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Analytical and Bioanalytical Chemistry

, Volume 406, Issue 25, pp 6319–6327 | Cite as

Identification of 3-chloro-1,2-propandiol using molecularly imprinted composite solid-phase extraction materials

  • Yun LiEmail author
  • Chuangmu Zheng
  • Xiulan SunEmail author
  • Ben Ouyang
  • Ping Ni
  • Yingzhi Zhang
Research Paper

Abstract

A novel molecularly imprinted material based on silica microparticles was synthesized by surface polymerization with 3-chloro-1,2-propandiol (3-MCPD) as a template molecule. The molecularly imprinted polymer (MIP) was characterized by infrared spectroscopy and scanning electron microscopy. The adsorption of 3-MCPD by MIP was measured by gas chromatography with electron capture detection (GC-ECD) and an equilibrium binding experiment. Scatchard analysis revealed that the maximum apparent binding capacities of the MIP and non-imprinted polymer (NIP) were 67.64 and 23.31 μmol/g, respectively. The new adsorbent was successfully used in solid-phase extraction (SPE) to selectively enrich and determine 3-MCPD in soy sauce samples. The MIP-SPE column achieves recoveries higher than 92.7 % with a relative standard deviation of less than 1.83 %. The MIP-SPE-GC protocol improved the selectivity and eliminated the effects of template leakage on quantitative analysis and could be used for the determination of 3-MCPD in other complex food samples.

Graphical Abstract

The MIP-SPE column developed by us achieves recoveries higher than 92.7 % with a relative standard deviation of less than 1.83 % for determining the 3-MCPD in the soy sauce matrix (mixed with 3-MCPD, 2-MPCD and 1,3-DCP).

Keywords

3-MCPD Molecular imprinting Silica Microparticles Adsorption 

Notes

Acknowledgments

The authors are mainly grateful to “973” National Basic Research Program of China (No. 2012CB720804), and the Commonweal Project of the Ministry of Agriculture (No. 201203069-1) for funding the research. This work has also been supported by Program for New Century Excellent Talents in Jiangsu University, Synergetic Innovation Center of Food Safety & Quality Control Jiangsu Province, the Priority Academic Program Development of Jiangsu Higher Education Institutions, and partly supported by “Risk Assessment for Agro-products Quality & Safety” Financial Fund of Ministry of Agriculture.

References

  1. 1.
    Crews C, Hasnip S, Chapman S, Hough P, Potter N, Todd J, Brereton P, Matthews W (2003) Survey of chloropropanols in soy sauces and related products purchased in the UK in 2000 and 2002. Food Addit Contam 20:916–922CrossRefGoogle Scholar
  2. 2.
    Baer I, de la Calle B, Taylor P (2010) 3-MCPD in food other than soy sauce or hydrolysed vegetable protein (HVP). Anal Bioanal Chem 396:443–456CrossRefGoogle Scholar
  3. 3.
    Vicente E, Arisseto AP, Monteiro V, Furlani RPZ, Toledo MCF (2011) A survey of chloropropanols (3-MCPD and 1,3-DCP) in soy sauces and similar products from Brazil. Toxicol Lett 205:S145–S146CrossRefGoogle Scholar
  4. 4.
    Crews C, Brereton P, Davies A (2001) The effects of domestic cooking on the levels of 3-monochloropropanediol in foods. Food Addit Contam 18:271–280CrossRefGoogle Scholar
  5. 5.
    Breitling-Utzmann CM, Hrenn H, Haase NU, Unbehend GM (2005) Influence of dough ingredients on 3-chloropropane-1,2-diol (3-MCPD) formation in toast. Food Addit Contam 22:97–103CrossRefGoogle Scholar
  6. 6.
    Cho WS, Han BS, Nam KT, Park K, Choi M, Kim SH, Jeong J, Jang DD (2008) Carcinogenicity study of 3-monochloropropane-1,2-diol in Sprague–Dawley rats. Food Chem Toxicol 46:3172–3177CrossRefGoogle Scholar
  7. 7.
    Byun JA, Ryu MH, Lee JK (2006) The immunomodulatory effects of 3-monochloro-1,2-propanediol on murine splenocyte and peritoneal macrophage function in vitro. Toxicol in Vitro 20:272–278CrossRefGoogle Scholar
  8. 8.
    Egmond H, Schothorst R, Jonker M (2007) Regulations relating to mycotoxins in food. Anal Bioanal Chem 389:147–157CrossRefGoogle Scholar
  9. 9.
    Robert MC, Oberson JM, Stadler RH (2004) Model studied on the formation of monochloropropanediols in the presence of lipase. J Agric Food Chem 52:5102–5108CrossRefGoogle Scholar
  10. 10.
    Kirkland DJ, Henderson L, Marzin D, Müller L, Parry JM, Speit G, Tweats DJ, Williams GM (2005) Testing strategies in mutagenicity and genetic toxicology: an appraisal of the guidelines of the European Scientific Committee for Cosmetics and Non-Food Products for the evaluation of hair dyes. Mutat Res 588:88–105CrossRefGoogle Scholar
  11. 11.
    Xing X, Cao Y, Wang L (2005) Determination of rate constants and activation energy of 3-chloro-1,2-propanediol hydrolysis by capillary electrophoresis with electrochemical detection. J Chromatogr A 1072:267–272CrossRefGoogle Scholar
  12. 12.
    Xing X, Cao Y (2007) Determination of 3-chloro-1,2-propanediol in soy sauces by capillary electrophoresis with electrochemical detection. Food Control 18:167–172CrossRefGoogle Scholar
  13. 13.
    Cifuentes A (2006) Recent advances in the application of capillary electromigration methods for food analysis. Electrophoresis 27:283–303CrossRefGoogle Scholar
  14. 14.
    Pesselman RL, Feit MJ (1988) Determination of residual epichlorohydrin and 3-chloropropanediol in water by gas chromatography with electron-capture detection. J Chromatogr A 439:448–452CrossRefGoogle Scholar
  15. 15.
    Spyres G (1993) Determination of 3-chloropropane-1,2-diol in hydrolysed vegetable proteins by capillary gas chromatography with electrolytic conductivity detection. J Chromatogr A 638:71–74CrossRefGoogle Scholar
  16. 16.
    Racamonde I, González P, Lorenzo RA, Carro AM (2011) Determination of chloropropanols in foods by one-step extraction and derivatization using pressurized liquid extraction and gas chromatography–mass spectrometry. J Chromatogr A 1218:6878–6883CrossRefGoogle Scholar
  17. 17.
    Ma F, Li P, Matthäus B, Zhang W, Zhang Q (2012) Optimization of ultrasonic-assisted extraction of 3-monochloropropane-1,2-diol (MCPD) and analysis of its esters from edible oils by gas chromatography–mass spectrometry. J Sep Sci 35:2241–2248CrossRefGoogle Scholar
  18. 18.
    González P, Racamonde I, Carro AM, Lorenzo RA (2011) Combined solid-phase extraction and gas chromatography–mass spectrometry used for determination of chloropropanols in water. J Sep Sci 34:2697–2704CrossRefGoogle Scholar
  19. 19.
    León N, Yusà V, Pardo O, Pastor A (2008) Determination of 3-MCPD by GC-MS/MS with PTV-LV injector used for a survey of Spanish foodstuffs. Talanta 75:824–831CrossRefGoogle Scholar
  20. 20.
    Küsters M, Bimber U, Ossenbrüggen A, Reeser S, Gallitzendörfer R, Gerhartz M (2010) Rapid and simple micromethod for the simultaneous determination of 3-MCPD and 3-MCPD esters in different foodstuffs. J Agric Food Chem 58:6570–6577CrossRefGoogle Scholar
  21. 21.
    Hamlet CG, Sutton PG (1997) Determination of the chloropropanols, 3-chloro-1,2-propandiol and 2-chloro-1,3-propandiol, in hydrolysed vegetable proteins and seasonings by gas chromatography/ion trap tandem mass spectrometry. Rapid Commum Mass Spectrom 11:1417–1424CrossRefGoogle Scholar
  22. 22.
    Rodman LE, Ross RD (1986) Gas–liquid chromatography of 3-chloropropanediol. J Chromatogr A 369:97–103CrossRefGoogle Scholar
  23. 23.
    Sato H, Kaze N, Yamamoto H, Watanabe Y (2013) 2-monochloro-1, 3-propanediol (2-MCPD) dynamics in DGF standard methods and quantification of 2-MCPD. J Am Oil Chen Soc 90(8):1121–1130CrossRefGoogle Scholar
  24. 24.
    Mamilla RY, Chetyala RK, Venna R, Gajjela R, Katragadda K, Govindasamy S, Mulukutla S, Datta D (2010) A sensitive and selective GC–MS method for analysis of process-related genotoxic impurities in atenolol. Chromatographia 71(7–8):733–736CrossRefGoogle Scholar
  25. 25.
    Carro AM, González P, Lorenzo RA (2013) Simultaneous derivatization and ultrasound-assisted dispersive liquid–liquid microextraction of chloropropanols in soy milk and other aqueous matrices combined with gas-chromatography–mass spectrometry. J Chromatogr A 1319:35–45CrossRefGoogle Scholar
  26. 26.
    Caro E, Marcé RM, Borrull F, Cormack PAG, Sherrington DC (2006) Application of molecularly imprinted polymers to solid-phase extraction of compounds from environmental and biological samples. Trac Trend Anal Chem 25:143–154CrossRefGoogle Scholar
  27. 27.
    Puoci F, Cirillo G, Curcio M, Iemma F, Spizzirri UG, Picci N (2007) Molecularly imprinted solid phase extraction for the selective HPLC determination of α-tocopherol in bay leaves. Anal Chim Acta 593:164–170CrossRefGoogle Scholar
  28. 28.
    Caro E, Masqué N, Marcé RM, Borrull F, Cormack PAG, Sherrington DC (2002) Non-covalent and semi-covalent molecularly imprinted polymers for selective on-line solid-phase extraction of 4-nitrophenol from water samples. J Chromatogr A 963:169–178CrossRefGoogle Scholar
  29. 29.
    Anderson RA, Ariffin MM, Cormack PAG, Miller EI (2008) Comparison of molecularly imprinted solid-phase extraction (MISPE) with classical solid-phase extraction (SPE) for the detection of benzodiazepines in post-mortem hair samples. Forensic Sci Int 174:40–46CrossRefGoogle Scholar
  30. 30.
    Benito-Peña E, Urraca JL, Sellergren B, Moreno-Bondi MC (2008) Solid-phase extraction of fluoroquinolones from aqueous samples using a water-compatible stochiometrically imprinted polymer. J Chromatogr A 1208:62–70CrossRefGoogle Scholar
  31. 31.
    Liang RN, Song DA, Zhang RM, Qin W (2010) Potentiometric sensing of neutral species based on a uniform-sized molecularly imprinted polymer as a receptor. Angew Chem 122:2610–2613CrossRefGoogle Scholar
  32. 32.
    Pan J, Yao H, Guan W, Ou H, Huo P, Wang X, Zou X, Li C (2011) Selective adsorption of 2,6-dichlorophenol by surface imprinted polymers using polyaniline/silica gel composites as functional support: equilibrium, kinetics, thermodynamics modeling. Chem Eng J 172:847–855CrossRefGoogle Scholar
  33. 33.
    Zhu R, Zhao W, Zhai M, Wei F, Cai Z, Sheng N, Hu Q (2010) Molecularly imprinted layer-coated silica nanoparticles for selective solid-phase extraction of bisphenol A from chemical cleansing and cosmetics samples. Anal Chim Acta 658:209–216CrossRefGoogle Scholar
  34. 34.
    Lorenzo AR, Carro MA, Alvarez-Lorenzo C, Concheiro A (2011) To remove or not to remove? The challenge of extracting the template to make the cavities available in molecularly imprinted polymers (MIPs). Int J Mol Sci 12(7):4327–4347CrossRefGoogle Scholar
  35. 35.
    Tokonami S, Shiigi H, Nagaoka T (2009) Review: micro- and nanosized molecularly imprinted polymers for high-throughput analytical applications. Anal Chim Acta 641:7–13CrossRefGoogle Scholar
  36. 36.
    Luo W, Zhu L, Yu C, Tang H, Yu H, Li X, Zhang X (2008) Synthesis of surface molecularly imprinted silica micro-particles in aqueous solution and the usage for selective off-line solid-phase extraction of 2,4-dinitrophenol from water matrixes. Anal Chim Acta 618:147–156CrossRefGoogle Scholar
  37. 37.
    Kandimalla BV, Ju HX (2004) Molecular imprinting: a dynamic technique for diverse applications in analytical chemistry. Anal Bioanal Chem 380:587–605CrossRefGoogle Scholar
  38. 38.
    Sun HW, Qiao FX (2008) Recognition mechanism of water-compatible molecularly imprinted solid-phase extraction and determination of nine quinolones in urine by high performance liquid chromatography. J Chromatogr A 1212:1–9CrossRefGoogle Scholar
  39. 39.
    Yu C, Mosbach K (1997) Molecular imprinting utilizing an amide functional group for hydrogen bonding leading to highly efficient polymers. J Org Chem 62(12):4057–4064CrossRefGoogle Scholar
  40. 40.
    Chandy G, Zampighi GA, Kreman M et al (1997) Comparison of the water transporting properties of MIP and AQP1. J Membr Biol 159(1):29–39CrossRefGoogle Scholar
  41. 41.
    Jiang D, Sun XL, Zhang Y (2012) Preparation and application of acrylamide molecularly imprinted composite solid-phase extraction materials. Anal Methods 4(11):3760–3766CrossRefGoogle Scholar
  42. 42.
    Anderson LI (2000) Molecular imprinting for drug bioanalysis: a review on the application of imprinted polymers to solid-phase extraction and binding assay. J Chromatogr Biomed Appl 739(1):163–173CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  1. 1.Key Laboratory of Agro-food Safety and Quality of Ministry of Agriculture, Institute of Quality Standards and Testing Technology for Agro-productsChinese Academy of Agricultural SciencesBeijingPeople’s Republic of China
  2. 2.State Key Laboratory of Food Science and Technology, School of Food Science and Technology, Synergetic Innovation Center of Food Safety and NutritionJiangnan UniversityWuxiPeople’s Republic of China
  3. 3.College of Tea & Food Science and TechnologyAnhui Agricultural UniversityHefeiPeople’s Republic of China

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