WO2014005377A1 - 一种在线质谱电离源内管状膜进样装置 - Google Patents

一种在线质谱电离源内管状膜进样装置 Download PDF

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Publication number
WO2014005377A1
WO2014005377A1 PCT/CN2012/081768 CN2012081768W WO2014005377A1 WO 2014005377 A1 WO2014005377 A1 WO 2014005377A1 CN 2012081768 W CN2012081768 W CN 2012081768W WO 2014005377 A1 WO2014005377 A1 WO 2014005377A1
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tubular film
ionization source
ionization
tubular
film
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French (fr)
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侯可勇
李芳龙
陈文东
李海洋
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0459—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for solid samples

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  • the invention belongs to a mass spectrometer, in particular to a device in which a tubular film is placed directly in an ionization zone and a heating lamp is used to heat the surface of the film.
  • the device can overcome the disadvantage that the diffusion of the sample by the ordinary membrane injection is first enriched and then the sample is injected by the capillary.
  • the tubular membrane sampling device in the ionization source rapidly passes the analysis sample through the membrane under the pressure difference between the inside and outside of the membrane and is directly ionized by the ionization source at the membrane surface.
  • the device increases the rate of transmission of the sample in the membrane and the ionization efficiency of the sample. Background technique
  • Membrane injection is widely used as a mass spectrometry injection device.
  • the membrane primarily serves to separate, enrich, and serve as a medium for isolating the atmospheric environment from the mass spectrometry vacuum. Since the polydimethylsiloxane film has selective permeability to different substances, volatile and semi-volatile organic substances can penetrate the film well. Therefore, the application of volatile and semi-volatile organic pollutants in an online analytical environment is very extensive.
  • the sheet-like film sampling device since the requirement of the mass spectrometer vacuum degree is required, the sheet-like film area requirement is sufficiently small, and the injection amount of the analysis sample is small, and the sheet-like film is thin and easy to be broken.
  • the ordinary tubular membrane injection device due to the thick film wall, the ordinary tubular membrane injection device has a long response time on the membrane, which results in a serious memory effect on the membrane, which is not conducive to rapid on-line detection of environmental samples.
  • the analysis sample is enriched by the membrane and then subjected to capillary injection. During this process, the sample will have a part of the diffusion loss, which will affect the analysis results.
  • the present invention designs an in-line mass spectrometry ionization source tubular film sampling device, which directly places the tubular film in the ionization zone, and the tubular film can be stretched 1-5 times in the axial direction, and then stretched.
  • the rear tubular film can effectively reduce the wall thickness of the tubular film.
  • the vacuum state of the mass spectrometer causes a large pressure difference between the inside and outside of the tubular film, and the sample can quickly permeate through the membrane.
  • the sample can be ionized by the ionization source immediately after passing through the membrane, overcoming the diffusion loss of the analytical sample in other membrane mounting methods.
  • the heat lamp accelerates the desorption of analytes from the membrane surface.
  • the arrangement of a plurality of tubular membranes in the array can increase the injection volume, so the device can increase the rate of penetration of the sample in the membrane and improve the ionization efficiency. Summary of the invention
  • An on-line mass spectrometry ionization source internal stretch film sampling device comprises an ionization zone, a tubular membrane is placed in the ionization zone, a metal capillary is connected at both ends of the tubular membrane as a sampling inlet and an outlet, and a particle filter is added before the sampling inlet, the upper end of the ionization zone
  • the ionization source and the heating lamp are placed in the opening, and the emergency cut-off solenoid valve is installed on the inlet and the outlet of the injection metal capillary, and the vacuum valve is used to adjust the vacuum degree of the ionization zone.
  • a peristaltic pump is arranged at the front end of the sampling inlet to feed the liquid sample into the tubular film, and is discharged from the outlet; when the gas sample is injected, an air pump is arranged at the front end of the sampling inlet to feed the gas sample into the tubular film. With the outlet discharge, a cyclic injection can be set when the analysis sample is small.
  • the tubular membrane material is a polydimethylsiloxane membrane, which is a semipermeable membrane which can be stretched 1-5 times in the axial direction, and the tubular membrane after stretching can effectively reduce the tubular membrane. Wall thickness. A heat lamp is used as the film heating device.
  • the tubular membrane is placed directly in the ionization zone, and a large pressure difference is formed inside and outside the tubular membrane by utilizing the mass spectrometry vacuum state and the atmospheric pressure state of the inner wall of the tubular membrane. Under the action of the pressure difference, the sample rapidly passes through the membrane and is directly ionized by the ionization source.
  • the heating lamp can accelerate the desorption of the sample on the outer wall of the tubular membrane.
  • the tubular membrane is placed directly in the ionization zone, and the vacuum conditions of the mass spectrometer are used to form a large pressure difference between the inner and outer sides of the membrane, and the diffusion rate of the sample on the membrane is accelerated.
  • the tubular film stretched 1-5 times can reduce the thickness of the membrane wall and effectively reduce the response time of the analytical sample on the membrane.
  • the ionization source is directly irradiated on the membrane so that the sample is ionized at the surface of the membrane, which improves the ionization efficiency of the sample.
  • the tubular membrane in the ionization zone can use an array of tubular membranes to facilitate high-flow injection and improve sample sensitivity.
  • a heating lamp is installed in the ionization zone to heat the outer surface of the tubular membrane, so that the sample is quickly desorbed from the membrane surface.
  • the tubular membrane sampling device in the ionization source can realize continuous online detection of environmental samples.
  • FIG. 1 is a schematic view showing the structure of a tubular film sampling device for use in an on-line mass spectrometry ionization source according to the present invention.
  • FIG. 2 is a schematic view showing the injection of a film into an array tubular film in the apparatus of the present invention. detailed description
  • the present invention provides a novel ionization source inner tubular membrane sampling device.
  • the present invention is applied to a mass spectrometer, wherein 1 is a tubular membrane, 2 is a sampling inlet, 3 is a sampling outlet, 4 is a particle filter, 5 is a sampling metal capillary, 6 is an emergency cutting solenoid valve, and 7 is heating.
  • Lamp is the ionization source
  • 9 is the repeller plate
  • 10 is the ionization zone
  • 11 is connected to the mass analyzer interface
  • 12 is the adjustment ionization zone vacuum valve.
  • the front end of the sampling inlet 2 is provided with a peristaltic pump to send the liquid sample into the tubular membrane 1 and discharged from the sampling outlet 3; when the gas sample is taken, the sampling end of the sampling inlet 2 is provided with an air pump to feed the gas sample into the stretch tubular membrane 1 , discharged from the sampling outlet 3.
  • An online mass spectrometry ionization source tubular film sampling device is disposed in a mass spectrometer ionization source, and the tubular film is directly placed in an ionization region of the mass spectrometry ionization source, and two ends of the tubular membrane are respectively connected with a metal capillary tube, and the metal capillary tube extends from the cavity of the mass spectrometry ionization source Out of the mass spectrometry ionization source cavity, the metal capillaries at both ends of the tubular membrane serve as sampling inlets and outlets respectively; a particle filter mesh is arranged in the metal capillary at the sampling inlet; and the metal capillary tubes at the sampling inlet and outlet are respectively provided with emergency cutoff Solenoid valve; a heating lamp is mounted outside the tubular membrane of the ionization zone in the mass spectrometry ionization source.
  • the tubular membrane is placed directly in the ionization zone to increase the permeability of the sample on the membrane, and the sample is permeated through the membrane on the membrane surface. Direct ionization by the ionization source increases the ionization efficiency of the sample.
  • a sample is sent to a stretched tubular membrane using a peristaltic pump or an air pump, and a particulate filter is added in front of the inlet to remove particulate matter from the sample to protect the membrane device.
  • the tubular film used in the present invention is a polydimethylsiloxane film, which is a semi-permeable film, which is stretched by 3 times and used, and the thickness of the tubular film after stretching is effectively reduced, and the sample can be reduced. Response time on the membrane. It is also possible to use an array of tubular membranes for tubular membranes to facilitate high-flow injections, improving analyte detection sensitivity.
  • the film is characterized in that inorganic substances such as nitrogen and oxygen in water and air are hard to penetrate the film, and volatile and semi-volatile organic pollutants easily pass through the film.
  • the sample is passed through the particle filter through the sampling port and into the tubular film.
  • a cyclic injection can be used.
  • Volatile and semi-volatile organic pollutants pass through the membrane rapidly under the pressure difference inside and outside the membrane, and are immediately ionized by the ionization source, and enter the mass analyzer under the action of the repeller plate to be analyzed and detected.
  • An emergency shut-off solenoid valve is installed at both the tubular membrane sampling inlet and outlet. When the membrane is in an emergency such as a rupture, the mass spectrum will change rapidly. At this time, the emergency cut-off solenoid valve will automatically close and protect the mass spectrometer.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Sampling And Sample Adjustment (AREA)

Description

种在线质谱电离源内管状膜进样装置 技术领域
本发明属于质谱分析仪器， 特别涉及一种管状膜直接放置在电离区内， 并利用加 热灯为膜表面加热的装置。该装置可以克服普通膜进样先富集再通过毛细管进样的样 品扩散损失大的缺点。该电离源内管状膜进样装置在膜内外压差和加热的作用下使分 析样品快速透过膜并在膜表面被电离源直接电离。该装置提高了样品在膜中的透过速 率和样品电离效率。 背景技术
膜进样作为质谱进样装置被广泛应用。膜在其中主要起到分离、富集样品和作为 隔离大气压环境与质谱真空状态的介质。由于聚二甲基硅氧烷膜对不同物质具有选择 透过性， 而挥发性和半挥发性有机物能很好的透过膜。所以在在线分析环境中挥发性 和半挥发性有机污染物的应用非常广泛。
普通片状膜进样装置， 由于需要保证质谱真空度的要求， 所以片状膜面积要求足 够小， 而导致分析样品的进样量较小， 并且片状膜较薄易破裂。 而普通管状膜进样装 置由于膜壁较厚， 分析样品在膜上的响应时间较长， 导致分析样品在膜上的记忆效应 比较严重， 所以不利于对环境样品的快速在线检测。 另外， 分析样品通过膜富集之后 再经过毛细管进样，在这过程中分析样品会有一部分的扩散损失，从而影响分析结果。
由此， 本发明设计了一种在线质谱电离源内管状膜进样装置， 将管状膜直接放在 电离区内， 管状膜可沿轴向被拉伸 1-5倍的长度后进行使用， 拉伸后的管状膜可以有 效减小管状膜壁厚。质谱的真空状态使管状膜内外形成较大的压差，样品能迅速透过 膜， 分析样品透过膜后能立即被电离源电离， 克服了其他膜安装方式中分析样品的扩 散损失。加热灯能加快分析物从膜表面解吸附。阵列排布多条管状膜可以增大进样量， 所以该装置能提高样品在膜中的透过速率， 并且能提高电离效率。 发明内容
本发明的目的在于提供一种在线质谱电离源内管状膜进样装置。
一种在线质谱电离源内拉伸膜进样装置， 包括电离区， 管状膜放置在电离区内， 管状膜两端连接金属毛细管作为采样进口和出口，采样进口前加一颗粒过滤网， 电离 区上端开孔放置电离源和加热灯，进样金属毛细管进口和出口上都装有紧急切断电磁 阀， 真空阀门用于调节电离区真空度。
进样为液体样品时， 采样进口前端设置蠕动泵将液体样品送入管状膜内， 从采用 出口排出； 进样为气体样品时， 采样进口前端设置抽气泵将气体样品送入管状膜内， 从采用出口排出， 当分析样品较少时可设置循环进样。 管状膜材料为聚二甲基硅氧烷膜， 该膜为半透膜， 其可沿轴向被拉伸 1-5倍的长 度后进行使用， 拉伸后的管状膜可以有效减小管状膜壁厚。加热灯用于作为膜加热装 置。
管状膜直接放置在电离区内，利用质谱真空状态和管状膜内壁的大气压状态使得 管状膜内外形成较大压差。在压差的作用下样品迅速透过膜并直接被电离源电离，加 热灯可以加快管状膜外壁上样品的解吸附。
本发明的优点：
管状膜直接放置在电离区内， 利用质谱的真空条件使膜内外侧形成较大压差， 加 速样品在膜上的扩散速率。 拉伸 1-5倍的管状膜能减小膜壁厚度， 有效减小分析样品 在膜上的响应时间。 电离源直接照射在膜上使得样品在膜表面就被电离，提高了样品 电离效率。
电离区内管状膜可以使用阵列管状膜利于大流量进样， 提高样品灵敏度。
电离区内安装加热灯给管状膜外表面加热， 使样品快速的从膜表面解吸附。 电离源内管状膜进样装置， 可以实现对环境样品的连续在线检测。 附图说明
图 1为本发明应用于一种在线质谱电离源内管状膜进样装置结构示意图。
图 2为本发明装置中膜进样为阵列管状膜进样结构示意图。 具体实施方式
为了提高样品在膜中的扩散速率和提高样品的电离效率。本发明提供了一种新型 的电离源内管状膜进样装置。
如图 1所示， 本发明应用于质谱仪器， 其中 1为管状膜， 2为采样进口， 3为采 样出口， 4为颗粒过滤网， 5采样金属毛细管， 6为紧急切断电磁阀， 7为加热灯， 8 为电离源， 9为推斥板， 10为电离区， 11连接质量分析器接口， 12为调节电离区真 空阀门。 其中液体样品时， 采样进口 2前端设置蠕动泵将液体样品送入管状膜 1内， 从采样出口 3排出； 气体样品时，采样进口 2前端设置抽气泵将气体样品送入拉伸管 状膜 1内， 从采样出口 3排出。
一种在线质谱电离源内管状膜进样装置， 设置于质谱电离源内， 管状膜直接放置 在质谱电离源的电离区内， 管状膜两端分别连接金属毛细管， 金属毛细管从质谱电离 源的腔体内伸出至质谱电离源腔体之外，管状膜两端的金属毛细管分别作为采样进口 和出口； 处于采样进口处的金属毛细管内设置有颗粒过滤网； 在采样进口和出口的金 属毛细管分别设有紧急切断电磁阀；在质谱电离源内的电离区管状膜外侧安装有加热 灯。
管状膜直接放置在电离区能提高样品在膜上的透过率，分析样品透过膜在膜表面 就被电离源直接电离， 提高了样品电离效率。在本发明的膜进样装置中， 利用蠕动泵 或抽气泵将样品送到拉伸管状膜内，在进样口前加一颗粒过滤网去除样品中颗粒物质 以保护膜装置。
本发明采用的管状膜为聚二甲基硅氧烷膜， 该膜为半透性膜， 将其拉伸 3倍长度 后使用， 拉伸后的管状膜壁厚有效减小， 能减小样品在膜上的响应时间。 也可以将管 状膜使用阵列管状膜利于大流量进样， 提高分析物检测灵敏度。 该膜的特征是， 水和 空气中的氮气、氧气等无机物较难透过膜， 而挥发性和半挥发性有机污染物很容易透 过膜。
检测时，分析样品经过颗粒过滤网经采样口进入到管状膜内，当分析样品较少时， 可以使用循环进样。在膜内外的压差作用下使得挥发性和半挥发性有机污染物迅速通 过膜， 并立即被电离源电离， 在推斥板作用下进入到质量分析器被分析检测。
管状膜采样进口和出口都安装了紧急切断电磁阀。当膜发生破裂等紧急状态时质 谱真空度会迅速变化， 此时紧急切断电磁阀会自动关闭， 保护质谱仪器。

Claims

权 利 要 求 书
1. 一种在线质谱电离源内管状膜进样装置， 设置于质谱电离源内， 其特征在于: 管状膜（1 )直接放置在质谱电离源的电离区 （9) 内， 管状膜两端分别连接金属 毛细管 （5 )， 金属毛细管 （5 ) 从质谱电离源的腔体内伸出至质谱电离源腔体之外， 管状膜两端的金属毛细管（5 )分别作为采样进口（2)和出口（3 ); 处于采样进口（2) 处的金属毛细管 （5 ) 内设置有颗粒过滤网 （4); 在采样进口 （2) 和出口 （3 ) 的金 属毛细管 （5 ) 分别设有紧急切断电磁阀 （6);
在质谱电离源内的电离区管状膜外侧安装有加热灯 （7)。
2. 根据权利要求 1所述的电离源内管状膜进样装置， 其特征在于： 质谱电离源 的腔体侧壁面上设有电离区抽气口，抽气口与分子泵的进口相连，抽气口与分子泵间 的连接管路上设置有真空阀门 （12)， 真空阀门 （12) 用以调节电离区真空度。
3. 根据权利要求 1所述的电离源内管状膜进样装置， 其特征在于： 将管状膜直 接放置在电离区； 管状膜可以为阵列排布的多条管状膜， 利于大流量进样， 以提高仪 器的灵敏度。
4. 根据权利要求 1或 3所述的电离源内管状膜进样装置， 其特征在于： 管状膜 材料为聚二甲基硅氧烷膜。
5. 根据权利要求 4所述的电离源内管状膜进样装置， 其特征在于： 聚二甲基硅 氧烷膜为半透膜， 商业购买的管状膜可沿轴向被拉伸 1-5倍的长度后进行使用， 拉伸 后可以有效减小管状膜壁厚。
6. 根据权利要求 1所述的电离源内管状膜进样装置， 其特征在于： 加热灯 （7) 安装在电离区腔体上作为膜加热装置。
PCT/CN2012/081768 2012-07-05 2012-09-21 一种在线质谱电离源内管状膜进样装置 Ceased WO2014005377A1 (zh)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101206204A (zh) * 2006-12-22 2008-06-25 中国科学院大连化学物理研究所 微型飞行时间质谱在线样品富集装置
CN101303330A (zh) * 2007-05-09 2008-11-12 中国科学院大连化学物理研究所 一种在线气体分析质谱中的膜进样样品富集装置
CN102208323A (zh) * 2011-04-27 2011-10-05 复旦大学 一种电化学与电喷雾电离质谱联用的装置和方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101206204A (zh) * 2006-12-22 2008-06-25 中国科学院大连化学物理研究所 微型飞行时间质谱在线样品富集装置
CN101303330A (zh) * 2007-05-09 2008-11-12 中国科学院大连化学物理研究所 一种在线气体分析质谱中的膜进样样品富集装置
CN102208323A (zh) * 2011-04-27 2011-10-05 复旦大学 一种电化学与电喷雾电离质谱联用的装置和方法

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