WO2015055128A1 - 一种大气压接口的离子源系统以及质谱仪 - Google Patents

一种大气压接口的离子源系统以及质谱仪 Download PDF

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WO2015055128A1
WO2015055128A1 PCT/CN2014/088733 CN2014088733W WO2015055128A1 WO 2015055128 A1 WO2015055128 A1 WO 2015055128A1 CN 2014088733 W CN2014088733 W CN 2014088733W WO 2015055128 A1 WO2015055128 A1 WO 2015055128A1
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ion source
atmospheric pressure
vacuum
mass spectrometer
ion
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PCT/CN2014/088733
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English (en)
French (fr)
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徐伟
卞存娟
翟雁冰
方向
熊行创
江游
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北京理工大学
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Priority to US15/029,398 priority Critical patent/US20160268115A1/en
Publication of WO2015055128A1 publication Critical patent/WO2015055128A1/zh

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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
    • H01J49/10—Ion sources; Ion guns
    • H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
    • H01J49/165—Electrospray ionisation
    • 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
    • H01J49/107—Arrangements for using several ion sources

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  • the invention relates to the field of mass spectrometry, in particular to an ion source system of an atmospheric pressure interface and a mass spectrometer.
  • Mass spectrometry is an analytical method for separating and detecting compounds at different mass-to-charge ratios (m/z) to achieve composition and structure identification.
  • Mass spectrometry is a biochemical analysis technology with high sensitivity and high selectivity. It has been widely used in academic research, industrial product development, legal identification, and supervision as a qualitative and quantitative chemical analysis method. In recent years, especially after major scientific and social events such as the anti-terrorism chemical war crisis, food, environmental safety and outer space exploration, the demand for on-site chemical analysis in China and the world has surged.
  • Ion sources operating at atmospheric pressure have the convenience of sample switching, and can be flexibly combined with various forms of mass analyzers as relatively independent modular ion sources. Used, it is getting more and more attention.
  • vacuum ion sources such as EI, CI, etc.
  • atmospheric pressure ion source mass spectrometers have low transmission efficiency due to the need to achieve atmospheric pressure to vacuum transition. It has been reported that the ion transport efficiency between the electrospray ionization source and the mass spectrometer is only 0.01% to 0.1%, while the atmospheric pressure matrix assisted laser decomposed ionization source has a lower transmission efficiency.
  • the atmospheric pressure interface When combined with an atmospheric pressure ion source, the atmospheric pressure interface has two major effects in the mass spectrometer: 1) current limiting; 2) ion transport.
  • Existing ion mass analyzers ion traps, time-of-flight, etc.
  • the atmospheric pressure interface needs to effectively limit the amount of intake air from the mass spectrometer. Therefore, small-aperture (125-1000 ⁇ m) capillary and cone-shaped current limiting devices are widely used in mass spectrometer atmospheric interface design.
  • the current limiting device also greatly limits the ion transmission efficiency while limiting the amount of intake air.
  • the overall transport efficiency of the ions depends on the ion collection efficiency from the ion source to the mass spectrometer inlet and the ion transport efficiency from the mass spectrometer inlet to the mass analyzer.
  • the small-aperture current limiting device limits the effective collection area of ions due to its size limitation; when the ions enter the current limiting device, the Coulomb interaction between the ions drives the ions to diffuse outward, resulting in the second loss of ions;
  • the ions of the flow device again experience a supersonic expansion effect caused by a high gas pressure difference at their outlet, causing the ion beam to further defocus.
  • miniaturized mass spectrometers have two ways of ionization: one is internal ionization, and the internal ionized vacuum ion source can only be used for gaseous samples. For liquid or solid samples, it must be gasified, but The gasification process is liable to cause damage to the structure of the material, so that accurate analysis results cannot be obtained. Second, external ionization, due to the aforementioned ion transport efficiency and vacuum requirements, there are very few miniaturized mass spectrometers for external ionization.
  • the open-type atmospheric pressure ion source combined with the miniaturized mass spectrometer is a Mini11 mass spectrometer based on Discrete Atmospheric Pressure Interface (DAPI) developed by Purdue University in 2008.
  • DAPI Discrete Atmospheric Pressure Interface
  • this type of mass spectrometer can only guarantee the vacuum degree.
  • Continuous injection the injection time is short, about 8ms, the continuous injection detection method can not be realized, and the scanning speed of the instrument is also reduced.
  • an object of the present invention is to provide a ion source system.
  • Ion source system for atmospheric pressure interface is sought, and an object of the present invention.
  • Another object of the present invention is to provide a mass spectrometer.
  • the ion source system of the atmospheric pressure interface provided by the present invention comprises an atmospheric pressure ion source, wherein a vacuum ion source is connected downstream of the atmospheric pressure ion source.
  • the atmospheric pressure ion source and the vacuum ion source are connected by a capillary or a tapered hole.
  • the capillary is selected from the group consisting of capillaries having an inner diameter of 50 to 250 ⁇ m.
  • the atmospheric pressure ion source is an electrospray ion source (ESI), a nano-electrospray ion source (nano-ESI), an atmospheric pressure chemical ionization source (APCI), a desorption electrospray ion source (DESI) or Low temperature plasma ion source (LTP).
  • ESI electrospray ion source
  • nano-ESI nano-electrospray ion source
  • APCI atmospheric pressure chemical ionization source
  • DESI desorption electrospray ion source
  • LTP Low temperature plasma ion source
  • the vacuum ion source is an electron impact ion source (EI), a chemical ionization ion source (CI), a glow discharge electron impact ion source (GDEI), an optical ion source, a plasma discharge ionization source or an ultraviolet Lamp (UV) ionization source.
  • EI electron impact ion source
  • CI chemical ionization ion source
  • GDEI glow discharge electron impact ion source
  • UV ultraviolet Lamp
  • the mass spectrometer provided by the present invention comprises an ion source and a vacuum chamber, wherein the ion source adopts the ion source system according to any one of the above technical solutions.
  • the vacuum ion source in the ion source system may be disposed in a vacuum chamber of the mass spectrometer.
  • the vacuum ion source in the ion source system may also be separately disposed in another vacuum chamber, and the vacuum chamber is connected to the vacuum chamber of the mass spectrometer through a capillary or a tapered hole.
  • the capillary is selected from the group consisting of capillaries having an inner diameter of 50 to 250 ⁇ m.
  • the ion source system and the corresponding mass spectrometer provided by the invention effectively combine the atmospheric pressure ion source and the vacuum ion source for the first time, and the injection sample is ionized twice by two ion sources in sequence, which has the following advantages:
  • the atmospheric pressure ion source is used as the primary ionization ion source, and can be applied to various forms of detection samples such as gas and solid, and has wider applicability.
  • the mass chamber vacuum chamber is ensured due to the current limiting action of the atmospheric pressure ion source
  • the stability of the vacuum in the body, and, due to the significant improvement of the ion transport efficiency, the low-power vacuum pump can meet the vacuum requirements of the mass spectrometer, and the continuous injection can be realized, thereby improving the scanning speed of the instrument, and is particularly suitable for miniaturization.
  • the mass spectrometer of the present invention can be obtained without extensive adjustment of the structure on the basis of the existing mass spectrometer, and is easy to manufacture, and has broad application prospects.
  • FIG. 1 is a schematic structural view of a mass spectrometer according to a second embodiment of the present invention.
  • FIG. 2 is a schematic structural view of a mass spectrometer according to a third embodiment of the present invention.
  • the reference numerals are as follows: 1. atmospheric pressure ion source; 2. vacuum ion source; 3, 4. vacuum chamber; 5. ion mass analyzer; 6. detector; 7. capillary; 8. cone hole; 10. Vacuum pump.
  • a first embodiment of the present invention provides an atmospheric pressure interface ion source system comprising an atmospheric pressure ion source and a vacuum ion source, wherein the vacuum ion source is disposed downstream of the atmospheric pressure ion source.
  • the sample to be tested is injected from one end of the atmospheric pressure ion source, firstly ionized by the atmospheric pressure ion source, and then enters the vacuum ion source, and enters the vacuum ion source due to charge loss during atmospheric pressure transition to vacuum.
  • the sample contains charged ions and uncharged molecules, and a second ionization by a vacuum ion source results in a sample that is almost completely ionized.
  • the atmospheric pressure ion source and the vacuum ion source are connected by a capillary or a tapered hole.
  • the capillary tube may be selected from a capillary tube having an inner diameter of 50 to 250 ⁇ m.
  • the atmospheric pressure ion source may be any existing atmospheric pressure ion source, including but not limited to an electrospray ion source, a nano-upgraded electrospray ion source, an atmospheric pressure chemical ionization source, a desorption electrospray ion source, and a low temperature. Plasma ion source, etc.
  • the vacuum ion source may be any existing vacuum ion source, including but not limited to an electron bombardment ion source, a chemical ionization ion source, a glow discharge electron bombardment ion source, an optical ion source, and a plasma discharge. Ionization source, ultraviolet lamp ionization source, etc.
  • a second embodiment of the present invention provides a mass spectrometer.
  • the atmospheric pressure ion source mass spectrometer includes an atmospheric pressure ion source 1 and a vacuum chamber 3, and an ion mass analyzer 5 is disposed in the vacuum chamber 3. , detector 6, etc.
  • the analysis and detection device, the vacuum degree of the vacuum chamber 3 is provided by the low-power vacuum pump 10, and in the vacuum chamber 3, a vacuum ion source 2 is also provided, through the capillary 7 (which may also be a tapered hole) and the atmospheric pressure ion source 1 Connected.
  • the capillary tube may be selected from a capillary tube having an inner diameter of 50 to 250 ⁇ m.
  • the atmospheric pressure ion source may be any existing atmospheric pressure ion source, including but not limited to an electrospray ion source, a nano-upgraded electrospray ion source, an atmospheric pressure chemical ionization source, a desorption electrospray ion source, and a low temperature. Plasma ion source, etc.
  • the vacuum ion source may be any existing vacuum ion source, including but not limited to an electron bombardment ion source, a chemical ionization ion source, a glow discharge electron bombardment ion source, an optical ion source, and a plasma discharge. Ionization source, ultraviolet lamp ionization source, etc.
  • the sample When the sample is detected by the above mass spectrometer, the sample first enters the atmospheric pressure ion source 1 for the first ionization from the inlet, and the obtained ions enter the vacuum chamber 3 through the atmospheric pressure interface capillary 7, and some ion charges are lost at this time. However, the sample molecules still exist, and the ions and molecules entering the vacuum chamber 3 enter the vacuum ion source 2, in which the second ionization is performed, and the ions obtained after the second ionization are sequentially entered into the mass analyzer 5 and the detector. 6 and so on for analysis and testing.
  • a third embodiment of the present invention provides an atmospheric pressure ion source mass spectrometer.
  • the atmospheric pressure ion source mass spectrometer includes an atmospheric pressure ion source 1 and a vacuum chamber 3, and an ion mass is provided in the vacuum chamber 3.
  • Conventional analysis and detection device such as analyzer 5, detector 6, etc.
  • the vacuum degree of the vacuum chamber 3 is provided by the low-power mechanical vacuum pump 10, and a vacuum ion source 2 is further disposed between the atmospheric pressure ion source 1 and the vacuum chamber 3.
  • the vacuum ion source 2 is connected to the atmospheric pressure ion source 1 through a capillary 7 (which may also be a tapered hole).
  • the vacuum ion source 2 is disposed in a separate vacuum chamber 4, and the vacuum chamber 4 passes through a tapered hole 8 (which may also be a capillary tube).
  • the vacuum chambers 3 are connected, and the vacuum of the vacuum chamber 4 is supplied by a low-power vacuum pump 9.
  • the capillary tube may be selected from a capillary tube having an inner diameter of 50 to 250 ⁇ m.
  • the atmospheric pressure ion source may be any existing atmospheric pressure ion source, including but not limited to an electrospray ion source, a nano-upgraded electrospray ion source, an atmospheric pressure chemical ionization source, a desorption electrospray ion source, and a low temperature. Plasma ion source, etc.
  • the vacuum ion source may be any existing vacuum ion source, including but not limited to an electron bombardment ion source, a chemical ionization ion source, a glow discharge electron bombardment ion source, an optical ion source, and a plasma discharge. Ionization source, ultraviolet lamp ionization source, etc.
  • the sample When the sample is detected by the mass spectrometer described above, the sample first enters the atmospheric pressure ion source 1 for the first ionization from the inlet, and the resulting ions enter the vacuum chamber 4 through the atmospheric pressure interface capillary 7, and there is a partial ion charge. Lost, but the sample molecules are still present, ions and molecules entering the vacuum chamber 4 enter the vacuum ion source 2 where a second ionization takes place. The ions obtained after the second ionization are sequentially introduced into the mass analyzer 5 and the detector 6 of the vacuum chamber 3 for analysis and detection.
  • the mass spectrometer shown in Figure 1 is used, wherein the atmospheric pressure ion source is a Nano-ESI ion source, and the vacuum ion
  • the source is a plasma discharge device, and the interface between the atmospheric pressure ion source and the vacuum ion source is a stainless steel capillary having an inner diameter of 125 ⁇ m.
  • the vacuum in the vacuum chamber ranges from 1 to 10 Torr, and the vacuum degree can be satisfied only by a small vacuum pump.
  • the sample to be tested After the sample to be tested is injected, it is ionized for the first time at the atmospheric pressure ion source, and then enters the plasma discharge device through the stainless steel capillary tube for secondary ionization, and then detected.
  • the samples to be tested are rhodamine b (A) and reserpine (B). Since the samples to be tested are solid, they cannot be detected by a conventional vacuum ion source mass spectrometer.
  • the resulting spectrum is shown in FIG.
  • the plasma discharge device When detected by the mass spectrometer of the present invention, the resulting spectrum is shown in FIG.
  • the plasma discharge device When the plasma discharge device is not powered, it is equivalent to ionizing the sample to be tested by the external atmospheric pressure ion source, and no phenomenon can be observed, indicating that the ion transmission efficiency of the atmospheric pressure interface ion source is extremely low, and almost no ion is transmitted to the analysis and detection. The device, so the corresponding peak is not observed on the spectrum.
  • the mass spectrometer of the present invention for secondary ionization, the ion transport efficiency can be significantly improved at a lower vacuum, and it can be used to detect samples other than gaseous.

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Abstract

一种大气压接口的离子源系统，包括大气压离子源（1），大气压离子源（1）下游连接有真空离子源（2）。一种质谱仪，采用该离子源系统作为离子源。该离子源系统采用了大气压离子源（1）和真空离子源（2）的组合，可适用于多种形态的检测样品，可将待测样品进行二次离子化，保证了离子的传输效率。该质谱仪能明显提高离子的传输效率，实现了连续进样检测，提高了仪器的扫描速度，特别适用于小型化质谱仪。

Description

一种大气压接口的离子源系统以及质谱仪 技术领域
本发明涉及质谱分析领域，具体涉及一种大气压接口的离子源系统以及质谱仪。
背景技术
质谱分析法(mass spectrometry)是将化合物按不同质荷比(m/z)进行分离检测、实现成分和结构鉴别的一种分析方法。质谱技术是一项具有高灵敏度和高选择性的生物化学分析技术，作为一种定性和定量的化学分析手段已经被广泛用于学术研究、工业产品研发、法律鉴定、监管等领域。近些年来，尤其是在反恐化学战危机、食品、环境安全和外太空探索等重大科学、社会事件以后，我国以及世界各国对现场化学分析的需求激增。
工作在大气压下的离子源(如nano-ESI、ESI、APCI、DESI、LTP等)具有样品切换方便的特点，并且作为相对独立的模块化离子源可以灵活地与各种形式的质量分析器联用，因而越来越受到重视。然而，与真空离子源(如EI、CI等)相比，大气压离子源质谱仪器由于需要实现大气压向真空过渡，所以离子的传输效率较低。有报道指出，电喷雾电离源与质谱分析器间的离子传输效率仅为0.01％～0.1％，而大气压基体辅助激光解析电离源的传输效率更低。
与大气压离子源相结合时，大气压接口在质谱仪中有两大影响：1)限流；2)离子传输。现有的离子质量分析器(离子阱、飞行时间等)只能在高真空条件下工作，为了保持质谱仪内部的高真空度，大气压接口需要有效地限制质谱仪的进气量。因此小孔径的(125-1000μm)毛细管与锥孔等限流设备被广泛应用在质谱仪大气压接口设计中。但是限流设备在限制进气量的同时也极大地限制了离子的传输效率。离子的总体传输效率取决于从离子源到质谱仪入口的离子采集效率和从质谱仪入口到质量分析器的离子传输效率。首先小孔径限流设备由于其尺寸的限制局限了离子的有效采集面积；当离子进入限流设备以后，离子间的库伦作用力驱使离子向外扩散，造成了离子的第二次损耗；通过限流设备的离子在其出口又经历了由高气压差产生的超音速膨胀效应，导致离子束进一步散焦。
如果要提高离子传输率，须采用大功率真空系统保证真空腔体内具有足够的真空度，但这样显然无法满足小型化质谱仪的需要。小型质谱仪需要小型化、低功耗的真空系统，所以其大气压接口需要具备更强的限流功能，也就是更小孔径的限流设备，这不可避免的降低了离子的采集面积与传输效率，其成为限制大气压离子源的小型化质谱仪发展的重要因素。
目前为止，小型化质谱仪有两种离子化方式：一是内部离子化，内部离子化的真空离子源只能用于气态样品，对于液态或固态样品而言，须将其进行气化，但气化过程易对物质的结构造成破坏，从而无法得到准确的分析检测结果。二是外部离子化，由于前述的离子传输效率以及真空要求的原因，外部离子化的小型化质谱仪极少。目前为止唯一可以与 开放式大气压离子源相结合的小型化质谱仪是2008年普渡大学研制的基于离散大气压接口(DAPI)的Mini11质谱仪，但是，该类型的质谱仪为保证其真空度要求，只能以不连续的方式进样，进样时间较短，大约为8ms左右，无法实现连续进样的检测方式，仪器的扫描速度也因此降低。
发明内容
为克服现有大气压接口离子源质谱仪离子传输效率低、真空离子源质谱仪受样品形态限制等一系列技术缺陷，寻找一种适用性更广的离子源系统，本发明的目的是提供一种大气压接口的离子源系统。
本发明的另一目的是提供一种质谱仪。
本发明提供的大气压接口的离子源系统，包括大气压离子源，其中，所述大气压离子源下游连接有真空离子源。
上述离子源系统中，所述大气压离子源和所述真空离子源通过毛细管或锥孔相连接。
优选地，所述毛细管选自内径为50～250μm的毛细管。
上述离子源系统中，所述大气压离子源为电喷雾离子源(ESI)、纳升级电喷雾离子源(nano-ESI)、大气压化学电离源(APCI)、解吸附电喷雾离子源(DESI)或低温等离子体离子源(LTP)。
上述离子源系统中，所述真空离子源为电子轰击离子源(EI)、化学电离离子源(CI)、辉光放电电子轰击离子源(GDEI)、光学离子源、等离子体放电电离源或紫外灯(UV)电离源。
本发明提供的质谱仪，包括离子源以及真空腔体，其中，所述离子源采用以上技术方案任一项所述的离子源系统。
上述质谱仪中，所述离子源系统中的真空离子源可设置于所述质谱仪的真空腔体内。
上述质谱仪中，所述离子源系统中的真空离子源还可单独设置于另一真空腔体内，此真空腔体通过毛细管或锥孔与所述质谱仪的真空腔体相连。
优选地，所述毛细管选自内径为50～250μm的毛细管。
本发明提供的离子源系统以及相应的质谱仪首次将大气压离子源和真空离子源进行了有效地结合，进样样品通过两种离子源依次进行两次离子化，具有以下优点：
(1)采用大气压离子源作为一次离子化离子源，可适用于气态、固态等多种形态的检测样品，适用性更加广泛。
(2)通过真空离子源的二次离子化，可增加最终进入分析、检测装置中的离子数量，从而提高了离子传输效率。
(3)本发明的质谱仪中，由于大气压离子源的限流作用，保证了质谱仪真空腔 体内真空度的稳定性，而且，由于离子传输效率的明显提高，采用小功率真空泵即可满足质谱仪的真空度要求，可实现连续进样，从而可提高仪器的扫描速度，特别适用于小型化质谱仪。
(4)本发明的质谱仪在现有质谱仪的基础上，无须在结构上进行大幅度调整即可得到，易于制造，具有广阔的应用前景。
附图说明
图1为本发明的第二种实施方式提供的质谱仪结构示意图；
图2为本发明的第三种实施方式提供的质谱仪结构示意图；
图3为本发明实施例所得的检测谱图；
其中，附图标记说明如下：1.大气压离子源；2.真空离子源；3、4.真空腔体；5.离子质量分析器；6.检测器；7.毛细管；8.锥孔；9、10.真空泵。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面结合附图描述本发明的示例性实施例的技术方案。显然，所描述的实施例只是本发明的一部分实施例，而不是全部的实施例。所描述的实施例仅用于图示说明，而不是对本发明范围的限制。基于本发明的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明的第一种实施方式提供了一种大气压接口的离子源系统，该离子源系统包括一大气压离子源和一真空离子源，其中，真空离子源设置在大气压离子源的下游。
使用该离子源系统时，待测样品由大气压离子源一端进样，首先通过大气压离子源进行第一次离子化，然后进入真空离子源，由于大气压向真空过渡时的电荷损失，进入真空离子源的样品中包含带有电荷的离子和不带电荷的分子，通过真空离子源进行第二次离子化，可得到几乎完全离子化的待测样品。
作为优选的技术方案，大气压离子源和真空离子源之间通过毛细管或锥孔连接。
作为优选的技术方案，毛细管可选自内径为50～250μm的毛细管。
作为优选的技术方案，大气压离子源可以为现有的任意一种大气压离子源，包括但不限于电喷雾离子源、纳升级电喷雾离子源、大气压化学电离源、解吸附电喷雾离子源、低温等离子体离子源等。
作为优选的技术方案，真空离子源可以为现有的任意一种真空离子源，包括但不限于电子轰击离子源、化学电离离子源、辉光放电电子轰击离子源、光学离子源、等离子体放电电离源、紫外灯电离源等。
本发明的第二种实施方式提供了一种质谱仪，如图1所示，该大气压离子源质谱仪包括大气压离子源1和真空腔体3，真空腔体3内设有离子质量分析器5、检测器6等常规 的分析、检测装置，真空腔体3的真空度由小功率真空泵10提供，在真空腔体3内，还设有真空离子源2，通过毛细管7(也可为锥孔)与大气压离子源1相连。
作为优选的技术方案，毛细管可选自内径为50～250μm的毛细管。
作为优选的技术方案，大气压离子源可以为现有的任意一种大气压离子源，包括但不限于电喷雾离子源、纳升级电喷雾离子源、大气压化学电离源、解吸附电喷雾离子源、低温等离子体离子源等。
作为优选的技术方案，真空离子源可以为现有的任意一种真空离子源，包括但不限于电子轰击离子源、化学电离离子源、辉光放电电子轰击离子源、光学离子源、等离子体放电电离源、紫外灯电离源等。
采用上述质谱仪检测样品时，样品从进样口首先进入大气压离子源1中进行第一次离子化，所得离子通过大气压接口毛细管7进入真空腔体3内，此时会有部分离子电荷丢失，但样品分子依然存在，进入真空腔体3的离子和分子进入真空离子源2中，在其中进行第二次离子化，第二次离子化后得到的离子再依次进入质量分析器5、检测器6等进行分析、检测。
本发明的第三种实施方式提供了一种大气压离子源质谱仪，如图2所示，该大气压离子源质谱仪包括大气压离子源1和真空腔体3，真空腔体3内设有离子质量分析器5、检测器6等常规的分析、检测装置，真空腔体3的真空度由小功率机械真空泵10提供，在大气压离子源1和真空腔体3之间还设有真空离子源2，真空离子源2通过毛细管7(也可为锥孔)与大气压离子源1相连，真空离子源2设置于单独的真空腔体4内，真空腔体4通过锥孔8(也可为毛细管)与真空腔体3相连，真空腔体4的真空度由小功率真空泵9提供。
作为优选的技术方案，毛细管可选自内径为50～250μm的毛细管。
作为优选的技术方案，大气压离子源可以为现有的任意一种大气压离子源，包括但不限于电喷雾离子源、纳升级电喷雾离子源、大气压化学电离源、解吸附电喷雾离子源、低温等离子体离子源等。
作为优选的技术方案，真空离子源可以为现有的任意一种真空离子源，包括但不限于电子轰击离子源、化学电离离子源、辉光放电电子轰击离子源、光学离子源、等离子体放电电离源、紫外灯电离源等。
采用上所述质谱仪检测样品时，样品从进样口首先进入大气压离子源1中进行第一次离子化，所得离子通过大气压接口毛细管7进入真空腔体4内，此时会有部分离子电荷丢失，但样品分子依然存在，进入真空腔体4的离子和分子进入真空离子源2中，在其中进行第二次离子化。第二次离子化后得到的离子再依次进入真空腔体3的质量分析器5、检测器6等进行分析、检测。
实施例
采用如图1所示的质谱仪，其中，大气压离子源为Nano-ESI离子源，真空离子 源为等离子体放电装置，大气压离子源和真空离子源之间的接口为内径为125μm的不锈钢毛细管，真空腔体内的真空范围为1-10Torr，仅由小型真空泵即可满足上述真空度要求。
待测样品进样后在大气压离子源进行第一次离子化，之后再通过不锈钢毛细管进入等离子体放电装置，进行二次离子化，然后进行检测。待测样品为罗丹明b(A)和利血平(B)，由于待测样品均为固体，故无法采用常规的真空离子源质谱仪进行检测。
采用本发明的质谱仪检测时，所得谱图如图3所示。当等离子体放电装置不加电时，即相当于单纯靠外部大气压离子源离子化待测样品，不能观察到任何现象，说明大气压接口离子源的离子传输效率极低，几乎没有离子传输至分析检测装置，故谱图上观测不到相应的峰。采用本发明的质谱仪进行二次离子化，在较低的真空度下，离子传输效率也能明显提高，而且可用于检测气态以外的样品。
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。

Claims (9)

  1. 一种大气压接口的离子源系统，包括大气压离子源，其特征在于，所述大气压离子源下游连接有真空离子源。
  2. 根据权利要求1所述的离子源系统，其特征在于，所述大气压离子源和所述真空离子源通过毛细管或锥孔相连接。
  3. 根据权利要求2所述的离子源系统，其特征在于，所述毛细管选自内径为50～250μm的毛细管。
  4. 根据权利要求1-3任一项所述的离子源系统，其特征在于，所述大气压离子源为电喷雾离子源、纳升级电喷雾离子源、大气压化学电离源、解吸附电喷雾离子源或低温等离子体离子源。
  5. 根据权利要求1-3任一项所述的离子源系统，其特征在于，所述真空离子源为电子轰击离子源、化学电离离子源、辉光放电电子轰击离子源、光学离子源、等离子体放电电离源或紫外灯电离源。
  6. 一种质谱仪，包括离子源以及真空腔体，其特征在于，所述离子源采用权利要求1-5任一项所述的离子源系统。
  7. 根据权利要求6所述的质谱仪，其特征在于，所述离子源系统中的真空离子源设置于所述质谱仪的真空腔体内。
  8. 根据权利要求6所述的质谱仪，其特征在于，所述离子源系统中的真空离子源单独设置于另一真空腔体内，此真空腔体通过毛细管或锥孔与所述质谱仪的真空腔体相连。
  9. 根据权利要求8所述的质谱仪，其特征在于，所述毛细管选自内径为50～250μm的毛细管。
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