Taraxacum kok-saghyz(TKS)is rich in natural rubber(NR),a natural organic macromolecular compound composed of cis-1,4-polyisoprene,and may become the second NR-bearing plant for biochemical engineering development.In t...Taraxacum kok-saghyz(TKS)is rich in natural rubber(NR),a natural organic macromolecular compound composed of cis-1,4-polyisoprene,and may become the second NR-bearing plant for biochemical engineering development.In this paper,a rapid and quantitative ultra-high performance liquid chromatography tandem mass spectrometry(UHPLCMS/MS)method was established for determination of macromolecular biosynthesis substrate(dimethylallyl pyrophosphate,DMAPP)and initiator(farnesyl pyrophosphate,FPP)contained in TKS.A Kromasil C18 chromatographic column was used for separation,and the multi-reaction monitoring mode(MRM)of triple quadrupole mass spectrometry was used for detection.Quantification was performed by external calibration method.The results showed that the limit of detection(LOD)and the limit of quantitation(LOQ)of DMAPP were 2.42μg/L and 7.26μg/L,respectively,and the LOQ and the LOD of FPP were 1.02μg/L and 3.05μg/L,respectively.At a concentration of 1—1000μg/L,both analytes had good determination coefficients(>0.999)of calibration curve.The recoveries of DMAPP and FPP were between 99.0%and 117.1%.In real samples detection,the contents of DMAPP and FPP in TKS samples were between 23.32—82.77μg/L and 12.03—85.67μg/L,respectively.Thus,this approach is a reliable method to quantify DMAPP and FPP in TKS.展开更多
Five thyreostats(TSs),namely tapazole,thiouracil,methylthiouracil,propylthiouracil,and phenylthiouracil,were determined in bovine urine using ultra-high performance liquid chromatography-tandem mass spectrometry(UHPLC...Five thyreostats(TSs),namely tapazole,thiouracil,methylthiouracil,propylthiouracil,and phenylthiouracil,were determined in bovine urine using ultra-high performance liquid chromatography-tandem mass spectrometry(UHPLC-MS/MS)in positive electrospray ionization mode.Extraction and clean-up were achieved using a ChemElut cartridge with tert-butyl methyl ether,without a derivatization step.Separation was achieved on an Acquity UPLC SS T3 column.The mobile phase was acetonitrile and water containing 0.2%(v/v)formic acid.The mass spectrometer was operated in multiple reaction monitoring mode.Urine samples were spiked with TS solution at levels corresponding to 5,10,15,and 20μg/L.The accuracy(internal standard corrected)ranged from 92%to 107%,with a repeatability precision(relative standard deviation,RSD)less than 15%for all five analytes.The RSDs within-laboratory reproducibility was less than 26%.The decision limits(CCα)and detection capabilities(CCβ)were obtained from a calibration curve and were in the ranges of 3.1-6.1μg/L and 4.0-7.4μg/L,respectively.The CCαand CCβvalues were below the recommended concentration,which was set at 10μg/L.The results show that the described method is suitable for the direct detection of TSs in bovine urine.This method can also be used to determine TSs in porcine urine.展开更多
Among pharmaceuticals and personal care products released into the aquatic environment, antibiotics are of particular concern, because of their ubiquity and health effects. Although scientists have recently paid more ...Among pharmaceuticals and personal care products released into the aquatic environment, antibiotics are of particular concern, because of their ubiquity and health effects. Although scientists have recently paid more attention to the threat of antibiotics to coastal ecosystems, researchers have often focused on relatively few antibiotics, because of the absence of suitable analytical methods. We have therefore developed a method for the rapid detection of 36 antibiotic residues in coastal waters, including tetracyclines (TCs), sulfanilamides (SAs), and quinolones (QLs). The method consists of solid-phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis, using electrospray ionization (ESI) in positive mode. The SPE was performed with Oasis HLB and Oasis MCX cartridges. Chromatographic separation on a C18 column was achieved using a binary eluent containing methanol and water with 0.1% formic acid. Typical recoveries of the analytes ranged from 67.4% to 109.3% at a fortification level of 100 ng/L. The precision of the method, calculated as relative standard deviation (RSD), was below 14.6% for all the compounds. The limits of detection (LODs) varied from 0.45 pg to 7.97 pg. The method was applied to determine the target analytes in coastal waters of the Yellow Sea in Liaoning, China. Among the tested antibiotics, 31 were found in coastal waters, with their concentrations between the LOD and 212.5 ng/L. These data indicate that this method is valid for analysis of antibiotics in coastal waters. The study first reports such a large number of antibiotics along the Yellow Sea coast of Liaoning, and should facilitate future comprehensive evaluation of antibiotics in coastal ecosystems.展开更多
A highly sensitive method was developed for the simultaneous determination of 8 steroid hormones in high-fat fish tissues using ultra high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).The 8 s...A highly sensitive method was developed for the simultaneous determination of 8 steroid hormones in high-fat fish tissues using ultra high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).The 8 steroid hormones were extracted from the tissues with diethyl ether.Differing from other common purification methods,the extract solutions were cleaned by gel permeation chromatography(GPC) using ethyl acetate-cyclohexane solution(1:1,v/v) as the mobile phase.The separation of target compounds was carried out by a BEH C18 column and a gradient elution consisting of acetonitrile and 0.2% aqueous formic acid(v/v).The compounds were detected under the multiple reaction monitoring(MRM) mode and quantified with external standard method.This method was validated with respect to linearity,specificity,accuracy and precision.A linearity with correlation coefficient larger than 0.995 was achieved in the range of 0.5 to 50 ng m L^(-1).The average recoveries at the spiked levels of 1.0,5.0,and 10.0 μg kg^(–1) varied between 81.7% and 90.8%,with the relative standard deviations(n=5) ranged from 3.50% to 10.0%.The limit of quantification(LOQ) for 8 steroid hormones ranged from 0.2 to 1.5 μg kg^(-1).It was concluded that this method can be successfully applied for the determination of 8 steroid hormones in complicated matrices including high-fat fish tissues.展开更多
To assess uncertainty of determination of MC-LR in environmental samples by solid phase extraction- ultra performance liquid chromatography- tandem mass spectrometry,the sources of the uncertainty were evaluated first...To assess uncertainty of determination of MC-LR in environmental samples by solid phase extraction- ultra performance liquid chromatography- tandem mass spectrometry,the sources of the uncertainty were evaluated firstly,and the expanded uncertainty was calculated finally.The results show that when MC-LR concentration in the water samples was 0.50 μg/L,the expanded uncertainty was 0.00628 μg/L(k=2).展开更多
The complex composition of herbal metabolites necessitates the development of powerful analytical techniques aimed to identify the bioactive components.The seeds of Descurainia sophia(SDS)are utilized in China as a co...The complex composition of herbal metabolites necessitates the development of powerful analytical techniques aimed to identify the bioactive components.The seeds of Descurainia sophia(SDS)are utilized in China as a cough and asthma relieving agent.Herein,a dimension-enhanced integral approach,by combining ultra-high performance liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry(UHPLC/IMQTOF-MS)and intelligent peak annotation,was developed to rapidly characterize the multicomponents from SDS.Good chromatographic separation was achieved within 38 min on a UPLC CSH C18(2.1×100 mm,1.7μm)column which was eluted by 0.1%formic acid in water(water phase)and acetonitrile(organic phase).Collision-induced dissociation-MS^(2)data were acquired by the data-independent high-definition MS^(E)(HDMS^(E))in both the negative and positive electrospray ionization modes.A major components knockout strategy was applied to improve the characterization of those minor ingredients by enhancing the injection volume.Moreover,a self-built chemistry library was established,which could be matched by the UNIFI software enabling automatic peak annotation of the obtained HDMS^(E)data.As a result of applying the intelligent peak annotation workflows and further confirmation process,a total of 53 compounds were identified or tentatively characterized from the SDS,including 29 flavonoids,one uridine derivative,four glucosides,one lignin,one phenolic compound,and 17 others.Notably,four-dimensional information related to the structure(e.g.,retention time,collision cross section,MS^(1)and MS^(2)data)was obtained for each component by the developed integral approach,and the results would greatly benefit the quality control of SDS.展开更多
This paper reported a new analytical method for the simultaneous determination of seven benzotriazole ultraviolet absorbers and seven antibacterial agents in textiles. After ultrasonic extraction for the textile sampl...This paper reported a new analytical method for the simultaneous determination of seven benzotriazole ultraviolet absorbers and seven antibacterial agents in textiles. After ultrasonic extraction for the textile samples in methanol, the solutions were analyzed by ultra-high performance liquid chromotagraphy/orbitrap high resolution mass spectrometry (UPLC/Orbitrap HRMS). It showed that a good chromatographic separation for these target compounds was achieved by a Hypersil GOLD column (100 mm × 2.1 mm × 1.9 μm) with a gradient elution of methanol and 0.1% aqueous formic acid solution (containing 0.5 mmol/L ammonium acetate). Triclosan and 4-chloro-3,5-dimethyl phenol (PCMX) were detected by the orbitrap HRMS in an electrospray ionization (ESI) negative mode while the other twelve target compounds were detected by orbitrap HRMS in ESI positive mode. Full scan experiment was performed over the range from m/z 100 to m/z 500. These target compounds were routinely detected with mass accuracy below 2 × 10-6 (2 ppm) at the optimized conditions. The results showed that the limits of detection (LODs) were in the range from 0.1 to 0.3 μg/kg. The blank samples were spiked at three levels and their average recoveries varied from 80.5% to 96.3% while the relative standard deviation (RSD) changed from 3.2% to 9.9%. The present method was also applied for the determination of those ultraviolet absorbers and antibacterial agents in the commercial textiles.展开更多
Chinese herbal compound is playing an important role on curing human diseases.And it has been a trend that Chinese herbal compound is being used all over the world in 21 century.However,our Chinese herbal compound is ...Chinese herbal compound is playing an important role on curing human diseases.And it has been a trend that Chinese herbal compound is being used all over the world in 21 century.However,our Chinese herbal compound is facing serious challenge for the lack of canonical system of quality criterion for Chinese herbal compound so it has been a urgent problem to set up the quality control standards and reveal therapeutic basis of Chinese herbal compound.In order to give full play to the advantages of Chinese herbal compound,modern scientific and technological is used to research of Chinese herbal compound,especially the high performance liquid chromatography tandem mass spectrometry(HPLC-MS),because it is high sensitive,rapid,and obtain more information.It is very necessary that HPLC-MS is uesed to elucidate the effective components of basic substances of Chinese Herbal Compound,and endow traditional Chinese medicine with modern scientific connotation.展开更多
A rapid method was presented for the determination of 19 polyphenols in tea by ultra-high performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry(UPLC-Q-TOF MS).Tea samples were extr...A rapid method was presented for the determination of 19 polyphenols in tea by ultra-high performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry(UPLC-Q-TOF MS).Tea samples were extracted by 50%(V/V)ethanol,then separated by Waters Acquity BEH C18 column using a binary solvent system composed of acetonitrile and water(0.1%formic acid)by gradient elution.The analytes were determined by Q-TOF MS in TOF MS and information dependent acquisition(IDA)-MS/MS mode.The results showed that mass accuracy error of the 19 polyphenols were lower than 5.0×10^(-6),good linear relationship was got in range of 0.2–500μg/L and correlation coefficient was higher than 0.9990.The LOD was in the range of 0.002–0.100 mg/kg and the LOQ was in the range of 0.004–0.200 mg/kg.Recovery of the method was in range of 78.4%–109.2%with spike levels of 0.004–2.000 mg/kg,relative standard deviations were lower than 10%.The method was simple,rapid and accurate.It could be used for the rapid screening and quantitative analysis of 19 polyphenols in tea.展开更多
A method of rapidly detecting three kinds of microcystins( MCs) in environmental water samples by using disk SPE- ultra high performance liquid chromatography- tandem mass spectrometry( UPLC- MS / MS) was established....A method of rapidly detecting three kinds of microcystins( MCs) in environmental water samples by using disk SPE- ultra high performance liquid chromatography- tandem mass spectrometry( UPLC- MS / MS) was established. Firstly,environmental water samples were extracted by disk SPE column( C_(18)),and three kinds of MCs were separated by Waters BEH C_(18) chromatographic column with acetonitrile- 0. 2% formic acid solution as the mobile phase. After the gradient elution separation,the external standard method was used for quantitative and qualitative analysis under MRM of UPLC- MS / MS. The results showed that the three kinds of MCs in the range of 0. 05- 10 μg / L showed good linear relation,and the correlation coefficients were higher than 0. 999 4,while the method detection limit was 0. 04 ng / L. Under 0. 1,1,and 5 μg / L standard addition for the same environmental sample,the average recovery was 82. 8%- 108. 8%,and the relative standard deviation of determination results was2. 1%- 10. 1%( n = 6). This method is rapid,sensitive and accurate,so it can be effectively applied in the monitoring of MCs in environmental water samples.展开更多
Consumption of shellfish contaminated with algal toxins produced by marine dinoflagellates can lead to diarrhetic shellfish poisoning (DSP). It was therefore essential that there are analytical techniques to identify ...Consumption of shellfish contaminated with algal toxins produced by marine dinoflagellates can lead to diarrhetic shellfish poisoning (DSP). It was therefore essential that there are analytical techniques to identify and quantify DSP toxins in shellfish. This new methodology could facilitate DSP monitoring and create a means of rapidly responding to incidents threatening public health. In the last years there were different analytical methods for DSP, such as mouse bioassay and LC-FLD. With the development of instrument, Liquid chromatography-mass spectrometry was substituted for other analytical methods with its good sensitivity and selectivity and without derivatization for the determination of DSP. In this report, a high performance liquid chromatogra-phytandem mass spectrometric(HPLC-MS/MS)method was developed for the simultaneous determination of okadaic acid (OA) and dinophysistoxins(DTX1) in Sinonovacula constricta. Optimization of pretreatment experiment was carried out to maximize recoveries and the effectiveness. The analytes were determined under multi-reactions monitoring (MRM) scan type with tandem mass analyzer using negative ion electrospray ionization (-ESI) mode .Finally, the detection and identification of OA and DTX-1 were based upon their retention times (RT) and the fragmentation patterns of their mass spectra. The method of LOQ for the two poisons was 0.02 mg·kg-1.The real sample test showed that this method could be used for sensitive, fast, and accurate determination of the two diarrheic shellfish poisons in shellfish.展开更多
A method of 24 allergens determination in cosmetics were established with high performance liquid chromatography tandem mass spectrometry. The targeted compounds were extracted with acetonitrile and determined with LC...A method of 24 allergens determination in cosmetics were established with high performance liquid chromatography tandem mass spectrometry. The targeted compounds were extracted with acetonitrile and determined with LC-MS/MS (MRM mode) with external method. The linearity between concentrations and peak area ratio was obtained from 1.0~5.0 mg/L. The limits of detection were 1.0 mg/L for the instrument and 5.0 mg/kg for the method respectively. The LOQ was 15.0 mg/L. The average recoveries of 24 allergens were between 85.9% and 110.0% at spiked levels of 5, 10 and 20 mg/kg with relative standard derivation (RSDs) of 5.5%~12.0%(n=10). The method could be used as a reliable means for simultaneous quantitative determination of allergens in cosmetics.展开更多
N-nitrosodimethylamine (NDMA) and several other N-nitrosamines have been detected as disinfection by-products in drinking waters in many countries around the world. An ultra-performance liquid chromatography- tandem...N-nitrosodimethylamine (NDMA) and several other N-nitrosamines have been detected as disinfection by-products in drinking waters in many countries around the world. An ultra-performance liquid chromatography- tandem mass spectrometry method with solid phase extraction sample preparation was developed to study the occurrence of N-nitrosamines in several water treatment plants and distribution systems in China. Isotope labeled N-nitrosodi-n-propylamine-dl4 (NDPA-dl4) was selected as the internal standard for quantification. The solid phase extraction procedures including pH, enrichment process and MS/MS parameters including capillary voltage, cone gas flow, cone voltage, collision energy were optimized to give average recoveries of 26% to 112% for nine N- nitrosamine species. The instrument detection limits were estimated to range from 0.5 to 5μg.L-1 for the nine N- nitrosamine species. NDMA and several other N-nitrosa- mines were found at fairly high concentrations in several water treatment plants and distribution systems. NDMA was found in all locations, and the highest concentrations in cities B, G, T, and W were 3.0, 35.7, 21.3, and 19.7 ng. L 1, respectively. A wide range of N-nitrosamines concentrations and species were observed in different locations. Higher concentrations of N-nitrosamines were detected in distribution systems that were further away from the treatment plants, suggesting that the contact time between the residual disinfectant and natural organic matter may play an important role in the formation of these compounds.展开更多
A rapid and high selective ultra-performance liquid chromatography(UPLC)with tandem mass spectrometry method for simultaneous determination of six compounds including albiflorin,paeoniflorin,picroside I,picroside II,s...A rapid and high selective ultra-performance liquid chromatography(UPLC)with tandem mass spectrometry method for simultaneous determination of six compounds including albiflorin,paeoniflorin,picroside I,picroside II,saikosaponin A,and saikosaponin D in rat plasma was developed and validated using butyl p-hydroxybenzoate as an internal standard.One-step direct protein precipitation with acetonitrile was used to extract the compounds from the rat plasma samples.Chromatographic separation was achieved using an ACQUITY UPLC BEH C18 column(100 mm×2.1 mm,1.7μm)at a flow rate of 0.4 m L/min,using gradient mode containing 0.1%formic acid in water and acetonitrile were used as the Mobile phase A and B.Electrospray ionization in negative ion mode and multiple reaction monitoring were used to identify and quantify active components.Calibration curves showed good linearity(R^2>0.9908)over a wide concentration range for all compounds.The intra-and interday precision(relative standard deviation)ranged 2.4%–7.0%and 2.6%–8.0%,respectively.The accuracy(relative error)was from-13.0%to 13.2%at all quality control levels.The recovery ranged from 81.1%to 92.5%.The validated method was successfully applied to pharmacokinetic study in rats after oral administration of Qing Gan-Shu Yu-Fang.The results show that one can draw a conclusion that these six active ingredients can be quickly absorbed and play a pharmacodynamic role rapidly in vivo.展开更多
A sensitive analytical method was developed to determine tetrodotoxin(TTX) in human plasma samples using protein precipitation, followed by ultra performance liquid chromatography(UPLC) analysis coupled with tande...A sensitive analytical method was developed to determine tetrodotoxin(TTX) in human plasma samples using protein precipitation, followed by ultra performance liquid chromatography(UPLC) analysis coupled with tandem mass spectrometry(MS/MS) using 11-deoxytetrodotoxin(11-deoxyTTX) as an internal standard. The plasma samples were prepared using protein precipitation prior to being analyzed by UPLC-MSfMS to identify TTX over a zwitterionic-hydrophilic interaction liquid chromatography column. The retention time values of TTX and 11-deoxyTTX were 4.12 and 3.67 min, respectively. TTX and 11-deoxyTTX were monitored and quantitated on the basis of their ion transitions for their respective precursor ions to their product ions(i.e., m/z 320.0→162. l for TTX and m/z 304.0→176.0 for 11-deoxyTTX) in the multiple reaction-monitoring mode. The lower limit of quantification of this method was determined to be 0.0199 ug/mL. This method showed good linearity for plasma samples that contained TTX concentrations in the range of 0.0199--1.99 ng/mL. The specificity, precision, accuracy, matrix effect, and stability characteristics of this method were also examined. The intra-assay precision and accuracy ranged from 1.89% to 6.00% and from 92.21% to 100.00%, whereas the inter-assay precision and accuracy ranged from 0.64% to 7.75% and from 99.38% to 101.26%, respectively. This new method therefore represents a rapid, accurate, reliable, and highly sensitive method for the qualitative and quantitative analyses of a trace amount of TTX in human plasma samples.展开更多
基金the supports of the National Key Research and Development of BioBased Rubber(2017YFB0306900&2017YFB0306901)the National Natural Science Foundation of China(51673012)+1 种基金the Fundamental Research Funds for the Central Universities(PYBZ1828)the Beijing Technology and Business Universtiy Youth Scholoars Funds(PXM2019014213000007)。
文摘Taraxacum kok-saghyz(TKS)is rich in natural rubber(NR),a natural organic macromolecular compound composed of cis-1,4-polyisoprene,and may become the second NR-bearing plant for biochemical engineering development.In this paper,a rapid and quantitative ultra-high performance liquid chromatography tandem mass spectrometry(UHPLCMS/MS)method was established for determination of macromolecular biosynthesis substrate(dimethylallyl pyrophosphate,DMAPP)and initiator(farnesyl pyrophosphate,FPP)contained in TKS.A Kromasil C18 chromatographic column was used for separation,and the multi-reaction monitoring mode(MRM)of triple quadrupole mass spectrometry was used for detection.Quantification was performed by external calibration method.The results showed that the limit of detection(LOD)and the limit of quantitation(LOQ)of DMAPP were 2.42μg/L and 7.26μg/L,respectively,and the LOQ and the LOD of FPP were 1.02μg/L and 3.05μg/L,respectively.At a concentration of 1—1000μg/L,both analytes had good determination coefficients(>0.999)of calibration curve.The recoveries of DMAPP and FPP were between 99.0%and 117.1%.In real samples detection,the contents of DMAPP and FPP in TKS samples were between 23.32—82.77μg/L and 12.03—85.67μg/L,respectively.Thus,this approach is a reliable method to quantify DMAPP and FPP in TKS.
文摘Five thyreostats(TSs),namely tapazole,thiouracil,methylthiouracil,propylthiouracil,and phenylthiouracil,were determined in bovine urine using ultra-high performance liquid chromatography-tandem mass spectrometry(UHPLC-MS/MS)in positive electrospray ionization mode.Extraction and clean-up were achieved using a ChemElut cartridge with tert-butyl methyl ether,without a derivatization step.Separation was achieved on an Acquity UPLC SS T3 column.The mobile phase was acetonitrile and water containing 0.2%(v/v)formic acid.The mass spectrometer was operated in multiple reaction monitoring mode.Urine samples were spiked with TS solution at levels corresponding to 5,10,15,and 20μg/L.The accuracy(internal standard corrected)ranged from 92%to 107%,with a repeatability precision(relative standard deviation,RSD)less than 15%for all five analytes.The RSDs within-laboratory reproducibility was less than 26%.The decision limits(CCα)and detection capabilities(CCβ)were obtained from a calibration curve and were in the ranges of 3.1-6.1μg/L and 4.0-7.4μg/L,respectively.The CCαand CCβvalues were below the recommended concentration,which was set at 10μg/L.The results show that the described method is suitable for the direct detection of TSs in bovine urine.This method can also be used to determine TSs in porcine urine.
基金Supported by Young Scientists Research Program (No. 2009507)the Key Laboratory of Marine Bioactive Substances and Modern Analytical Techniques (No. MBSMAT-2010-04),SOA of China
文摘Among pharmaceuticals and personal care products released into the aquatic environment, antibiotics are of particular concern, because of their ubiquity and health effects. Although scientists have recently paid more attention to the threat of antibiotics to coastal ecosystems, researchers have often focused on relatively few antibiotics, because of the absence of suitable analytical methods. We have therefore developed a method for the rapid detection of 36 antibiotic residues in coastal waters, including tetracyclines (TCs), sulfanilamides (SAs), and quinolones (QLs). The method consists of solid-phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis, using electrospray ionization (ESI) in positive mode. The SPE was performed with Oasis HLB and Oasis MCX cartridges. Chromatographic separation on a C18 column was achieved using a binary eluent containing methanol and water with 0.1% formic acid. Typical recoveries of the analytes ranged from 67.4% to 109.3% at a fortification level of 100 ng/L. The precision of the method, calculated as relative standard deviation (RSD), was below 14.6% for all the compounds. The limits of detection (LODs) varied from 0.45 pg to 7.97 pg. The method was applied to determine the target analytes in coastal waters of the Yellow Sea in Liaoning, China. Among the tested antibiotics, 31 were found in coastal waters, with their concentrations between the LOD and 212.5 ng/L. These data indicate that this method is valid for analysis of antibiotics in coastal waters. The study first reports such a large number of antibiotics along the Yellow Sea coast of Liaoning, and should facilitate future comprehensive evaluation of antibiotics in coastal ecosystems.
基金supported by the Natural Science Foundation of Zhejiang Province,China(No.LY17C200009)the Foundation of Zhejiang Educational Committee(No.Y201328477)
文摘A highly sensitive method was developed for the simultaneous determination of 8 steroid hormones in high-fat fish tissues using ultra high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).The 8 steroid hormones were extracted from the tissues with diethyl ether.Differing from other common purification methods,the extract solutions were cleaned by gel permeation chromatography(GPC) using ethyl acetate-cyclohexane solution(1:1,v/v) as the mobile phase.The separation of target compounds was carried out by a BEH C18 column and a gradient elution consisting of acetonitrile and 0.2% aqueous formic acid(v/v).The compounds were detected under the multiple reaction monitoring(MRM) mode and quantified with external standard method.This method was validated with respect to linearity,specificity,accuracy and precision.A linearity with correlation coefficient larger than 0.995 was achieved in the range of 0.5 to 50 ng m L^(-1).The average recoveries at the spiked levels of 1.0,5.0,and 10.0 μg kg^(–1) varied between 81.7% and 90.8%,with the relative standard deviations(n=5) ranged from 3.50% to 10.0%.The limit of quantification(LOQ) for 8 steroid hormones ranged from 0.2 to 1.5 μg kg^(-1).It was concluded that this method can be successfully applied for the determination of 8 steroid hormones in complicated matrices including high-fat fish tissues.
文摘To assess uncertainty of determination of MC-LR in environmental samples by solid phase extraction- ultra performance liquid chromatography- tandem mass spectrometry,the sources of the uncertainty were evaluated firstly,and the expanded uncertainty was calculated finally.The results show that when MC-LR concentration in the water samples was 0.50 μg/L,the expanded uncertainty was 0.00628 μg/L(k=2).
基金This work was financially supported by the National Key Research and Development Program of China(Grant No.2018YFC1704500)Tianjin Committee of Science and Technology of China(Grant No.21ZYJDJC00080)National Natural Science Foundation of China(Grant No.81872996).
文摘The complex composition of herbal metabolites necessitates the development of powerful analytical techniques aimed to identify the bioactive components.The seeds of Descurainia sophia(SDS)are utilized in China as a cough and asthma relieving agent.Herein,a dimension-enhanced integral approach,by combining ultra-high performance liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry(UHPLC/IMQTOF-MS)and intelligent peak annotation,was developed to rapidly characterize the multicomponents from SDS.Good chromatographic separation was achieved within 38 min on a UPLC CSH C18(2.1×100 mm,1.7μm)column which was eluted by 0.1%formic acid in water(water phase)and acetonitrile(organic phase).Collision-induced dissociation-MS^(2)data were acquired by the data-independent high-definition MS^(E)(HDMS^(E))in both the negative and positive electrospray ionization modes.A major components knockout strategy was applied to improve the characterization of those minor ingredients by enhancing the injection volume.Moreover,a self-built chemistry library was established,which could be matched by the UNIFI software enabling automatic peak annotation of the obtained HDMS^(E)data.As a result of applying the intelligent peak annotation workflows and further confirmation process,a total of 53 compounds were identified or tentatively characterized from the SDS,including 29 flavonoids,one uridine derivative,four glucosides,one lignin,one phenolic compound,and 17 others.Notably,four-dimensional information related to the structure(e.g.,retention time,collision cross section,MS^(1)and MS^(2)data)was obtained for each component by the developed integral approach,and the results would greatly benefit the quality control of SDS.
文摘This paper reported a new analytical method for the simultaneous determination of seven benzotriazole ultraviolet absorbers and seven antibacterial agents in textiles. After ultrasonic extraction for the textile samples in methanol, the solutions were analyzed by ultra-high performance liquid chromotagraphy/orbitrap high resolution mass spectrometry (UPLC/Orbitrap HRMS). It showed that a good chromatographic separation for these target compounds was achieved by a Hypersil GOLD column (100 mm × 2.1 mm × 1.9 μm) with a gradient elution of methanol and 0.1% aqueous formic acid solution (containing 0.5 mmol/L ammonium acetate). Triclosan and 4-chloro-3,5-dimethyl phenol (PCMX) were detected by the orbitrap HRMS in an electrospray ionization (ESI) negative mode while the other twelve target compounds were detected by orbitrap HRMS in ESI positive mode. Full scan experiment was performed over the range from m/z 100 to m/z 500. These target compounds were routinely detected with mass accuracy below 2 × 10-6 (2 ppm) at the optimized conditions. The results showed that the limits of detection (LODs) were in the range from 0.1 to 0.3 μg/kg. The blank samples were spiked at three levels and their average recoveries varied from 80.5% to 96.3% while the relative standard deviation (RSD) changed from 3.2% to 9.9%. The present method was also applied for the determination of those ultraviolet absorbers and antibacterial agents in the commercial textiles.
文摘Chinese herbal compound is playing an important role on curing human diseases.And it has been a trend that Chinese herbal compound is being used all over the world in 21 century.However,our Chinese herbal compound is facing serious challenge for the lack of canonical system of quality criterion for Chinese herbal compound so it has been a urgent problem to set up the quality control standards and reveal therapeutic basis of Chinese herbal compound.In order to give full play to the advantages of Chinese herbal compound,modern scientific and technological is used to research of Chinese herbal compound,especially the high performance liquid chromatography tandem mass spectrometry(HPLC-MS),because it is high sensitive,rapid,and obtain more information.It is very necessary that HPLC-MS is uesed to elucidate the effective components of basic substances of Chinese Herbal Compound,and endow traditional Chinese medicine with modern scientific connotation.
基金supported by National Key Research and Development Program of China(2018YFC1603400)。
文摘A rapid method was presented for the determination of 19 polyphenols in tea by ultra-high performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry(UPLC-Q-TOF MS).Tea samples were extracted by 50%(V/V)ethanol,then separated by Waters Acquity BEH C18 column using a binary solvent system composed of acetonitrile and water(0.1%formic acid)by gradient elution.The analytes were determined by Q-TOF MS in TOF MS and information dependent acquisition(IDA)-MS/MS mode.The results showed that mass accuracy error of the 19 polyphenols were lower than 5.0×10^(-6),good linear relationship was got in range of 0.2–500μg/L and correlation coefficient was higher than 0.9990.The LOD was in the range of 0.002–0.100 mg/kg and the LOQ was in the range of 0.004–0.200 mg/kg.Recovery of the method was in range of 78.4%–109.2%with spike levels of 0.004–2.000 mg/kg,relative standard deviations were lower than 10%.The method was simple,rapid and accurate.It could be used for the rapid screening and quantitative analysis of 19 polyphenols in tea.
文摘A method of rapidly detecting three kinds of microcystins( MCs) in environmental water samples by using disk SPE- ultra high performance liquid chromatography- tandem mass spectrometry( UPLC- MS / MS) was established. Firstly,environmental water samples were extracted by disk SPE column( C_(18)),and three kinds of MCs were separated by Waters BEH C_(18) chromatographic column with acetonitrile- 0. 2% formic acid solution as the mobile phase. After the gradient elution separation,the external standard method was used for quantitative and qualitative analysis under MRM of UPLC- MS / MS. The results showed that the three kinds of MCs in the range of 0. 05- 10 μg / L showed good linear relation,and the correlation coefficients were higher than 0. 999 4,while the method detection limit was 0. 04 ng / L. Under 0. 1,1,and 5 μg / L standard addition for the same environmental sample,the average recovery was 82. 8%- 108. 8%,and the relative standard deviation of determination results was2. 1%- 10. 1%( n = 6). This method is rapid,sensitive and accurate,so it can be effectively applied in the monitoring of MCs in environmental water samples.
文摘Consumption of shellfish contaminated with algal toxins produced by marine dinoflagellates can lead to diarrhetic shellfish poisoning (DSP). It was therefore essential that there are analytical techniques to identify and quantify DSP toxins in shellfish. This new methodology could facilitate DSP monitoring and create a means of rapidly responding to incidents threatening public health. In the last years there were different analytical methods for DSP, such as mouse bioassay and LC-FLD. With the development of instrument, Liquid chromatography-mass spectrometry was substituted for other analytical methods with its good sensitivity and selectivity and without derivatization for the determination of DSP. In this report, a high performance liquid chromatogra-phytandem mass spectrometric(HPLC-MS/MS)method was developed for the simultaneous determination of okadaic acid (OA) and dinophysistoxins(DTX1) in Sinonovacula constricta. Optimization of pretreatment experiment was carried out to maximize recoveries and the effectiveness. The analytes were determined under multi-reactions monitoring (MRM) scan type with tandem mass analyzer using negative ion electrospray ionization (-ESI) mode .Finally, the detection and identification of OA and DTX-1 were based upon their retention times (RT) and the fragmentation patterns of their mass spectra. The method of LOQ for the two poisons was 0.02 mg·kg-1.The real sample test showed that this method could be used for sensitive, fast, and accurate determination of the two diarrheic shellfish poisons in shellfish.
基金supported by The National Natural Science Foundation of China(Grant No.31360447)The National Natural Science Foundation of Hainan Province(Grant No.20162036)
文摘A method of 24 allergens determination in cosmetics were established with high performance liquid chromatography tandem mass spectrometry. The targeted compounds were extracted with acetonitrile and determined with LC-MS/MS (MRM mode) with external method. The linearity between concentrations and peak area ratio was obtained from 1.0~5.0 mg/L. The limits of detection were 1.0 mg/L for the instrument and 5.0 mg/kg for the method respectively. The LOQ was 15.0 mg/L. The average recoveries of 24 allergens were between 85.9% and 110.0% at spiked levels of 5, 10 and 20 mg/kg with relative standard derivation (RSDs) of 5.5%~12.0%(n=10). The method could be used as a reliable means for simultaneous quantitative determination of allergens in cosmetics.
文摘N-nitrosodimethylamine (NDMA) and several other N-nitrosamines have been detected as disinfection by-products in drinking waters in many countries around the world. An ultra-performance liquid chromatography- tandem mass spectrometry method with solid phase extraction sample preparation was developed to study the occurrence of N-nitrosamines in several water treatment plants and distribution systems in China. Isotope labeled N-nitrosodi-n-propylamine-dl4 (NDPA-dl4) was selected as the internal standard for quantification. The solid phase extraction procedures including pH, enrichment process and MS/MS parameters including capillary voltage, cone gas flow, cone voltage, collision energy were optimized to give average recoveries of 26% to 112% for nine N- nitrosamine species. The instrument detection limits were estimated to range from 0.5 to 5μg.L-1 for the nine N- nitrosamine species. NDMA and several other N-nitrosa- mines were found at fairly high concentrations in several water treatment plants and distribution systems. NDMA was found in all locations, and the highest concentrations in cities B, G, T, and W were 3.0, 35.7, 21.3, and 19.7 ng. L 1, respectively. A wide range of N-nitrosamines concentrations and species were observed in different locations. Higher concentrations of N-nitrosamines were detected in distribution systems that were further away from the treatment plants, suggesting that the contact time between the residual disinfectant and natural organic matter may play an important role in the formation of these compounds.
基金supported financially by the National Natural Science Foundation of China (Grant No. 81973604, 81803690and 81703684)the Innovative Talents Funding of Heilongjiang University of Chinese Medicine(Grant No.2018RCD25)+8 种基金the National natural science foundation matching project (Grant No. 2018PT02)the National natural Science Foundation Matching Project (Grant No. 2017PT01)the Graduate Innovative Research Project Foundation of Heilongjiang University of Chinese Medicine (Grant No. 2019yjscx013)the Postdoctoral Initial Fund of Heilongjiang Provincethe University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province (Grant No. UNPYSCT2017215 and UNPYSCT2017219)the Natural Science Foundation of Heilongjiang Province (Grant No. H2015037)the Heilongjiang University of Chinese Medicine Doctoral Innovation Foundation (Grant No. 2014bs05)the Application Technology Research and Development Projects of Harbin Technology Bureau (Grant No. 2014RFQXJ149)Heilongjiang Postdoctoral Scientific Research Developmental Fund (Grant No.LBHQ16210 and LBH-Q17161)
文摘A rapid and high selective ultra-performance liquid chromatography(UPLC)with tandem mass spectrometry method for simultaneous determination of six compounds including albiflorin,paeoniflorin,picroside I,picroside II,saikosaponin A,and saikosaponin D in rat plasma was developed and validated using butyl p-hydroxybenzoate as an internal standard.One-step direct protein precipitation with acetonitrile was used to extract the compounds from the rat plasma samples.Chromatographic separation was achieved using an ACQUITY UPLC BEH C18 column(100 mm×2.1 mm,1.7μm)at a flow rate of 0.4 m L/min,using gradient mode containing 0.1%formic acid in water and acetonitrile were used as the Mobile phase A and B.Electrospray ionization in negative ion mode and multiple reaction monitoring were used to identify and quantify active components.Calibration curves showed good linearity(R^2>0.9908)over a wide concentration range for all compounds.The intra-and interday precision(relative standard deviation)ranged 2.4%–7.0%and 2.6%–8.0%,respectively.The accuracy(relative error)was from-13.0%to 13.2%at all quality control levels.The recovery ranged from 81.1%to 92.5%.The validated method was successfully applied to pharmacokinetic study in rats after oral administration of Qing Gan-Shu Yu-Fang.The results show that one can draw a conclusion that these six active ingredients can be quickly absorbed and play a pharmacodynamic role rapidly in vivo.
基金Supported by the National Key Research and Development Program of China(No.2016YFF0201104)the Construction of Public Service Platform for Research and Test of Marine Pilot Technology of China(No.Bhsfs009)the Project of Xiamen Southern oceanographic Center,China(No.16PFW008SF15).
文摘A sensitive analytical method was developed to determine tetrodotoxin(TTX) in human plasma samples using protein precipitation, followed by ultra performance liquid chromatography(UPLC) analysis coupled with tandem mass spectrometry(MS/MS) using 11-deoxytetrodotoxin(11-deoxyTTX) as an internal standard. The plasma samples were prepared using protein precipitation prior to being analyzed by UPLC-MSfMS to identify TTX over a zwitterionic-hydrophilic interaction liquid chromatography column. The retention time values of TTX and 11-deoxyTTX were 4.12 and 3.67 min, respectively. TTX and 11-deoxyTTX were monitored and quantitated on the basis of their ion transitions for their respective precursor ions to their product ions(i.e., m/z 320.0→162. l for TTX and m/z 304.0→176.0 for 11-deoxyTTX) in the multiple reaction-monitoring mode. The lower limit of quantification of this method was determined to be 0.0199 ug/mL. This method showed good linearity for plasma samples that contained TTX concentrations in the range of 0.0199--1.99 ng/mL. The specificity, precision, accuracy, matrix effect, and stability characteristics of this method were also examined. The intra-assay precision and accuracy ranged from 1.89% to 6.00% and from 92.21% to 100.00%, whereas the inter-assay precision and accuracy ranged from 0.64% to 7.75% and from 99.38% to 101.26%, respectively. This new method therefore represents a rapid, accurate, reliable, and highly sensitive method for the qualitative and quantitative analyses of a trace amount of TTX in human plasma samples.