Imidazolium-based mesoporous organosilicas with bridging organic groups for microextraction by packed sorbent of phenoxy acid herbicides, polycyclic aromatic hydrocarbons and chlorophenols
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The authors describe the preparation of two kinds of periodic mesoporous organosilicas (PMOs). The first kind is monofunctional and has a bridged alkyl imidazolium framework (PMO-IL). The other is a two-dimensional (2D) hexagonal bifunctional periodic mesoporous organosilica (BFPMO) with bridged IL-phenyl or -ethyl units. The CPMOs were utilized as highly sensitive and stable sorbents for microextraction by packed sorbent. The materials were characterized by SEM, TEM, FT-IR, and N2 adsorption–desorption analysis. The adsorption capacities of the sorbents were investigated by using phenoxy acid herbicides as model analytes. The effects of bifunctionality and type of additional surface groups (phenyl or ethyl) on the efficiency of the extraction is emphasized. Three kinds of environmental contaminants, viz. phenoxy acid herbicides (CPAs), polycyclic aromatic hydrocarbons and chlorophenols were then studied with respect to their extraction by the sorbents. The interactions between the CPAs and the sorbents were evaluated by pH-changing processes to explore the interactions that play a major role. The selectivity of the sorbents was investigated by extraction of other types of analytes of with various polarity and charge. The BFPMOs display the typical good chemical stability of silica materials. The extraction properties are much better compared to commercial silicas. This is assumed to be due to the highly ordered mesoporous structures and the different types of probable interactions with analytes. The performance of the method was evaluated by extraction of CPAs as model analytes from aqueous samples, and quantification by GC with FID detection. Under optimized conditions, low limits of detection (0.1–0.5 μg.L−1) and a wide linearity (0.5–200 μg.L−1) were obtained. The method was applied to the trace analysis of CPAs in farm waters and rice samples.
KeywordsPreconcentration BFPMO Selectivity Tetrabutylammonium Transmission electron microscopy Gas chromatography Central composite design Rice analysis
Financial support from Tarbiat Modares University is gratefully acknowledged.
Compliance with ethical standards
The author(s) declare that they have no competing interests.
- 1.Abdel-Rehim M (2004) New trend in sample preparation: on-line microextraction in packed syringe for liquid and gas chromatography applications: I. Determination of local anaesthetics in human plasma samples using gas chromatography–mass spectrometry. J Chromatogr B 801:317–321. https://doi.org/10.1016/j.jchromb.2003.11.042 CrossRefGoogle Scholar
- 5.Klimowska A, Wielgomas B (2018) Off-line microextraction by packed sorbent combined with on solid support derivatization and GC-MS: application for the analysis of five pyrethroid metabolites in urine samples. Talanta 176:165–171. https://doi.org/10.1016/j.talanta.2017.08.011 CrossRefPubMedGoogle Scholar
- 7.Matysik S, Matysik FM (2009) Microextraction by packed sorbent coupled with gas chromatography—mass spectrometry: application to the determination of metabolites of monoterpenes in small volumes of human urine. Microchim Acta 166:109–114. https://link.springer.com/article/. https://doi.org/10.1007/s00604-009-0170-2 CrossRefGoogle Scholar
- 8.Prieto A, Schrader S, Bauer C, Möder M (2011) Synthesis of a molecularly imprinted polymer and its application for microextraction by packed sorbent for the determination of fluoroquinolone related compounds in water. Anal Chim Acta 685:146–152. https://doi.org/10.1016/j.aca.2010.11.038 CrossRefPubMedGoogle Scholar
- 11.Bagheri H, Banihashemi S, Zandian FK (2016) Microextraction of antidepressant drugs into syringes packed with a nanocomposite consisting of polydopamine, silver nanoparticles and polypyrrole. Microchim Acta 183:195–202. https://link.springer.com/article/. https://doi.org/10.1007/s00604-015-1606-5 CrossRefGoogle Scholar
- 13.Karimi B, Elhamifar D, Yari O, Khorasani M, Vali H, Clark JH, Hunt AJ (2012) Synthesis and characterization of Aalkyl-imidazolium-based periodic mesoporous organosilicas: a versatile host for the immobilization of perruthenate (RuO4−) in the aerobic oxidation of alcohols. Chem Eur J 18:13520–13530. https://doi.org/10.1002/chem.201200380 CrossRefPubMedGoogle Scholar
- 14.Vathyam R, Wondimu E, Das S, Zhang C, Hayes S, Tao Z, Asefa T (2011) Improving the adsorption and release capacity of organic-functionalized mesoporous materials to drug molecules with temperature and synthetic methods. J Phys Chem C 115:13135–13150. https://doi.org/10.1021/jp1108587 CrossRefGoogle Scholar
- 15.Abolghasemi MM, Karimi B, Yousefi V (2013) Periodic mesoporous organosilica with ionic liquid framework as a novel fiber coating for headspace solid-phase microextraction of polycyclic aromatic hydrocarbons. Anal Chim Acta 804:280–286. https://doi.org/10.1016/j.aca.2013.10.022 CrossRefPubMedGoogle Scholar
- 16.Van Der Voort P, Esquivel D, De Canck E, Goethals F, Van Driessche I, Romero-Salguero FJ (2013) Periodic mesoporous organosilicas: from simple to complex bridges; a comprehensive overview of functions, morphologies and applications. Chem Soc Rev 42:3913–3955. https://doi.org/10.1039/C2CS35222B CrossRefPubMedGoogle Scholar
- 22.Karimi B, Elhamifar D, Clark JH, Hunt AJ (2010) Ordered mesoporous Organosilica with ionic-liquid framework: an efficient and reusable support for the palladium-catalyzed Suzuki–Miyaura coupling reaction in water. Chem Eur J 16:8047–8053. https://doi.org/10.1002/chem.201000538 CrossRefPubMedGoogle Scholar
- 23.Karimi B, Elhamifar D, Clark JH, Hunt AJ (2011) Palladium containing periodic mesoporous organosilica with imidazolium framework (Pd@ PMO-IL): an efficient and recyclable catalyst for the aerobic oxidation of alcohols. Org Biomol Chem 9:7420–7426. https://doi.org/10.1039/C1OB05752A CrossRefPubMedGoogle Scholar
- 25.Karimi B, Khorasani M, Vali H, Vargas C, Luque R (2015) Palladium nanoparticles supported in the nanospaces of imidazolium-based bifunctional PMOs: the role of plugs in selectivity changeover in aerobic oxidation of alcohols. ACS Catal 5:4189–4200. https://doi.org/10.1021/acscatal.5b00237
- 26.Amiri A, Saadati-Moshtaghin HR, Zonoz FM (2018) A hybrid material composed of a polyoxometalate of type BeW 12 O 40 and an ionic liquid immobilized onto magnetic nanoparticles as a sorbent for the extraction of organophosphorus pesticides prior to their determination by gas chromatography. Microchim Acta 185:176. https://doi.org/10.1007/s00604-018-2713-x CrossRefGoogle Scholar
- 27.Gu W, Zhu X (2017) Nanoparticles of type Fe 3 O 4-SiO 2-graphene oxide and coated with an amino acid-derived ionic liquid for extraction of Al (III), Cr (III), cu (II), Pb (II) prior to their determination by ICP-OES. Microchim Acta 184:4279–4286. https://doi.org/10.1007/s00604-017-2469-8 CrossRefGoogle Scholar
- 32.Li N, Chen J, Shi YP (2017) Magnetic polyethyleneimine functionalized reduced graphene oxide as a novel magnetic solid-phase extraction adsorbent for the determination of polar acidic herbicides in rice. Anal Chim Acta 949:23–34. https://doi.org/10.1016/j.aca.2016.11.016 CrossRefPubMedGoogle Scholar