Use of packed-fiber solid-phase extraction for sample clean-up and preconcentration of vitamin B_(12) before determination

A rapid and simple preconcentration step applying packed-fiber solid-phase extraction columns has been investigated to vitamin B12. The extraction performance of the new method was investigated preliminarily on vitamin functional drink. The analysis used a reversed-phase C18 column, with a photo-diode array detector at 220 nm. The samples were preconcentrated with packed-fiber solid-phase extraction columns. Good linearity was observed in vitamin functional drink. The repeatability of extraction performance, expressed as relative standard deviations, was from 3.5% to 4.3%. The limit of detection （LOD） is 5 ng mL^-1 （S/N = 3）. Finally, the method had been applied for the determination of vitamin B12 in vitamin functional drink.

Fast determination of multi-mycotoxins in corn by dispersive solid-phase extraction coupled with ultra-performance liquid chromatography with tandem quadrupole time-of-flight mass spectrometry

A fast analytical method for the simultaneous determination of 9 mycotoxins, including alfatoxins （B1, B2, G1, and G2）, fumonisins （B1, B2 and B3）, zearalenone, and deoxynivalenol in corn using dispersive solid-phase extraction method and ultra-performance liquid chromatography coupled to tandem quadrupole time-of-lfight mass spectrometry （UPLC-Q-TOF-MS） was developed and validated. Samples were extracted with acetonitrile-water （84：16, v：v, containing 1% acetic acid） using ultrasonic extraction. The extracts were puriifed with a dispersive SPE method using C18 as a cleaning agent. The ifnal clear extracts were dried by nitrogen blowing and subsequently redissolved in methanol-water （5：5, v：v）. The samples were then analyzed by UPLC-Q-TOF-MS with 0.1% formic acid in ammonium acetate-methanol as mobile phase. The mean recoveries were ranged from 68.0 to 120.0%, and the relative standard deviation （RSD） ranged from 0.18 to 6.29%. Limits of detections ranged from 0.05 to 50 μg kg？1, and limits of quantiifcation ranged from 0.1 to 200 μg kg？1, which were below the legal limits set by the European Union for the legislated mycotoxins. The developed method was applied to 130 corn samples. Among the mycotoxins studied, alfatoxins B1 and fumonisins B1, B2 and B3 were the most predominant mycotoxins, and their concentrations were 0–593.12, 0–2.01×104, 0–6.94×103 and 0–3.05×103 μg kg–1, respectively.

Solid-phase extraction of trace Au(Ⅲ) with SDG and determination by the catalytic spectrophotometric method

The new catalytic kinetic spectrophotometric method for Au（III） determination was developed and validated. It was based on the catalytic effect of gold on the oxidation of sudan red III by ammonium peroxodisulfate （（NH4）2S2O8） with nitrilo triacetic acid as an activator in microemulsion and H2SO4 medium. Under optimum conditions, there was the linearity of the calibration curve in the concentration range from 0 to 20 μg/L Au（Ⅲ） at 520 nm. The relative standard deviation was 3.0% with a correlation coefficient of 0.9986. The detection limit achieved was 9.75 × 10^-5 μg/mL. A new method using a column packed with sulfhydryl dextrose gel （SDG） as a solid-phase extractant has been developed for the preconcentration and separation of Au（Ⅲ） ions. The method has been applied to the determination of trace gold with satisfactory results.

Determination of Trace Amount of Polycyclic Aromatic Hydrocarbons in Urban Sewage by Solid-phase Extraction Coupled with High Performance Liquid Chromatograph

[Method] This study aimed to determine trace amount of polycyclic aromatic hydrocarbons(PAHs) in urban sewage by using solid-phase extraction(SPE) coupled with high performance liquid chromatograph(HPLC).[Method] From the aspects of solid-phase extraction column,elution solvent,elution volume,elution speed and so forth,the test conditions of SPE-HPLC method were optimized,and trace amount of PAHs in urban sewage was determined.[Result] The optimized solid-phase extraction conditions were SUPELCLEAN LC-18 solid-phase extraction column,methylene dichloride as elution solvent,15 ml elution volume,2 ml/min elution speed,5 ml/min loading speed,1 000 ml water with 200 ml methanol loading volume.Under the optimized extraction conditions,the recovery was high,namely 76.3%-105.2%;relative standard deviation was 3.8%-6.0%,showing good precision;detection limit was low,only 0.000 8-0.048 0 μg/L.[Conclusion] This method is user-friendly,with high sensitivity and good precision,and suitable for continuous determination of a large volume of water samples.

Isolation and Purification of Unstable Iridoid Glucosides from Traditional Chinese Medicine by Preparative High Performance Liquid Chromatography Coupled with Solid-phase Extraction

An efficient preparative method was successfully developed for isolation and purification of unstable components from medicinal plant extracts, using a combined method of preparative high performance liquid chro-matography(HPLC) and solid-phase extraction(SPE). The aim of this study was to obtain an effective method with high preparative efficiency and importantly to avoid the transformation of unstable compounds. The preparative HPLC system was based on an LC/MS controlled four-channel autopurification system. The SPE method was performed with a C18 packing material to trap the target compounds and to remove the acidic additive derived from the mobile phase. Using this method, the unstable iridoid glucosides(IGs) as model compounds were successfully isolated and purified from the extract of Hedyotis diffusa Willd. Six IGs(including one new minor IG) and one nucleotide compound were simultaneously obtained, each with a purity of 91% as determined by HPLC. The structures of the isolated compounds were identified by UPLC/Q-TOF MS, UV, 1D and/or 2D NMR. It was demonstrated that the combination of preparative HPLC with SPE is a versatile tool for preparative purification of unstable compounds from complex natural products.

Comparison of liquid-liquid extraction-thin layer chromatography with solid-phase extraction-high-performance thin layer chromatography in detection of urinary morphine

Liquid-liquid extraction-thin layer chromatography （LLE-TLC） has been a common and routine combined method for detection of drugs in biological materials. Solid-phase extraction （SPE） is gradually replacing the tra- ditional LLE method. High performance thin layer chromatography （HPTLC） has several advantages over TLC. The present work studied the higher efficiency of a new SPE-HPTLC method over that of a routine LLE-TLC method, in extraction and detection of urinary morphine. Fifty-eight urine samples, primarily identified as mor- phine-positive samples by a strip test, ＇were re-screened by LLE-TLC and SPE-HPTLC. The results of LLE-TLC and SPE-HPTLC were then compared with each other. The results showed that the SPE-HPTLC detected 74% of total samples as morphine-positive samples whereas the LLE-TLC detected 48% of the same samples. We further discussed the effect of codeine abuse on TLC analysis of urinary morphine. Regarding the importance of morphine detection in urine, the present combined SPE-HPTLC method is suggested as a replacement method for detection of urinary morphine by many reference laboratories.

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.

Separation and Enrichment of Melamine in Feed by a New Molecularly Imprinted Solid-phase Extraction Column

[ Objective] The research aimed to develop a new molecular imprinting solid-phase extraction column for the separation and enrichment of melamine in feed. [ Method] The molecular imprinting polymer of melamine was prepared by mass polymerization method. This polymer was used as filler to prepare molecular imprinting polymer solid-phase extraction（MIP-SPE） column of melamine. The solid-phase extraction conditions were optimized and melamine content in concentrated solution was determined by using HPLC. [ Result] Melamine eould be separated selectively from feed and enriehed by self-made MIP-SPE column. It could wipe off complex matrix from feed and the addition recovery rate was 95%. The contrast experiment between MIP-SPE column and NMIP-SPE （ non-imprinted polymer- solid phase extraction） column showed that the extraction efficiency of the former was obviously higher than the latter. [ Conclusion] The home-made MIP- SPE column could be used to separate and enrich melamine in feed efficiently, with a broad application prospect.

A solid-phase extraction approach for the identification of pharmaceutical–sludge adsorption mechanisms

It is important to understand the adsorption mechanism of chemicals and active pharmaceu-tical ingredients （API） on sewage sludge since wastewater treatment plants are the last barrier before the release of these compounds to the environment. Adsorption models were developed considering mostly hydrophobic API-sludge interaction. They have poor predictive ability, especially with ionisable compounds. This work proposes a solid-phase extraction （SPE） approach to estimate rapidly the API-sludge interaction. Sludge-filled SPE cartridges could not be percolated with API spiked mobile phases so different powders were tested as SPE sludge supports. Polytetrafluoroethylene （PTFE） was selected and tested at different PTFE/sludge ratios under eight different adsorption conditions with three API ionisable compounds. The PTFE/sludge mixtures with 50% or less sludge could be used in SPE mode for API sorption studies with methanol/water liquid phases. The results gave insights into API-sludge interactions. It was found that π-π, hydrogen-bonding and charge-charge interactions were as important as hydrophobicity in the adsorption mechanism of charged APIs on sludge.

A New Molecularly Imprinted Polymer for Solid-phase Extraction of Cotinine from Human Urine

A molecularly imprinted polymer （MIP）, prepared around a cotinine template, has been synthesized. The feasibility of using the polymer for solid-phase extraction （SPE） of cotinine from biological samples has been investigated. The results show that cotinine can be quantitatively retained and eluted from the polymer. Experiments with human urine samples indicate that clean target analyte is obtained for HPLC with UV detection using the protocol.

Determination of N-Methylcarbamate Pesticides in Vegetables by Solid-phase Extraction and Pressurized Capillary Electrochromatography

Capillary electrochromatography （CEC） is a hybrid technique that couples the good selectivity of high-performance liquid chromatography （HPLC） and the high separation efficiency of capillary electrophoresis （CE）. Both charged and uncharged compounds can be separated effectively using CEC. In some cases, however, the bubbles that generated in the capillary column in pure CEC performed on commercial CE instruments will cause unstable current and even disrupt the separation when the concentration of buffer is very high. By applying pressure on the electrochromatographic separation via a micro-HPLC pump, pressurized capillary electrochromatography （ pCEC ） combines two driving factors of the electroosmotic flow （EOF） and the pressure flow, thereby increasing the speed and the selectivity of separation and suppressing the bubble formation. Moreover,

Application of Online Solid-phase Extraction Technology in the Field of Environmental Analysis

For purpose of purification and enrichment, environmental samples usually need to be pretreated before analysis because of low concentration of residual organic matters. Solid-phase extraction （SPE） is one of the frequently used methods of pretreatment. This article introduces the methodological principle and flow channel of SPE as well as the categories of frequently used small extraction column, analyzes the application of online SPE technology in environmental analysis, generalizes the advantages of online SPE and sets forth its developmental trend.

Simultaneous Determination of Four Estrogens in Compost Based on Ultrasonic Solvent Extraction, Solid-Phase Extraction Clean-Up and Analysis by UHPLC-MS/MS

A rapid, cost effective and reliable analytical method was developed and validated for the simultaneous determination of four estrogens (17 β-estradiol, 17 α-ethinylestradiol, estrone, and estriol) in compost samples from the biodegradation of biological infectious hazardous wastes. Ultrasonic solvent extraction, using methanol as extraction solvent, coupled with SPE clean-up, using cartridges HLB 60 mg - 6 ml Supelco® and acetonitrile for reconstitution of eluents, was used for the simultaneous extraction of the four estrogens. Mean recoveries in the range of 98% - 107% were obtained. All compounds were separated in a single gradient run by UHPLC KinetexTM 2.6 μm XB-C18 100 ÅLC (50 × 4.6 mm) column. Analytes were detected via multiple reaction monitoring (MRM) using an AB SCIEX API-5000TM triple quadrupole (Applied Biosystems/MDS SCIEX) with electrospray ionization in negative mode. Isocratic mobile phase of Water:ACN (50:50) resulted to be the optimum. Limits of detection and quantification were on the order of 0.66 ng·g-1 and 2 ng·g-1 for all the estrogens. These limits were lower than most of the values reported in the literature for similar matrices. Suitable level of linearity, good repeatability and reproducibility with coefficients of variation is lower than 11.7%, 6.8% and 8.3%, respectively.

Multiresidue Method for Determination of 67 Pesticides in Water Samples Using Solid-Phase Extraction with Centrifugation and Gas Chromatography-Mass Spectrometry

A new multi-residue method based on solid-phase extraction (SPE) with centrifugation was developed for determination and quantitation of 67 pesticides in water samples. Two SPE cartridges were tested: Chromabond C18 and Oasis HLB. Parameters that influence the extraction efficiency such as the eluent volume, the sample loading volume, the addition of organic solvent to water sample, sorbent drying and elute concentration were optimized. The innovation of this work was the examination of the use of a centrifugation technique in both the drying and elution steps. When combined with centrifugation, the volume of the elution solvent was reduced to 2 mL and the time for sorbent drying decreased also to 10 min under vacuum. Under the optimized conditions, this method showed good recoveries higher than 65% - 68% for the 67 analyzed pesticides using the C18 and HLB cartridges with relative standard deviations lower than 9.7% - 12.3%. Limits of quantification were between 2 and 20 ng.L–1. The simplicity of the described method, use of less of organic solvent, short procedure time, and good recoveries demonstrate the advantages of this environmentally friendly approach for routine analysis of numerous samples.

A novel surface molecularly imprinted polymer as the solid-phase extraction adsorbent for the selective determination of ampicillin sodium in milk and blood samples

Surface molecularly imprinted polymers （SMIPs） for selective adsorption of ampicillin sodium were synthesized using surface molecular imprinting technique with silica gel as a support. The physical and morphological characteristics of the polymers were investigated by scanning electron microscope （SEM）, Fourier transform infrared spectroscopy （FT-IR）, thermogravimetric analysis （TGA）, elemental analysis and nitrogen adsorption-desorption test. The obtained results showed that the SMIPs displayed great adsorption capacity （13.5 lag/mg）, high recognition ability （the imprinted factor is 3.2） and good binding kinetics for ampicillin sodium. Finally, as solid phase extraction adsorbents, the SMIPs coupled with HPLC method were validated and applied for the enrichment, purification and determination of anapicillin sodium in real milk and blood samples. The averages of spiked accuracy ranged from 92.1% to 107.6%. The relative standard deviations of intra- and inter-day precisions were less than 4.6%. This study provides a new and promising method for enriching, extracting and determining ampicillin sodium in complex biological samples.

Determination of Triclocarban, Triclosan and Methyl-Triclosan in Environmental Water by Silicon Dioxide/Polystyrene Composite Microspheres Solid-Phase Extraction Combined with HPLC-ESI-MS

This paper developed a sensitive and efficient analytical method for triclocarban (TCC), triclosan (TCS) and Methyl-triclosan (MTCS) determination in environmental water, which involves enrichment by using silicon dioxide/polystyrene composite microspheres solid-phase extraction and detection with HPLC-ESI-MS. The influence of several operational parameters, including the eluant and its volume, the flow rate and acidity of water sample were investigated and optimized. Under the optimum conditions, the limits of detection were 1.0 ng/L, 2.5 and 4.5 ng/L for TCC, TCS, and MTCS, respectively. The linearity of the method was observed in the range of 5-2000 ng/L, with correlation coefficients (r2) >.99. The spiked recoveries of TCC, TCS and MTCS in water sampleswereachieved in the range of 89.5% -96.8% with RSD below 5.7%. The proposed method has been successfully applied to analyze real water samples and satisfactory results were achieved.

Improved preparation and identification of aristolochic acid-DNA adducts by solid-phase extraction with liquid chromatography-tandem mass spectrometry

Aristolochic acid （AA） is a known nephrotoxin and potential carcinogen, which can form covalent DNA adducts after metabolic activation in vivo and in vitro. A simple method for preparation and characterization of aristolochic acid-DNA adducts was developed. Four AA-adducts were synthesized by a direct reaction of AAI/AAII with 2′-deoxynucleosides. The reaction mixture was first cleaned-up and pre-concentrated using solid phase extraction （SPE）, and further purified by a reversed-phase high performance liquid chromatography （HPLC）. By the application of developed SPE procedure, matrices and byproducts in reaction mixture could be greatly reduced and adducts of high purity （more than 94% as indicated by HPLC） were obtained. The purified AA-DNA adducts were identified and characterized with liquid-electrospray ionization-quadrupole-time of flight-mass spectrometry （LC-ESI-Q-TOF-MS/MS） and LC-Diode array detector-fluorescence （LC-DAD-FL） analysis. This work provides a robust tool for possible large-scale preparation of AA-DNA adduct standards, which can promote the further studies on carcinogenic and mutagenic mechanism of aristolochic acids.

Herbicide quinclorac analysis in paddy soil samples by solid-phase extraction and high performance liquid chromatography

Quinclorac is one of the main herbicides used in paddy fields in China.Quinclorac residues in paddy soil may significantly influence the growth of sensitive crops such as tobacco.An analytical method employing high performance liquid chromatography(HPLC)with a diode array detector(DAD)was developed to determine quinclorac residues in paddy soil samples.Quinclorac was extracted from paddy soil samples by 5% ammonia methanol solution(v/v)and cleancd up by solid-phase extraction(SPE)with Bond Elute SAX cartridge.Recoveries of quinclorac at 0.005-1.000 μg·g^-1 were 82.36%-l06.30%,with relative standard deviations(RSDs)of 2.45%-6.83%.The limit of detection(LOD)was 0.001 μg·g^-1 at a signal-to-noise ratio of 3,and the limit of quantification(LOQ)was 0.005 μg·g^-1 The same quinclorac residue samples were further analyzed and confirmed by ultra-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).The proposed method was successfully applied to the analysis of quinclorac residues from the paddy fields with previous quinclorac treatment in Jiangxi Province.

Molecularly Imprinted Micro-Solid-Phase Extraction for the Selective Determination of Phenolic Compounds in Environmental Water Samples with High Performance Liquid Chromatraphy

2,4,6-trichlorophenol molecularly imprinted suspension polymer has been prepared and applied to the molecularly imprinted micro-solid-phase extraction procedure for selective preconcentration of phenolic compounds from environmental water samples. The influence of functional monomer, cross-linker, polymerization condition, porogen, and the ratio of template molecule and functional monomer to cross-linker on the size of the obtained particles were investigated. It was found that methyacrylic acid as functional monomer, divinylbenzene as cross-linker, the molar ratio of template molecule and functional monomer to cross-linker was 1:4:20, the amount of AIBN was 100 mg, ultraviolet radiation at 365 nm were the optimal conditions, and at these conditions, the polymers had the best adsorption efficiency and had the monodispersity of 2 - 3 μm microsphere particles. The characteristics of the MIMSPE method were valid by high performance liquid chromatography. This MIMSPE-HPLC method has been successfully applied to the direct preconcentration and determination of phenolic compounds (phenol, 4-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, pentachlorophenol) in environmental water samples.