Degradation Dynamics and Residue Analysis of Flubendiamide in Cabbage and Soil by Liquid Chromatography-Tandem Mass Spectrometry with Dispersive Solid Phase Extraction

To formulate a scientific basis for a reasonable spray dose and safe interval period of 20% flubendiamide water dispersible granule (WDG) on controlling vegetable pests, degradation dynamics of flubendiamide in cabbage and soil was analyzed in this study. Dissipation and residue of flubendiamide in 20% flubendiamide WDG in cabbage and soil under field conditions were investigated by liquid chromatography-tandem mass spectrometry with dispersive solid phase extraction. Results showed that the degradation dynamic equations of flubendiamide in cabbage and soil were based on the first-order reaction dynamic equations. The half-lives of the degradation of flubendiamide were 3.51 d to 3.96 d and 3.43 d to 3.87 d in the cabbage of Yangzhou and Jingzhou, respectively, and 4.42 d to 5.13 d and 4.37 d to 4.99 d in the soil of Yangzhou and Jingzhou, respectively. The terminal residues of flubendiamide in the cabbage of Yangzhou and Jingzhou were 0.0247 mg·kg-1 to 0.0393 mg·kg-1 and 0.0225 mg·kg-1 to 0.0273 mg·kg-1, respectively, when 20% flubendiamide WDG was applied at a dose of0.050g·m-2. Flubendiamide is safe to be applied in cabbage fields at the recommended dose.

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.

Detection of Tetracycline Antibiotics in Water by Dispersive Micro-solid Phase Extraction using Fe_(3)O_(4)@[Cu_(3)(btc)_(2)]Magnetic Composite Combined with Liquid Chromatography-Tandem Mass Spectrometry

Residues of tetracycline antibiotics(TCs) in environments may be harmful to human.Due to their high polarities,it is extremely challenging to efficiently enrich TCs with low concentrations in natural waters for analysis.In this work,a magnetic metal-organic framework Fe_(3)O_(4)@[Cu_(3)(btc)_(2)]was synthesized and applied as a dispersive micro-solid phase extraction adsorbent for TCs enrichment.Effects of dispersive micro-solid phase extraction conditions including extraction time,solution p H,and elution solvent on the extraction efficiencies of TCs were investigated.Results show that TCs could be enriched efficiently by Fe_(3)O_(4)@[Cu_(3)(btc)_(2)],and electrostatic interaction between TCs and Fe_(3)O_(4)@[Cu_(3)(btc)_(2)]dominated this process.Combined with liquid chromatography-tandem mass spectrometry,four TCs residues (oxytetracycline,tetracycline,chlortetracycline,and doxycycline) in natural waters were determined.The detection limits (LOD,S/N=3) of the four antibiotics were 0.01-0.02μg/L,and the limits of quantitation (LOQ,S/N=10)were 0.04-0.07μg/L.The recoveries obtained from river water and aquaculture water spiked with three TCs concentration levels ranged from 70.3%to 96.5%with relative standard deviations of 3.8%-12.8%.Results indicate that the magnetic metal-organic framework based dispersive micro-solid phase extraction is simple,rapid and high-loading for antibiotics enrichment from water,which further expand the practical application of metal-organic frameworks in sample pretreatment for environmental pollutant analysis.

Matrix Solid-phase Dispersion Extraction of Alkaloids from the Roots of Aconitum kusnezoffii Reichb

Matrix solid-phase dispersion（MSPD） was developed for the extraction of four alkaloids, including aconitine, mesaconitine, hypaconitine and deoxyaconitine, from the roots ofAconitum kusnezoffii Reichb. The determination of the analyte was carried out by high performance liquid chromatography with UV detection. The alkaline alumina was used as sorbent. The mixture of acetonitrile and water was used as elution solvent. Several extraction parameters, such as type of sorbent, the ratio of sample to solid support material, type of the elution solvent and the volume of the elution solvent were tested. Mean recoveries ranged from 93.16% to 102.73%, with relative standard deviations from 0.27% to 4.17%. With the extraction efficiency and time expenditure taken into account, MSPD extraction should be a comparatively good method.

Determination of Eleutheroside B and E in Acanthopanax Preparations by High-P erformance Liquid Chromatography with Solid-Phase Extraction

Aim An HPLC method for analyzing eleutheroside B (ELU B) and eleutheroside E(ELU E) , two of the main active substances of Acanthopanax preparations were studied. Methods Thesamples were analyzed on a kromasil ODS column with water-acetonitrile as a gradient mobile phase.The flow rate was 0.8 mL·min^(-1) and detecting wavelengths were 206 nm for ELU B, 220 nm for ELUE, solid phase extraction (SPE) and internal standard-salicin were selected. Results The recoveriesof Acanthopanax tablets and injection were 90.4% - 96.8% and 96.4% - 99.8% for ELU B, 87.7% -93.3%and 95.7% - 98.5% for ELU E, respectively. The linear ranges were 4.45 - 22.25 μg· mL^(-1) (r =0.999 8) and 5.11 - 25.55 μg·mL^(-1) ( r = 0.999 7) respectively. Conclusion This method can savethe time for cleaning the chromatographic system and improve sensitivity for Acanthopanaxpreparations , thus providing a way to evaluate the quality of Acanthopanax preparations.

Determination of seven active components in Salvia miltiorrhiza herb by matrix solid phase dispersion combined with ion liquid extraction followed by high performance liquid chromatography

A low cost,rapid and sensitive preparation method of silica gel supported ionic liquid(SGSIL)combined with matrix solid phase dispersion(MSPD)followed by high performance liquid chromatography(HPLC)with ultraviolet detection(UV)is proposed,and it was applied to determine the seven active compounds in Salvia Miltiorrhiza herb.SGSIL and ionic liquid[BMIM]BF4 were used as the adsorbent and the green elution reagent in the MSPD procedure.Several extraction conditions including type of filler and elution solvent,the volume of elution solvent,material liquid ratio were optimized.Under the optimum conditions,the SGSIL-MSPD-HPLC method showed a low limit of detection(LOD,S/N=3)of 0.0122-0.8788μg/mL for standard solution,limit of quantification(LOQ,S/N=10)of 0.0406-2.9292μg/mL for standard solution,wide linear range from 1.56 to 2000μg/mL for all compounds for standard solution,correlation coefficients(r)of more than 0.9990,acceptable reproducibility(relative standard deviations,RSDs<3.54%),and precision of RSDs<3.36%for intra-day,RSDs<3.50%for inter-day.The satisfactory recoveries ranged from 96.4 to 102.5,with RSDs less than 3.45%.The developed SGSIL-MSPD method is easier and more suitable for the determination of the seven active compounds in Salvia Miltiorrhiza herb than the traditional ultrasonic extraction.It was an effective and efficient method for the extraction and quantification of the seven active compounds in traditional Chinese herbal samples.

Synthesis and Solid Phase Extraction Performance Study of NNAL-specific Molecularly Imprinted Polymers Using Dummy Templates

Dummy molecularly imprinted polymers （DMIPs） for 4-（methylnitrosamino）-1-（3-pyridyl）-1-butanol （NNAL） were produced using three structural analogues as dummy template molecules. The chosen analogues were 4-（acetymethylamino）-1-（3-pyridyl）-butanol, 4- （methylamino）-1-（3-pyridyl）-1-butanol, and 1-（3-pyridyl）-1,4,-butanediol. The molecular recognition characteristics of the produced polymers were evaluated by X-ray photoelec- tron spectroscopy （XPS） and Fourier transform infrared spectroscopy （FT-IR）. Interactions between NNAL and methacrylic acid should be cooperative hydrogen bonds while the ni- trogen atom of the pyridine ring and the oxygen atom of the nitroso group in NNAL are two of the hydrogen-bond acceptors. It was further demonstrated that DMIP synthesized by 4-（acetymethylamino）-1-（3-pyridyl）-butanol had the best binding performance by XPS and FT-IR. Then dummy molecularly imprinted solid phase extraction （DMISPE） was developed for the determination of the analyte using the hit polymer as the sorbing material. Under optimal conditions, the recovery of NNAL dissolved in standard solution reached 93%. And the investigated polymer exhibited much higher binding of NNAL when nicotine was acted as the competitive molecule. Also the proposed method was applied to the measurement of NNAL spiked in blank urine samples with recoveries ranging from 87.2% to 101.2%.

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.

Influences of solid particles on the formation of the third phase crud during solvent extraction

The influences of solid particles in leach solution on the formation of the third phase crud during solvent extraction of copper were studied. Analyzed from the point of view of pH value and surface tension, the study results showed that the solid particle is one of the most important contributors for the formation of the third phase crud. During solvent extraction, if the pH value was greater than 2.30, the number of solid particles in the mother solution increased, in which case the possibility of forming the third phase crud could also increase, and the interface tension value might grow in pace with the quantity of the third phase crud.

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.

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 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.

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.

Prediction of dispersed phase holdup in pulsed disc and doughnut solvent extraction columns under different mass transfer conditions

Using experimental data from a number of pulsed disc and doughnut solvent extraction columns, a unified correla- tion for the prediction of dispersed phase holdup that considers the effects of mass transfer is presented. Pulsed disc and doughnut solvent extraction columns （PDDC） have been used for a range of important applications such as ura- nium extraction and nuclear fuel recycling. Although the dispersed phase holdup in a PDDC has been presented by some researchers, there is still the need to develop a robust correlation that can predict the experimental dispersed phase holdup over a range of operating conditions including the effects of mass transfer direction. In this study, dis- persed phase holdup data from different literature sources for a PDDC were used to refit constants for the correlation presented by Kumar and Hartland lind. Eng. Chem. Res.,27 （1988）,131-138] which did not consider the effect of col- umn geometry. In order to incorporate the characteristic length of the PDDC （i.e. the plate spacing）, the unified cor- relation for holdup proposed by Kumar and Hartland based on data from eight different types of columns [Ind. Eng. Chem. Res.,34 （1995） 3925-3940] was refitted to the PDDC data. New constants have been presented for each hold- up correlation for a PDDC based on regression analysis using published holdup data from PDDCs that cover a range of onerating conditions and nhwical nronerties and consider the direction of mass transfer.

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.

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.

Determination of Sulfadimidine in Royal Jelly by C_(18)-functionalized Magnetic Silica Nanoparticles Solid Phase Extraction-High Performance Liquid Chromatography-Tandem Mass Spectrometry

[Objective] This study aimed to develop a method of C_18-functionalized magnetic silica nanoparticles solid phase extraction-high performance liquid chro- matography-tandem mass spectrometry for the determination of sulfadimidine in royal jelly. [Method] The royal jelly samples were pretreated by MCX SPE column and C_18-functionalized magnetic silica nanoparticles, and the purified samples were de- tected by HPLC-MS/MS. [Result] The detection method showed a good linear rela- tionship in the range of 5-80 ugkg （r=0.993 1）. The recovery ranges were between 93%- 104% with the relative standard deviations （RSD） below 11.3%. [Conclusion] Combined with automation equipment, the method is simple, fast, time-saving, and easy to real- ize the automation of sulfadimidine in the royal jelly samples before determination.

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%.

Comparison of Headspace Solid-Phase Microextraction with Simultaneous Steam Distillation Extraction for the Analysis of the Volatile Constituents in Chinese Apricot

Volatile constituents in fully mature fruits of apricot （Prunus armeniaca L.） cultivar Xinshiji were extracted using headspace solid-phase microextraction （HS-SPME） and simultaneous steam distillation extraction （SSDE） and then analyzed using capillary gas chromatography and gas chromatography-mass spectrometry. A total of 70 components were identified by HSSPME, including 20 esters, 19 hydrocarbons, 5 alcohols, 5 ketones, 4 acids, 4 lactones, 3 aldehydes, and 10 miscellaneous components, with the esters being the dominant constituent. On the basis of the odor unit values, it is believed that the following compounds probably contributed to the fresh apricot odor： hexyl acetate, β-ionone, butyl acetate, （E）-2-hexenal, linalool, limonene, γ-decalactone, and hexanal. A total of 49 components were also detected by SSDE, including 13 hydrocarbons, 9 alcohols, 7 aldehydes, 9 esters, 4 ketones, 4 lactones, 2 acids, and 1 miscellaneous component, of which the monoterpene alcohols were the dominant constituents. It could be judged from the odor unit values that the following compounds were the major contributors to boiled apricot aroma： β-ionone, linalool, hexyl acetate, γ-dodecalactone, γ- decalactone, （E）-2-hexenal, hexanal, γ-octalactone, phenylacetaldehyde, butyl acetate, limonene, α-terpineol, and δ-decalactone. The results show that HS-SPME is a simple, rapid, and solvent-free method, which is an alternative to the classical SSDE.

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.