摘要:As a powerful analysis approach,matrix assisted laser desorption/ionization mass spectrometry(MALDI-MS) has attracted considerable attention in biomolecular analysis.However,this approach could hardly be used in the detection for samples with molecular mass lower than 500.In this work,poly (styrene-co-maleic anhydride) microbead@silver nanoshell(PSMA@Ag) composite microbeads with core-shell structure were synthesized using a polydopamine modification method.FT-IR results demonstrated the successful coating of polydopamine(PDA).SEM images along with UV-Vis results indicated that Ag nanoparticles were uniformly modified onto the surface of PSMA microbeads.The prepared PSMA@Ag microbeads were directly applied in matrix assisted laser desorption/ionization mass spectrometry,successfully detecting 2 pmol proline (Mw=115) and 1 pmol serine(Mw=105) in 0.5 μL sample,respectively.This work verified the positive effect of PSMA@Ag microbeads in MALDI-MS laser desorption/ionization process,and provided a promising route for MALDI analysis of the biomolecules with low molecular mass.
关键词:core-shell structure;dopamine;silver;matrix assisted laser desorption/ ionization mass spectrometry (MALDI-MS)
摘要:A new method of high performance liquid chromatography-fluorescence detection(HPLC-FLD) was developed for the detection of 2-methylisoborneol(2-MIB),geosmin(GSM) and 3-methyl-1-butanol(3-MB),with 6-carbonyl chloride levofloxacin(LFC-Cl) as derivatization reagent and magnetic graphene oxide(MGO) as magnetic dispersive solid phase extraction(MDSPE) adsorbent.Through optimizing derivatization conditions,three kinds of volatile organic compounds(VOCs) could be completely derivatized in 0.05 mol/L 4 dimethylaminopyridine(DMAP)acetonitrile solution within 90 min at 60 ℃ under ultrasonic assisted conditions.Through optimizing MDSPE conditions,three VOCs derivatives could be enriched and purified by a 20 min extraction of 20 mg adsorbent followed by a 3 min desorption of acetonitrile containing 1% formic acid.Under the optimized chromatographic conditions,the baseline separation and high sensitive detection of three VOCs derivatives were realized within 15 min.The limits of detection(LOD) and limits of quantitation(LOQ) of this method were in the ranges of 0.020-0.95 ng/L and 0.10-3.3 ng/L,respectively.The linearity,precision and recoveries were satisfactory.Compared with the reported methods,this method had the advantages of high sensitivity,simple sample pretreatment and universal instruments.It was suitable for the rapid determination of three VOCs in pond water and vegetables,providing a new approach for the monitoring of food and environmental water samples.
摘要:Inductively coupled plasma emission spectrometer(ICP-AES) and inductively coupled plasma mass spectrometer(ICP-MS) were used to determine the contents of eight heavy metals,ie.As,Cu,Cd,Cr,Hg,Ni,Pb and Zn in the soil of mangrove wetland at Zhanjiang Bay.Single factor index,Nemerow index and geoaccumulation index were used for pollution assessment.The sources of heavy metals were investigated by correlation analysis and factor analysis.The results obtained are as follows:Except for Ni,the average mass fractions for the other seven heavy metals do not exceed the national soil environmental quality standard(GB15618-2018),but Ni,Zn,Cu,Hg,As and Cd exceed the environmental background values for Guangdong latosol,while As,Ni,Hg and Zn exceed the national environmental standard seriously.The Nemerow indexes for eight heavy metals range from 0373 to 22576,with an average of 3378,which means a serious pollution state.The single factor pollution indexes for eight heavy metals in turn are ranked as follows:Ni>Hg>Zn>Cd>As>Cu>Pb>Cr.The evaluation results of geoaccumulative indexes are consistent with those of Nemerow indexes,indicating that Hg,Zn and Ni are important factors affecting soil environmental quality in the study area.Viewing from the stations,the stations of Beiyacun and Guanhaichanglang in the north of the Bay,and Shiqiaocun in the west are serious polluted,about 33% of the total number of stations mainly attribute to Cd,Hg and Zn pollution.Statistical analysis results showed that,except for Ni,there are significant correlations among As,Cu,Cd,Cr,Hg,Pb and Zn,while the correlation between Ni and other elements is not significant.Based on the field survey results,it is inferred that the heavy metal pollutions mainly derive from the input of human activities,such as industrial pollution,ship sewage,aquaculture sewage,domestic sewage,and agricultural non-point source pollution,next from the input of natural factors.
摘要:Four stereoisomers of anti benzo[a]pyrene diol epoxide deoxyguanosine adduct(anti-BPDE-N2-dG) were synthesized in vitro.By optimizing the reaction conditions,the yields of four isomers were two times higher than those of the reported synthesis methods.The synthesis provided standard substance for the quantitative detection of anti BPDE N2 dG in vivo.The reaction mixture of anti-BPDE-N2-dG stereoisomers were further separated and purified by reversed phase high performance liquid chromatography(HPLC),in which a pentafluorophenyl silica gel column(PFP column,250 mm×4.6 mm,5 μm) was introduced for the first time.It was found that the four isomers could be separated completely on the PFP column within 45 min,using acetonitrile-0.1% formic acid water(225∶775) as mobile phase at a flow rate of 1.2 mL/min.Compared with the conventional C18 column(250 mm×4.6 mm,5 μm) taking 160 min or silicone polymer coating phenyl column(250 mm×4.6 mm,5 μm) needing 85-100 min for separation of the four isomers,the reported method greatly shortened the separation and purification time.The four stereoisomers of the anti BPDE N2 dG were identified and characterized by a combination of HPLC-MS/MS,UV and circular dichroism(CD) spectra.The order of the peaks in chromatograms were determined as trans(-),trans(+),cis(+) and cis(-)-anti-BPDE-N2-dG.In addition,in the analysis of HPLC-MS/MS in MRM mode,the four stereoisomers were rapidly and well separated on the PFPP column within 30 min using a mobile phase consisted of acetonitrile-0.1% formic acid(28∶72) at a flow rate of 0.5 mL/min.This work demonstrates that the introduction of the PFPP column is very helpful for the separation,purification and detection of anti-BPDE-N2-dG isomers.
关键词:benzo[a]pyrene DNA adducts;anti benzo[a]pyrene diol epoxide deoxyguanosine adducts(anti-BPDE-N2-dG);pentafluorophenyl silica gel column;high performance liquid chromatography(HPLC);MS/MS
摘要:The interaction between cresol and laccase was studied by computer simulation and spectroscopy.Firstly,the simulation showed that the three cresol isomers interact with laccase,then results of molecular docking showed that laccase and cresol isomers combine with each other by hydrogen bond and hydrophobic force,and the binding sites are similar.The molecular dynamics simulation verified the reliability of the docking and binding sites by comparing the flexibility of the residues before and after binding.Secondly,m-cresol with better results was selected.The interaction between m-cresol and laccase,and the change of laccase secondary structure were studied by spectroscopic method.Fluorescence quenching experiments confirmed that laccase and m cresol are static quenching to form a non-fluorescence complex,which is consistent with the result of molecular docking.The infrared results revealed that the secondary structure of laccase changes after the interaction between laccase and m-cresol,in which β-turns and β-antiparallel translate into β-sheets,random coils and α-helices.It corresponds to the results of molecular dynamics simulation.This study provides theoretical basis and data support for laccase conversion of cresol pollutants in the environment.
摘要:Ru(bpy)2+3 has an excellent electrochemiluminescence(ECL) properties.However,the good solubility makes it meet a huge problem with the immobilization.In this experiment,an ECL biosensor for detection of glucose was fabricated by modifying Pt NPs-Ru complexes composed of Pt nanoparticles and Ru(bpy)2+3 onto the electrode surface for immobilization of glucose oxidase(GOx).In fact,the ECL signal of Ru(bpy)2+3-triethylamine system could be efficiently quenched by H2O2.With increase of glucose concentration,amount of H2O2 generated in situ by glucose under the catalysis of GOx increased,and the ECL signal gradually decreased,thus achieving the detection of glucose.A good linear relationship between ECL intensity and the logarithm of glucose concentration in the range of 1.0×10-8-5.0×10-5 mol/L was obtained,with a detection limit of 5.2×10-9 mol/L.The biosensor showed good stability and high selectivity.The Pt NPs-Ru complexes provide a good platform for construction of ECL sensor and a new method for detection of glucose.
摘要:A gas chromatography-tandem mass spectrometric(GC-MS/MS) method was established for the simultaneous determination of the contents of thirteen organophosphate retardants in lithium ion battery electrolyte.Organophosphate retardants in lithium ion battery electrolyte were ultrasonically extracted with ethyl acetate as extraction solvent.The extract was then condensed and filtered,followed by the analysis of GC-MS/MS.The external standard method was used to calibrate the concentrations of the retardants.The limits of detection(LODs) varied from 0.3 μg/kg to 30 μg/kg at a ratio of signal to noise(S/N) of 3,and the limits of quantification(LOQs) ranged from 1 μg/kg to 100 μg/kg at a ratio of signal to noise(S/N) of 10.The spiked average recoveries ranged from 80.4% to 94.6% with relative standard deviations(RSDs) of 3.8%-10%.The proposed method was simple,rapid,accurate and sensitive,and could meet the demands for routine analysis of organophosphate retardants in lithium ion battery electrolyte.
关键词:organophosphate retardants;ultrasonic extraction;gas chromatography-tandem mass spectrometry;lithium ion battery electrolyte
摘要:A method based on QuEChERS pretreatment technique and ultra high performance liquid chromatography-tandem mass spectrometry(UHPLC-MS/MS) was developed for the simultaneous determination of 31 sulfonylurea herbicide residues in soil.After optimizing the pretreatment and chromatographic conditions,methanol and 0.1% formic acid +5 mmol/L ammonium acetate,1% acetic acid-acetonitrile and 25.00 mg/mL C18 were used as the mobile phases,extraction solvents and purification agents,respectively.There were good linear relations for 31 sulfonylurea herbicides with their correlation coefficients(r2) no less than 0.998 0.The limits of quantitations(S/N=10) were in the range of 0.012-2.321 μg/kg.Average recoveries for the analytes at three spiked levels of 10,100 and 400 μg/kg ranged from 71.8% to 119% with their relative standard deviations(RSD) of 0.62%-13%.Except for nicosulfuron,trifloxysulfuron sodium,rimsulfuron,flazasulfuron and halosulfuron methyl,other compounds showed weak matrix effects.With easy operation,good sensitivity and accuracy,this method is suitable for the simultaneous detection of 31 sulfonylurea herbicide residues in soil.
关键词:QuEChERS;ultra high performance liquid chromatography-tandem mass spectrometry(UHPLC-MS/MS);soil;sulfonylurea herbicides
摘要:The existence forms of molecular ion peaks of 18 acid dyes with different structures and properties,and the high accuracy mass number of fragmentation fragments(resolution>70 000,m/z 200) were studied by quadrupole/electrostatic field orbitrap high resolution mass spectrometry(Q-Orbitrap-HRMS),and the element composition was obtained by element simulation,and then the cracking laws of acid red 1,acid blue 9 and acid red 18 were investigated.Results showed that the molecular ion peaks of these dyes were changed into negatively charged ions by removing all Na ions,in which the bivalent excimer ions with multiple sulfonic groups(SO-3) were the base peaks.With the increase of energy,the fracture process mainly concentrated on the single bond of compound branch chain,in which a tautomer of azido-azo existed in the azo group structure,the azo bond(—N‖N—) of the high bond energy was rearranged into a nitrogen-nitrogen single bond(—NH—N‖),and the C—N bond and —NH—N‖bond were easily broken.While with the neutral loss of the small molecule,the characteristic fragment ion of m/z 79955 7(SO-3) was generated.The optimum ionization modes and the existence forms of molecular ion peaks of 18 acid dyes were determined by direct injection.The mass spectrometry cracking law for acid red 1,acid blue 9 and acid red 18 provides a reference for the analysis of electrospray ionization mass spectrometry behaviors of similar dyes.
关键词:acid dyes;quadrupole/electrostatic field orbitrap high resolution mass spectrometry(Q-Orbitrap-HRMS);molecular ion peak;fragmentation fragment
摘要:An analytical method was developed for the simultaneous determination of kasugamycin and benziothiazolinone residues in citrus by dispersive solid phase extraction/ultra performance liquid chromatography-tandem mass spectrometry(DSPE/UPLC-MS/MS).Citrus whole fruit and pulp were extracted with acetonitrile containing 0.5% formic acid and 0.5% aqueous ammonia-water(7∶3,by volume),respectively,then purified with octadecyl silica gel(C18) and separated on a Waters ACQUITY UPLC HSS T3 column by gradient elution with 0.2% aqueous formic acid-methanol as mobile phase,finally analyzed in multiple reaction monitoring(MRM) mode and quantified by matrix matched standard curve external standard method.Results showed that there were good linear relationships for the target compounds in the range of 0.5-200 μg/L with their correlation coefficients(r2) larger than 0.999.The limits of detection(LODs) and the limits of quantitation(LOQs) were in the concentration ranges of 0.006-0.04 μg/kg and 5-10 μg/kg,respectively.The spiked recoveries ranged from 73.4% to 104% with relative standard deviations(RSDs,n=6) of 1.6%-96%.With easy operation and high sensitivity,the method is suitable for the simultaneous determination of kasugamycin and benziothiazolinone residues in citrus.
关键词:dispersive solid phase extraction;ultra performance liquid chromatography-tandem mass spectrometry;citrus;kasugamycin;benziothiazolinone
摘要:A molecularly imprinted electrochemical sensor for the detection of salicylic acid(SA) was prepared based on graphene modified glassy carbon electrode,with SA as the template molecule and o phenylenediamine(o PPD) and pyrrole(Py) as the functional monomers.The surface morphology of imprinted membrane was observed by scanning electron microscopy(SEM),and the performance of molecular imprinted sensor was investigated based on square wave voltammetry(SWV) and cyclic voltammetry(CV).Results showed that,under the optimal conditions,there was an excellent linear relationship for the electrochemical sensor between peak current and negative logarithm of SA concentration in the range of 1.0×10-8-1.0×10-2 mol/L,with a detection limit of 8.6×10-9 mol/L.The sensor exhibited a good selectivity toward SA,and the recoveries ranged from 101% to 106% with a relative standard deviation(RSD) of 3.8%.With the advantages of simple preparation,good anti interference ability,high sensitivity and low cost,the molecularly imprinted sensor showed a potentiality in practice application.
摘要:An ultra high performance liquid chromatography-tandem mass spectrometry with solid phase extraction was developed for the determination of bisphenol A(BPA),bisphenol F(BPF),tetrachlorobisphenol A(TCBPA),tetrabromobisphenol A(TBBPA),4 nonylphenol(NP),4-octylphenol(4-n-OP) in human urine.Human urine sample was purified by solid phase extraction after glucuronidase,then separated on an Acquity UPLC HSS T3 column(2.1 mm×100 mm,1.8 μm).The 6 analytes were determined in negative electrospray(ESI-) under multiple reaction monitoring(MRM) mode,and quantified by isotope labeled internal standard method.There were good linear relationships for 6 analytes in the range of 0.5-50 μg/L with their correlation coefficients larger than 0.995.The limits of detection and the limits of quantitation were in the ranges of 0.05-0.60 μg/L and 0.17-2.00 μg/L,respectively.Recoveries at three spiked levels of 2,10 and 50 μg/L ranged from 81.4% to 112% with relative standard deviations(RSD) of 6.8%-30%.The method was utilized in the determination of 160 human urine samples with a detection rate of 93.8% for BPA in the range of 0.24-2954 μg/L,and other substances were not detected.With the advantages of convenient operation,good accuracy and stability,this method is suitable for the determination of bisphenols and alkylphenols in human urine.
关键词:bisphenols;alkylphenols;urine;ultra high performance liquid chromatography-tandem mass spectrometry;solid phase extraction
摘要:A rutin electrochemical sensor was developed by electrodepositing copper nanoparticles on a glassy carbon electrode modified with multi walled carbon nanotubes(MWNTs)-Nafion.The electrochemical performance of the sensor was investigated by cyclic voltammetry and electrochemical impedance spectroscopy in potassium ferricyanide-potassium ferrocyanide system.The morphology of the sensor was studied by scanning electron microscopy,and differential pulse voltammetry was used for the detection of rutin.Results showed that the sensor had a good catalytic effect on rutin.Under the optimized conditions,the linear range of the sensor for rutin was from 1.0×10-8 mol/L to 1.0×10-6 mol/L,with a detection limit of 8.4×10-9 mol/L(S/N=3) and recoveries of 98.1%-101%.With the advantages of simple fabrication,wide linear range and high sensitivity,the sensor provided a new and effective method for the determination of rutin in Flos Sophorae Immaturus and other samples.
摘要:A rapid visual method based on aptamer sensor was established for screening of illegally added salbutamol(SAL) in health products.The detection element of this sensor was the SAL-aptamer,and the affinity between SAL-aptamer and ssDNA-binding proteins(SSB) acted as a “switch” of the sensor.SAL-aptamer modified micromagnatic beads(MB)(MB-aptamer),and horseradish peroxidase(HRP) and SSB jointly modified silica microsphere(SiO2@SSB@HRP) were prepared,respectively.Then MB-aptamer and SiO2@SSB@HRP were connected by the affinity between SAL-aptamer and SSB.SAL,as a key,triggered the “switch” to result in disconnection between SSB and SAL-aptamer during the inspection process,and the free SiO2@SSB@HRP was separated by magnetic action to carry out a color reaction.Under the optimized conditions,the color reaction showed visible gradient variation according to the change of SAL concentration.The color reaction catalyzed by HRP was quantitatively characterized with an ultraviolet-visible spectrophotometer,there was a linear relationship for absorbance wtih SAL concentration in the range of 0.1-10 μmol/L(r2=0.995 9),with a detection limit of 0.1 μmol/L.The mean recoveries at three spiked levels were all in the range of 86.0%-106%,with relative standard deviations of 3.9%-12%.The method is simple,sensitive and rapid,and it could meet the requirements for the rapid screening of illegally added SAL in real samples.
关键词:salbutamol;aptamer;rapid visual screening method;illegal addition;health products relieving cough and asthma
摘要:A two dimensional photonic crystal molecularly imprinted hydrogel(MIPs) sensor with specific recognition to glycoproteins was prepared by using concanavalin A(Con A) as the imprinted molecule,methylidenebisacrylamide(MBA) as the cross linking agents,acrylamide(AAm) and 4 vinylbenzeneboronic acid as the functional monomers,tetramethylethylenediamine(TEMED) as an initiator and ammonium persulfate(APS) as a catalyst.Polymerization was carried out to form a Con A imprinted hydrogel on the surface of two dimensional photonic crystal.After elution with 10% acetic acid solution,a MIPs sensor for specific recognition to Con A was constructed.Results showed that the diameter of Debye ring changed most significantly,and the target object was the most sensitive to be identified when the cross linking degree of MIPs was 10%.The sensor could be used in the enrichment and real time detection of target molecules as it had a good response to Con A in the concentration range of 0-05 mg/mL.Moreover,the introduction of phenyl boronic acid increased the recognition sites of the imprinted cavities,and further improved the specific recognition of the MIPs toward the carbohydrate molecules.The hydrogel sensor presented a good selectivity when binding to the proteins in ovalbumin(OVA),bovine hemoglobin(BHb),lysozyme(Lyz),trypsin(Try) solution under the same concentration.This method is easy to operate,low cost,reusable and needless for any special equipments.Furthermore,it could be extended to the real time and fast detection for other glycoproteins.
摘要:A high performance liquid chromatographic(HPLC) method with environmental chamber was developed for the determination of emission quantity of volatile aldehydes in adhesive.Adhesive was spread on the surface of support which was then placed at the center of an environmental chamber.A sufficient volume of environmental chamber air was drawn at an appropriate flow through silicagel tubes impregnated with 2,4-dinitrophenylhydrazine(DNPH) reagent.Aldehydes reacted with DNPH to form non volatile dinitrophenylhydrazones which were desorbed with acetonitrile,and then analyzed by HPLC.The separation was performed on a Kromasil KR100-5 C18 column(250 mm×4.6 mm,5 μm) by gradient elution with acetonitrile and water as mobile phases at a flow rate of 1.0 mL/min.The column temperature was 40 ℃,and the detection wavelength was 360 nm.Results showed that 13 aldehydes had good linear relationships(r≥0.997 7),and the limits of detection(LOD) were in the range of 1.6-20.8 μg/m3.Recoveries for the analytes ranged from 86.3% to 115% with relative standard deviations(RSD) of 3.5%-8.6%.With good precision and accuracy,the method provided a new approach for determination of emission quantity of volatile aldehydes in adhesive after application.
摘要:An electrochemical method with linear gold nanoparticles modified carbon fiber ultramicroelectrodes(LGN/CFME) was proposed for the detection of aloe emodin(AE).The LGN/CFME were prepared with chloroauric acid reduced with sodium citrate,depositing on the surface of CFME by one step potentiostatic deposition.The electrocatalytic performance of the CFME towards AE before and after electrode modification was investigated,and the optimal deposition time was 12 min.Results showed that there was a good linear relationship between oxidation peak current and AE concentration in the range of 2.0×10-6-1.0×10-4 mol/L,with a correlation coefficient(r2) of 0.965 3 and a linear regression equation of Ip(nA)=0.318 1 C(μmol/L)+25.01.The detection limit(S/N=3) was 6.19×10-7 mol/L.The method could be applied in the determination of AE in aloe juice.
摘要:Lipidomics is a new branch of science relying on analytical techniques,which is used to fully characterize the lipid molecules related closely to gene regulation,protein expression and lipid metabolism.With the further development of mass spectrometry and its coupled technologies,lipidomics has been gradually becoming rapid,automated and high throughput.However,data processing in large scale lipidomics analysis is still highly challenging.Chemometrics is mainly used in the baseline correction and background deduction,chromatographic peak identification,isotope distribution resolving,etc.Therefore,automated data processing strategies based on chemometrics have attracted attentions from many researchers.In this paper,the chemometric methods applied in lipidomics data processing in recent years are briefly reviewed,and the future development tendency of automated data processing in lipidomics are also prospected.
摘要:Currently,the identification of phosphopeptides mainly depends on mass spectrometry,but the low abundance of phosphopeptide and the interference of non phosphopeptide affect the analysis and identification of mass spectrometry.Therefore,the enrichment of phosphopeptide before mass spectrometry is a prerequisite for further study of phosphoproteomics.This review summarizes the mechanisms and advantages or disadvantages of those traditional and new developed methods for phosphopeptides enrichment,including immobilized metal ion affinity chromatography(IMAC), metal oxide affinity chromatography(MOAC), strong cation/anion exchange chromatography(SCX/SAX), hydrophilic interaction chromatography(HILIC), ectrostatic repulsion-hydrophilic interaction chromatography(ERLIC), chemical derivatization, matrix assisted laser desorption/ionization(MALDI) plate specific enrichment method, and coupled methods.
关键词:phosphopeptide;separation and enrichment;mass spectrometry;review
摘要:Fatty acids are one of the main energy sources for living organisms,and are also the main components of the cytomembrane skeletons.This paper summaries the classifications,methods for separation and mass spectrometric detection for fatty acids and their relationships with the occurrence and development of chronic diseases,and helps to obtain a deeper understanding for fatty acids′ involvement in the occurrence,development and prognosis of chronic diseases.