Development trend and prospect of solid phase extraction technology

Solid phase extraction is widely used in sample pretreatment,concentration and analysis processes due to high selectivity and suitability for low concentration sample system.In this review,we systematically summarized and discussed the development trends of solid phase extraction by bibliometrics method.By analyzing papers output scale,the research and development direction of solid phase extraction technology is prospected.We also give an overview on current strategies of novel solid phase extraction from the separation medium and separation technology.The paper aims to describe the global research profile and the development trends of solid phase extraction,to help researchers to accurately grasp the research trend and to provide support for scientific research institutions to formulate scientific policies and strategic plans.Furthermore,the prospect of the development and application of solid phase extraction is also discussed.

Determination of resveratrol in red wine by solid phase extraction-flow injection chemiluminescence method

A sensitive flow injection chemiluminescence method has been developed for the detection of resveratrol in red wine based on the fact that resveratrol can greatly enhance chemiluminescence reaction between KMnO4 and HCHO in sulfuric acid medium. Analytes were pre-concentrated on solid sorbents （C18 solid-phase extraction cartridges）. Under the optimum conditions, the proposed method allows the measurement of resveratrol over the range of 1.32 × 10^-8 to 1.32 × 10^-5 mol/L with a detection limit of 3.30 ×10^-9 mol/L, and the relative standard deviation for 1.32 ×10^-5 mol/L resveratrol （n = 11） is 3.8%. This method has been successfully applied for the determination of the resveratrol in red wine. Furthermore, the possible reaction mechanism was also discussed.

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.

Solid Phase Extraction Chemiluminescence Determination of Methamidaphos on Vegetables

The determination of the methamidaphos pesticide residue on vegetables with a simple solid phase extract（SPE） flow injection（FI） -chemiluminescence（CL） method is described. The method is based on the enhancing effect of methamidaphos on the CL reaction of luminol with hydrogen peroxide in an alkaline solution. Under the optimal conditions, the CL intensity is linear to the methamidaphos mass concentration in a range of 0. 2-13μg/mL （ r= 0. 9992）. The detection limit（3σ） is 0. 047μg/mL. The relative standard deviations for the analysis of three samples are 1.8%, 2.5% and 3.7% （ n = 5 ）, respectively. The recovery is in a range of 90%-109% by the method. In this work, this method was successfully applied to the determination of the methamidaphos residue on some vegetable samples.

Determination of volatile organic compounds in river water by solid phase extraction and gas chromatography

A simple, rapid, and reproducible method is described employing solid phase extraction(SPE) using dichloromethane followed by gas chromatography(GC) with flame ionization detection(FID) for determination of volatile organic compound(VOC) from the Buriganga River water of Bangladesh. The method was applied to detect the benzene, toluene, ethylbenzene, xylene and cumene(BTEXC) in the sample collected from the surface or 15 cm depth of water. Two hundred ml of n hexane pretreated and filtered water samples were applied directly to a C 18 SPE column. BTEXC were extracted with dichloromethane and average concentrations were obtained as 0 104 to 0 372 μg/ml. The highest concentration of benzene was found as 0 372 μg/ml with a relative standard deviation(RSD) of 6 2%, and cumene was not detected. Factors influencing SPE e.g., adsorbent types, sample load volume, eluting solvent, headspace and temperatures, were investigated. A cartridge containing a C 18 adsorbent and using dichloromethane gave better performance for extraction of BTEXC from water. Average recoveries exceeding 90% could be achieved for cumene at 4℃ with a 2 7% RSD.

Rapid analysis of fifteen sulfonamide residues in pork and fish samples by automated on-line solid phase extraction coupled to liquid chromatography–tandem mass spectrometry

The aim of this work was to develop an automated on-line solid phase extraction(SPE)with liquid chromatography-tandem mass spectrometry method for the detection of fifteen sulfonamides in pork and fish samples.Samples were extracted with 0.2%formic acid acetonitrile solution,purified by on-line SPE device with HLB column,then separated by XBridge C18 column,using 0.1%formic acid solution and acetonitrile as the mobile phase.Mass spectrometric data was acquired under multiple reaction monitoring(MRM)mode using positive ionization electrospray.Internal standard method was used in the quantification,good linear relationship was got in range of 0.1–100 ng/mL and correlation coefficient was higher than 0.9990.The limits of detection were in the range of 0.125–2.00g/kg and the limits of quantitation were in the range of 0.250–5.00g/kg.Recoveries of the method were in range of 78.3%–99.3%,relative standard deviation were lower than 10%.The method was simple,sensitivity,and could be used for routine supervision and analysis of fifteen sulfonamides in pork and fish.

Simultaneous Determination of Bisphenols and Alkylphenols in Water by Solid Phase Extraction and Ultra Performance Liquid Chromatography-tandem Mass Spectrometry

To establish an analytical method for determination of four bisphenols （BPA, BPB, BPF, and BPS） and two alkylphenols （4-n-OP, 4-n-NP） in water by ultra performance liquid chromatography- tandem mass spectrometry （UPLC/MS/MS）. The water samples were extracted and condensed with solid-phase extraction （SPE） using C18 cartridges and eluted by acetonitrile. Separation was carried out with Acquity BEH C8 column and detection were performed by UPLC/MS/MS. Quantification was calculated by using the internal standard BPA-d16 and 4-n-NP-d8. The linear correlation coefficients of these compounds in the range of 1.0-100.0μg/L were all over 0.999. The minimum detectable concentrations were 0.75-1.0 ng/L, and the recoveries ranged from 87.0% to 106.9%.

Preconcentration of copper with multi-walled carbon nanotubes pretreated by potassium permanganate cartridge for solid phase extraction prior to flame atomic absorption spectrometry

A procedure for the preconcentration of copper was described in this paper using multi-walled carbon nanotubes (MWCNTs) oxidized by potassium permanganate as the adsorbent for the enrichment of trace copper in water samples. Important parameters, such as the sample pH, the concentration and volume of eluent, sample flow rate and volume, and interference of coexisting ions, were investigated. The obtained results indicated that proposed method possessed an excellent analytical performance. The linear range, the detection limit, and precison (RSD) were 1–100 ng/mL (R(2) = 0.9993), 0.32 ng/mL and 2.88%, respectively. The results showed that copper could be adsorbed quantitatively on the pretreated MWCNTs with potassium permanganate, and proposed method was very useful in the monitoring of copper in the environment.

Comparison of Different Cartridges of Solid Phase Extraction for Determination of Polyphenols in Tobacco by UPLC/MS/MS and Multivariate Analysis

The comparison of solid phase extraction（SPE） for the preconcentration and isolation of polyphenols in tobacco samples was carried out by ultra-high performance liquid chromatography/tandem mass spectrometry （UPLC/MS/MS） and multivariate analysis.Several adsorbing materials of SPE（C18,NH2,SAX and OASIS） were investigated.It was found that the C18 and OASIS cartridges can not only speed up the purification process,but also simplify the SPE operation.A UPLC/MS/MS was used for the determination of polyphenols in tobacco samples after purification.All analytes were separated and determined in 2min.The limit of detection was 0.05 ng/mL.Cluster analysis（CA） and principal component analysis（PCA） were used for the analysis of 4 varieties（flue-cured tobacco,oriental tobacco,sun-cured tobacco and burley） in order to interpret the effect of planting and machining process on the concentration of polyphenols.The different types of tobacco samples could be easily clustered by CA.PCA on the chemical composition of tobacco resulted in two principal components（PCs） that take 84.2% of the total variance.The PCA and CA indicate that the polyphenols can be used for distinguishing tobacco types.

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.

Solid phase extraction of methomyl and thiodicarb from environmental water with an activated carbon cartridge and their determination by HPLC

A solid phase extraction procedure of methomyl and thiodicarb from environmental water was presented. This method utilizes a 40—60 mesh activated carbon cartridge and high performance liquid chromatography (HPLC). The 40—60 mesh activated carbon works faster and yield higher adsorption efficiency. Detection limits of methomyl and thiodicarb in environmental water are 0 1 μg/L and 0 2 μg/L, respectively. Average recoveries of fortified methomyl and thiodicarb in water are in the range of 90 7%—98 8% and 88 9%—103 6%, respectively. The relative standard deviations are lower than 7%. This method is simple, rapid, accurate and precise.

Sensitive measurement of silver ions in environmental water samples integrating magnetic ion-imprinted solid phase extraction and carbon dot fluorescent sensor

Increasing use of silver in various fields has caused Ag^(+)pollution in water environment,taking great threats to people’s health.As a consequence,establishing rapid and reliable methods for sensitive determination of Ag^(+)is of great significance.Fluorescent(FL)sensors based on carbon dots(CDs),an excellent carbonaceous nanomaterial with strong and stable fluorescence,have absorbed extensive attentions in analysis of pollutants due to its advantages of carbon sources being readily available,low cost,easy operation and fast response.Moreover,ion-imprinting is a better way to increase the selectivity of the proposed method.Present work described an effective method for the sensitive measurement of silver ion in water samples in combination with magnetic ion-imprinted solid phase extraction and CDs based fluorescent sensor,which took full advantages of easy separation and high enrichment of magnetic solid phase extraction,high selectivity of ion-imprinting technology,and sensitivity and rapid response of fluorescent sensor from CDs.Sulfur-doped CDs derived from dithizone and magnetic ion-imprinted nanomaterial were prepared,and characterized with Fourier transform infrared spectroscopy and transmission electron microscope,etc.Magnetic Ag^(+)imprinted nanomaterial based solid phase extraction was employed for separating and enriching Ag^(+)from water samples.The significant parameters were optimized in detail.Under the optimal conditions,the proposed method provided good linearity in the range of 0.01-0.4μmol/L and low detection limit of 3 nmol/L.The reliability of the proposed method was validated with real water samples,and the results demonstrated that the proposed method was simple,robust,selective and sensitive detection tool for Ag^(+)in real water samples.

Detection of Endocrine Disruptors in Water around Landfills

[Objectives]This study was conducted to explore the occurrence levels of endocrine disruptors(EDCs)in rural areas around a county landfill in Tongren City.[Methods]The water around the landfill was sampled and analyzed.A solid-phase extraction and high performance liquid chromatography-tandem mass spectrometry(SPE-UPLC-MS/MS)method was established for the determination of 27 EDCs.After the HLB solid-phase extraction column was activated,a water sample,which was adjusted with phosphoric acid to a pH of 2(±0.5)and added with 500 mg of disodium EDTA,was loaded,and 5 ml of water and 20%methanol water was added for washing.Next,10 ml of elution solution was added for elution,and the collected eluate was evaporated under reduced pressure at 40℃to near dryness,and 1 ml of reconstitution solution was added to a constant volume.An ACQUITY UPLC BEH C18(100×2.1 mm,2.6μm)chromatographic column was adopted for LC separation by gradient elution with pure water solution-acetonitrile as the mobile phase.For MS detection,the MRM mode was adopted for collection,and the positive and negative ion modes were switched for simultaneous determination,and the internal standard method was used for quantification.[Results]The correlation coefficient R2 was greater than 0.99 in the linear range of each target substance.The limits of quantitation in the method were between 0.05 and 2.00 ng/L,and the recoveries ranged from 75.3%to 105.7%.[Conclusions]The method has high sensitivity,good accuracy and strong practical value.

液相色谱-质谱联用测定乌头碱血药浓度及其药代动力学参数的方法学研究

乌头碱(aconitine)是存在于乌头属多种植物中的一种双酯二萜生物碱,具有镇[1]、抗炎[2]、抗癫痫[3]、抗肿瘤[4]、提高免疫功能[5]等多种生理活性,但因其具有强烈的心脏毒性和神经毒性,安全系数小,治疗剂量与中毒剂量接近(小鼠LD501.8mg/kg,op;人绝对致死量为2～5mg)[7],限制了对该化合物作为药用的进一步研究,目前仅将其作为致心率失常模型的工具药使用,尚未见其药代动力学的报道.在本文中首次应用液相色谱-质谱联用法对乌头碱在大鼠体内的药代动力学进行了研究.……

A Study on Bisphenol A,Nonylphenol,and Octylphenol in Human Urine amples Detected by SPE-UPLC-MS

Objective To establish a comprehensive analytical method based on SPE‐UPLC‐MS for the simultaneous determination of bisphenol A （BPA）, nonylphenol （NP）, and octylphenol （OP） in urine samples. Methods Sixty urine samples collected from healthy subjects were analyzed for BPA, NP, and OP concentrations. The samples were de‐conjugated by adding β‐glucuronidase and sulfatase. After the enzymatic treatment, the samples were subjected to the OASIS HLB column solid phase extraction cartridges so as to be cleaned and concentrated. The UPLC separation was performed on a Acquity UPLCTM BEH C18 column （2.1×100 mm, 1.7 μm） with a gradient elution system of methanol‐water as the mobile phase. Triple‐quadrupole mass spectrometry analyzer was used for the qualitative and quantitative analysis of UPLC‐MS/MS system. Results The limit of detection of BPA, NP, and OP was 0.10, 0.10, and 0.15 ng/mL, respectively. The recoveries of BPA, NP and OP were 80.1%‐108%, 81.3%‐109%, and 81.5%‐98.7%, respectively. Among the 60 urine samples, BPA was detected in 8 samples at the level of 0.297‐32.7ng/mL, NP was detected in 29 samples at the level of 1.69‐27.8 ng/mL, and OP was detected in 17 samples at the level of 0.407‐11.1 ng/mL. Conclusion The method is simple with high sensitivity and selectivity, and is suitable for the determination of BPA, NP, and OP in urine. As shown by our analysis , BPA, NP, and OP appear to be prevalent in human urine. This is particularly true for NP. The results from our study is therefore valuable for future studies to assess the exposure to BPA, NP, and OP in the general population.

TiO_2 nanotubes as solid-phase extraction adsorbent for the determination of polycyclic aromatic hydrocarbons in environmental water samples

An analytical method based on TiO2 nanotubes solid-phase extraction （SPE） combined with gas chromatography （GC） was established for the analysis of seven polycyclic aromatic hydrocarbons （PAHs）： acenaphtylene, acenaphthene, anthracene, fluorene, phenanthrene, fluoranthene and pyrene. Factors affecting the extraction efficiency including the eluent type and its volume, adsorbent amount, sample volume, sample pH and sample flow rate were optimized. The characteristic data of analytical performance were determined to investigate the sensitivity and precision of the method. Under the optimized extraction conditions, the method showed good linearity in the range of 0.01-0.8 μg/mL, repeatability of the extraction （RSD were between 6.7% and 13.5%, n = 5） and satisfactory detection limits （0.017-0.059 μg/mL）. The developed method was successfully applied to the analysis of surface water （tap, river and dam） samples. The recoveries of PAHs spiked in environmental water samples ranged from 90% to 100%. All the results indicated the potential application of titanate nanotubes as solid-phase extraction adsorbents to pre-treat water samples.

Determination of Tetracyclines and Their Epimers in Agricultural Soil Fertilized with Swine Manure by Ultra-High-Performance Liquid Chromatography Tandem Mass Spectrometry

A rapid, sensitive and specific ultra-high-performance liquid chromatography tandem mass spectrometry （UPLC-MS） method was developed for the analysis of tetracycline antibiotics, including tetracycline （TC）, oxytetracycline （OTC）, chlortetracycline （CTC） and their 4-epimers （4-epiTCs） in agricultural soil fertilized with swine manure. Soil samples were extracted and cleaned-up with 10 mL EDTA-McIlvaine buffer solution （pH 4.0）, then cleaned-up and pre-concentrated using the Oasis MAX cartridge and then eluted with 1 mL solution by mixing formic acid, methanol and water at a ratio of 2：15：83 （v/v/v）. The purified samples were separated by an ACQUITY UPLC BEH C18 column using acetonitrile and water containing 0.1% formic acid mobile phase and detected by a single quadrupole MS. The limits of detection for the soil extraction method （LODsoil） ranged from 0.6-2.5 lag kg-~ with recoveries from 23.3-159.2%. Finally, the method was applied to an agricultural field in an area with intensive pig-fattening farming. Tetracyclines were detected in soil from 2.8 to 42.4 μg kg-1 soil. These results demonstrate that soil from swine farms can become severely contaminated with tetracycline antibiotics and their metabolites.

Automatic analytical approach for the determination of 12 illicit drugs and nicotine metabolites in wastewater using on-line SPE-UHPLC-MS/MS

In this study,we developed a novel on-line solid phase extraction(SPE)-ultra-high-performance liquid chromatography tandem mass spectrometry(UHPLC-MS/MS)-based analytical method for simultaneously quantifying 12 illicit drugs and metabolites(methamphetamine,amphetamine,morphine,codeine,6-monoacetylmorphine,benzoylecgonine,3,4-methylenedioxymethamphetamine,3,4-methylenedioxyamphetamine,cocaine,ketamine,norketamine,and methcathinone)and cotinine(COT)in wastewater samples.The analysis was performed by loading 2 m L of the sample onto an Oasis hydrophilic-lipophilic balance cartridge and using a cleanup step(5%methanol)to eliminate interference with a total run time of 13 min.The isotope-labeled internal standard method was used to quantify the target substances and correct for unavoidable losses and matrix effects during the on-line SPE process.Typical analytical characteristics used for method validation were sensitivity,linearity,precision,repeatability,recovery,and matrix effects.The limit of detection(LOD)and limit of quantification(LOQ)of each target were set at 0.20 ng/L and 0.50 ng/L,respectively.The linearity was between 0.5 ng/L and250 ng/L,except for that of COT.The intra-and inter-day precisions were<10.45%and 25.64%,respectively,and the relative recovery ranged from 83.74%to 162.26%.The method was used to analyze various wastewater samples from 33 cities in China,and the results were compared with the experimental results of identical samples analyzed using off-line SPE.The difference rate was between 19.91%and-20.44%,and the error range could be considered acceptable.These findings showed that on-line SPE is a suitable alternative to off-line SPE for the analysis of illicit drugs in samples.

Detection of geosmin and 2-methylisoborneol by liquid-liquid extraction-gas chromatograph mass spectrum (LLE-GCMS) and solid phase extraction-gas chromatograph mass spectrum (SPE-GCMS)

Two sample preparation methods were introduced and compared in this paper to establish a simple,quick and exact analysis of geosmin and 2-methylisoborneol.LC-18 column was employed in solid phase extraction(SPE),1.0 mL of hexane was adopted in liquid-liquid extraction(LLE),and the extracts were analyzed by gas chromatograph mass spectrum(GCMS)in selected ion mode.Mean recoveries of SPE were low for 2-methylisoborneol(2-MIB)and geosmin(GSM)with values below 50%.For LLE,the recoveries were satisfyingly above 50%for 2-MIB and 80%for GSM.Detection limits of the LLE method were as low as 1.0 ng/L for GSM and 5.0 ng/L for 2-MIB.A year-long investigation on odor chemicals of drinking water in Shanghai demonstrated that in the summer,there was a serious odor problem induced by a high concentration of 2-MIB.The highest concentration of 152.82 ng/L appeared in July in raw water,while GSM flocculation was minimal with concentrations below odor threshold.

Determination of 4-tert-octylphenol in surface water samples of Jinan in China by solid phase extraction coupled with GC-MS

Octylphenols, considered as xenoestrogens, mainly exist as 4-tert-octylphenol （OP） in aquatic environments. The high stability and accumulation of OP in aquatic systems have caused endocrine disruption. The OP in surface water in Jinan, China was analyzed by gas chromatography-mass spectrometry （GC-MS） coupled with solid phase extraction （SPE）. Water samples were extracted by SPE on a cartridge system containing C-18 as sorbent. To increase sensitivity and selectivity, OP was derivatized to 4-tert-octyl-phenoxy silane. With the use of phenanthrene-d10 as internal standard, the detection limit based on signal-to-noise ratio （S/N = 3） was 0.06 ng/mL. The average recovery was from 84.67% to 109.7%. The precision of the method given as the relative standard deviations （RSD） was within the range 6.24%-12.96%. In the target water samples, the concentrations of OP were as follows： 15.88-71.24 ng/L for Jinxiuchuan Reservoir, 3.850-26.68 ng/L for the city moat, 6.930-41.56 ng/L for Daming Lake, 66.03-474.2 ng/L for Xiaoqing River, 14.66-17.72 ng/L for the Yellow River, and 10.60-26.43 ng/L for Queshan Reservoir. The Xiaoqing River was seriously polluted due to the discharge of wastewater from Jinan. Jinxiuchuan Reservoir had a higher concentration of OP compared with the Yellow River and Queshan Reservoir, which is ascribed to the surrounding human activities. These data are reported for the first time, providing strong support for the control of OP pollution in Jinan.