title: Synthesis of mimic molecularly imprinted ordered mesoporous silica adsorbent by thermally reversible semicovalent approach for pipette-tip solid-phase extraction-liquid chromatography fluorescence determination of estradiol in milk.
abstract: A mimic molecularly imprinted ordered mesoporous silica (MIOMS) adsorbent was prepared utilizing a thermally reversible semicovalent approach. The thermally reversible covalent template-monomer complex was firstly synthesized by employing 4,4'-sulfonyldiphenol (BPS) and (3-isocyanatopropyl) triethoxysilane (ICPTES) as template and monomer, respectively. The template-monomer complex was incorporated into ordered mesoporous silica via a simple self-assembly process. The adsorption experiment illustrated that the imprint-removed silica (MIOMS-ir) had higher special recognition ability (250μgg(-1)) for estradiol (E2) than the non-imprinted silica (NIOMS-ir) (25μgg(-1)). MIOMS-ir was applied as an adsorbent in pipette-tip solid-phase extraction (PT-SPE) coupled with liquid chromatography-fluorescence detector (LC-FLD) for determination of E2 in milk samples. Under the optimized conditions, only 3mg of the adsorbent, 0.3mL of water as washing solvent, and 0.5mL of acetonitrile-acetic acid (96:4, v/v) as elution solvent were used in the pretreatment procedure of milk samples. Good calibration linearity was obtained in a range of 25ngL(-1) to 1000ngL(-1), and the recoveries at three spiked levels were ranged from 95.4% to 107.0% with relative standard deviations (RSDs) ≤3.1% (n=3). The proposed MIOMS-ir-PT-SPE-LC-FLD method combined the advantages of PT-SPE and ordered mesoporous material such as ease assembly, low cost, high extraction efficiency and large specific surface area, so it is a potential pretreatment strategy for the extraction and determination of E2 in complex milk samples.
authors.affiliation: Key Laboratory of Medicinal Chemistry and Molecular Diagnosis, Department of Preventive Medicine and Health Management, Hebei University, Baoding, 071002, China.
authors.forename: Lu
authors.initials: L
authors.lastname: Wang
authors.affiliation: Key Laboratory of Medicinal Chemistry and Molecular Diagnosis, Department of Preventive Medicine and Health Management, Hebei University, Baoding, 071002, China. Electronic address: yanhy@hbu.edu.cn.
authors.forename: Hongyuan
authors.initials: H
authors.lastname: Yan
authors.affiliation: Key Laboratory of Medicinal Chemistry and Molecular Diagnosis, Department of Preventive Medicine and Health Management, Hebei University, Baoding, 071002, China.
authors.forename: Chunliu
authors.initials: C
authors.lastname: Yang
authors.affiliation: Key Laboratory of Medicinal Chemistry and Molecular Diagnosis, Department of Preventive Medicine and Health Management, Hebei University, Baoding, 071002, China.
authors.forename: Zan
authors.initials: Z
authors.lastname: Li
authors.affiliation: Department of Biochemistry, Baoding University, Baoding, 071002, China.
authors.forename: Fengxia
authors.initials: F
authors.lastname: Qiao
mesh_terms: D000327:Adsorption; D000818:Animals; D002851:Chromatography, High Pressure Liquid / Q000379:methods; D052244:Endocrine Disruptors / Q000032:analysis*; D004958:Estradiol / Q000032:analysis*; D004967:Estrogens / Q000032:analysis*; D005453:Fluorescence; D008892:Milk / Q000737:chemistry*; D054802:Molecular Imprinting; D010636:Phenols / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*; D012822:Silicon Dioxide / Q000737:chemistry*; D052616:Solid Phase Extraction / Q000379:methods
chemical_list: C492426:(3-isocyanatopropyl) triethoxysilane; D052244:Endocrine Disruptors; D004967:Estrogens; D010636:Phenols; D012821:Silanes; D004958:Estradiol; D012822:Silicon Dioxide
keywords: Estradiol; Milk samples; Mimic molecular imprinting; Ordered mesoporous silica; Pipette-tip solid-phase extraction