A combination of high-field asymmetric waveform ion mobility spectrometry （FAIMS） with mass spectrometer （MS） was analyzed. FAIMS separates ions from the volatile organic compounds in the gas-phase as an ion-filte...A combination of high-field asymmetric waveform ion mobility spectrometry （FAIMS） with mass spectrometer （MS） was analyzed. FAIMS separates ions from the volatile organic compounds in the gas-phase as an ion-filter for MS. The sample ions were created at ambient pressure by ion source, which was equipped with a 10.6 eV UV discharge lamp （A=116.5 nm）. The drift tube of FAIMS is composed of two parallel planar electrodes and the dimension is 10 mm×8 mm×0.5 mm. FAIMS was investigated when driven by the high-filed rectangular asymmetric waveform with the peak-to-peak voltage of 1.36 kV at the frequency of 1 MHz and the duty cycle of 30%. The acetone, the butanone, and their mixture were adopted to characterize the FAIMS-MS. The mass spectra obtained from MS illustrate that there are ion-molecular reactions between the ions and the sample neutral molecular. And the proton transfer behavior in the mixture of the acetone and the butanone is also observed. With the compensation voltage tuned from -30 V to 10 V with a step size of 0.1 V, the ion pre-separation before MS is realized.展开更多
Real-time and on-line monitoring volatile organic compounds（VOCs） are valuable for real-time evalua- ting air quality and monitoring the key source of pollution. A self-developed proton transfer reaction-mass spectr...Real-time and on-line monitoring volatile organic compounds（VOCs） are valuable for real-time evalua- ting air quality and monitoring the key source of pollution. A self-developed proton transfer reaction-mass spectro- meter（PTR-MS） was constructed and applied to on-line monitoring trace VOCs in ambient air in Hefei, China. With the help of a self-developed catalytic converter, the background signal of the instrument was detected and the stability of the instrument was evaluated. The relative standard deviation of signal at m/z 21 was only 0.74% and the detection limit of PTR-MS was 97 part per trillion（97x 10-12, volume ratio）. As a case of the air monitoring in Hefei, the am- bient air at Dongpu reservoir spot was on-line monitored for 13 d with our self-developed PTR-MS. Meanwhile, a solid-phase micro-extraction（SPME） technique coupled to gas chromatography-mass spectrometry/mass spectrometry （GC-MS/MS） was also used for the off-line detection of the air. The results show that our self-developed PTR-MS can be used for the on-line and long-term monitoring of VOCs in air at part per trillion level, and the change trend of VOCs concentration monitored with PTR-MS was consistent with that detected with the conventional SPME-GC-MS. This self-developed PTR-MS can fully satisfy the requirements of air quality monitoring and real-time monitoring of the key pollution sources.展开更多
利用密度泛函理论(DFT),在B3LYP/cc-pVDZ水平上,对三过氧化三丙酮(Triacetone triperoxide,TATP)及其质子化离子[TATP+H]+进行了构型优化和质子亲和势(Proton Affinity,PA)计算,研究结果表明,PA(TATP)=866.73kJ/mol大于PA(H2O)=691.0kJ/...利用密度泛函理论(DFT),在B3LYP/cc-pVDZ水平上,对三过氧化三丙酮(Triacetone triperoxide,TATP)及其质子化离子[TATP+H]+进行了构型优化和质子亲和势(Proton Affinity,PA)计算,研究结果表明,PA(TATP)=866.73kJ/mol大于PA(H2O)=691.0kJ/mol,TATP与H3O+可发生质子转移反应.在自行研制的质子转移反应质谱(Proton transfer reaction mass spectrometry,PTR-MS)装置上,研究了TATP与H3O+反应生成的特征离子.当漂移管中E/N=1.4×10-15V.cm2时,在荷质比m/z=91,75,74,59,43等处观察到了产物离子.降低E/N至0.5×10-15V.cm2后,在m/z=223处观察到了质子化产物离子([TATP+H]+),验证了计算结果;结合[TATP+H]+的构型,分析了TATP质子转移反应产物离子可能的归属及其形成过程.结合PTR-MS漂移管内E/N的改变引起m/z=223,91,43等离子的变化特征,可实现TATP的准确识别和快速定量检测,检测下限达到5.0×10-10mol/L(±50%).展开更多
采用质子传递反应-飞行时间质谱仪(Proton Transfer Reaction-Time of Flight-Mass Spectrometry,PTR-TOFMS)与气相色谱-质谱联用技术(Gas Chromatography-Mass Spectrometer,GC-MS)对不同品种武夷岩茶(水仙、肉桂)香气成分进行分析,结...采用质子传递反应-飞行时间质谱仪(Proton Transfer Reaction-Time of Flight-Mass Spectrometry,PTR-TOFMS)与气相色谱-质谱联用技术(Gas Chromatography-Mass Spectrometer,GC-MS)对不同品种武夷岩茶(水仙、肉桂)香气成分进行分析,结果表明:武夷水仙以反式橙花叔醇、(E,E)-2,4-庚二烯醛、芳樟醇及其氧化物等为主;武夷肉桂是反式橙花叔醇、α-法尼烯、苯甲醛为主,且在武夷山肉桂中存在高浓度的m/z 207、223、281、291几个未知化合物。2种分析技术所检测到的香气成分和相对含量比例差异显著,两者各有优劣,相互补充,联合分析更加完整,更有利于准确地进行香气分析,同时发现PTR-TOF-MS法更能真实地反映茶叶香气的完整信息。展开更多
在自行研制的质子转移反应质谱(Proton Transfer Reaction Mass Spectrometry,PTR-MS)装置上以丁酮、乙醚等几种常见易制毒化学品为例给出检测结果.发现各自对应唯一的质子化离子峰,谱峰识别简单;分析其他易制毒化学品质子亲和势,说明PT...在自行研制的质子转移反应质谱(Proton Transfer Reaction Mass Spectrometry,PTR-MS)装置上以丁酮、乙醚等几种常见易制毒化学品为例给出检测结果.发现各自对应唯一的质子化离子峰,谱峰识别简单;分析其他易制毒化学品质子亲和势,说明PTR-MS可以对大部分易制毒化学品检测;对浓度为54±3 nmol/L的甲苯标准气体检测结果为51±0.5 nmol/L,绝对量检测准确;通过分析经铂丝催化后的本底信号得到PTR-MS对易制毒化学品的检测限,其中对甲苯检测下限可达5.0×10-2(±50%)nmol/L.结果表明,PTR-MS可选择合适的漂移管约化场E/N,实现对痕量易制毒化学品快速筛选和准确识别.展开更多
以《大气污染物综合排放标准))(GB 16297-1996)中有机物的实时在线测量为目的,对自行研制的质子转移反应质谱(proton transfer reaction mass spectrometry,PTR-MS)装置的参数进行了优化和测量。利用高纯N_2稀释的单一有机物PTR-MS测量...以《大气污染物综合排放标准))(GB 16297-1996)中有机物的实时在线测量为目的,对自行研制的质子转移反应质谱(proton transfer reaction mass spectrometry,PTR-MS)装置的参数进行了优化和测量。利用高纯N_2稀释的单一有机物PTR-MS测量结果表明,在E/N=144 Td条件下,质子化的有机物离子为主要的产物离子峰,没有明显的碎片离子存在。测试了进样系统中催化转化装置的性能,给出了11种挥发性有机物的探测灵敏度和检测下限,讨论了PTR-MS的测量精度。测试结果表明,自行研制的PTR-MS能够实时在线监测《大气污染物综合排放标准》中规定的有机污染物。展开更多
研制可快速、在线分析挥发性有机物(volatile organic compounds,VOCs)的质谱仪器是现代气态有机质谱的重要发展方向。本研究自行研制了小型高性能质子转移反应飞行时间质谱仪(proton transfer reaction time of flight mass spectromet...研制可快速、在线分析挥发性有机物(volatile organic compounds,VOCs)的质谱仪器是现代气态有机质谱的重要发展方向。本研究自行研制了小型高性能质子转移反应飞行时间质谱仪(proton transfer reaction time of flight mass spectrometry,PTR-TOF MS),仪器采用结构简单可靠的空心阴极放电源作为水蒸气电离源,以产生水合质子;线性漂移管作为分子离子反应管。该离子源产生的水合离子纯度高,为水合离子与VOCs的分子离子反应提供可控的反应条件。传输接口部分使用射频四极杆作为离子导向装置,以提高离子传输效率;配合小尺寸飞行时间质量分析器,兼顾仪器的灵敏度与分辨率。质子转移反应的测定原理使该仪器可以分析除少数烷烃外的绝大多数VOCs,同时分析过程不受空气组分的影响。分子离子峰为主的产物离子形式使谱图便于解析,适合高通量分析。测试结果表明,该仪器在m/z 115处全高半峰宽(full width half maximum,FWHM)分辨率优于2500,对丙酮、苯、甲苯的检出限在6×10^(-12)~9.6×10^(-11) mol/mol之间。将该仪器应用于人体呼吸气的成分分析,取得了良好的结果。展开更多
文摘A combination of high-field asymmetric waveform ion mobility spectrometry （FAIMS） with mass spectrometer （MS） was analyzed. FAIMS separates ions from the volatile organic compounds in the gas-phase as an ion-filter for MS. The sample ions were created at ambient pressure by ion source, which was equipped with a 10.6 eV UV discharge lamp （A=116.5 nm）. The drift tube of FAIMS is composed of two parallel planar electrodes and the dimension is 10 mm×8 mm×0.5 mm. FAIMS was investigated when driven by the high-filed rectangular asymmetric waveform with the peak-to-peak voltage of 1.36 kV at the frequency of 1 MHz and the duty cycle of 30%. The acetone, the butanone, and their mixture were adopted to characterize the FAIMS-MS. The mass spectra obtained from MS illustrate that there are ion-molecular reactions between the ions and the sample neutral molecular. And the proton transfer behavior in the mixture of the acetone and the butanone is also observed. With the compensation voltage tuned from -30 V to 10 V with a step size of 0.1 V, the ion pre-separation before MS is realized.
基金Supported by the National Natural Science Foundation of China（Nos.21477132, 21577145）, the National Key Technology Research and Development Program of China（No.2015BAI01B04）, the National Key Research Program of China （No.2016YFC0200200）, the Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology of China（No.2014FXCX007） and the Functional Development Program of Instrument and Equipment in Chinese Academy of Sciences.
文摘Real-time and on-line monitoring volatile organic compounds（VOCs） are valuable for real-time evalua- ting air quality and monitoring the key source of pollution. A self-developed proton transfer reaction-mass spectro- meter（PTR-MS） was constructed and applied to on-line monitoring trace VOCs in ambient air in Hefei, China. With the help of a self-developed catalytic converter, the background signal of the instrument was detected and the stability of the instrument was evaluated. The relative standard deviation of signal at m/z 21 was only 0.74% and the detection limit of PTR-MS was 97 part per trillion（97x 10-12, volume ratio）. As a case of the air monitoring in Hefei, the am- bient air at Dongpu reservoir spot was on-line monitored for 13 d with our self-developed PTR-MS. Meanwhile, a solid-phase micro-extraction（SPME） technique coupled to gas chromatography-mass spectrometry/mass spectrometry （GC-MS/MS） was also used for the off-line detection of the air. The results show that our self-developed PTR-MS can be used for the on-line and long-term monitoring of VOCs in air at part per trillion level, and the change trend of VOCs concentration monitored with PTR-MS was consistent with that detected with the conventional SPME-GC-MS. This self-developed PTR-MS can fully satisfy the requirements of air quality monitoring and real-time monitoring of the key pollution sources.
文摘利用密度泛函理论(DFT),在B3LYP/cc-pVDZ水平上,对三过氧化三丙酮(Triacetone triperoxide,TATP)及其质子化离子[TATP+H]+进行了构型优化和质子亲和势(Proton Affinity,PA)计算,研究结果表明,PA(TATP)=866.73kJ/mol大于PA(H2O)=691.0kJ/mol,TATP与H3O+可发生质子转移反应.在自行研制的质子转移反应质谱(Proton transfer reaction mass spectrometry,PTR-MS)装置上,研究了TATP与H3O+反应生成的特征离子.当漂移管中E/N=1.4×10-15V.cm2时,在荷质比m/z=91,75,74,59,43等处观察到了产物离子.降低E/N至0.5×10-15V.cm2后,在m/z=223处观察到了质子化产物离子([TATP+H]+),验证了计算结果;结合[TATP+H]+的构型,分析了TATP质子转移反应产物离子可能的归属及其形成过程.结合PTR-MS漂移管内E/N的改变引起m/z=223,91,43等离子的变化特征,可实现TATP的准确识别和快速定量检测,检测下限达到5.0×10-10mol/L(±50%).
文摘采用质子传递反应-飞行时间质谱仪(Proton Transfer Reaction-Time of Flight-Mass Spectrometry,PTR-TOFMS)与气相色谱-质谱联用技术(Gas Chromatography-Mass Spectrometer,GC-MS)对不同品种武夷岩茶(水仙、肉桂)香气成分进行分析,结果表明:武夷水仙以反式橙花叔醇、(E,E)-2,4-庚二烯醛、芳樟醇及其氧化物等为主;武夷肉桂是反式橙花叔醇、α-法尼烯、苯甲醛为主,且在武夷山肉桂中存在高浓度的m/z 207、223、281、291几个未知化合物。2种分析技术所检测到的香气成分和相对含量比例差异显著,两者各有优劣,相互补充,联合分析更加完整,更有利于准确地进行香气分析,同时发现PTR-TOF-MS法更能真实地反映茶叶香气的完整信息。
文摘在自行研制的质子转移反应质谱(Proton Transfer Reaction Mass Spectrometry,PTR-MS)装置上以丁酮、乙醚等几种常见易制毒化学品为例给出检测结果.发现各自对应唯一的质子化离子峰,谱峰识别简单;分析其他易制毒化学品质子亲和势,说明PTR-MS可以对大部分易制毒化学品检测;对浓度为54±3 nmol/L的甲苯标准气体检测结果为51±0.5 nmol/L,绝对量检测准确;通过分析经铂丝催化后的本底信号得到PTR-MS对易制毒化学品的检测限,其中对甲苯检测下限可达5.0×10-2(±50%)nmol/L.结果表明,PTR-MS可选择合适的漂移管约化场E/N,实现对痕量易制毒化学品快速筛选和准确识别.
文摘以《大气污染物综合排放标准))(GB 16297-1996)中有机物的实时在线测量为目的,对自行研制的质子转移反应质谱(proton transfer reaction mass spectrometry,PTR-MS)装置的参数进行了优化和测量。利用高纯N_2稀释的单一有机物PTR-MS测量结果表明,在E/N=144 Td条件下,质子化的有机物离子为主要的产物离子峰,没有明显的碎片离子存在。测试了进样系统中催化转化装置的性能,给出了11种挥发性有机物的探测灵敏度和检测下限,讨论了PTR-MS的测量精度。测试结果表明,自行研制的PTR-MS能够实时在线监测《大气污染物综合排放标准》中规定的有机污染物。
文摘研制可快速、在线分析挥发性有机物(volatile organic compounds,VOCs)的质谱仪器是现代气态有机质谱的重要发展方向。本研究自行研制了小型高性能质子转移反应飞行时间质谱仪(proton transfer reaction time of flight mass spectrometry,PTR-TOF MS),仪器采用结构简单可靠的空心阴极放电源作为水蒸气电离源,以产生水合质子;线性漂移管作为分子离子反应管。该离子源产生的水合离子纯度高,为水合离子与VOCs的分子离子反应提供可控的反应条件。传输接口部分使用射频四极杆作为离子导向装置,以提高离子传输效率;配合小尺寸飞行时间质量分析器,兼顾仪器的灵敏度与分辨率。质子转移反应的测定原理使该仪器可以分析除少数烷烃外的绝大多数VOCs,同时分析过程不受空气组分的影响。分子离子峰为主的产物离子形式使谱图便于解析,适合高通量分析。测试结果表明,该仪器在m/z 115处全高半峰宽(full width half maximum,FWHM)分辨率优于2500,对丙酮、苯、甲苯的检出限在6×10^(-12)~9.6×10^(-11) mol/mol之间。将该仪器应用于人体呼吸气的成分分析,取得了良好的结果。
