title: Metal-organic framework MIL-101(Cr) as a sorbent of porous membrane-protected micro-solid-phase extraction for the analysis of six phthalate esters from drinking water: a combination of experimental and computational study.
abstract: An attractive metal-organic framework (MOF) MIL-101(Cr) material was synthesized at the nanoscale and applied as a sorbent in the porous membrane-protected micro-solid-phase extraction (μ-SPE) device for the pre-concentration of phthalate esters (PAEs) in drinking water samples for the first time. Parameters influencing the extraction efficiency, such as the selection of sorbent materials, pH adjustment, the effect of salt, magnetic-stirring extraction time, the desorption solvent and the desorption time, were investigated. Under the optimum conditions, the limits of detection from gas chromatography-mass spectrometric analysis for PAEs varied from 0.004 to 0.02 μg L(-1). The linear ranges were from 0.1 to 50 μg L(-1) or from 0.2 to 50 μg L(-1) for the analytes with the relative standard deviations fluctuating from 0.8 to 10.9% (n = 5). The enrichment factors (EFs) for the target PAEs were varied from 143 to 187. MIL-101(Cr) exhibited remarkable advantages compared to activated carbon and MIL-100(Fe). On the other hand, the computational method was first used to predict the adsorption of MIL-101(Cr) towards PAEs. The molecular interactions and the free binding energies between MIL-101(Cr) and PAEs were observed and calculated in terms of the molecular modeling method. MIL-101(Cr) showed high potential in the analysis of PAEs at trace levels in drinking water. The computational result was consistent with the detected enrichment factors. The computational modeling accurately predicted the extraction efficiency of MOF-based material towards the target analytes. Therefore, the combination of experimental and computational study provided a new strategy on the trace contaminant analysis.
authors.affiliation: School of Pharmacy, Shenyang Pharmaceutical University, Shenyang Liaoning Province 110016, P. R. China.
authors.forename: Ting
authors.initials: T
authors.lastname: Wang
authors.forename: Jian
authors.initials: J
authors.lastname: Wang
authors.forename: Conglu
authors.initials: C
authors.lastname: Zhang
authors.forename: Zhao
authors.initials: Z
authors.lastname: Yang
authors.forename: Xinpeng
authors.initials: X
authors.lastname: Dai
authors.forename: Maosheng
authors.initials: M
authors.lastname: Cheng
authors.forename: Xiaohong
authors.initials: X
authors.lastname: Hou
mesh_terms: D000327:Adsorption; D002857:Chromium / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D060766:Drinking Water / Q000032:analysis*; D004952:Esters / Q000737:chemistry; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods; D057230:Limit of Detection; D000073396:Metal-Organic Frameworks; D010795:Phthalic Acids / Q000032:analysis* / Q000302:isolation & purification; D016062:Porosity; D052616:Solid Phase Extraction / Q000379:methods*; D014874:Water Pollutants, Chemical / Q000032:analysis* / Q000302:isolation & purification
chemical_list: D056831:Coordination Complexes; D060766:Drinking Water; D004952:Esters; C000589635:MIL-101; D000073396:Metal-Organic Frameworks; D010795:Phthalic Acids; D014874:Water Pollutants, Chemical; D002857:Chromium; C032279:phthalic acid