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
Ion mobility spectrometry （IMS） is a very fast, highly sensitive, and inexpensive technique, it permits efficient monitoring of volatile organic compounds like alcohols. In this article, positive ion mobility spectr...Ion mobility spectrometry （IMS） is a very fast, highly sensitive, and inexpensive technique, it permits efficient monitoring of volatile organic compounds like alcohols. In this article, positive ion mobility spectra for six alcohol organic compounds have been systematically studied for the first time using a high-resolution IMS apparatus equipped with a discharge ionization source. Utilizing protonated water cluster ions （H2O）nH^＋ as the reactant ions and clean air as the drift gas, alcohol organic compounds, ethanol, 1- propanol, 2-propanol, 1-butanol, 1-pentanol and 2-octanol, all exhibit product ion characteristic peaks in their respective ion mobility spectrometry, that is a result of proton transfer reactions between the alcohols and reaction ions （H2O）nH^＋. The mixture of these alcohols, including two isomers, has been detected, and the results showed that they could be distinguished effectively in the ion mobility spectrum. The reduced mobility values have been determined, which are in very well agreement with the traditional ^63Ni-IMS experimental values. The exponential dilution method was used to calibrate the alcohol concentrations, and a detection limit available for the alcohols is in order of magnitude of a few ng/L.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
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Project supported by the National Natural Science Foundation of China(No.20577049)the Excellent Youth Foundation of Anhui Province Scientific Committee(No.06045098)the Hefei Institues of Physical Science,Chinese Academy of Sciences.
文摘Ion mobility spectrometry （IMS） is a very fast, highly sensitive, and inexpensive technique, it permits efficient monitoring of volatile organic compounds like alcohols. In this article, positive ion mobility spectra for six alcohol organic compounds have been systematically studied for the first time using a high-resolution IMS apparatus equipped with a discharge ionization source. Utilizing protonated water cluster ions （H2O）nH^＋ as the reactant ions and clean air as the drift gas, alcohol organic compounds, ethanol, 1- propanol, 2-propanol, 1-butanol, 1-pentanol and 2-octanol, all exhibit product ion characteristic peaks in their respective ion mobility spectrometry, that is a result of proton transfer reactions between the alcohols and reaction ions （H2O）nH^＋. The mixture of these alcohols, including two isomers, has been detected, and the results showed that they could be distinguished effectively in the ion mobility spectrum. The reduced mobility values have been determined, which are in very well agreement with the traditional ^63Ni-IMS experimental values. The exponential dilution method was used to calibrate the alcohol concentrations, and a detection limit available for the alcohols is in order of magnitude of a few ng/L.
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。
