摘要:A class-specific molecularly imprinted polymer(MIP) with strong selectivity and adsorbability for triazines and their metabolites was synthesized by bulk polymerization using atrazine as template molecule,methacrylate acid(MAA) as functional monomer,and trimethylolpropane trimethacrylate(TRIM) as cross-linker. And a rapid method was developed for the determination of 8 triazines and their metabolites in maize,wheat and cotton samples by molecularly imprinted solid phase extraction and high performance liquid chromatography tandem mass spectrometry(MISPE/HPLC-MS/MS).The proportion of atrazine and methacrylate acid was screened and optimized by ultraviolet spectrometry.The morphology of polymer was observed with scanning electron microscope and transmission electron microscope.The recognition performance of structure analogues on the molecularly imprinted polymer was studied by HPLC-MS/MS.The result indicated that the synthesized molecularly imprinted polymer had a strong affinity and specificity for atrazine and its structure analogues,and the molecularly imprinted solid phase extraction cartridge had a good selectivity and purifying ability.The mean recoveries of these compounds in maize,wheat and cotton were in the range of 61.1%-107.6%,with relative standard deviations(RSD) below 11%.The limits of detection(S/N=3) were in the range of 0.4- 8.1 μg/kg. The MISPE-HPLC-MS/MS method could be applied in the routine surveillance of actual samples.
关键词:triazine pesticides;class-specific;molecularly imprinted polymer;solid phase extraction;high performance liquid chromatography tandem mass spectrometry(HPLC-MS/MS);residue
摘要:Selecting tap water,sea water and the Organisation for the Prohibition of Chemical Weapons(OPCW) official test water as background matrices,a high performance liquid chromatography-quadrapole time-of-flight mass spectrometric(HPLC-Q-TOF /MS) method was developed for the determination of ricin on the base of instrumental parameter optimization.The limits of detection(LODs) of ricin were 0.05,0.20 and 1.00 μg/mL for the three matrices,respectively.The relative molecular mass of ricin was determined to be 62 884.97 Da.In order to improve the analytical sensitivity of complex water samples,immunocapture with magnetic beads linked by anti-ricin monoclonal antibody 6A6 was adopted to enrich and purify ricin in different water samplesELISA was used to draw the standard curve of immunocapture.The method showed a good linearity for ricin in the concentration range of 5.00-100 μg/mL.The average recoveries at spiked levels of 15,30 μg/mL were in the range of 82.1%-88.8%with RSDs of 4.2%-5.9%.The HPLC-Q-TOF/MS method with immunocapture was applied in the determination of ricin spiked in different matrices.The LODs for ricin in the three different matrices reached to 2.5,10,50 ng/mL,respectively.The results demonstrated that the method could be rapidly and effectively used in the determination of trace ricin in water samples.
摘要:With the initialization of benzoyl peroxide and N,N-dimethyl aniline,the molecular imprinted polymer(MIP)microspheres were firstly prepared by using ethopabate as template,methacrylic acid as functional monomer and pentaerythritol triacrylate as crosslinking agent.The optimized porogen was acetonitrile and the optimum molar ratio of template,monomer and cross-linker was 1 ∶6 ∶20.After determining the concentrations of ethopabate and structurally related compounds by high performance liquid chromatographic method,the adsorption properties of the polymers were studied by static equilibrium adsorption,adsorption dynamics and selective binding experiment.The adsorption capacity and imprinting factor were calculated to be 15.0 μmol?g-1 and 4.93,respectively.The physical and chemical properties of MIP microsperes were investigated with scanning electron microscope,Fourier transform infrared spectroscopy and differential scanning calorimeter.The result showed that the microspheres had uniform morphology,significantly high imprinting effect and good thermal stability.The above characteristics are favorable to the selective separation and purification of ethopabate from complex matrix using the microspheres.Therefore,the proposed oxidation-reduction system for initialization not only has the advantages of simple preparation,low cost and good specificity,but also offers a new paradigm for the preparation of molecular imprinted polymers.
摘要:The interaction of pentafluoropropionic acid(IPC-PFFA-3) with human serum albumin(HSA) was studied using molecular docking,molecular dynamics(MD) simulation,fluorescence spectroscopy,synchronous fluorescence and competition experiments.The results of the molecular docking indicated that the binding force between IPC-PFFA-3 and HSA was hydrogen bond.Fluorescence data revealed that the fluorescence quenching of HSA by IPC-PFFA-3 was a static quenching procedure.The thermodynamic parameters showed that binding was spontaneous and was driven mainly by hydrogen bond.Competitive drug displacement results suggested that the binding site of IPC-PFFA-3 with HSA lie on Sudlows site Ⅱ.The experimental results were supported by the molecular docking.MD and synchronous fluorescence suggested that HSA does have a sight conformational change when it binds with IPC-PFFA-3 and the structure of HSA-IPC-PFFA-3 is very stable.
摘要:The volatile compounds in sesame oil were analyzed by headspace gas chromatography-mass spectrometry(GC-MS) with calibrated lineshape isotope profile search(CLIPs) function intergrated in MassWorksTMsoftware.71 kinds of components including pyrazines,pyrroles,pyridines,thiazoles,thiophenes,indoles,oxazoles,furans,aldehydes and phenols,etc.could be identified,which account for 90.2% of the total normalized peak areas.Among them,aldehydes,phenols,pyrazines and furans account for 37.4%,20.1%,10.0%and 6.7%,respectively.They were principal contributors of sesame oil flavor components.The application of CLIPs can provide the accurate molecular weight of compounds and an important basis for the low-resolution quadrupole mass spectrometer to identify the elemental composition and the structure of compound.The study provided a new technical means for the component analysis of sesame oils.
摘要:In order to search for a new method for the quick detection of walnut oil quality,the adulterated walnut oil samples were tested by low field-nuclear magnetic resonance(LF-NMR),and the relaxation data of CPMG sequence were analyzed and processed by chemometric methods including principal component analysis(PCA) and partial least squares regression(PLSR).The adulterated walnut oil samples with soybean oil,corn oil or sunflower oil and pure walnut oil were used for the LF-NMR detection and evaluation.The experimental results showed that PCA can distinguish pure walnut oil and different kinds of adulterated walnut oil.Moreover,the adulterated walnut oil samples display regular distribution with different adulterated ratios.The CPMG data and actual adulteration value were adopted for the quantitative analysis of walnut oil adulteration level by PLSR.Therefore,the combination of LF-NMR technology and chemometrics could provide a fast,non-destruction and accurate method for the detection of walnut oil adulteration,and show a great application potential in control and evaluation of edible oil products quality.
关键词:chemometrics;principal component analysis(PCA);partial least squares regression(PLSR);low field-nuclear magnetic resonance(LF-NMR);adulterated walnut oil
摘要:A solid phase extraction and precolumn chemical derivatization technique coupled with liquid chromatography-electrospray ionization/mass spectrometric(LC-ESI/MSn) method was developed for the analysis of theophylline and its metabolites in human urine after oral administration of theophylline tablets to discover its metabolism pathway in vivo.The mass spectral fragmentation behaviors of theophylline,metabolites and their derivatives were also discussed.Human urine between 0 hour and 6 hour was collected immediately after administration of theophylline tablets.Then the urine samples were pretreated by solid phase extraction through a Bond Elute C18 column.Methanol part was collected to be dried by N2 at 50 ℃,and then subjected to derivatization with N,N-dimethyl ethylamine chloride.The separation of urine samples was achieved on a Shimpack C18 column with methanol-water-formic acid(20∶80∶1) as mobile phase,and the detection was fulfilled with electro spray ionization(ESI) in positive mode.Through this method,theophylline and four metabolites(1-methyl uric acid,1,3-dimethyl uric acid,1-methyl-N-acetyl derivative and 3-methyl xanthine) were identified or tentatively identified,in which one of these metabolites was firstly recovered in theophylline.Under positive mode,theophylline and its metabolites always lost 18 u,28 u or 57 u fragments in MS2 spectrum and their derivatives lost 45 u fragments regularly in MS2 spectrum.Through the comparison with the underivatized urine samples,the samples derivatized were found to be able to enhance the sensitivity of theophylline,1 methyl uric acid and 3 methyl xanthine in mass spectrometry.This method replenished the metabolite file of theophylline in human,and provided a new approach for the identification of theophylline,metabolites and their structural analogues with low concentration in biosamples.
关键词:theophylline;in vivo metabolites;LC-MSn;precolumn derivatization
摘要:An automatic analysis method was developed for the determination of 16 β-agonists residues including orciprenaline,clorprenaline,cimaterol,terbutaline,tulobuterol,cimbuterol,salbutamol,zilpaterol,clenbuterol,ractopamine,fenoterol,mabuterol,bromochlorobuterol,mapenterol,phenylethanolamine A and brombuterol in pig urine by liquid chromatography-tandem mass spectrometry(LC-MS/MS).The sample was digested overnight at 37 ℃, and purified by turboflow online cation solid-phase exaction(online-MCX-SPE)at a flow rate of 3 mL/min.The elution was selected with 5% ammonium in methanol-water(9∶1).The separation of 16 compounds was carried out on a CAPCELL MGⅡ chromatographic column,using 0.1% formic acid methanol-01% formic acid solution containing 5 mmol/L ammonium formate as mobile phase,and determined in positive electro-spray ionization mode.Under the optimized conditions,the calibration curves of 16 agonists were linear in the concentration range of 0.01-50 μg/L with correlation coefficients(r2) not less than 0.998 3.The limits of detection(LOD) were in the range of 0.01- 0.025 μg/L and the limits of quantitation(LOQ)were 0.025-0.10 μg/L.The recoveries of the method ranged from 62.4% to 117.1% with relative standard deviations(RSDs)of 3.9%-16.3%.The determination of 213 pig urines demonstrated that the method was simple and automatic,and was suitable for the quick confirmation of 16 β agonists in large batch of pig urines.
摘要:A method was developed for the determination of 18 sulfonamide residues in pork by using modified QuEChERS/high performance liquid chromatography with online post column photochemical derivatization and fluorescence detector.The residues in the samples were extracted with 1% acetic acid acetonitrile solution,cleaned by QuEChERS(Quick,Easy,Cheap,Effective,Rugged and Safe) method using a mixture of PSA,C18 and GCB as sorbent.The target compounds were separated by HPLC on a Platisil ODS column(4.6 mm×250 mm,5 μm),and then treated by on-line photochemical derivatization and detected with a fluorescence detector.The optimal conditions were as follows:excitation wavelength:320 nm,emission wavelength:450 nm, column temperature: 36 ℃,mobile phase:0.3% acetic acid-methanol by gradient elution.Under the optimized conditions,a good baseline separation of 18 analytes was obtained.The calibration curves were linear in the range of 0.05-110.28 μg?mL-1 for 18 sulfonamides,with correlation coefficients(r) larger than 0.992 0 .The method detection limits(S/N=3) for target compounds ranged from 1 μg/kg to 18 μg/kg,the limits of quantitation(S/N=10) were in the range of 3-60 μg?kg-1.The spiked recoveries of 18 sulfonamide residues varied from 71.2% to 113.4%,in which the majority recoveries were in the range of 80%-100%.The relative standard deviations(RSDs) were 0.8%-8.7%.The method showed advantages of rapidness,simplicity, less organic solvents,reliability,good accuracy and precision,and could meet the requirements for qualification and quantification analysis of 18 sulfonamide residues in pork.
摘要:A quick ultra performance convergence chromatography(UPC2) with photodiode array detector method was developed for the simultaneous determination of three carotenoids(e.g.β-carotene,zeaxanthin and lutein) in spirulina dietary supplement products.Effects of chromatogramic column, co-solvent,backpressure,column temperature and extraction solvent were optimized.The optimal conditions were as follows:The samples were extracted ultrasonically with dichloromethane-ethanol(2∶1),followed by clean-up of extract using 0.22 μm GHP filter.The separation of compounds was carried out on an ACQUITY UPC2 HSS C18 SB column(150 mm×3.0 mm,1.8 μm) by gradient elution with carbon dioxide and methanol system.The column temperature was set at 40 ℃and the backpressure was 2 000 psi.The quantification analysis was achieved by the external standard method.Good linear relationships were obtained for 3 carotenoids in the certain concentrations with correlation coefficients not less than 0.999 3.The limits of detection(LODs) of 3 carotenoids were in the range of 0.012-0.035 mg/g,and the limits of quantitation(LOQs) were in the range of 0.040-0.120 mg/g.The mean recoveries ranged from 82.5%to 95.7%at different spiked levels with relative standard deviations(RSDs) of 7.6%-9.8%.The method is rapid and accurate,and could be used for the analysis of carotenoids in spirulina dietary supplement products.
摘要:An ultra performance liquid chromatography tandem mass spectrometric(UPLC-MS/MS)method was successfully developed for the simultaneous determination of ribavirin and its metabolites 1H-1,2,4-triazole-3-carboxamide(TCONH2) and 1-β-D-ribofuranosyl-1,2,4-triazole-3-carboxylic acid(RTCOOH).13C5-labelled ribavirin was used as an internal standard in this approach.After precipitation of proteins in chicken plasma by adding methanol,the pretreated sample was separated on a ZORBAX SB-Aq column(100 mm×3 mm,18 μm) by a gradient elution program using 0.1% formic acid water solution and methanol as mobile phase.The target analytes were detected by electrospray ionization-mass spectrometry under positive MRM mode.The result indicated that the calibration curves were linear in the ranges of 5- 5 000 μg/L for ribavirin and TCONH2,and 50-5 000 μg/L for RTCOOH,with correlation coefficients of 0.994 7,0.999 2,0.997 6,respectively.The average recoveries of ribavirin,TCONH2 and RTCOOH were in the range of 84.1%-108.2% with intra-assay relative standard deviations(RSDs,n=6) of 1.6%-13.4% and inter-assay RSDs(n=12) of 3.8%-16.9% .The limits of detection(LOD) for ribavirin,TCONH2 and RTCOOH in chicken plasma were 2 μg/L,2 μg/L and 10 μg/L,respectively.With merits of rapid analysis,good repeatability and wide linearity range,the method could be a powerful tool for the study of ribavirin pharmacokinetics and metabolism in chicken plasma.
关键词:ribavirin;TCONH2;RTCOOH;ultra performance liquid chromatography tandem mass spectrometry(UPLC-MS/MS);plasma
摘要:The separation of linalool enantiomer was investigated by ultra performance convergence chromatography(UPC2)using β-cyclodextrin as chiral stationary. The influences of different organic modifiers,active back pressure(ABPR),column temperature and injection volume on separation of linalool enantiomer were studied.The results showed that the acetonitrile as an organic modifier was better than methanol.The retention time and degree of separation were gradually reduced with the column temperature increasing from 30 ℃ to 55 ℃. When the concentration of linalool was 0.01% and injection volume was 3 μL,linalool enantiomers could be successfully separated in 3 min with the best peak shape and good resolution. Therefore,the optimal conditions were as follows:chromatographic column:CAPCELL PAK Chiral CD-Ph(150 mm×3.0 mm,4.6 μm);mobile phase:CO2-acetonitrile(97∶3); flow rate:1.2 mL/min;column temperature:30 ℃; injection volume:3 μL;detection wavelength:215 nm;active back pressure(ABPR):1 700 psi.The thermodynamic mechanism for linalool enantiomeric separation under ultra performance convergence chromatography was preliminarily studied,which could provide the experimental foundation for using UPC2 separated chiral compounds.
摘要:An analytical method was established for the simultaneous determination of residues of abamectin,emamectin benzoate,imidacloprid,indoxacard,zineb in vegetables by ultra high pressure liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).The samples were extracted with acetonitrile after treated with 0.1% NaOH(containing 10 mmol/L L-cysteine and 10 mmol/L EDTA-Na2),and cleaned up by 0.2 g C18+0.05 g GCB matrix dispersive solid phase extraction.Five kinds of pesticides were separated on a Thermo Hypersil BDS C18(100 mm × 4.6 mm,2.6 μm) column using 10 mmol/L NH4OH-acetonitrile as mobile phase by gradient elution,and determined by MS/MS.The results showed that the calibration curves were linear in the ranges of 50-2 000 μg/L for zineb,and 5-200 μg/L for the rest of analytes.The correlation coefficients were in the range of 0.995 1-0.999 9.The spiked concentration ranges were 0.5-500 μg/kg for five compounds in bean,chilli,pakchoi,cucumber,asparagus and tomato samples,and the spiked recoveries were in the range of 70.8%-103.6% with relative standard deviations(RSD) of 4.5%-13.9%.The limits of detection for zineb ranged from 8.2 μg/kg to 30 μg/kg,and the limits of quantitation were in the range of 27-100 μg/kg.The limits of detection for the rest of compounds were in the range of 0.02-0.7 μg/kg,and the limits of quantitation were 0.07-2.3 μg/kg.The method was rapid,accurate,economical and practical,and could meet the needs of daily inspection.
关键词:abamectin;emamectin benzoate;imidacloprid;indoxacarb;zineb;dispersive solid phase extraction;ultra high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)
摘要:β-CD has a special large molecular cavity with an external hydrophilic and an internal hydrophobic properties,and it could form inclusion complex with 4-tert-octylphenol(OP) and 4-n-nonylphenol(NP),respectively.In this paper,the stoichiometric ratios and the equilibrium constants between β-CD and the above two alkylphenols(APs) were determined by UV spectrophotometry.The results indicated that OP and NP both form inclusion complexes by a molar ratio of 1∶1 with β-CD, and the equilibrium constants were 71.06 L/mol and 1 402.72 L/mol,respectively.At the same time,the equilibrium constants between β-CD and APs were also studied by capillary electrophoresis under the conditions of 10 mmol/L sodium dihydrogen phosphate-10 mmol/L sodium borate-20 mmol/L sodium cholate(pH 9.0).The double reciprocal was introduced to measure the equilibrium constants,and the values for OP and NP were 68.20 L/mol and 1 357.80 L/mol,respectively.According to F test and t test,the equilibrium constants between β-CD and APs obtained from two methods have no difference.
摘要:A method for the simultaneous determination of trimethyltin(TMT),dimethyltin(DMT) and monomethyltin(MMT) in wine was developed by headspace extraction coupled with gas chromatography and flame photometric detection(GC-FPD) after in-situ derivatization with sodium tetraethylborate(NaBEt4).The headspace conditions(temperature,time and oscillating mode),derivatization parameters(amount of NaBEt4,pH value and salinity) and GC conditions were optimized.In the optimal experimental conditions,the limits of detection(LODs) were 1.2,1.0,1.2 μg/kg for TMT,DMT and MMT,respectively.For the three representative matrices of dry white,dry red and pink wine,the average recoveries at three spiked levels of 5.0,10.0,100.0 μg/kg were in the range of 80.5%-101.4%,and the relative standard deviations(RSDs,n=6) ranged from 3.2%to 8.5%.The proposed method was validated to have high sensitivity and high accuracy,also with the special advantages of simplicity and rapidness.The total analysis time for one sample is not more than 25 min by the proposed method,and it is suitable for the rapid screening of methyltin compounds in wine.
关键词:methyltin;wine;ethylation;headspace;gas chromatography and flame photometric detection(GC-FPD)
摘要:A high performance liquid chromatographic(HPLC) method was established for the determintion of furan-2,5-dicarboxylic acid in beverages.The Venusil HILIC(4.6 mm×250 mm,5 μm) was used as chromatographic column with a column temperature of 40 ℃.0.02 mol/L ammonium acetate(glacial acetic acid adjust pH 3.5)-acetonitrile (50∶50,by volume)was used as the mobile phase with a flow rate of 1.0 mL/min.The detection wavelength was set at 265 nm.The samples were mixed after constant volume.The solution was analyzed by hydrophilic interaction liquid chromatography after filtration. A good linearity was obtained for furan-2,5-dicarboxylic acid in the range of 0.5-100 mg/L.The limits of detection(LOD) and limits of quantitation(LOQ) for the method were 0.15 mg/kg and 0.5 mg/kg,respectively.The spiked recoveries of target compound in mineral water,cola drink and orange juice beverage were in the range of 93.2%-109.0%,with relative standard deviations(RSD,n=6) of 0.9%-4.2%.The method was rapid,simple and high sensitive,and was suitable for the determination of furan-2,5-dicarboxylic acid in beverages.
摘要:A method was developed for the simultaneous determination of benzo(а)pyrene(Bap)and bisphenol A(BPA)in drinking water by high performance liquid chromatography(HPLC) with solid phase extraction(SPE).Benzo(a)pyrene and bisphenol A were concentrated from drinking water sample with an ENVI-18 column.The chromatographic separation was performed on a BEH-C18 column using acetonitrile - water as mobile phase with gradient elution.The benzo(a)pyrene and bisphenol A were detected with fluorescence detector(FLD).The results showed that the linear ranges of two compounds ranged from 0.1 to 20.0 μg/L with correlation coefficients(r)more than 0.999.High recoveries(86.1%-101%) and good reproducibility(2.9%-4.6%) were obtained.The limits of detection were 0.2 ng/L and 2.0 ng/L,respectively.The method was simple,feasible and accurate,and could be applied in the quantification of benzo(a)pyrene and bisphenol A in drinking water.
关键词:drinking water;fluorescence detector(FLD);high performance liquid chromatography(HPLC);solid phase extraction;benzo(а)pyrene;bisphenol A
摘要:A gas chromatographic method was developed for the determination of iodine in 45 kinds of daily food.The sample was ashed with K2CO3 and ZnSO4 solution,then dissolved with acidic water.After derivatized with butanone,the sample solution was separated by GC on a DB-1701 column,and detected with ECD detector.The external standard method was used for quantitation analysis.Effects of different ashing conditions were investigated,and the sensitivity,accuracy and precision of the method were verified.The detection limits of iodine was 1.0 ng?g-1,and the average recovery from spiked sample was 99.5%with RSD of 3.6%.The advantages of sensitivity,accurancy,short analysis time and good anti-interference made the method be suitable for the routine safety monitoring of iodine in daily food.
摘要:In this paper, a method for rapidly detection the total organic components of PM2.5 by using 13C solid-NMR technique was reported.Reliable information on the organic chemical structure could be obtained without cumbersome sample pre-treatment by this method.Organic components data of PM2.5 from Taiyuan,Xinxiang and Guangzhou were obtained by 13C solid-NMR technique.The result showed that the method was simple,rapid and highly sensitive,and could be applied in the determination of total organic composition of atmospheric aerosol.
摘要:Magnetic solid-phase extraction(MSPE)is a novel sample preparation technique using magnetic materials as sorbents,which can be quickly separated from sample solution under external magnetic field.The development of new magnetic sorbents has become a subject of great interest in the MSPE field.MSPE using ionic liquid(IL)modified magnetic particles as sorbent has attracted more and more attention in the extraction and separation of trace or ultra trace organic pollutants and inorganic ions in food,environmental and biological samples.The technique possesses some advantages of MSPE such as simple operation,quick extraction and low matrix interference,as well as unique characteristics of IL including tailored structure and easy chemical functionalization. Some preparation methods of IL modified magnetic materials are provided,including physical coating method,chemical bonding method and embedding method,and some extraction modes of IL-MSPE such as traditional MSPE,mixed hemimicelles based MSPE and dispersive liquid-liquid microextraction based MSPE. The applications of IL-MSPE as a sample preparation in the extraction and separation of organic pollutants,metal ions and biological molecules using chromatography and spectroscopy techniques in the latest 5 years are reviewed,and the future trends of IL-MSPE technique are also discussed.