title: Aluminum based metal-organic framework-polymer monolith in solid-phase microextraction of penicillins in river water and milk samples.
abstract: In this study, aluminum based metal-organic framework (Al-MOF)-organic polymer monoliths were prepared via microwave-assisted polymerization of ethylene dimethacrylate (EDMA), butyl methacrylate (BMA) with different weight percentages of Al-MOF (MIL-53; 37.5-62.5%) and subsequently utilized as sorbent in solid-phase microextraction (SPME) of penicillins (penicillin G, penicillin V, oxacillin, cloxacillin, dicloxacillin, nafcillin). The Al-MOF-polymer was characterized using Fourier transform infrared (FTIR) spectroscopy, powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and SEM-energy-dispersive X-ray spectroscopy (SEM-EDS) to clarify the retained crystalline structure well as the homogeneous dispersion of Al-MOF (MIL-53) in polymer monolith. The developed Al-MOF-polymer (MIL-53) monolithic column was evaluated according to its extraction recovery of penicillins. Several parameters affecting the extraction recoveries of penicillins using fabricated Al-MOF-polymer (MIL-53) monolithic column including different MIL-53 weight percentages, column length, pH, desorption solvent, and mobile phase flow rate were investigated. For comparison, different Al-based MOFs (MIL-68, CYCU-4 and DUT-5) were fabricated using the optimized condition for MIL-53-polymer (sample matrix at pH 3, 200μL desorption volume using methanol, 37.5% of MOF, 4-cm column length at 0.100mLmin(-1) flow rate). Among all the Al-MOF-polymers, MIL-53(Al)-polymer still afforded the best extraction recovery for penicillins ranging from 90.5 to 95.7% for intra-day with less than 3.5% relative standard deviations (RSDs) and inter-day precision were in the range of 90.7-97.6% with less than 4.2% RSDs. Meanwhile, the recoveries for column-to-column were in the range of 89.5-93.5% (<3.4% RSDs) while 88.5-90.5% (<5.8% RSDs) for batch-to-batch (n=3). Under the optimal conditions, the limit of detections were in the range of 0.06-0.26μgL(-1) and limit of quantifications between 0.20 and 0.87μgL(-1). Finally, the MIL-53-polymer was applied for the extraction of penicillin in river water and milk by spiking trace-level penicillin for as low as 50μgL(-1) and 100μgL(-1) with recoveries ranging from 80.8% to 90.9% (<6.7% RSDs) in river water and 81.1% to 100.7% (<7.1% RSDs) in milk sample, respectively.
authors.affiliation: Department of Chemistry, Chung Yuan Christian University, 200 Chung Pei Road, Chung Li, Taoyuan 320, Taiwan.
authors.forename: Stephen
authors.initials: S
authors.lastname: Lirio
authors.affiliation: Department of Chemistry, Chung Yuan Christian University, 200 Chung Pei Road, Chung Li, Taoyuan 320, Taiwan.
authors.forename: Wan-Ling
authors.initials: WL
authors.lastname: Liu
authors.affiliation: Department of Chemistry, Chung Yuan Christian University, 200 Chung Pei Road, Chung Li, Taoyuan 320, Taiwan.
authors.forename: Chen-Lan
authors.initials: CL
authors.lastname: Lin
authors.affiliation: Department of Chemistry, Chung Yuan Christian University, 200 Chung Pei Road, Chung Li, Taoyuan 320, Taiwan. Electronic address: chiaher@cycu.edu.tw.
authors.forename: Chia-Her
authors.initials: CH
authors.lastname: Lin
authors.affiliation: Department of Chemistry, Chung Yuan Christian University, 200 Chung Pei Road, Chung Li, Taoyuan 320, Taiwan. Electronic address: hyhuang@cycu.edu.tw.
authors.forename: Hsi-Ya
authors.initials: HY
authors.lastname: Huang
mesh_terms: D000535:Aluminum / Q000737:chemistry*; D000818:Animals; D004784:Environmental Monitoring / Q000379:methods*; D005504:Food Analysis / Q000379:methods*; D008689:Methacrylates / Q000737:chemistry; D008892:Milk / Q000737:chemistry*; D010406:Penicillins / Q000032:analysis*; D058105:Polymerization; D011108:Polymers / Q000737:chemistry*; D045483:Rivers / Q000737:chemistry*; D052617:Solid Phase Microextraction; D014961:X-Ray Diffraction
chemical_list: D008689:Methacrylates; D010406:Penicillins; D011108:Polymers; C004919:ethylene dimethacrylate; D000535:Aluminum; C016284:butyl methacrylate
keywords: Metal-organic framework (MOF); Milk; Penicillin; Polymer monolithic column; Solid-phase microextraction (SPME)