Magnetic Solid-Phase Extraction of Phthalate Esters from Environmental Water Samples using Fibrous Phenyl-functionalized Fe3O4@SiO2@KCC-1

A new kind of phenyl-functionalized magnetic fibrous mesoporous silica(Fe3 O4@Si O2@KCC-1-phenyl) was prepared by copolymerization as an efficient adsorbent for the magnetic extraction of phthalate esters from environmental water samples. The obtained Fe3 O4@Si O2@KCC-1-phenyl showed monodisperse fibrous spherical morphology, fairly strong magnetic response(29 emu/g), and an abundant π-electron system, which allowed rapid isolation of the Fe3 O4@Si O2@KCC-1-phenyl from solutions upon applying an appropriate magnetic field. Several variables that affect the extraction efficiency of the analytes,including the type of the elution solvent, amount of adsorbent, extraction time and reusability, were investigated and optimized. Under optimum conditions, the Fe3 O4@Si O2@KCC-1-phenyl was used for the extraction of four phthalate esters from environmental water samples followed by high-performance liquid chromatographic analysis. Validation experiments indicated that the developed method presented good linearity(0.1-20 ng/m L), low limit of detection(7.5-29 μg/L, S/N =3). The proposed method was applied to the determination of phthalate esters in different real water samples, with relative recoveries of 93%-103.4%and relative standard deviation of 0.8%-8.3%.

Trace determination and characterization of ginsenosides in rat plasma through magnetic dispersive solid-phase extraction based on core-shell polydopamine-coated magnetic nanoparticles

Enrichment of trace bioactive constituents and metabolites from complex biological samples is challenging.This study presented a one-pot synthesis of magnetic polydopamine nanoparticles(Fe3O4@-SiO2@PDA NPs)with multiple recognition sites for the magnetic dispersive solid-phase extraction(MDSPE)of ginsenosides from rat plasma treated with white ginseng.The extracted ginsenosides were characterized by combining an ultra-high-performance liquid chromatography coupled to a highresolution mass spectrometry with supplemental UNIFI libraries.Response surface methodology was statistically used to optimize the extraction procedure of the ginsenosides.The reusability of Fe3O4@-SiO2@PDA NPs was also examined and the results showed that the recovery rate exceeded 80%after recycling 6 times.Furthermore,the proposed method showed greater enrichment efficiency and could rapidly determine and characterize 23 ginsenoside prototypes and metabolites from plasma.In comparison,conventional methanol method can only detect 8 ginsenosides from the same plasma samples.The proposed approach can provide methodological reference for the trace determination and characterization of different bioactive ingredients and metabolites of traditional Chinese medicines and food.

Rapid and sensitive analysis of trace b-blockers by magnetic solidphase extraction coupled with Fourier transform ion cyclotron resonance mass spectrometry

A rapid and sensitive method for analyzing trace b-blockers in complex biological samples,which involved magnetic solid-phase extraction(MSPE)coupled with Fourier transform ion cyclotron resonance mass spectrometry(FTICR-MS),was developed.Novel nanosilver-functionalized magnetic nanoparticles with an interlayer of poly(3,4-dihydroxyphenylalanine)(polyDOPA@Ag-MNPs)were synthesized and used as MSPE adsorbents to extract trace b-blockers from biological samples.After extraction,the analytes loaded on the polyDOPA@Ag-MNPs were desorbed using an organic solvent and analyzed by FTICR-MS.The method was rapid and sensitive,with a total detection procedure of less than 10 min as well as limits of detection and quantification in the ranges of 3.5-6.8 pg/mL and 11.7-22.8 pg/mL,respectively.The accuracy of the method was also desirable,with recoveries ranging from 80.9%to 91.0%following the detection of analytes in human blood samples.All the experimental results demonstrated that the developed MSPE-FTICR-MS method was suitable for the rapid and sensitive analysis of trace b-blockers in complex biological samples.

Preparation of Amino-functionalized Guanidinium Ionic Liquid-Modified Magnetic Materials and Application in Solid-Phase Extraction of Pollutants in Water

In the present work,a novel amino-functionalized hexaalkylguanidinium chloride ionic liquid was prepared and grafted on the surface of magnetic materials through polyethyleneimine to enrich polycyclic aromatic hydrocarbons in water in combination with HPLC equipped with an ultraviolet detector.The effect of several parameters on the extraction efficiency was investigated,including the desorption solvent,the amounts of sorbents,the extraction time,the desorption time and the salt amount.Under the optimized conditions,the method validation exhibited good linearity with correlation coefficients above 0.994 in the range of 0.2-300 ng/mL and low limits of detection and quantification of 0.05 and 0.2 ng/mL,respectively.Besides,relative recoveries were in the range of 80-120%,and the intra-day and inter-day repeatability were good with the relative standard deviations of less than 20%.Finally,the guanidinium ionic liquid modified magnetic materials were applied for the extraction of polycyclic aromatic hydrocarbons from real water samples to demonstrate the utility,and the results show that the proposed method has good prospect for effective enrichment and determination of pollutants in water.

Metal-organic framework derived magnetic nanoporous carbon as an adsorbent for the magnetic solid-phase extraction of chlorophenols from mushroom sample

In this work, a metal-organic framework derived nanoporous carbon （MOF-5-C） was fabricated and modified with Fe3O4 magnetic nanoparticles. The resulting magnetic MOF-5-derived porous carbon （Fe304@MOF-5-C） was then used for the magnetic solid-phase extraction of chlorophenols （CPs） from mushroom samples prior to high performance liquid chromatography-ultraviolet detection. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and N2 adsorption were used to characterize the adsorbent. After experimental optimization, the amount of the adsorbent was chosen as 8.0 mg, extraction time as 10 min, sample volume as 50 mL, desorption solvent as 0.4 mL （0.2 mL × 2） of alkaline methanol, and sample pH as 6. Under the above optimized conditions, good linearity for the analytes was obtained in the range of 0.8-100.0 ng g 1 with the correlation coefficients between 0.9923 and 0.9963. The limits of detection （SIN= 3） were in the range of 0.25-0.30 ng g-1, and the relative standard deviations were below 6.8%. The result showed that the Fe304@MOF-5-C has an excellent adsorption capacity for the analytes.

Preparation of Fe_(3)O_(4)@SW-MIL-101-NH_(2) for selective preconcentration of chlorogenic acid metabolites in rat plasma,urine,and feces samples

An innovative sandwich-structural Fe-based metal-organic framework magnetic material(Fe_(3)O_(4)@SWMIL-101-NH_(2))was fabricated using a facile solvothermal method.The characteristic properties of the material were investigated by field emission scanning electron microscopy,transmission electron microscopy(TEM),energy-dispersive X-ray spectroscopy,Fourier transform infrared spectroscopy,X-ray powder diffraction,vibrating sample magnetometry,and Brunauer-Emmett-Teller measurements.Fe_(3)O_(4)@SW-MIL-101-NH_(2) is associated with advantages,such as robust magnetic properties,high specific surface area,and satisfactory storage stability,as well as good selective recognition ability for chlorogenic acid(CA)and its metabolites via chelation,hydrogen bonding,and p-interaction.The results of the static adsorption experiment indicated that Fe_(3)O_(4)@SW-MIL-101-NH_(2) possessed a high adsorption capacity toward CA and its isomers,cryptochlorogenic acid(CCA)and neochlorogenic acid(NCA),and the adsorption behaviors were fitted using the Langmuir adsorption isotherm model.Then,a strategy using magnetic solid-phase extraction(MSPE)and ultra-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry(UPLC-Q-TOF MS/MS)was developed and successfully employed for the selective pre-concentration and rapid identification of CA metabolites in rat plasma,urine,and feces samples.This work presents a prospective strategy for the synthesis of magnetic adsorbents and the high-efficiency pretreatment of CA metabolites.

A magnetic adsorbent based on salicylic acid-immobilized magnetite nano-particles for pre-concentration of Cd(II) ions

In this research,an eco-friendly magnetic adsorbent based on Fe_(3)O_(4)/salicylic acid nanocomposite was fabricated using a facile one-pot co-precipitation method.The crystalline and morphological characterization of the prepared nanocomposite was performed by field emission scanning electron microscopy,X-ray diffraction,and Fourier transform infrared spectroscopy.The nanocomposite was employed as a magnetic solid-phase extraction agent for separation of Cd(II)ions from synthetic solutions.Some experimental factors affecting the extraction efficiency were investigated and optimized.Following elution with acetic acid(pH 3.5),the pre-concentrated analyte was quantified by flame atomic absorption spectrometry.In optimal conditions,a linear calibration graph was achieved in the concentration range of 0.2–30 ng·mL^(−1) with a determination coefficient(R^(2))of 0.9953.The detection limit,the enhancement factor,inter-and intra-day relative standard deviations(for six consecutive extractions at the concentration level of 10 ng·mL^(−1))were 0.04 ng·mL^(−1),100,2.38%and 1.52%,respectively.To evaluate the accuracy of the method,a certified reference material(NIST SRM 1643e)was analyzed,and there was a good agreement between the certified and the measured values.It was successfully utilized to determine cadmium in industrial wastewater samples and the attained relative recovery values were between 96.8%and 103.2%.