A high efficient adsorbent for plant growth regulators based on ionic liquid and β-cyclodextrin functionalized magnetic graphene oxide

Abstract

Four types of ionic liquids which composed of cation with imidazole ring and anion with benzene, naphthalene, anthraquinone and naphthoquinone ring were prepared and named VOIm⁺BenSO₃^-, VOIm⁺NapSO₃^-, VOIm⁺AQSO₃^- and VOIm⁺NQSO₃^-, respectively. Then, ionic liquids and β-cyclodextrin functionalized magnetic graphene oxide materials were firstly synthesized for the extraction of 23 plant growth regulators in vegetable samples. The synthesized materials anticipated the unique properties of ionic liquids, β-cyclodextrin, graphene oxide and Fe₃O₄@SiO₂, including high surface area, high supramolecular recognition capability, superparamagnetism and large delocalized π-electron system, which were successfully characterized. Among four kinds of ionic liquids functionalized adsorbents, the VOIm⁺AQSO₃^- modified material exhibited high adsorption capability to 7 plant growth regulators compared with Fe₃O₄@SiO₂/GO/β-CD, Fe₃O₄@SiO₂/GO and other three types of ionic liquids based adsorbents. Parameters that could affect the recoveries of 7 plant growth regulators were investigated, such as mass ratio of Fe₃O₄@SiO₂/GO/β-CD to ionic liquids, salt concentration, pH, amount of adsorbent, extraction time and desorption solvent. Under the optimal condition, the magnetic solid phase extraction method using VOIm⁺AQSO₃^- and β-cyclodextrin functionalized magnetic graphene oxide material (Fe₃O₄@SiO₂/GO/β-CD/IL) as adsorbent was developed and coupled with ultra-high performance liquid chromatography-triple quadrupole linear ion trap mass spectrometry for the determination of 7 plant growth regulators in vegetable samples. Validation results showed that the limit of detection and limit of quantitation were in the range of 0.01-0.18 μg/kg and 0.03-0.58 μg/kg, respectively. The satisfactory linearities were acquired in the concentration of 2-50 μg/kg with the correlation coefficients higher than 0.9982. Taken together, the synthesized Fe₃O₄@SiO₂/GO/β-CD/IL was a highly effective magnetic solid phase extraction adsorbent for the enrichment of trace level of plant growth regulators in vegetable samples.

Keywords: Graphene oxide; Ionic liquid; Magnetic solid phase extraction; Plant growth regulators; β-cyclodextrin.