CAS  Google Scholar 

  42. Hartl A, Stenzel WR. Development of a method for the determination of citrinin in barley, rye and wheat by solid phase extraction on aminopropyl columns and HPLC-FLD. Mycotoxin Res. 2007;23:127–31.

    Article  CAS  PubMed  Google Scholar 

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Acknowledgements

Special thanks are given to P. Kejzlar and J. Hlavatá (Technical University of Liberec, Institute for Nanomaterials, Advanced Technology and Innovation, Department of the Preparation and Analysis of Nanostructures) for providing SEM scans.

Funding

This work was supported by the Charles University Grant Agency, project no. 726 316. I. Lhotská received a financial support from the project of specific research of Charles University, project no. SVV 260 412. A. Machyňáková and K. Hroboňová received a financial support from Slovak Research and Development Agency with contract no. APVV-15-0355. This work was also supported by the EFSA-CDN project (no. CZ.02.1.01/0.0/0.0/16_019/0000841) co-funded by ERDF.

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Authors and Affiliations

  1. The Department of Analytical Chemistry, Faculty of Pharmacy, Charles University, Heyrovského 1203, 500 05, Hradec Králové, Czech Republic

    Ivona Lhotská, Aneta Kholová, Petr Solich, František Švec & Dalibor Šatínský

  2. Institute of Analytical Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, 812 37, Bratislava, Slovakia

    Andrea Machyňáková & Katarína Hroboňová

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  1. Ivona Lhotská
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Lhotská, I., Kholová, A., Machyňáková, A. et al. Preparation of citrinin-selective molecularly imprinted polymer and its use for on-line solid-phase extraction coupled to liquid chromatography. Anal Bioanal Chem 411, 2395–2404 (2019). https://doi.org/10.1007/s00216-019-01682-9

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  • DOI: https://doi.org/10.1007/s00216-019-01682-9

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