Abstract
Dummy molecularly imprinted polymers (DMIPs) were grafted on the surface of microspheres (CG161M) by surface imprinting and layer by layer self-assembling process and applied as adsorbent for the rapid and selective detection of phthalate compounds, such as diethyl phthalate (DEP), dibutyl phthalate (DBP) and dioctyl phthalate (DOP). Dioctyl phthalate (DOP) was chosen as a dummy template for diethyl phthalate (DEP) and dibutyl phthalate (DEP), allowing selective and specific identification of DEP and DBP and did not affect the accuracy of the analysis even if the template has not been eluted completely. The synthesized composites were characterized by Fourier transform infrared spectrometer, scanning electron microscope, static/kinetic adsorption, thermogravimetric analysis and nitrogen adsorption analysis. The maximum adsorption capacities of the MIPs for DEP, DBP and DOP were 0.006, 0.008 and 0.007 mg g−1, respectively. The adsorption of phthalates reached equilibrium within 260 min and complied well with pseudo-second-order kinetic model and Langmuir model. Moreover, MIPs-based sorbents combined with hollow fibre stirring bar sorptive extraction followed by gas chromatography–mass spectrometry was applied to the recognition of DEP, DBP and DOP in several food samples. Under the optimum conditions, the limits of detection (LODs) for DEP, DBP and DOP were 0.0047, 0.0054 and 0.0031 mg L−1, with spiked recoveries of 73.06–106.02% and relative standard deviations (RSDs) within 3.91–6.89%, exhibiting high adsorption capacity and good selectivity of DMIPs towards DEP, DBP and DOP. Since the template of surface molecularly imprinted polymers could be changed with the analytes, MIP-based molecularly imprinted polymers combining with hollow fibre stirring bar sorptive extraction can be a promising and selective method for recognition and separation of a certain series of analytes with similar skeleton in complicated samples without sample clean-up.
Graphical Abstract
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Data Availability
No datasets were generated or analysed during the current study.
References
Abdar A, Amiri A, Mirzaei M (2023) Electrospun mesh pattern of polyvinyl alcohol/zirconium-based metal-organic framework nanocomposite as a sorbent for extraction of phthalate esters. J Chromatogr A 1707:464295. https://doi.org/10.1016/j.chroma.2023.464295
Bhogal S, Mohiuddin I, Kim K-H, Malik AK, Kaur K (2023) Restricted access medium magnetic molecularly imprinted polymers: validation of their suitability as an effective quantitation tool against phthalates in food products packaged in plastic. Chem Eng J 457:141270. https://doi.org/10.1016/j.cej.2023.141270
Caldeirão L, Fernandes JO, Da Silva OW, Godoy HT, Cunha SC (2021) Phthalic acid esters and adipates in herbal-based soft drinks: an eco-friendly method. Anal Bioanal Chem 413(11):2903–2910. https://doi.org/10.1007/s00216-021-03219-5
Chao H, Wang H, Ma S, Bo C, Ou J, Gong B (2021) Recent application of molecular imprinting technique in food safety. J Chromatogr A 1657:462579. https://doi.org/10.1016/j.chroma.2021.462579
Chen L, Xu S, Li J (2011) Recent advances in molecular imprinting technology: current status, challenges and highlighted applications. Chem Soc Rev 40(5):2922–3021. https://doi.org/10.1039/c0cs00084a
Chen S, Fu J, Li Z, Zeng Y, Yang Y (2019) Preparation and application of magnetic molecular imprinted polymers for extraction of cephalexin from pork and milk samples. J Chromatogr A 1602:124–211. https://doi.org/10.1016/j.chroma.2019.06.032
Chen RN, Kang SH, Li J, Lu LN, Luo XP, Wu L (2021a) Comparison and recent progress of molecular imprinting technology and dummy template molecular imprinting technology. Anal Methods 13(39):4538–4619. https://doi.org/10.1039/d1ay01014j
Chen F, Li X, Dong Y, Li J, Li Y, Li H, Chen L, Zhou M, Hou H (2021b) Biodegradation of phthalic acid esters (PAEs) by Cupriavidus oxalaticus strain E3 isolated from sediment and characterization of monoester hydrolases. Chemosphere 266:129061. https://doi.org/10.1016/j.chemosphere.2020.129061
Feng G, Sun J, Wang M, Wang M, Li Z, Wang S, Zheng L, Wang J, She Y, Abd El-Aty A (2021) Preparation of molecularly imprinted polymer with class-specific recognition for determination of 29 sulfonylurea herbicides in agro-products. J Chromatogr A 1647:462143. https://doi.org/10.1016/j.chroma.2021.462143
Gao J, Fan D, Chu Q, Lyu H, Xie Z (2022) Fabrication of a novel surface molecularly imprinted polymer based on zeolitic imidazolate framework-7 for selective extraction of phthalates. Microchem J 178:107399. https://doi.org/10.1016/j.microc.2022.107399
Guo L, Ma X, Xie X, Huang R, Zhang M, Li J, Zeng G, Fan Y (2019) Preparation of dual-dummy-template molecularly imprinted polymers coated magnetic graphene oxide for separation and enrichment of phthalate esters in water. Chem Eng J 361:245–311. https://doi.org/10.1016/j.cej.2018.12.076
Guo M, Ye J, Zheng C, Meng J (2022) Dual-recognition membrane adsorbers combining hydrophobic charge-induction chromatography with surface imprinting via multicomponent reaction. J Chromatogr A 1668:462918. https://doi.org/10.1016/j.chroma.2022.462918
Hao Y, Gao Y, Gao L, He Y, Wang S (2021) Amphiphilic core-shell magnetic adsorbents for efficient removal and detection of phthalate esters. Chem Eng J 423(1):129817. https://doi.org/10.1002/adma.202003065
Hu X, Cao Y, Tian Y, Qi Y, Fang G, Wang S (2020) A molecularly imprinted fluorescence nanosensor based on upconversion metal–organic frameworks for alpha-cypermethrin specific recognition. Microchim Acta 187(11):1–10. https://doi.org/10.1007/s00604-020-04610-2
Huang Z, He J, Li Y, Wu C, You L, Wei H, Li K, Zhang S (2019) Preparation of dummy molecularly imprinted polymers for extraction of Zearalenone in grain samples. J Chromatogr A 1602:11–18. https://doi.org/10.1016/j.chroma.2019.05.022
Jiménez-Skrzypek G, González-Sálamo J, Varela-Martínez DA, González-Curbelo MÁ, Hernández-Borges J (2020) Analysis of phthalic acid esters in sea water and sea sand using polymer-coated magnetic nanoparticles as extraction sorbent. J Chromatogr A 1611:460620. https://doi.org/10.1016/j.chroma.2019.460620
Küçük M, Osman B, Ozer ET (2024) Dummy molecularly imprinted polymer-based solid-phase extraction method for the determination of some phthalate monoesters in urine by gas chromatography-mass spectrometry analysis. J Chromatogr A 1713:464532. https://doi.org/10.1016/j.chroma.2023.464532
Li L, Yang L, Xing Z, Lu X, Kan X (2013) Surface molecularly imprinted polymers-based electrochemical sensor for bovine hemoglobin recognition. Analyst 138(22):6962–6967. https://doi.org/10.1039/C3AN01435E
Li L, Cui Y, Ren L, Li C, Liu Y, Jin Z (2021) Magnetic dummy molecularly imprinted polymer nanoparticles as sorbent for dispersive solid-phase microextraction of phthalate monoesters in human urine samples. Microchem J 167:106266. https://doi.org/10.1016/j.microc.2021.106266
Li XX, Zhong YP, Huang C, Zhu J, Chen L (2017) Effect of amylose/amylopectin ratios on plasticizer migration in esterified starch-based films. Xiandai Shipin Keji 33(5): 97–6. https://doi.org/10.13982/j.mfst.1673-9078.2017.5.016
Lin Z, Cheng W, Li Y, Liu Z, Chen X, Huang C (2012) A novel superparamagnetic surface molecularly imprinted nanoparticle adopting dummy template: an efficient solid-phase extraction adsorbent for bisphenol A. Anal Chim Acta 720:71–76. https://doi.org/10.1016/j.aca.2012.01.020
Liu Y, Wang D, Du F, Zheng W, Liu Z, Xu Z, Hu X, Liu H (2019) Dummy-template molecularly imprinted micro-solid-phase extraction coupled with high-performance liquid chromatography for bisphenol A determination in environmental water samples. Microchem J 145:337–338. https://doi.org/10.1016/j.microc.2018.10.054
Liu Q, Ye J, Han Y, Wang P, Fei Z, Chen X, Zhang Z, Tang J, Cui M, Qiao X (2021) Defective UiO-67 for enhanced adsorption of dimethyl phthalate and phthalic acid. J Mol Liq 321:114477. https://doi.org/10.1016/j.molliq.2020.114477
Ma J-K, Wei S-L, Tang Q, Huang X-C (2022) A novel enrichment and sensitive method for simultaneous determination of 15 phthalate esters in milk powder samples. LWT 153:112426. https://doi.org/10.1016/j.lwt.2021.112426
Martín-Gómez B, Stephen Elmore J, Valverde S, Ares AM, Bernal J (2024) Recent applications of chromatography for determining microplastics and related compounds (bisphenols and phthalate esters) in food. Microchem J 197:109903. https://doi.org/10.1016/j.microc.2024.109903
Notardonato I, Di Fiore C, Iannone A, Russo MV, Blasi MF, Favero G, Mattei D, Protano C, Vitali M, Avino P (2021) Fast and reliable determination of phthalic acid esters in the blood of marine turtles by means of solid phase extraction coupled with gas chromatography-ion trap/mass spectrometry. Toxics 9(11):279. https://doi.org/10.3390/toxics9110279
Ortega-Zamora C, Jiménez-Skrzypek G, González-Sálamo J, Hernández-Borges J (2021) Extraction of phthalic acid esters from soft drinks and infusions by dispersive liquid-liquid microextraction based on the solidification of the floating organic drop using a menthol-based natural deep eutectic solvent. J Chromatogr A 1646:462132. https://doi.org/10.1016/j.chroma.2021.462132
Ran H, Lin ZZ, Hong CY, Zeng J, Yao QH, Huang ZY (2019) Self-assembly PS@dual-emission ratiometric fluorescence probe coupled with core-shell structured MIP for the detection of malachite green in fish. J Photochem Photobiol A 372:260–10. https://doi.org/10.1016/j.jphotochem.2018.12.029
Ratautaite V, Bubniene U, Plausinaitis D, Boguzaite R, Ramanavicius A (2021) Molecular imprinting technology for determination of uric acid. Int J Mol Sci 22(9):5032. https://doi.org/10.3390/ijms22095032
Ren L, Wang G, Huang Y, Guo J, Li C, Jia Y, Chen S, Zhou JL, Hu H (2021) Phthalic acid esters degradation by a novel marine bacterial strain Mycolicibacterium phocaicum RL-HY01: characterization, metabolic pathway and bioaugmentation. Sci Total Environ 791:148303. https://doi.org/10.1016/j.scitotenv.2021.148303
Sambolino A, Ortega-Zamora C, González-Sálamo J, Dinis A, Cordeiro N, Canning-Clode J, Hernández-Borges J (2022) Determination of phthalic acid esters and di (2-ethylhexyl) adipate in fish and squid using the ammonium formate version of the QuEChERS method combined with gas chromatography mass spectrometry. Food Chem 380:132174. https://doi.org/10.1016/j.foodchem.2022.132997
Sengar MS, Kumari P, Sengar N, Singh SK (2024) Molecularly imprinted polymer technology for the advancement of its health surveillances and environmental monitoring. ACS Appl Polym Mater 6(2):1086–1120. https://doi.org/10.1021/acsapm.3c02185
Shen J, Yang W, Zhu W, Che J, Ding H, Song F, Zhang W, Jiang P, Xu W, Huang W (2023) Preparation and characterisation of photoresponsive molecularly imprinting polymer nanoparticles with hollow structure for extraction and enrichment of dibutyl phthalate. React Funct Polym 186:105536. https://doi.org/10.1016/j.reactfunctpolym.2023.105536
Sitko R, Zawisza B, Kowalewska Z, Kocot K, Polowniak M (2011) Fast and simple method for determination of fatty acid methyl esters (FAME) in biodiesel blends using X-ray spectrometry. Talanta 85(4):2000–2007. https://doi.org/10.1016/j.talanta.2011.07.046
Socas-Rodríguez B, González-Sálamo J, Herrera-Herrera AV, Santana-Mayor Á, Hernández-Borges J (2018) Determination of phthalic acid esters in different baby food samples by gas chromatography tandem mass spectromet. Anal Bioanal Chem 410(22):5617–5712. https://doi.org/10.1007/s00216-018-0977-y
Sun X, Peng J, Wang M, Wang J, Tang C, Yang L, Lei H, Li F, Wang X, Chen J (2018) Determination of nine bisphenols in sewage and sludge using dummy molecularly imprinted solid-phase extraction coupled with liquid chromatography tandem mass spectrometry. J Chromatogr A 1552:10–17. https://doi.org/10.1016/j.chroma.2018.04.004
Sun X, Wang M, Yang L, Wen H, Wang L, Li T, Tang C, Yang J (2019) Preparation and evaluation of dummy-template molecularly imprinted polymer as a potential sorbent for solid phase extraction of imidazole fungicides from river water. J Chromatogr A 1586:1–8. https://doi.org/10.1016/j.chroma.2018.11.077
Tan D, Han C, Yu Z, Sun X, Chen J, Shao X, Wang D (2022) Dummy molecularly imprinted polymers for class-selective extraction of amphetamine-type stimulants from alcoholic and nonalcoholic beverages. J Chromatogr A 1663:462759. https://doi.org/10.1016/j.chroma.2021.462759
Wang D, Xu Z, Liu Y, Liu Y, Li G, Si X, Lin T, Liu H, Liu Z (2020) Molecularly imprinted polymer-based fiber array extraction of eight estrogens from environmental water samples prior to high-performance liquid chromatography analysis. Microchem J 159:105376. https://doi.org/10.1016/j.microc.2020.105376
Wang S, Pan M, Liu K, Xie X, Yang J, Hong L, Wang S (2022) A SiO2@MIP electrochemical sensor based on MWCNTs and AuNPs for highly sensitive and selective recognition and detection of dibutyl phthalate. Food Chem 381:132225. https://doi.org/10.1016/j.foodchem.2022.132225
Wei SL, Liu WT, Huang XC, Ma JK (2018) Preparation and application of a magnetic plasticizer as a molecularly imprinted polymer adsorbing material for the determination of phthalic acid esters in aqueous samples. J Sep Sci 41(19):3806–3809. https://doi.org/10.1002/jssc.201800535
Xu Y, Weng R, Lu Y, Wang X, Zhang D, Li Y, Qiu J, Qian Y (2018) Evaluation of phthalic acid esters in fish samples using gas chromatography tandem mass spectrometry with simplified QuEChERS technique. Food Anal Methods 11:3293–3311. https://doi.org/10.1007/s12161-018-1313-z
Xu S, Zhang X, Xu Z, Duan Y, Liu Z, Zhang Y (2024) Exposure and risk assessment of phthalates in environmental water using a three-template molecularly imprinted fiber array strategy. J Hazard 461:132491. https://doi.org/10.1016/j.jhazmat.2023.132491
Youli Q, Long J, Yu L (2018) Theoretical support for the enhancement of infrared spectrum signals by derivatization of phthalic acid esters using a pharmacophore model. Spectrosc Lett 51(3):155–158. https://doi.org/10.1080/00387010.2018.1442353
Zhang X, Sun X, Wang M, Wang Y, Wu Q, Ji L, Li Q, Yang J, Zhou Q (2020) Dummy molecularly imprinted microspheres prepared by pickering emulsion polymerization for matrix solid-phase dispersion extraction of three azole fungicides from fish sample. J Chromatogr A 1620:461013. https://doi.org/10.1016/j.chroma.2020.461013
Zhang X, Gao J, Chu Q, Lyu Xie Z (2022) Specific recognition and determination of trace phthalic acid esters by molecularly imprinted polymer based on metal organic framework. Anal Chim Acta 1227:340292. https://doi.org/10.1016/j.aca.2022.340292
Zhao Q-Y, Zhao H-T, Yang X, Zhang H, Dong A-J, Wang J, Li B (2018) Selective recognition and fast enrichment of anthocyanins by dummy molecularly imprinted magnetic nanoparticles. J Chromatogr A 1572:9–11. https://doi.org/10.1016/j.chroma.2018.08.029
Zhu J, Lu B, Liu S, Xu A, Tang G, Chen Z, Pan Y, Tang G, Yang F, Zhou Y (2020) Magnetic graphene dispersive solid-phase extraction for the determination of phthalic acid esters in flavoring essences by gas chromatography tandem mass spectrometry. J Chromatogr Sci 58(8):770–779. https://doi.org/10.1093/chromsci/bmaa032
Funding
Financial supports from Fundamental Research Funds for the Central Universities (No. 31920220160 and 31920210037) are gratefully acknowledged. This work was also supported by Northwest Minzu University's Double First-class and Characteristic Development Guide Special Funds-Chemistry Key Disciplines in Gansu Province (No. 11080316).
Author information
Authors and Affiliations
Contributions
Jia Li and Runan Chen wrote the main manuscript text, Jing Ma and Binlian Jiang prepared figures and tables. All authors reviewed the manuscript.
Corresponding author
Ethics declarations
Ethical Approval
This article does not contain any studies with human participants or animals performed by any of the authors.
Competing Interests
The authors declare no competing interests.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Li, J., Chen, R., Ma, J. et al. Dummy Template–Based Molecularly Imprinted Solid-Phase Microextraction Coating for Analysis of Plasticizers in Food Samples. Food Anal. Methods 17, 712–726 (2024). https://doi.org/10.1007/s12161-024-02596-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12161-024-02596-8