Pharmaceuticals and personal care products(PPCPs)are a unique group of emerging and nonpersistent contaminants.In this study,27 PPCPs in various water samples were extracted by solid phase extraction(SPE),and determin...Pharmaceuticals and personal care products(PPCPs)are a unique group of emerging and nonpersistent contaminants.In this study,27 PPCPs in various water samples were extracted by solid phase extraction(SPE),and determined by isotope dilution method using liquid chromatography coupled to tandem triple quadruple mass spectrometer(LC-MS/MS).A total of 27 isotopically labeled standards(ILSs)were applied to correct the concentration of PPCPs in spiked ultrapure water,drinking water,river,effluent and influent sewage.The corrected recoveries were 73%-122%with the relative standard deviation(RSD)<16%,except for acetaminophen.The matrix effect for all kinds of water samples was<22%and the method quantitation limits(MQLs)were 0.45-8.6 ng/L.The developed method was successfully applied on environmental water samples.The SPE extracts of spiked ultrapure water,drinking water,river and wastewater effluent were stored for 70 days,and the ILSscorrected recoveries of 27 PPCPs were obtained to evaluate the correction ability of ILSs in the presence of variety interferences.The recoveries of 27 PPCPs over 70 days were within the scope of 72%-140%with the recovery variation<37%in all cases.The isotope dilution method seems to be of benefit when the extract has to be stored for long time before the instrument analysis.展开更多
The possibility of determining atomic fractions of the isotopes of carbon directly in urea, nitrobenzene, benzophenone, benzoic acid and 2-Hydroxybenzoic acid in compounds isotopically modified by all carbon centers, ...The possibility of determining atomic fractions of the isotopes of carbon directly in urea, nitrobenzene, benzophenone, benzoic acid and 2-Hydroxybenzoic acid in compounds isotopically modified by all carbon centers, as well as by one or several identical carbon centers is considered. The mass peaks of the mass spectrum that allows determining the atomic fraction of carbon isotopes are selected. The respective formulas are proposed. Until now, isotope analysis of these compounds has been carried out by converting them to carbon monoxide or dioxide, and it has been impossible to determine the atomic fraction of carbon at individual centers.展开更多
目的建立同位素作内标、液液微萃取-GC-MS测定水中邻苯二甲酸酯的分析方法。方法考察萃取剂种类、萃取体积、萃取时间、盐浓度对萃取效率的影响,对各种影响条件进行优化,确定最佳萃取条件,在25 ml容量瓶中依次加入2 g Na Cl,20 ml水样,...目的建立同位素作内标、液液微萃取-GC-MS测定水中邻苯二甲酸酯的分析方法。方法考察萃取剂种类、萃取体积、萃取时间、盐浓度对萃取效率的影响,对各种影响条件进行优化,确定最佳萃取条件,在25 ml容量瓶中依次加入2 g Na Cl,20 ml水样,加100μl正己烷萃取剂,2 500 r/min旋涡3 min,静置分层,萃取层供GC-MS分析。结果该方法 DINP、DIDP的线性范围为0.5 mg/L^5 mg/L,其余为0.1 mg/L^1.0 mg/L,线性相关系数为0.995~0.999,方法检出限为0.02μg/L^0.5μg/L,DMP、DEP、DMEP、DEEP回收率为50%~76%,其余成分的回收率为90%~110%。结论该方法操作简单、快速、成本低、环保高效、富集效率高,能用于水样中邻苯二甲酸酯检测。展开更多
We report the synthesis of isotopically-labeled graphite films on nickel substrates by using cold-wall chemical vapor deposition(CVD).During the synthesis,carbon from^(12)C-and^(13)C-methane was deposited on,and disso...We report the synthesis of isotopically-labeled graphite films on nickel substrates by using cold-wall chemical vapor deposition(CVD).During the synthesis,carbon from^(12)C-and^(13)C-methane was deposited on,and dissolved in,a nickel foil at high temperature,and a uniform graphite film was segregated from the nickel surface by cooling the sample to room temperature.Scanning and transmission electron microscopy,micro-Raman spectroscopy,and X-ray diffraction prove the presence of a graphite film.Monolayer graphene films obtained from such isotopically-labeled graphite films by mechanical methods have electron mobility values greater than 5000 cm^(2)·V^(-1)·s^(-1)at low temperatures.Furthermore,such films exhibit the half-integer quantum Hall effect over a wide temperature range from 2 K to 200 K,implying that the graphite grown by this cold-wall CVD approach has a quality as high as highly oriented pyrolytic graphite(HOPG).The results from transport measurements indicate that^(13)C-labeling does not significantly affect the electrical transport properties of graphene.展开更多
以[^(14)C]碳酸钡为放射性同位素原料,通过格氏反应、Curtius重排、亲核加成、硫代及关环等7步反应,制备了同位素碳-14标记的毒氟磷粗品,经反相高效液相色谱(RP-HPLC)纯化获得标记物纯品^(14)C-毒氟磷(N-[2-(4-甲基苯并[2-^(14)C]噻唑基...以[^(14)C]碳酸钡为放射性同位素原料,通过格氏反应、Curtius重排、亲核加成、硫代及关环等7步反应,制备了同位素碳-14标记的毒氟磷粗品,经反相高效液相色谱(RP-HPLC)纯化获得标记物纯品^(14)C-毒氟磷(N-[2-(4-甲基苯并[2-^(14)C]噻唑基)]-2-氨基-2-氟代苯基-O,O-二乙基甲基膦酸酯,38.3 m Ci)。7步反应的化学收率/放化收率为10%。其结构经核磁共振氢谱、质谱和放射性高效液相色谱(HPLC-FSA)分析确认。放射性薄层成像分析(TLC-IIA)、高效液相色谱-液体闪烁测量联用分析(HPLC-LSC)、高效液相色谱-流动液体闪烁测量/二极管阵列检测器/质谱联用分析(HPLC-FSA/PDA/MS)和LSC分析表明,^(14)C-毒氟磷的放化纯度和化学纯度均大于98%,比活度为58.0 m Ci/mmol,可作为放射性示踪剂,用于毒氟磷的代谢和环境行为等研究。展开更多
以[^(14)C]碳酸钡为放射性同位素原料,通过乙炔环三聚、苯羧基化和甲基化、胺化、环化、亲核取代、格氏、还原、氧化等反应和反相高效液相色谱(HPLC)纯化获得了2种放射性同位素碳-14标记毒氟磷[N-[2-(4-甲基[苯基-U-^(14)C_6]苯并噻唑基...以[^(14)C]碳酸钡为放射性同位素原料,通过乙炔环三聚、苯羧基化和甲基化、胺化、环化、亲核取代、格氏、还原、氧化等反应和反相高效液相色谱(HPLC)纯化获得了2种放射性同位素碳-14标记毒氟磷[N-[2-(4-甲基[苯基-U-^(14)C_6]苯并噻唑基)]-2-氨基-2-氟苯基-O,O-二乙基甲基膦酸酯(2,20.6 m Ci)和N-[2-(4-甲基苯并噻唑基)]-2-氨基-2-氟苯基-O,O-二乙基[^(14)C]甲基膦酸酯(3,32.4 m Ci)],其结构经核磁共振氢谱(~1H NMR)和在线放射性高效液相色谱-二极管阵列检测器/质谱联用(HPLC-FSA/PDA/MS)分析确认,反应总放化收率/化学收率分别为31%和67%.放射性薄层层析-同位素成像分析(TLC-IIA)、离线放射性高效液相色谱(HPLC-LSC),HPLC-FSA/PDA/MS和液体闪烁测量(LSC)分析表明,两种标记物的放化纯度和化学纯度均大于98%,比活度分别为25.5,55.5 m Ci/mmol.该标记物可作为放射性示踪剂,用于毒氟磷的代谢、残留和环境行为等研究.展开更多
基金This work was supported by the Major Science and Technology Program for Water Pollution Control and Treatment in China(Nos.2017ZX07202-001 and 2017ZX07202-004).
文摘Pharmaceuticals and personal care products(PPCPs)are a unique group of emerging and nonpersistent contaminants.In this study,27 PPCPs in various water samples were extracted by solid phase extraction(SPE),and determined by isotope dilution method using liquid chromatography coupled to tandem triple quadruple mass spectrometer(LC-MS/MS).A total of 27 isotopically labeled standards(ILSs)were applied to correct the concentration of PPCPs in spiked ultrapure water,drinking water,river,effluent and influent sewage.The corrected recoveries were 73%-122%with the relative standard deviation(RSD)<16%,except for acetaminophen.The matrix effect for all kinds of water samples was<22%and the method quantitation limits(MQLs)were 0.45-8.6 ng/L.The developed method was successfully applied on environmental water samples.The SPE extracts of spiked ultrapure water,drinking water,river and wastewater effluent were stored for 70 days,and the ILSscorrected recoveries of 27 PPCPs were obtained to evaluate the correction ability of ILSs in the presence of variety interferences.The recoveries of 27 PPCPs over 70 days were within the scope of 72%-140%with the recovery variation<37%in all cases.The isotope dilution method seems to be of benefit when the extract has to be stored for long time before the instrument analysis.
文摘The possibility of determining atomic fractions of the isotopes of carbon directly in urea, nitrobenzene, benzophenone, benzoic acid and 2-Hydroxybenzoic acid in compounds isotopically modified by all carbon centers, as well as by one or several identical carbon centers is considered. The mass peaks of the mass spectrum that allows determining the atomic fraction of carbon isotopes are selected. The respective formulas are proposed. Until now, isotope analysis of these compounds has been carried out by converting them to carbon monoxide or dioxide, and it has been impossible to determine the atomic fraction of carbon at individual centers.
基金This work was supported by The University of Texas at Austin and by the Texas Nanotechnology Research Superiority Initiative,Southwest Nanotechnology Institute(TNRSI)/SWAN.
文摘We report the synthesis of isotopically-labeled graphite films on nickel substrates by using cold-wall chemical vapor deposition(CVD).During the synthesis,carbon from^(12)C-and^(13)C-methane was deposited on,and dissolved in,a nickel foil at high temperature,and a uniform graphite film was segregated from the nickel surface by cooling the sample to room temperature.Scanning and transmission electron microscopy,micro-Raman spectroscopy,and X-ray diffraction prove the presence of a graphite film.Monolayer graphene films obtained from such isotopically-labeled graphite films by mechanical methods have electron mobility values greater than 5000 cm^(2)·V^(-1)·s^(-1)at low temperatures.Furthermore,such films exhibit the half-integer quantum Hall effect over a wide temperature range from 2 K to 200 K,implying that the graphite grown by this cold-wall CVD approach has a quality as high as highly oriented pyrolytic graphite(HOPG).The results from transport measurements indicate that^(13)C-labeling does not significantly affect the electrical transport properties of graphene.
文摘以[^(14)C]碳酸钡为放射性同位素原料,通过格氏反应、Curtius重排、亲核加成、硫代及关环等7步反应,制备了同位素碳-14标记的毒氟磷粗品,经反相高效液相色谱(RP-HPLC)纯化获得标记物纯品^(14)C-毒氟磷(N-[2-(4-甲基苯并[2-^(14)C]噻唑基)]-2-氨基-2-氟代苯基-O,O-二乙基甲基膦酸酯,38.3 m Ci)。7步反应的化学收率/放化收率为10%。其结构经核磁共振氢谱、质谱和放射性高效液相色谱(HPLC-FSA)分析确认。放射性薄层成像分析(TLC-IIA)、高效液相色谱-液体闪烁测量联用分析(HPLC-LSC)、高效液相色谱-流动液体闪烁测量/二极管阵列检测器/质谱联用分析(HPLC-FSA/PDA/MS)和LSC分析表明,^(14)C-毒氟磷的放化纯度和化学纯度均大于98%,比活度为58.0 m Ci/mmol,可作为放射性示踪剂,用于毒氟磷的代谢和环境行为等研究。
文摘以[^(14)C]碳酸钡为放射性同位素原料,通过乙炔环三聚、苯羧基化和甲基化、胺化、环化、亲核取代、格氏、还原、氧化等反应和反相高效液相色谱(HPLC)纯化获得了2种放射性同位素碳-14标记毒氟磷[N-[2-(4-甲基[苯基-U-^(14)C_6]苯并噻唑基)]-2-氨基-2-氟苯基-O,O-二乙基甲基膦酸酯(2,20.6 m Ci)和N-[2-(4-甲基苯并噻唑基)]-2-氨基-2-氟苯基-O,O-二乙基[^(14)C]甲基膦酸酯(3,32.4 m Ci)],其结构经核磁共振氢谱(~1H NMR)和在线放射性高效液相色谱-二极管阵列检测器/质谱联用(HPLC-FSA/PDA/MS)分析确认,反应总放化收率/化学收率分别为31%和67%.放射性薄层层析-同位素成像分析(TLC-IIA)、离线放射性高效液相色谱(HPLC-LSC),HPLC-FSA/PDA/MS和液体闪烁测量(LSC)分析表明,两种标记物的放化纯度和化学纯度均大于98%,比活度分别为25.5,55.5 m Ci/mmol.该标记物可作为放射性示踪剂,用于毒氟磷的代谢、残留和环境行为等研究.
