摘要:Based on ultra performance liquid chromatography coupled with ion trap-time of flight mass spectrometry(UPLC-IT-TOF MS),a non targeted metabolomics method was developed for the investigation on metabolite difference between human chronic myeloid leukemia cells and their adriamycin resistant cells,ie.K562 and K562-ADM.Specifically,impacts of disruption methods,extraction solvent systems and volumes on the extraction effects for metabolites in QC samples were examined.Results showed that the ultrasonic disruption method in an 800 μL of 80% methanol solvent system could obtain more feature peaks from leukemia cells with good repeatability and stability.Then,the established method was applied to investigate the metabolite difference between K562 and K562-ADM.The data was processed by principal component analysis(PCA) and orthogonal partial least squares discrimination analysis(OPLS-DA),and the significant differences between the metabolome of K562 and that of K562-ADM cells were obtained,in which forty metabolites significantly contributed to the differences,and they were mainly involved in amino acid metabolism, sphingolipid metabolism,purine metabolism and pyrimidine metabolism.The established method could be used to investigate the metabolite differences between K562 and K562-ADM,and further provide some help for future metabolomics researches on drug resistance of leukemia cells.
关键词:leukemia cells;non targeted metabolomics;ultra performance liquid chromatography-tandem mass spectrometry;adriamycin resistance
摘要:Aiming at the demand for rapid detection of heavy metals in soil,a selection for characteristic wavelength variables was performed based on model population analysis method,and a method of X ray fluorescence spectroscopy was proposed for the detection of contents of heavy metals in farmland soils.X ray spectrum values of 91 configured soil samples were collected,and used to establish a soil heavy detection model.The characteristic wavelength variables were extracted by the multi feature series method.Firstly,the interval combination optimization algorithm(ICO) was used for rough selection of the wavelength.Secondly,the competitive adaptive reweighted sampling(CARS) was adopted to remove those irrelevant variables in the interval wavelength.Finally,the successive projections algorithm(SPA) was performed for wavelength reduction.The ICO-CARS-SPA algorithm with multiple features was used to select the feature variables in the X ray fluorescence spectrum to obtain 5(26,25,29,39,33) characteristic wavelength points.Based on this,a partial least squares(PLS) detection model for the contents of five heavy metals,i.e.Cu,Zn,As,Pb,Cr in soil was developed,which was compared with other traditional characteristic wavelength selection methods.Results showed that the variables selected by the ICO-CARS-SPA algorithm were combined with partial least squares(PLS) to have the best modeling effect.The determination coefficients of Cu,Zn,As,Pb,Cr were 0.993 3,0.992 6,0.995 6,0.993 2,0.988 6,respectively.The root mean square errors of five metals were 6.938 5,23698 4,3.632 6,8.510 6 and 14.764 5,and the mean relative biases of the prediction sets were 0.255 1,0.065 0,0.102 5,0.241 4,0.104 7,respectively.The ICO-CARS-SPA algorithm based on X-ray fluorescence spectroscopy combined with multi-feature series strategy could eliminate invalid wavelengths,thus increasing contribution of effective information,simplifying detection model complexity,and providing a theoretical support for selecting an appropriate feature band extraction method for the prediction model of soil heavy metal content.
关键词:X-ray fluorescence(XRF);soil heavy metals;wavelength optimization;model population analysis
摘要:A portable microplate analyzer based on a smartphone was developed for rapid high throughput quantitative detection of human serum albumin(HSA).A lens with large aperture and a LED with uniform plate were firstly used in this article to assist the smartphone to achieve a uniform imaging for the whole 96 microplate.A custom designed smartphone application was used for automatic analysis.There was a good linear relationship between results obtained with this analyzer and those of microplate reader for detection of HSA standard samples,with a correlation coefficient of 0.989 3 and the detection range of 21.45-60.06 g/L,which proved that the developed analyzer has great accuracy and reliability.In addition,the detection results of human serum samples also showed good agreement between the clinical analyzer and the proposed one,revealing that the developed analyzer could also be used for clinical HAS detection.With the characteristics of low cost and being small in size,the analyzer is suitable for those underdeveloped areas,primary care institutions and ordinary families,and is of great significance for rapid on site diagnosis on the disease.
关键词:digital colorimetric method;96 microplate;smartphone;human serum albumin detection
摘要:To realize the nondestructive discriminant analysis of the pigments used in polychrome relics,the diffuse reflectance spectra for 12 kinds of pigments reference samples were collected.According to the shapes of the spectra,the reference samples were divided into two categories:red yellow and blue green.Principal component analysis(PCA) was used to reduce the dimensions of the spectra data sets of the two kinds of reference samples,and three principal components were extracted.The difference between the pigments was confirmed by using the scatter plot of PCA,and the spectral wavelength range with the highest contribution to the difference was discussed with the components matrix.Based on the PCA analysis results,the linear discriminant analysis(LDA) was used to fit the discriminant function which was applied in the analysis of two paintings samples from Renshou Hall of the Summer Palace.According to the distance between the scatter diagram of sample score discrimination and the reference samples of each category,the pigments used for cultural relics were determined to be hematite and ultramarine,respectively.Results showed that the discriminant function could be used to distinguish the kinds of pigments accurately,and analyze and identify the cultural relics pigments nondestructively.Nevertheless,the pollution or aging of cultural relics samples may affect the analysis,the surface cleaning is thus required in advance.
摘要:In this paper,a method based on the capacitively coupled contactless conductivity detection(C4D) signal was proposed for the rapid detection of soil available potassium content as many problems had occurred in the determination of soil available potassium content by traditonal methods,such as complex operation and long detection time.The Henan fluvo aquic soil samples were firstly characterized through high performance capillary electrophoresis with C4D device to obtain their C4D signals.Subsequently,the peak spectrums of the signals were identified by using derivative method and the Gaussian curve fitting method,then the peaks were filtered based on setting conditions.A model for single Gaussian peak was established base on Gaussian peaks,peak position,full width at half maxima and peak area of the Gaussian curve.Then Levenberg-Marquardt(L-M) algorithm was combined with the Gaussian peak fitting algorithm to optimize the characteristic parameters used to describe the information of C4D signal.The relational model between peak spectrum and soil available potassium content was established by the combination of the Gaussian characteristic parameters and partial least squares regression method(PLS),achieving the prediction of soil available potassium content.The experimental results showed that it was feasible to use the Gaussian peak fitting algorithm based on L-M algorithm combined with PLS method for C4D signal to determine soil available potassium content with high accuracy.The coefficient of determination(R2) was 0.856 4,and the residual predictive deviation(RPD) was 2.639.The method was suitable for the rapid analysis on content of soil available potassium.
关键词:soil available potassium;contactless conductivity detection signal;Gaussian peak fitting;Levenberg-Marquardt(L-M)
摘要:A sensor for the detection of enzyme free glucose was fabricated with three dimensional Cu2O@Cu/TiO2 NTAs nanocomposites.Firstly,the three dimensional TiO2 nanotube arrays(TiO2 NTAs) were prepared by anodizing,and then a Cu film was electrodeposited on the surface of TiO2 NTAs by square wave pulse method.After calcination,the Cu2O@Cu/TiO2 NTAs nanocomposites were prepared.Results of X-ray diffractometer showed that Cu and Cu2O coexisted in the material.Combined with the analysis of SEM and TEM,Cu2O was uniformly grown on the outer surface of TiO2 tube wall,and the results of selected area electron diffraction displayed that the material presented a mixed crystal structure.The differential pulse voltammetry(DPV) showed that the oxidation peak of Cu2O@Cu/TiO2 NTAs was obvious at +0.56 V,indicating that the nanocomposite has strong electrocatalytic effect for glucose and could be used to detect it.There was a linear relationship of the method for glucose in the range of 0.19-35 mmol/L,with a sensitivity of 372.0 μA·L·mmol-1·cm-2 and a detection limit of 3 μmol/L.The electrochemical impedance exhibited that charge transfer resistance of Cu2O/TiO2 NTAs was 526.2 Ω,which was 292 times higher than that of Cu2O@Cu/TiO2 NTAs(merely 1.8 Ω).It displayed that Cu as the middle transition layer reduced the electronic conduction impedance.The sensor was used for the determination of glucose in serum sample.There was no significant difference between the results of the test and those of the hospital.Cu2O@Cu/TiO2 NTAs could be used as an enzyme free glucose sensor with its high sensitivity,fast response and good selectivity.
摘要:A novel high performance liquid chromatography-triple quadrupole mass spectrometry(HPLC-QqQ/MS),based on solid phase extraction(SPE) with inorganic porous materials as the adsorbents,was developed for the rapid separation and detection of ginsenosides in Yiqiyangxue oral liquid,a Chinese medicine compound.The adsorption activities of SAPO-34,SAPO-11,ZSM-5,zeolite Y,SBA-15 and multi walled carbon nanotubes(MWCNTs) on ginsenoside Re,Rg1,Rb1 and Ro were investigated.Under the optimized conditions,MWCNTs exhibited the best separation performance as they could reach an adsorption and desorption equilibrium towards ginsenosides within two minutes,respectively.The adsorption rates and desorption recoveries were higher than 98.6% and 96.8%,respectively.The limits of detection were in the range of 0.01-0.05 μg/mL,and the average recoveries were between 90.5%and 99.7% with relative standard deviations of 2.2%-4.9%.Moreover,the developed method was validated to be accurate and sensitive enough to detect and quantify trace amount of ginsenosides.Finally,the new method was successfully used for the separation and detection of the 4 ginsenosides in Yiqiyangxue oral liquid.Results revealed that the method has no obvious adsorption effect on the components other than ginsenosides,reducing the matrix interference and increasing the accuracy of quantification.Hence,HPLC-QqQ/MS combined with the proposed MWCNTs based SPE has a great application potential in the rapid detection of ginsenosides.
摘要:A high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS) was developed for the simultaneous determination of seven macrolide antibiotics,ie.tilmicosin,roxithromycin,spiramycin,tylosin,erythromycin,clarithromycin and azithromycin in additive premix,concentrate supplement,complete feed and concentrated feed.The samples were extracted with 1% ammoniated acetonitrile solution,followed by Oasis PRiME HLB solid phase extraction for further purification.The analytes were separated on an ACQUITY UPLC BEH C18 column(2.1 mm×100 mm,1.7 μm) by gradient elution using 0.1% formic acid solution and acetonitrile as mobile phases,then analyzd by MS/MS with electrospray ionization in positive mode,and quantified by external standard method.Results showed that there were good linear relationships for 3 target analytes,ie.tilmicosin,spiramycin and erythromycin in the concentration range of 0.5-50 μg/L(r2>0.99) and for the other 4 target analytes in the range of 0.25-50 μg/L(r2>0.99).The limits of detection and the limits of quantitation were in the ranges of 1.25-2.5 μg/kg and 2.5-5.0 μg/kg,respectively.At three spiked levels of 5,10 and 50 μg/kg,the average recoveries for target compounds ranged from 61.4% to 103% with relative standard deviations of 0.43%-15%.The developed method is simple,rapid,sensitive and low matrix interference,and it is suitable for the routine supervision and quantitative detection of macrolide antibiotics in different feeds.
关键词:macrolide antibiotics;feed;high performance liquid chromatography-tandem mass spectrometry;solid phase extraction
摘要:In this paper,a method was established for the quantitative detection of petroleum substances using mobile phone as detector.D values for Euclidean distance based on RGB and blank value calculation were applied to colorimetry to improve the precision of the method.Influences of different smart phones on the detection results under high illuminance were investigated.Results showed that the detection effects were significantly improved with the increase of aperture value(F).Influences of white balance mode and light source on the standard curve of D values were investigated to obtain the suitable conditions for warm color system detection,namely a 2 800 K white balance mode and a 300 W iodine tungsten lamp as light source.Under the above conditions,this method was applied in the detection of standard sample with a correlation coefficient larger than 0.99 and a testing range similar to that of spectrophotometry.The relative error for standard sample was 2.13% and the relative standard deviation was 3.0%,and the recoveries for standard addition ranged from 92.0% to 105%.This proposed method is accurate,convenient,low cost and easy to maintain,and it is suitable for real time online detection of remote automation.
摘要:A high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS) was established for the determination of chloramphenicol,thiamphenicol and florfenicol in propolis and propolis derived dietary supplements including tablet,hard capsule and soft capsule.The samples were dissolved and dispersed with 0.1 mol/L hydrochloric acid solution,blended well with a vortex mixer,followed by ultrasonical extraction and purification with an HLB solid phase extraction column(SPE) tandemly connected with a NH2-SPE column.The extract was separated on an Waters ACQUITY UPLC-BEH C18 column(2.1 mm×100 mm,1.7 μm) by gradient elution using a mobile phase consisting of 0.1% formic acid and acetonitrile.The analytes were analyzed by HPLC-MS/MS with electrospray ionization(ESI) source in negative ion mode,and quantified by external standard method.Under the optimal conditions,there were good linear relationships for 3 analytes in the concentration range of 0.10-20.0 μg/L with correlation coefficients(r2) larger than 0.999.The limits of detection(LOD) and limits of quantitation(LOQ) for three targets in propolis,propolis tablet and propolis soft capsule were in the ranges of 0.037-0.083 μg/kg and 0.12-0.28 μg/kg,while the LODs and LOQs for those in propolis hard capsule were 0.39-0.47 μg/kg and 1.28-1.57 μg/kg,respectively.The recoveries at spiked levels of 2.5,5.0,10.0 μg/kg were between 66.6% and 120%,with relative standard deviations(RSD) of 0.80%-11%.This method was applied to the detection on 45 actual samples collected in laboratory.The samples of propolis derived dietary supplements were detected positive for chloramphenicol and florfenicol,among which the positive detection rate for chloramphenicol was 22.22%,and the maximum residue was 14.32 μg/kg,while the positive detection rate for florfenicol was 17.78%,and the maximum residue was 21.62 μg/kg.With the characteristics of simplicity,high sensitivity and good reproducibility,the method could meet the requirements for determination of chloramphenicol,thiamphenicol and florfenicol residues in propolis and propolis-derived dietary supplements.
关键词:high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS);propolis;propolis derived dietary supplements;chloramphenicol;thiamphenicol;florfenicol
摘要:In this paper,a fluorescent probe for the dectection of cimetidine was fabricated based on fluorescence resonance energy transfer effect(FRET) between carambola carbon quantum dots(CB-CQDs) and silver nanoparticles(AgNPs).The CB-CQDs with high fluorescence intensity and good luminescence performance were synthesized by hydrothermal method using natural fruit carambola as the only raw material,which morphology and properties were characterized by ultraviolet-visible spectroscopy(UV-Vis),infrared spectroscopy(FTIR),transmission electron microscopy(TEM) and fluorescence spectrometry(FL),respectively.It was found that,when AgNPs was added into a pH 6.0 Britton-Robinson buffer solution containing CB-CQDs,the fluorescence signal of CB-CQDs at λex/λem=319 nm/397 nm was gradually quenched through the FRET effect,in which CB-CQDs and AgNPs acted as fluorescence donor and fluorescence acceptor,respectively.While in the presence of cimetidine,the fluorescence signal of CB-CQDs was restored and fluorescence signal “turned on” again,forming an “off-on” cimetidine sensor,and the basic mechanism was further discussed.Under the optimized conditions,there was a good linear relationship between fluorescence recovery value(ΔIF) and cimetidine concentration in the range of 9.0×10-8-1.0×10-6 mol/L,with a correlation coefficient(r) of 0.998 6.The detection limit was calculated to be 1.9×10-8 mol/L based on the 3σ/k principle.This method was successfully applied to the detection of cimetidine in real samples with satisfactory results.
关键词:carambola;carbon quantum dots;silver nanoparticles;fluorescence resonance energy transfer;cimetidine
摘要:An ultra performance liquid chromatography-triple quadrupole tandem mass spectrometric(UPLC-MS/MS) method was developed for the determination of α-lactalbumin(α-La) and β-lactoglobulin(β-Lg) in whey powder under positive ion multiple reaction monitoring(MRM) mode.The samples were firstly alkylated with iodoacetamide,followed by enzymatic hydrolysis with alkaline trypsin,then separated on a Waters ACQUITY UPLC-BEH C18,300 - column with 0.1% formic acid water solution and 0.1% formic acid acetonitrile solution as mobile phases by gradient elution.Results showed that there were good linear relationships for α-La and β-Lg in the ranges of 40-1 000 nmol/L and 80-2 000 nmol/L,respectively.The limits of quantitation(S/N=10) for α-La and β-Lg were 0.020 g/100 g,respectively.The average recoveries of two analytes from spiked whey powder samples were in the range of 84.7%-95.6%,with relative standard deviations(RSDs,n=6) of 1.6%-5.8%.Based on the above method,the targets in four kinds of whey powder samples,i.e.70% demineralised whey powder,90% demineralised whey powder,whey protein concentrate and α-lactalbumin powder from five countries were determined and contrasted.With the advantages of simple operation,accuracy and reliability,the established method was suitable for the determination of α-La and β-Lg in whey powder.
关键词:ultra performance liquid chromatography-triple quadrupole tandem mass spectrometry(UPLC-MS/MS);α-lactalbumin(α-La);β-lactoglobulin(β-Lg);whey powder
摘要:An ultra performance liquid chromatography-tandem mass spectrometric(UPLC-MS/MS) method was established for the determination of eight bisphenols and alkylphenols in cosmetics.Powders,waters,creams and gel cosmetics were extracted by ultrasonic extraction with acetonitrile-1% ammonium hydroxide solution(4∶1,by volume),then separated on a BEH Phenyl column(2.1 mm×100 mm,25 μm) by gradient elution with methanol and 0.1% ammonium hydroxide solution as mobile phases,and finally determined in multiple reaction monitoring(MRM) mode.Results showed that the calibration curves for eight bisphenols and alkylphenols exhibited good linear relationships in the certain concentration ranges,with correlation coefficients more than 0.997.The limits of detection(LOD) for eight bisphenols and alkylphenols were in the range of 0.001 25-0.025 mg/kg,and the limits of quantitation(LOQ) were 0.005-0.05 mg/kg.The average recoveries were in the range of 75.1%-107%,with relative standard deviations(RSD,n=6) of 0.1%-1.6%.This method is sensitive,versatile and reproducible,and is suitable for the separation of isomers and the simultaneous determination of eight bisphenols and alkylphenols endocrine disruptors in cosmetics.
关键词:ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS);cosmetics;bisphenols;alkylphenols;endocrine disruptors
摘要:A novel method was developed for the indirect determination of thiophene in metal catalysts by ion chromatography(IC) with pyrolysis.After combusted in the high temperature oven,the sulfur of thiophene in catalyst was transformed into SO2 and SO3,and then absorbed and oxidized to SO2-4by absorbing solution containing H2O2.The content of thiophene could be calculated indirectly from the content of SO2-4in the absorbing solution,which was detected by ion chromatography with suppressed conductivity detector.IonPac AS18(4.0 mm×250 mm) and IonPac AG18(4.0 mm×50 mm) columns were used for elution of the analyte with 15 mmol/L KOH as eluent.In the IC detection,the linear relationship for SO2-4was excellent in the range of 2.0-60 mg/L with a correlation coefficient of 0.999 8.The limit of detection(LOD,S/N=3) for SO2-4was 1.42 μg/L,and the LOD and the limit of quantitation(LOQ) for thiophene in metal catalysts were 0.25 μg/g and 182 μg/g,respectively.The recovery for thiophene ranged from 94.7% to 97.8%,with the relative standard deviation(RSD) of 1.5%-2.0%.The novel method is stable,rapid and sensitive,and it provides a new idea for the analysis of thiophene in the chemical production and some organic impurities in solid samples.
摘要:A high performance liquid chromatography-tandem mass spectrometric(HPLC-MS/MS) method was established for the determination of bimatoprost in eyelash enhancing cosmetics serums.The samples were extracted with 50%(by vloume) methanol,then separated on an Agilent Poroshell 120 EC-C18(4.6 mm×100 mm,2.7 μm) column by isocratic elution,with 5 mmol·L-1 ammonium acetate containing 0.02% formic acid-acetonitrile(55∶45) as mobile phases at a flow rate of 0.3 mL·min-1.The analyte was detected by HPLC-MS/MS with electrospray ionization source in positive ion mode(ESI+) and multiple reaction monitoring(MRM),and quantified by external standard method.Results showed that there existed a good linear relationship for bimatoprost in the range of 0.50-100 ng·mL-1 with a correlation coefficient(r2) of 0.998 2.The limit of detection(LOD,S/N=3) and limit of quantitation(LOQ,S/N=10) were 0.015 and 0.05 μg·g-1,respectively.The recoveries at low,medium and high spiked levels were 98.6%,101% and 99.2%,with relative standard deviations(RSDs) of 2.4%,2.1% and 1.2%,respectively.The method is simple,rapid and high sensitive,and is suitable for the rapid determination of bimatoprost in eyelash enhancing cosmetics serums.
关键词:bimatoprost;eyelash enhancing;cosmetics;high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS)
摘要:Accurate detection of gas plays an important role in modern war,aerospace,emergency rescue,etc.Non dispersive infrared(NDIR) sensors are a kind of tools for qualitative and quantitative detection of gas based on the infrared absorption at specific wavelength,which has the advantages of real time detection,wide detection range,low consumption and long lifetime.The principles,instrumental structures and related applications of NDIR sensors are reviewed in this paper,and an outlook for the future trend of NDIR sensors is provided.
摘要:Graphitic carbon nitride(g-C3N4),a novel two dimensional carbon based nanomaterial,has been widely applied in catalysis degradation,biosensor,energy storage and biomedicine.The in built N rich functional groups and electronic delocalization properties endow g-C3N4 with complex adsorption capabilities,including complexion,hydrophobic effect,π-π conjugation,hydrogen bond and electrostatic interaction.Particularly,the large specific surface area,satisfactory pH tolerance,facile and inexpensive preparation of g-C3N4 make itself qualified as an extraordinarily wonderful adsorbent.In recent years,g-C3N4 and its composites have been applied to the sample pretreatment in solid phase extraction,magnetic solid phase extraction and solid phase microextraction.In this review,the applications of g-C3N4 materials in sample pretreatment are summarized,and the future trends and prospects of g-C3N4 and its composites in sample pretreatment are also presented.
摘要:Covalent organic frameworks(COFs) are a novel kind of crystalline organic polymer constructed with monomers via covalent bonds.COFs possess some properties such as large specific surface areas,good thermal and chemical stability,predictable control of structures and functions,etc.Based on the outstanding properties,COFs have a wide range of applications in gas storage,drug delivery,proton conduction and heterogeneous catalysis.The diverse structures and abundant functional groups also make COFs attractive in separation science including chromatography and sample pretreatment.COFs and their composites have been employed as potential sorbents for solid phase extraction,magnetic solid phase extraction and solid phase microextraction.In addition,COFs have been used as new stationary phases for gas chromatography,high performance liquid chromatography and capillary electrochromatography.The latest progress of COFs in separation science in the past 3 years has been summarized in this article,specially highlighting the key advancements of COFs in sample pretreatment such as aqueous media,food matrices,biological samples and offering a comprehensive overview in separation of organic molecules including chiral and isomeric compounds.This review also provides a reference and outlook for further exploration on the applications of COFs.