CN107104031B - 激发态二溴甲烷质子化增强剂 - Google Patents
激发态二溴甲烷质子化增强剂 Download PDFInfo
- Publication number
- CN107104031B CN107104031B CN201710285292.1A CN201710285292A CN107104031B CN 107104031 B CN107104031 B CN 107104031B CN 201710285292 A CN201710285292 A CN 201710285292A CN 107104031 B CN107104031 B CN 107104031B
- Authority
- CN
- China
- Prior art keywords
- methylene bromide
- excitation state
- protonation
- reinforcing agent
- ionized region
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 230000005284 excitation Effects 0.000 title claims abstract description 27
- 239000012744 reinforcing agent Substances 0.000 title claims abstract description 13
- 230000005588 protonation Effects 0.000 claims abstract description 18
- 239000005416 organic matter Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 14
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 230000005945 translocation Effects 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 9
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 230000005281 excited state Effects 0.000 abstract description 3
- 230000010748 Photoabsorption Effects 0.000 abstract description 2
- 238000000752 ionisation method Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 description 6
- 238000004949 mass spectrometry Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000001793 charged compounds Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- -1 aldehydes alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
- H01J49/161—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission using photoionisation, e.g. by laser
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
本发明所涉及的激发态二溴甲烷质子化增强剂,是一种新的质子化增强剂,可在低气压电离过程性提高极性有机物的质子化效率,从而提升低气压电离质谱仪的检测能力。相对于二氟甲烷和二氯甲烷,二溴甲烷具有较高的光吸收截面,可以产生较多的激发态分子,形成更多的激发态二溴甲烷质子化媒介,有益于提高质子化增强效率;二溴甲烷高激发态能级低,需要的激发光子能量低,激发光源容易获得。
Description
技术领域
本发明所涉及的激发态二溴甲烷质子化增强剂,是一种新的质子化增强剂,可促进低气压电离过程中极性有机物的质子化效率,提高低气压电离质谱仪的检测能力。相对于二氟甲烷和二氯甲烷,二溴甲烷具有较高的光吸收截面,可以产生较多的激发态分子,形成更多的激发态二溴甲烷质子化媒介,有益于提高质子化增强效率;二溴甲烷高激发态能级低,需要的激发光子能量低,激发光源容易获得。
背景技术
光电离技术是一种被广泛应用于化学分析的软电离技术,其中,低气压光电离是近几年新发展起来一种新的软电离技术,已被逐渐应用在质谱检测中。应用该技术的质谱仪,具有灵敏度高,产生杂散离子少,测量响应时间短等特点,可实现对大气痕量挥发性有机物的实时高灵敏检测。低气压电离是在数千帕斯卡条件下工作的光电离技术,待测物分子可以直接被光电离,也可以通过分子离子反应被电离,其分子离子反应过程如反应式(1)和(2)所示,式中:A指待测物分子,R指提供质子或氢原子的反应物。
A+R+→AH++[R-H] (1)
A++R→AH++[R-H] (2)
低气压光电离技术的实施条件是待测物质需有足够大的光电离截面或存在足够多的质子化剂。低气压电离质谱对于苯及其衍生物等挥发性有机物的检测灵敏度和质子转移反应质谱相当。然而对于醛类醇类等光电离截面小的物质,低气压电离的检测效率的不高。因此,提高质子化浓度是提高低气压电离质谱检测能力的关键。
发明内容
为了进一步发展低气压电离质谱,提高其检测能力,使其能够灵敏快速地检测更多种类的挥发性有机物,本发明提供一种应用于低气压电离质谱技术的激发态二溴甲烷质子化增强剂。在我们的实验过程中发现,在以真空紫外灯(氪灯)为光源的低气压光电离源中掺杂二溴甲烷质子化增强剂,可显著提高醛类和醇类等极性有机物分子的质子化效率,从而提升低气压光电离质谱对挥发性有机物的检测灵敏度。
本发明专利采用的技术方案是:1、在真空紫外光光源附近注入二溴甲烷蒸汽;2、在反应电离区注入待测气态极性有机物样品;3、二溴甲烷与待测气态样品混和;4、二溴甲烷在真空紫外光辐照下被激发,形成激发态的二溴甲烷;3、待测气态样品分子与激发态的二溴甲烷在反应电离区内碰撞,发生质子转移反应,转化为带正电的质子化有机物离子。
该发明的有益效益是:相对于二氟甲烷和二氯甲烷,二溴甲烷具有较高的光吸收截面,可以产生较多的激发态分子,形成更多的激发态二溴甲烷质子化媒介,有益于提高质子化增强效率;二溴甲烷高激发态能级低,需要的激发光子能量低,激发光源容易获得。这两项效益总体上提高了质子化效率,降低了质子化剂的用量。
附图说明
附图为本发明二溴甲烷质子化增强剂应用方法和低气压电离源示意图,图中:1.真空紫外光源;2.氟化锂窗片;3.反应电离区;4.离子出口;5.二溴甲烷供给管;6.样品供给管。
具体实施方式
激发态二溴甲烷质子化增强剂生成和有机物质子化增强所涉及的低气压光电离源由真空紫外光源1,氟化锂窗片2,反应电离区3,离子出口4,二溴甲烷供给管5,样品供给管6六部分组成。具体实施方案如下:
一、真空紫外光源1产生真空紫外光,透过氟化锂窗片2,辐照反应电离区3;
二、二溴甲烷由二溴甲烷供给管5输入反应电离区3,输入速率由其他调节装置控制;
三、待测气态样品由样品供给管6输入反应电离区3,输入速率由其他调节装置控制;
四、二溴甲烷和在气态样品反应电离区混和;
五、在真空紫外光辐照下被激发,转化为激发态二溴甲烷;
六、激发态的二溴甲烷与样品有机物分子在反应电离区3中发生相互碰撞,有机物分子被质子化;
七、质子化的有机物离子最后从离子出口4进入检测装置。
Claims (3)
1.一种激发态二溴甲烷质子化增强剂,其在低气压电离源内被激发生成,能增强样品有机物的质子化,所述低气压电离源由真空紫外光源、氟化锂窗片、反应电离区、离子出口、二溴甲烷供给管和样品供给管组成,其特征在于:真空紫外光源产生的真空紫外光透过氟化锂窗片辐照反应电离区,二溴甲烷由二溴甲烷供给管输入反应电离区,待测气态样品由样品供给管输入反应电离区,反应电离区气压维持在100~2000Pa范围内,二溴甲烷在真空紫外光辐照下转化为激发态二溴甲烷,激发态二溴甲烷与样品有机物分子在反应电离区中发生相互碰撞,有机物分子被质子化,质子化的有机物离子最后从离子出口进入检测装置;其中质子化介质为中性激发态二溴甲烷,激发态二溴甲烷可将反应物的质子转移给有机物,形成质子化的有机物离子。
2.根据权利要求1所述的激发态二溴甲烷质子化增强剂,其特征在于:使二溴甲烷激发的激发光光源为真空紫外灯。
3.根据权利要求1所述的激发态二溴甲烷质子化增强剂,其特征在于:激发态二溴甲烷产生和反应电离区内二溴甲烷气体分压的应用范围为0.01~20Pa。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710285292.1A CN107104031B (zh) | 2017-04-27 | 2017-04-27 | 激发态二溴甲烷质子化增强剂 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710285292.1A CN107104031B (zh) | 2017-04-27 | 2017-04-27 | 激发态二溴甲烷质子化增强剂 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107104031A CN107104031A (zh) | 2017-08-29 |
CN107104031B true CN107104031B (zh) | 2018-10-16 |
Family
ID=59657317
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710285292.1A Expired - Fee Related CN107104031B (zh) | 2017-04-27 | 2017-04-27 | 激发态二溴甲烷质子化增强剂 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107104031B (zh) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101413919A (zh) * | 2007-08-01 | 2009-04-22 | 中国科学院大连化学物理研究所 | 一种对样品进行识别与解析的方法及离子迁移谱仪 |
CN201993338U (zh) * | 2010-11-30 | 2011-09-28 | 中国科学院大连化学物理研究所 | 一种质谱快速在线富集的吹扫式膜进样-缓冲腔装置 |
CN106373855A (zh) * | 2016-10-26 | 2017-02-01 | 广西电网有限责任公司电力科学研究院 | 一种快速分析气体或液体中有机污染物的质谱装置 |
-
2017
- 2017-04-27 CN CN201710285292.1A patent/CN107104031B/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101413919A (zh) * | 2007-08-01 | 2009-04-22 | 中国科学院大连化学物理研究所 | 一种对样品进行识别与解析的方法及离子迁移谱仪 |
CN201993338U (zh) * | 2010-11-30 | 2011-09-28 | 中国科学院大连化学物理研究所 | 一种质谱快速在线富集的吹扫式膜进样-缓冲腔装置 |
CN106373855A (zh) * | 2016-10-26 | 2017-02-01 | 广西电网有限责任公司电力科学研究院 | 一种快速分析气体或液体中有机污染物的质谱装置 |
Also Published As
Publication number | Publication date |
---|---|
CN107104031A (zh) | 2017-08-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Berndt et al. | Hydroxyl radical-induced formation of highly oxidized organic compounds | |
Bian et al. | Formations of active species and by-products in water by pulsed high-voltage discharge | |
Gravestock et al. | A multidimensional study of the reaction CH2I+ O2: products and atmospheric implications | |
JP2016520952A (ja) | 試料ガス流の粒子をイオン化する方法および装置 | |
CN106158574A (zh) | 光诱导离子源质子转移反应质谱仪 | |
Demarcke et al. | Laboratory studies in support of the detection of sesquiterpenes by proton-transfer-reaction-mass-spectrometry | |
Huang et al. | Kinetic understanding of the ultrahigh ionization efficiencies (up to 28%) of excited-state CH2Cl2-induced associative ionization: A case study with nitro compounds | |
Poulet et al. | Kinetics and products of the bromine monoxide+ chlorine monoxide reaction | |
Marotta et al. | DC corona electric discharges for air pollution control, 2—ionic intermediates and mechanisms of hydrocarbon processing | |
CN107104031B (zh) | 激发态二溴甲烷质子化增强剂 | |
CN103811265A (zh) | 一种掺杂剂辅助电离源及其在离子迁移谱中的应用 | |
Zhao et al. | A mechanism study of positive ionization processes in flowing atmospheric-pressure afterglow (FAPA) ambient ion source with controlled plasma and ambient conditions | |
Guo et al. | An ultrasensitive SPI/PAI ion source based on a high-flux VUV lamp and its applications for the online mass spectrometric detection of sub-pptv sulfur ethers | |
Zhang et al. | Chemical ionization mass spectrometry: Developments and applications for on-line characterization of atmospheric aerosols and trace gases | |
Kukui et al. | Chemical ionisation mass spectrometer for measurements of OH and Peroxy radical concentrations in moderately polluted atmospheres | |
CN107195529B (zh) | 一种基于激发态质子电子协同转移反应的离子化方法及其装置 | |
Kersten et al. | Evidence of neutral radical induced analyte ion transformations in APPI and near-VUV APLI | |
CN207425794U (zh) | 一种基于激发态质子电子协同转移反应的离子源 | |
US20130260473A1 (en) | Ionisation method for a universal gas analyzer | |
CN107870194A (zh) | 基质辅助激光解吸‑气相极化诱导质子转移质谱 | |
Španěl et al. | Different reactivities of H3O+ (H2O) n with unsaturated and saturated aldehydes: ligand‐switching reactions govern the quantitative analytical sensitivity of SESI‐MS | |
CN207602515U (zh) | 利用激发态化学反应提供质子化水的质子转移反应离子源 | |
Limão-Vieira et al. | Valence and lowest Rydberg electronic states of phenol investigated by synchrotron radiation and theoretical methods | |
Wen et al. | Self-reaction of C2H5O2 and its cross-reaction with HO2 studied with vacuum ultraviolet photoionization mass spectrometry | |
CN107871650B (zh) | 激发态二氯甲烷质子化剂 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181016 |