A rapid, sensitive and specific ultra-high-performance liquid chromatography tandem mass spectrometry （UPLC-MS） method was developed for the analysis of tetracycline antibiotics, including tetracycline （TC）, oxyte...A rapid, sensitive and specific ultra-high-performance liquid chromatography tandem mass spectrometry （UPLC-MS） method was developed for the analysis of tetracycline antibiotics, including tetracycline （TC）, oxytetracycline （OTC）, chlortetracycline （CTC） and their 4-epimers （4-epiTCs） in agricultural soil fertilized with swine manure. Soil samples were extracted and cleaned-up with 10 mL EDTA-McIlvaine buffer solution （pH 4.0）, then cleaned-up and pre-concentrated using the Oasis MAX cartridge and then eluted with 1 mL solution by mixing formic acid, methanol and water at a ratio of 2：15：83 （v/v/v）. The purified samples were separated by an ACQUITY UPLC BEH C18 column using acetonitrile and water containing 0.1% formic acid mobile phase and detected by a single quadrupole MS. The limits of detection for the soil extraction method （LODsoil） ranged from 0.6-2.5 lag kg-~ with recoveries from 23.3-159.2%. Finally, the method was applied to an agricultural field in an area with intensive pig-fattening farming. Tetracyclines were detected in soil from 2.8 to 42.4 μg kg-1 soil. These results demonstrate that soil from swine farms can become severely contaminated with tetracycline antibiotics and their metabolites.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 establish an analytical method for determination of four bisphenols （BPA, BPB, BPF, and BPS） and two alkylphenols （4-n-OP, 4-n-NP） in water by ultra performance liquid chromatography- tandem mass spectrometry ...To establish an analytical method for determination of four bisphenols （BPA, BPB, BPF, and BPS） and two alkylphenols （4-n-OP, 4-n-NP） in water by ultra performance liquid chromatography- tandem mass spectrometry （UPLC/MS/MS）. The water samples were extracted and condensed with solid-phase extraction （SPE） using C18 cartridges and eluted by acetonitrile. Separation was carried out with Acquity BEH C8 column and detection were performed by UPLC/MS/MS. Quantification was calculated by using the internal standard BPA-d16 and 4-n-NP-d8. The linear correlation coefficients of these compounds in the range of 1.0-100.0μg/L were all over 0.999. The minimum detectable concentrations were 0.75-1.0 ng/L, and the recoveries ranged from 87.0% to 106.9%.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
In this study, a new technique was developed using rapid ultra-performance liquid chromatography (UPLC)-based separation coupled with electrochemical detection by a boron-doped diamond (BDD) electrode for the detectio...In this study, a new technique was developed using rapid ultra-performance liquid chromatography (UPLC)-based separation coupled with electrochemical detection by a boron-doped diamond (BDD) electrode for the detection and quantification of three commonly used parabens (methylparaben (MP), ethylparaben (EP) and propylparaben (PP)). We aimed to reduce the analysis time by using UPLC coupled with a short reverse phase C 18 monolithic column (25 mm×4.6 mm). Operating the monolithic column at low back-pressure resulted in high flow rates. A mobile phaseconsisting of a 25:75 (v/v) ratio of acetonitrile:0.05 Mphosphate buffer (pH 5) at a flow rate of 2.5 mL·min?1 was used to perform the separation. The amperometric detection with the BDD electrode was found to be optimal and reliably reproducible at a detection potential of 1.5 V vs. Ag/AgCl. Under these conditions, the separation of the three targetanalytes (MP, EP and PP) was achieved in 2 min and was linear within a sample concentration range of 0.1 to 50.0 mg·L?1 (r2 values of 0.9970, 0.9994 and 0.9994 for MP, EP and PP, respectively). This method was successfully applied to determine the concentrations of each parabeninsix real samples with therecoveries ranging from of 80.3% - 98.9% for all three parabensfrom samples spiked at 12, 22 and 32 mg·L?1. Therefore, the proposed method can be used as an alternative rapid and selective method for the determination of paraben levels in real samples.展开更多
[Objectives] To study the chemical components and relative content of Achyranthes bidentata leaves and provide a scientific basis for further development and utilization of A. bidentata leaves.[Methods] The chemical c...[Objectives] To study the chemical components and relative content of Achyranthes bidentata leaves and provide a scientific basis for further development and utilization of A. bidentata leaves.[Methods] The chemical components of A. bidentata leaves were rapidly analyzed using the ultra high performance liquid chromatography-time of flight-high resolution mass spectrometry (UHPLC-TOF-MS).[Results] Thirty eight chemical compounds were identified in samples of A. bidentata leaves collected from Wen County of Henan Province, in which seven chemical compounds had the relative content higher than 5%, linoleic acid reached 25.7% and inokosterone A reached 13.8%.[Conclusions] A. bidentata leaves contain many kinds of chemical compounds. This study is expected to provide a certain basis for further extraction of linoleic acid and inokosterone A.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
Introduction: Conventional metabolite analyses often require manual sample preparation, generating variability of measurements. This study describes a new method to quantify radiometabolites in blood, combining ultra ...Introduction: Conventional metabolite analyses often require manual sample preparation, generating variability of measurements. This study describes a new method to quantify radiometabolites in blood, combining ultra high performance liquid chromatography (UHPLC) and turbulent flow chromatography, an alternative fully automated process allowing analyte’s extraction. Methods: A new radiotracer for dopamine transporter imaging, namely LBT-999, was used to demonstrate the method’s robustness. Matrix effect, Turboflow column loading, linearity, specificity and precision were evaluated with in vitro samples of LBT-999 in human plasma. Radiodetector sensitivity and preliminary evaluation were respectively determined by analysis of calibrated samples of [18F]LBT-999 and blood samples from 4 healthy subjects injected with [18F]LBT-999, withdrawn at 5, 15, 30 and 45 min pi. Results: With three sequential loadings (3 × 100 μL) of the Turboflow column, mean coefficients of variation were 1%, below 2%, 2% and 30.9% for matrix effect, specificity, repeatability and intermediate precision, respectively. Correlation coefficients for linearity were superior to 0.97. Limits of detection and quantification of the radiodetector were fixed at 3 and 9 c/s. Retention times for [18F]LBT-999 and the two radiometabolites detected by radio-UHPLC were 6.5, 4.8 and 9.6 min. Forty-five min after the injection, parent fraction was still predominant with 57.8% ± 25% of the total radioactivity. Conclusions: An innovative approach, allying UHPLC and Turboflow column, was developed and its sensitivity, linearity, specificity and repeatability validated. Preliminary results of the clinical trial are in accordance with literature data, demonstrating its efficiency in radiometabolites quantification.展开更多
Centrifugal ultrafiltration after methanol extraction of whole plasma was used as an optimal condition for the preparation of blood plasma before metabonomic studies. The plasma samples from 102 lung cancer patients a...Centrifugal ultrafiltration after methanol extraction of whole plasma was used as an optimal condition for the preparation of blood plasma before metabonomic studies. The plasma samples from 102 lung cancer patients and 34 healthy volunteers were prepared with this approach. With ultra-performance liquid chromatography（UPLC） coupled with quadrupole time-of-flight mass spectrometry（Q-TOF MS） analysis, the samples were investigated in order to find potential disease biomarkers. After data acquisition, orthogonal signal correction partial least squares models were built to differentiate the healthy volunteers from lung cancer patients and to identify metabolites that showed significantly different expression between the two groups. Several metabolite ions were identified as potential biomarkers according to the variable importance in the project（VIP） value in both ion modes. Five lysophosphatidylcholines were further identified as specifically lysoPC 16：0, isomer of lysoPC 16：0, lysoPC 18：0, lysoPC 18：1 and lysoPC 18：2. These results suggest that UPLC coupled with Q-TOF MS is an effective technique for the analysis of plasma metabolites in metabonomic studies.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
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
目的比较江西特色炮制技术对升麻化学成分的影响,筛选优质饮片品种。方法采用超高效液相色谱-四极杆-飞行时间串联质谱(ultra performance liquid chromatography-quadrupole-time of flight tandem mass spectrometry,UPLC-Q-TOF-MS)技...目的比较江西特色炮制技术对升麻化学成分的影响,筛选优质饮片品种。方法采用超高效液相色谱-四极杆-飞行时间串联质谱(ultra performance liquid chromatography-quadrupole-time of flight tandem mass spectrometry,UPLC-Q-TOF-MS)技术,在正、负离子模式下分析升麻不同炮制品的化学成分,通过对照品、相对分子质量、质谱裂解规律和文献信息进行鉴定。利用SIMCA-P13.0软件建立升麻各炮制品主成分分析(principal component analysis,PCA)和偏最小二乘法-判别分析(partial least squares discriminant analysis,PLS-DA)模型,获取PCA得分图、PLA-DA得分图和变量重要性投影(variable importance plot,VIP)值,筛选造成升麻炮制前后主要差异的物质基础。利用MetaboAnatyst网页绘图工具,制作得到热图,可更直观地观察升麻化学成分经炮制后的变化趋势。结果鉴定出71个化学成分,PCA显示经不同方法炮制后升麻组间差异性大,PLS-DA筛选出VIP值>1的33个化学成分作为炮制前后差异性的主要化学标记物。其中生品和蜜炙升麻中三萜类含量较高,蜜麸、蜜糠炒升麻中酚酸类物质含量较高,蜜麸升麻中阿魏酸含量较高。结论酚酸类和三萜皂苷类是区分升麻不同炮制品最重要的化合物类别,为江西特色升麻饮片的药效物质基础及优势品种研究提供了依据。展开更多
基于食品基质中松仁过敏原Pin k 2建立了一种超高效液相色谱-串联质谱法。将松仁经过研磨、脱脂、浸提、酶解后经Easy-nLC 1000-QExactive高分辨质谱仪进行分离分析,结合Uniprot蛋白数据库以及ProteinPilotTM软件对质谱图进行数据处理,...基于食品基质中松仁过敏原Pin k 2建立了一种超高效液相色谱-串联质谱法。将松仁经过研磨、脱脂、浸提、酶解后经Easy-nLC 1000-QExactive高分辨质谱仪进行分离分析,结合Uniprot蛋白数据库以及ProteinPilotTM软件对质谱图进行数据处理,经BLAST验证特异性,最终筛选3条松仁特异性肽段。方法学验证结果表明,方法在0.001~50mg/mL范围内线性关系良好,定量限为1mg/kg;在饼干、巧克力和饮料3种空白基质中的平均回收率为88.50%~107.57%,相对标准偏差不高于6.08%,基质效应为89.77%~96.13%。该方法具有灵敏度高、特异性好的优势,可应用于饼干、巧克力、饮料等食品样品中松仁过敏原的检测,为我国食品标签真实性检验及食品中隐性过敏原的检测提供技术支持。展开更多
文摘A rapid, sensitive and specific ultra-high-performance liquid chromatography tandem mass spectrometry （UPLC-MS） method was developed for the analysis of tetracycline antibiotics, including tetracycline （TC）, oxytetracycline （OTC）, chlortetracycline （CTC） and their 4-epimers （4-epiTCs） in agricultural soil fertilized with swine manure. Soil samples were extracted and cleaned-up with 10 mL EDTA-McIlvaine buffer solution （pH 4.0）, then cleaned-up and pre-concentrated using the Oasis MAX cartridge and then eluted with 1 mL solution by mixing formic acid, methanol and water at a ratio of 2：15：83 （v/v/v）. The purified samples were separated by an ACQUITY UPLC BEH C18 column using acetonitrile and water containing 0.1% formic acid mobile phase and detected by a single quadrupole MS. The limits of detection for the soil extraction method （LODsoil） ranged from 0.6-2.5 lag kg-~ with recoveries from 23.3-159.2%. Finally, the method was applied to an agricultural field in an area with intensive pig-fattening farming. Tetracyclines were detected in soil from 2.8 to 42.4 μg kg-1 soil. These results demonstrate that soil from swine farms can become severely contaminated with tetracycline antibiotics and their metabolites.
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.
基金supported by the Preventive medicine and public health research project of Anhui,China(No.2011Y0103)the Natural Science Foundation of Anhui,China(No.11040606M216)
文摘To establish an analytical method for determination of four bisphenols （BPA, BPB, BPF, and BPS） and two alkylphenols （4-n-OP, 4-n-NP） in water by ultra performance liquid chromatography- tandem mass spectrometry （UPLC/MS/MS）. The water samples were extracted and condensed with solid-phase extraction （SPE） using C18 cartridges and eluted by acetonitrile. Separation was carried out with Acquity BEH C8 column and detection were performed by UPLC/MS/MS. Quantification was calculated by using the internal standard BPA-d16 and 4-n-NP-d8. The linear correlation coefficients of these compounds in the range of 1.0-100.0μg/L were all over 0.999. The minimum detectable concentrations were 0.75-1.0 ng/L, and the recoveries ranged from 87.0% to 106.9%.
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).
文摘In this study, a new technique was developed using rapid ultra-performance liquid chromatography (UPLC)-based separation coupled with electrochemical detection by a boron-doped diamond (BDD) electrode for the detection and quantification of three commonly used parabens (methylparaben (MP), ethylparaben (EP) and propylparaben (PP)). We aimed to reduce the analysis time by using UPLC coupled with a short reverse phase C 18 monolithic column (25 mm×4.6 mm). Operating the monolithic column at low back-pressure resulted in high flow rates. A mobile phaseconsisting of a 25:75 (v/v) ratio of acetonitrile:0.05 Mphosphate buffer (pH 5) at a flow rate of 2.5 mL·min?1 was used to perform the separation. The amperometric detection with the BDD electrode was found to be optimal and reliably reproducible at a detection potential of 1.5 V vs. Ag/AgCl. Under these conditions, the separation of the three targetanalytes (MP, EP and PP) was achieved in 2 min and was linear within a sample concentration range of 0.1 to 50.0 mg·L?1 (r2 values of 0.9970, 0.9994 and 0.9994 for MP, EP and PP, respectively). This method was successfully applied to determine the concentrations of each parabeninsix real samples with therecoveries ranging from of 80.3% - 98.9% for all three parabensfrom samples spiked at 12, 22 and 32 mg·L?1. Therefore, the proposed method can be used as an alternative rapid and selective method for the determination of paraben levels in real samples.
基金Supported by Key Scientific and Technological Research Project in Higher Education Institutions of Henan Province(17A350002)Project of National Natural Science Foundation of China(81172953)
文摘[Objectives] To study the chemical components and relative content of Achyranthes bidentata leaves and provide a scientific basis for further development and utilization of A. bidentata leaves.[Methods] The chemical components of A. bidentata leaves were rapidly analyzed using the ultra high performance liquid chromatography-time of flight-high resolution mass spectrometry (UHPLC-TOF-MS).[Results] Thirty eight chemical compounds were identified in samples of A. bidentata leaves collected from Wen County of Henan Province, in which seven chemical compounds had the relative content higher than 5%, linoleic acid reached 25.7% and inokosterone A reached 13.8%.[Conclusions] A. bidentata leaves contain many kinds of chemical compounds. This study is expected to provide a certain basis for further extraction of linoleic acid and inokosterone A.
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Introduction: Conventional metabolite analyses often require manual sample preparation, generating variability of measurements. This study describes a new method to quantify radiometabolites in blood, combining ultra high performance liquid chromatography (UHPLC) and turbulent flow chromatography, an alternative fully automated process allowing analyte’s extraction. Methods: A new radiotracer for dopamine transporter imaging, namely LBT-999, was used to demonstrate the method’s robustness. Matrix effect, Turboflow column loading, linearity, specificity and precision were evaluated with in vitro samples of LBT-999 in human plasma. Radiodetector sensitivity and preliminary evaluation were respectively determined by analysis of calibrated samples of [18F]LBT-999 and blood samples from 4 healthy subjects injected with [18F]LBT-999, withdrawn at 5, 15, 30 and 45 min pi. Results: With three sequential loadings (3 × 100 μL) of the Turboflow column, mean coefficients of variation were 1%, below 2%, 2% and 30.9% for matrix effect, specificity, repeatability and intermediate precision, respectively. Correlation coefficients for linearity were superior to 0.97. Limits of detection and quantification of the radiodetector were fixed at 3 and 9 c/s. Retention times for [18F]LBT-999 and the two radiometabolites detected by radio-UHPLC were 6.5, 4.8 and 9.6 min. Forty-five min after the injection, parent fraction was still predominant with 57.8% ± 25% of the total radioactivity. Conclusions: An innovative approach, allying UHPLC and Turboflow column, was developed and its sensitivity, linearity, specificity and repeatability validated. Preliminary results of the clinical trial are in accordance with literature data, demonstrating its efficiency in radiometabolites quantification.
基金Supported by the National Natural Science Foundation of China(No.30801513)the Knowledge Innovation Program of Chinese Academy of Sciences(No.KSCX2-YW-R-170)
文摘Centrifugal ultrafiltration after methanol extraction of whole plasma was used as an optimal condition for the preparation of blood plasma before metabonomic studies. The plasma samples from 102 lung cancer patients and 34 healthy volunteers were prepared with this approach. With ultra-performance liquid chromatography（UPLC） coupled with quadrupole time-of-flight mass spectrometry（Q-TOF MS） analysis, the samples were investigated in order to find potential disease biomarkers. After data acquisition, orthogonal signal correction partial least squares models were built to differentiate the healthy volunteers from lung cancer patients and to identify metabolites that showed significantly different expression between the two groups. Several metabolite ions were identified as potential biomarkers according to the variable importance in the project（VIP） value in both ion modes. Five lysophosphatidylcholines were further identified as specifically lysoPC 16：0, isomer of lysoPC 16：0, lysoPC 18：0, lysoPC 18：1 and lysoPC 18：2. These results suggest that UPLC coupled with Q-TOF MS is an effective technique for the analysis of plasma metabolites in metabonomic studies.
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.
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.
文摘目的比较江西特色炮制技术对升麻化学成分的影响,筛选优质饮片品种。方法采用超高效液相色谱-四极杆-飞行时间串联质谱(ultra performance liquid chromatography-quadrupole-time of flight tandem mass spectrometry,UPLC-Q-TOF-MS)技术,在正、负离子模式下分析升麻不同炮制品的化学成分,通过对照品、相对分子质量、质谱裂解规律和文献信息进行鉴定。利用SIMCA-P13.0软件建立升麻各炮制品主成分分析(principal component analysis,PCA)和偏最小二乘法-判别分析(partial least squares discriminant analysis,PLS-DA)模型,获取PCA得分图、PLA-DA得分图和变量重要性投影(variable importance plot,VIP)值,筛选造成升麻炮制前后主要差异的物质基础。利用MetaboAnatyst网页绘图工具,制作得到热图,可更直观地观察升麻化学成分经炮制后的变化趋势。结果鉴定出71个化学成分,PCA显示经不同方法炮制后升麻组间差异性大,PLS-DA筛选出VIP值>1的33个化学成分作为炮制前后差异性的主要化学标记物。其中生品和蜜炙升麻中三萜类含量较高,蜜麸、蜜糠炒升麻中酚酸类物质含量较高,蜜麸升麻中阿魏酸含量较高。结论酚酸类和三萜皂苷类是区分升麻不同炮制品最重要的化合物类别,为江西特色升麻饮片的药效物质基础及优势品种研究提供了依据。
文摘基于食品基质中松仁过敏原Pin k 2建立了一种超高效液相色谱-串联质谱法。将松仁经过研磨、脱脂、浸提、酶解后经Easy-nLC 1000-QExactive高分辨质谱仪进行分离分析,结合Uniprot蛋白数据库以及ProteinPilotTM软件对质谱图进行数据处理,经BLAST验证特异性,最终筛选3条松仁特异性肽段。方法学验证结果表明,方法在0.001~50mg/mL范围内线性关系良好,定量限为1mg/kg;在饼干、巧克力和饮料3种空白基质中的平均回收率为88.50%~107.57%,相对标准偏差不高于6.08%,基质效应为89.77%~96.13%。该方法具有灵敏度高、特异性好的优势,可应用于饼干、巧克力、饮料等食品样品中松仁过敏原的检测,为我国食品标签真实性检验及食品中隐性过敏原的检测提供技术支持。
