WO2015176567A1 - 大气压接口装置以及质谱仪 - Google Patents

大气压接口装置以及质谱仪 Download PDF

Info

Publication number
WO2015176567A1
WO2015176567A1 PCT/CN2015/073158 CN2015073158W WO2015176567A1 WO 2015176567 A1 WO2015176567 A1 WO 2015176567A1 CN 2015073158 W CN2015073158 W CN 2015073158W WO 2015176567 A1 WO2015176567 A1 WO 2015176567A1
Authority
WO
WIPO (PCT)
Prior art keywords
atmospheric pressure
hole
mass spectrometer
interface device
hole portion
Prior art date
Application number
PCT/CN2015/073158
Other languages
English (en)
French (fr)
Inventor
徐伟
韦永政
卞存娟
方向
Original Assignee
北京理工大学
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 北京理工大学 filed Critical 北京理工大学
Publication of WO2015176567A1 publication Critical patent/WO2015176567A1/zh

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • 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

Definitions

  • the present invention relates to the field of mass spectrometry, and more particularly to an atmospheric pressure interface device for a mass spectrometer.
  • Mass spectrometry is an analytical method for separating and detecting compounds according to different mass-to-charge ratios to achieve composition and structure identification. Mass spectrometry has been widely used in biological and chemical analysis as a qualitative and quantitative chemical analysis method because of its high specificity and sensitivity.
  • an ion source such as a nano-ESI nanoliter electrospray ionization source, an ESI electrospray ionization source, an APCI atmospheric pressure chemical ionization source, etc.
  • an excitation source for the sample to be analyzed.
  • These ion sources are characterized by convenient sample switching and are increasingly used as a relatively independent modular ion source for flexible use with a wide range of mass analyzers.
  • mass spectrometers based on atmospheric ion sources have low ion transport efficiency due to the need to achieve atmospheric pressure to vacuum transition.
  • the ion transport efficiency between the electrospray ionization source and the mass spectrometer is only 0.01% to 0.1%, while the other atmospheric matrix assisted laser decomposed ionization source is less efficient.
  • the atmospheric pressure interface When combined with an atmospheric pressure ion source, the atmospheric pressure interface creates two effects in the mass spectrometer, namely current limiting and efficient ion transport.
  • Existing ion mass analyzers such as ion traps, can only operate under high vacuum conditions.
  • the atmospheric pressure interface needs to effectively limit the amount of gas introduced by the mass spectrometer. Therefore, small-aperture (125 to 1000 ⁇ m) capillary and other current limiting devices are widely used in mass spectrometer atmospheric pressure 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 on the ion transport efficiency from the mass spectrometer inlet to the mass analyzer.
  • Small aperture current limiting devices have limited the effective collection area of ions due to their size limitations. When the ions enter the current limiting device, the Coulomb interaction between the ions drives the ions to diffuse outward, causing a second loss of ions. The ions passing through the current limiting device experience a supersonic expansion effect at the outlet of the mass spectrometer caused by the high gas pressure difference, causing the ion beam to further defocus.
  • U.S. Patent No. 8,304,718 B2 proposes a mass spectrometer based on a discrete atmospheric interface which is one of the few miniaturized mass spectrometers that can be combined with an open ion source.
  • discontinuous injection mode Next, the instantaneous injection volume is close to the injection volume of a large commercial mass spectrometer, thus ensuring the single transmission efficiency of ions.
  • the injection path of the atmospheric pressure interface is sealed by a section of silicone rubber tube, and the rubber tube is easily deteriorated due to the pressure of the solenoid valve and the corrosion of the sample and the oxidation of the air.
  • the injection path of the interface includes a rubber tube and two small-caliber capillary tubes with a length of about 10 cm. A considerable part of the ions are lost in the path during the transmission process, and the efficiency of ion transport is low.
  • the technical problem to be solved by the present invention is that when the open ion source emits ions to the mass analyzer, the ion transport efficiency is low, and the atmospheric pressure injection interface of the mass spectrometer is not durable.
  • the present invention provides an atmospheric pressure interface device, comprising an interface end plate and a sealing device, wherein the interface end plate is provided with a through hole, the through hole includes a tapered hole portion and a column hole portion, and the tapered hole portion has a conical cylindrical shape a larger end of the opening is open to a surface of the interface end plate and corresponds to the sealing device, the column hole portion has a cylindrical shape, one end of which is open on the other surface of the interface end plate, and the other One end is connected to one end of the tapered hole portion having a small aperture, a center line of the tapered hole portion is coincident with a center line of the column hole portion, and the sealing device is disposed outside the interface end plate and can be opened and closed The through hole is sealed.
  • the interface end plate has a thickness of 5 to 30 mm at the opening.
  • the taper hole portion has a maximum pore diameter of 1 to 10 mm
  • the column hole portion has a pore diameter of 100 to 1000 ⁇ m
  • the taper hole portion and the column hole portion have a hole depth ratio of 1:10 to 10 :1.
  • the interface end plate is made of stainless steel.
  • the sealing device includes a telescopic rod and a driving mechanism for driving the telescopic rod to retract, the end of the telescopic rod is fixed with a sealing head and corresponds to the position of the through hole, and when the telescopic rod is extended The sealing head seals the through hole.
  • the portion of the sealing head corresponding to the through hole is hemispherical.
  • the portion of the sealing head that is remote from the through hole is cylindrical.
  • the sealing head is made of polytetrafluoroethylene or polyetheretherketone.
  • the atmospheric pressure interface device further includes a housing having a vacuum chamber, an opening is formed in an end wall of the housing, and a surface of the interface end plate on which the post hole portion is opened is fixed An outer surface of the end wall, the post hole portion communicates with the vacuum chamber via the opening.
  • the technical solution proposed by the present invention further includes: providing a mass spectrometer comprising an ion source, a mass analyzer, a detector, and the atmospheric pressure interface device, wherein the ion source is disposed outside the casing, The mass analyzer and the detector are disposed in the vacuum chamber.
  • the ion source discharges a distance between one end of the ion and the interface end plate of 1 to 10 mm.
  • the mass analyzer is an ion trap
  • the ion trap front electrode plate and the ion trap rear electrode plate are respectively disposed at two ends of the ion trap
  • the ion trap front electrode plate is provided with an opening.
  • the through hole corresponds to a position of the opening.
  • the distance between the opening and the through hole is 1 to 5 mm.
  • the mass spectrometer further includes a vacuum pump system for evacuating the vacuum chamber.
  • the atmospheric pressure interface device and the mass spectrometer proposed by the present invention have the advantages and advantages that the atmospheric pressure interface device proposed by the present invention avoids the use of an easily aging silicone rubber tube as a sampling passage thereof, and does not have a silicone rubber tube.
  • the aging becomes sticky, which leads to uneven injection or even inability to inject.
  • the tapered hole portion of the through hole and the structural design of the column hole portion ensure the ion transmission rate.
  • the tapered hole structure of the through hole can simultaneously receive ions released by a plurality of ion sources, increasing the intensity of the peak.
  • the through hole of the atmospheric pressure interface device can be sealed by a sealing device to ensure vacuum sealing of the vacuum chamber.
  • the mass spectrometer proposed by the invention is easy to manufacture and has broad application prospects.
  • FIG. 1 is a schematic structural view of an embodiment of a mass spectrometer according to the present invention.
  • Figure 2 is an enlarged schematic view of a portion A of Figure 1, showing the structure of the through hole of the atmospheric pressure interface device of the present invention
  • Figure 5 is a mass spectroscopic image of a third use example of the mass spectrometer proposed by the present invention.
  • Fig. 7 is a mass spectroscopic image of a fifth use example of the mass spectrometer proposed by the present invention.
  • the atmospheric pressure interface device proposed by the present invention mainly comprises an interface end plate 1, a sealing device 3, and a housing 2 having a vacuum chamber 4.
  • the interface end plate 1 is provided with a through hole 10.
  • the through hole 10 includes a tapered hole portion 100 and a column hole portion 101, wherein a surface on which the tapered hole portion 100 is opened is an outer surface of the interface end plate 1, and the other surface on which the column hole portion 102 is opened is the interface end plate 1.
  • the tapered hole portion 100 has a conical cylindrical shape, and a larger end of the opening thereof opens to the outer surface of the interface end plate 1 and corresponds to the sealing device 3.
  • the column hole portion 101 has a cylindrical shape, one end of which is open to the inner surface of the interface end plate 1, and the other end of which is connected to the smaller end of the taper hole portion 100, and the inner surface of the interface end plate 1 is fixed to the housing. 2 the surface of the end wall 20.
  • the center line of the tapered hole portion 100 coincides with the center line of the column hole portion 101.
  • the thickness of the opening end hole 10 of the interface end plate 1 is preferably 5 to 30 mm.
  • the maximum pore diameter of the tapered hole portion 100 is preferably 1 to 10 mm
  • the pore diameter of the column hole portion 101 is preferably 100 to 1000 ⁇ m
  • the ratio of the pore depth of the tapered hole portion 100 to the column hole portion 101 is preferably 1:10 to 10:1.
  • the dimensions of the interface end plate 1, the tapered hole portion 100, and the column hole portion 101 are not unique, and can be flexibly selected according to actual needs and the time size of the structure such as the interface end plate 1.
  • the thickness of the through hole 10 at the interface end plate 1 is 12 mm, that is, the overall hole depth of the through hole 10 is 12 mm, wherein the maximum aperture of the tapered hole portion 100 is 5 mm, and the minimum aperture of the tapered hole portion 100 is
  • the hole diameter of the column hole portion 101 is 500 ⁇ m
  • the hole depth ratio of the taper hole portion 100 to the column hole portion 101 is 2:1, that is, the hole depth of the taper hole portion 100 is 8 mm, and the hole depth of the column hole portion 101 is 4 mm.
  • the sealing device 3 is provided on the outer surface side of the interface end plate 1 and can seal the through hole 10 in an openable and closable manner.
  • the sealing device 3 includes a telescopic rod 30 and a driving mechanism 31 for driving the telescopic rod thereof.
  • the end of the telescopic rod 30 is fixed with a sealing head. 32 and corresponds to the position of the through hole 10.
  • the portion of the sealing head 32 corresponding to the through hole 10 is hemispherical, and when the telescopic rod 30 is extended, the sealing head 32 is sealed to the through hole 10.
  • the sealing device 3 is a solenoid valve, and specifically, the modified electromagnetic pinch valve is preferably used, but is not limited thereto.
  • the sealing head 32 is fixed to one end portion of the telescopic rod 30, that is, the sealing head 32 is fixed to the end portion of the telescopic rod 30 that protrudes from the electromagnetic valve.
  • the portion of the sealing head 32 adjacent to the through hole 10 is hemispherical, and the hemispherical sealing head 32 can optimize the sealing effect on the through hole 10. Further, the portion of the sealing head 32 relatively far from the through hole 10 is cylindrical, but is not limited thereto.
  • the material of the sealing head 32 is polyetheretherketone (PEEK), but it is not limited thereto, and the material thereof may be selected from polytetrafluoroethylene or metal aluminum.
  • the housing 2 defines a vacuum chamber 4.
  • An opening 200 is defined in one end wall 20 of the housing 2.
  • the interface end plate 1 is fixed to the outer surface of the end wall 20, and specifically, the inner surface of the interface end plate 1 is fixed to the outer surface of the end wall 20.
  • the column hole portion 101 communicates with the vacuum chamber 4 via the opening 200, that is, the through hole 10 communicates with the vacuum chamber 4.
  • the interface end plate 1 is made of stainless steel, and other materials having high corrosion resistance and wear resistance can be selected for detecting corrosive samples, so that the applicability is more extensive.
  • the interface end plate 1 can also be selected from other materials, such as aluminum, but not limited thereto.
  • the interface end plate 1 can be selected from existing structures, such as a connecting flange, and is not limited thereto.
  • the mass spectrometer proposed by the present invention comprises the atmospheric pressure interface device proposed by the present invention, the ion source 5 disposed outside the casing 2, and the mass analyzer 6 and the detector 7 disposed in the vacuum chamber 4 thereof. .
  • the ion source 5 is selected from atmospheric pressure chemical ionization (APCI), and is suitable for gaseous volatile samples.
  • APCI atmospheric pressure chemical ionization
  • the type of the ion source 5 is not unique, and may be Different samples to be tested may be selected from other types.
  • Nano-Electron Spray Ionization Nano-ESI
  • the number of ion sources 5 is not unique, and a plurality of ion sources 5 can be simultaneously used to simultaneously release ion samples through the through holes 10 to the mass analyzer 6 for enhancing the peak intensity of the mass spectrometer spectrum.
  • the mass analyzer 6 selects an ion trap, and is further preferably a rectangular linear ion trap.
  • the type of the ion trap is not unique, and may be selected according to different samples to be tested or other conditions. Other types. Or parallel other ion guiding devices, such as ion lens, ion funnel, quadrupole, etc., in front of the ion trap.
  • the ion trap front electrode plate 60 and the ion trap rear electrode plate 61 are respectively disposed at two ends of the ion trap, and the ion trap front electrode plate 60 is opened. Opening 600.
  • the distance between one end of the ion source 5 and the interface end plate 1 is 3 mm, and the distance may preferably be 1 to 10 mm, but not limited thereto.
  • the through hole 10 corresponds to the position of the opening 600, and the distance between the two is 2 mm, and the distance may preferably be 1 to 5 mm, but is not limited thereto.
  • the mass spectrometer further includes a vacuum pump system 8 for maintaining the vacuum state of the vacuum chamber 4.
  • the vacuum pump system 8 can be selected from conventional configurations, such as a turbo vacuum pump with a control plate that is in communication with the vacuum chamber 4. Since a trace amount of gas is introduced into the vacuum chamber 4 when the ion sample is injected, the through hole 10 can be sealed by the sealing device 3 after each detection, and then the vacuum chamber 4 is evacuated by the vacuum pump system 8, In order to maintain its vacuum to the required value.
  • the vacuum degree of the vacuum chamber 4 should be kept below 10 -3 Torr, and in the present embodiment, it is preferably 10 -5 Torr, but not limited thereto.
  • the ion source 5 ionizes the sample to be measured and emits sample ions.
  • the sample ions sequentially pass through the tapered hole portion 100 and the column hole portion 101 into the vacuum chamber 7, and the sample ions enter the vacuum chamber 7 and pass through the opening 600 in the ion trap front electrode plate 60 to enter the mass analyzer 6.
  • the mass analyzer 6 separates these sample ions according to the difference in mass-to-charge ratio and sequentially enters the detector 7 for inspection, and finally obtains a mass spectroscopic image.
  • the sample to be tested is N,N-Diethyl-3-methyl benzoyl amide (DEET), and the ionization mode of the DEET sample is selected as APCI, that is, the ion source in the mass spectrometer of the present invention.
  • APCI N,N-Diethyl-3-methyl benzoyl amide
  • 5 use APCI ion source.
  • the mass spectrometry image obtained by the mass spectrometer of the present invention is shown in FIG. 3 (in FIG. 3 to FIG. 7 , the lon intensity is the ion intensity of the ion source releasing ions, and m/z is the ratio of the number of protons to the number of charges, that is, the mass-to-charge ratio. ).
  • the sample to be tested is corrosive Rhodamine B (also known as Rose Red B) at a concentration of 2 ppm, and the ionization mode of the Rhodamine B sample is selected to be Nano-ESI, that is, the present invention
  • the ion source 5 in the mass spectrometer is a Nano-ESI ion source.
  • the mass spectrum image obtained by the mass spectrometer of the present invention is shown in FIG.
  • the sample to be tested is still Rhodamine B, and its concentration is 2 ppm, and the ionization mode of the Rhodamine B sample is selected as Nano-ESI, that is, the ion source 5 in the mass spectrometer of the present invention is selected from Nano-ESI.
  • Ion source 5 and in this use case, the present invention uses two Nano-ESI ion sources to simultaneously release Rhodamine B sample ions.
  • the mass spectrum image obtained by the mass spectrometer of the present invention is shown in Fig. 5.
  • the sample to be tested is a polymer PEG having a concentration of 100 ppm
  • the ionization mode of the PEG sample is selected from Nano-ESI, that is, the ion source 5 in the mass spectrometer of the present invention is a Nano-ESI ion source.
  • the mass spectrum image obtained by the mass spectrometer of the present invention is shown in Fig. 6.
  • the sample to be tested is a peptide MRFA (Met-Arg-Phe-Ala) at a concentration of 20 ppm
  • the ionization mode of the MRFA sample is selected from Nano-ESI, that is, the ion source in the mass spectrometer of the present invention. 5 Use the Nano-ESI ion source.
  • the mass spectrum image obtained by the mass spectrometer of the present invention is shown in FIG.
  • the mass spectrometer proposed by the present invention is used as a mass spectrometer device for a non-continuous injection atmospheric pressure interface, and the atmospheric pressure interface device and the driving mechanism such as the electromagnetic valve do not. It has aging and has certain corrosion resistance, which ensures the consistency of each injection. In addition, after continuous testing, the mass spectrometer works reproducibly. It can also be seen from the third use case and its mass spectrogram image 5 that when the mass spectrometer proposed by the present invention ionizes a test sample simultaneously using a plurality of ion sources 5, the intensity of the peak can be significantly increased.
  • the atmospheric pressure interface device and the mass spectrometer provided by the invention have the following industrial applicability: the atmospheric pressure interface device avoids the use of a silicone rubber tube which is easy to aging as a sampling passage thereof, and does not cause aging and viscosity of the silicone rubber tube, thereby causing the injection. Uneven or even unable to inject.
  • the tapered hole portion of the through hole and the structural design of the column hole portion ensure the ion transmission rate.
  • the tapered hole structure of the through hole can simultaneously receive ions released by a plurality of ion sources, increasing the intensity of the peak.
  • the through hole of the atmospheric pressure interface device can be sealed by a sealing device to ensure vacuum sealing of the vacuum chamber.
  • the mass spectrometer is easy to manufacture and has broad application prospects.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

一种大气压接口装置以及质谱仪。大气压接口装置包括接口端板（1）以及密封装置（3）。接口端板（1）上开设有通孔（10）。通孔（10）包括锥孔部（100）以及柱孔部（101）。锥孔部（100）呈圆锥筒形，其孔径较大一端开口于接口端板（1）的一表面且对应于密封装置（3）。柱孔部（101）呈圆柱筒形，其一端开口于接口端板（1）的另一表面，其另一端连接于锥孔部（100）的孔径较小的一端，锥孔部（100）的中心线与柱孔部（101）的中心线重合。密封装置（3）设于接口端板（1）外侧且可开闭地密封通孔（10）。大气压接口装置保证了离子传输速率，保证了真空腔室（4）的真空密封性。本发明提出的质谱仪易于制造，具有广阔的应用前景。

Description

大气压接口装置以及质谱仪 技术领域
本发明涉及质谱技术领域，特别涉及质谱仪的大气压接口装置。
背景技术
质谱分析法是将化合物按不同质荷比进行分离检测，实现成分和结构鉴别的一种分析方法。质谱技术因其具有的高特异性和灵敏度，作为一种定性和定量的化学分析手段，已经被广泛的用于生物和化学分析等领域。
现有的质谱分析方法中，通常使用工作在大气压下的离子源(如nano-ESI纳升电喷雾电离源、ESI电喷雾电离源、APCI大气压化学电离源等)作为需分析样品的激发源。这类离子源具有样品切换方便的特点，并且作为相对独立的模块化的离子源，其可以灵活地与各类质量分析器联用，因此越来越受到重视。然而，与基于真空离子源的质谱仪器相比，基于大气压离子源的质谱仪器，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。在一些现有的基于ESI的质谱仪器中，电喷雾电离源与质谱分析器间的离子传输效率仅为0.01％至0.1％，而另外一种大气压基质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会产生两方面影响，即限流以及高效离子传输。现有的离子质量分析器，例如离子阱，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至1000μm)毛细管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，同时取决于从质谱仪入口到质量分析器的离子传输效率。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，在质谱仪出口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。
美国专利，专利号US8304718B2，提出一种基于离散大气压接口的质谱仪，这种质谱仪器是少数可与开放式离子源结合的小型化质谱仪之一。其在非连续进样模式 下，瞬间进样量接近大型商用质谱仪的进样量，从而保证了离子的单次传输效率。但是，该质谱仪为保证其在不进样时保持真空度，大气压接口的进样路径上采用一段硅橡胶管进行密封，由于电磁阀压力以及样品的腐蚀和空气的氧化，使得橡胶管容易老化变粘，有时甚至无法打开，导致样品每次的进样量不一致，甚至导致无法进样，使得质谱仪器显示的谱峰强度的重复性受到影响。再者，由于接口的设计上采用橡胶材料，因此其难以用于测量具有腐蚀性的样品。该接口的进样路径包括一段橡胶管和两段小口径的毛细管，长度约为10cm，离子在传输的过程中就会有相当一部分损失在路径中，离子传输的效率较低。
因此，提供一种可以与开放式离子源技术相结合、离子传输效率较高、适用广泛且易于制造的质谱仪器，特别是质谱仪的大气压接口装置，已成为本领域内亟待解决的一大技术问题。
发明内容
本发明要解决的技术问题是，开放式离子源向质量分析器放出离子时，离子的传输效率较低，且质谱仪的大气压进样接口耐用性不佳。
为解决上述技术问题，本发明采用如下技术方案：
本发明提出一种大气压接口装置，包括接口端板以及密封装置，所述接口端板上开设有通孔，所述通孔包括锥孔部以及柱孔部，所述锥孔部呈圆锥筒形，其孔径较大一端开口于所述接口端板的一表面且对应于所述密封装置，所述柱孔部呈圆柱筒形，其一端开口于所述接口端板的另一表面，其另一端连接于所述锥孔部的孔径较小的一端，所述锥孔部的中心线与所述柱孔部的中心线重合，所述密封装置设于所述接口端板外侧且可开闭地密封所述通孔。
根据本发明的一实施方式，所述接口端板的开设所述通孔处的厚度为5至30mm。
根据另一实施方式，所述锥孔部的最大孔径为1至10mm，所述柱孔部的孔径为100至1000μm，所述锥孔部与柱孔部的孔深比为1:10至10:1。
根据另一实施方式，所述接口端板的材质为不锈钢。
根据另一实施方式，所述密封装置包括伸缩杆以及驱动所述伸缩杆伸缩的驱动机构，所述伸缩杆一端部固定有密封头且与所述通孔位置对应，所述伸缩杆伸出时，所述密封头密封所述通孔。
根据另一实施方式，所述密封头对应所述通孔的部分呈半球形。
根据另一实施方式，所述密封头的远离所述通孔的部分呈圆柱形。
根据另一实施方式，所述密封头的材质为聚四氟乙烯或者聚醚醚酮。
根据另一实施方式，所述大气压接口装置还包括具有真空腔体的壳体，所述壳体的一端壁上开设有开口，所述接口端板的开设有所述柱孔部的表面固定于所述端壁的外表面，所述柱孔部经由所述开口与真空腔体连通。
为了解决上述技术问题，本发明提出的技术方案还包括：提出一种质谱仪，包括离子源、质量分析器、检测器以及所述的大气压接口装置，所述离子源设于所述壳体外，所述质量分析器与所述检测器设于所述真空腔体内。
根据另一实施方式，所述离子源放出离子一端与所述接口端板之间的距离为1至10mm。
根据另一实施方式，所述质量分析器为离子阱，所述离子阱两端分别设有离子阱前电极板以及离子阱后电极板，所述离子阱前电极板上开设有开孔。
根据另一实施方式，所述通孔与所述开孔的位置对应。
根据另一实施方式，所述开孔与所述通孔之间距离为1至5mm。
根据另一实施方式，所述质谱仪还包括真空泵系统，用以对所述真空腔室抽真空。
由上述技术方案可知，本发明提出的大气压接口装置以及质谱仪的功效及优点在于：本发明提出的大气压接口装置避免了使用容易老化的硅橡胶管作为其进样通道，不会出现硅橡胶管老化变粘，进而导致的进样不均甚至无法进样的情况。通孔的锥孔部以及柱孔部的结构设计，保证了离子传输速率。另外，通孔的锥孔部结构可以同时接收多个离子源释放的离子，增大谱峰的强度。该大气压接口装置的通孔可通过密封装置进行密封，保证了真空腔室的真空密封性。本发明提出的质谱仪易于制造，具有广阔的应用前景。
附图说明
图1是本发明提出的质谱仪的一实施例的结构示意图；
图2是图1中A部分的放大结构示意图，表示本发明提出的大气压接口装置的通孔的结构；
图3是本发明提出的质谱仪的第一使用例的质谱图像；
图4是本发明提出的质谱仪的第二使用例的质谱图像；
图5是本发明提出的质谱仪的第三使用例的质谱图像；
图6是本发明提出的质谱仪的第四使用例的质谱图像；
图7是本发明提出的质谱仪的第五使用例的质谱图像。
其中，附图标记说明如下：
1.接口端板；10.通孔；100.锥孔部；101.柱孔部；2.壳体；20.端壁；200.开口；3.密封装置；30.伸缩杆；31.驱动机构；32.密封头；4.真空腔室；5.离子源；6.质量分析器；60.离子阱前电极板；600.开孔；61.离子阱后电极板；7.检测器；8.真空泵系统。
具体实施方式
体现本发明特征与优点的典型实施例将在以下的说明中详细叙述。应理解的是本发明能够在不同的实施例上具有各种的变化，其皆不脱离本发明的范围，且其中的说明及图示在本质上是作说明之用，而非用以限制本发明。
大气压接口装置实施方式
如图1和图2所示，在本实施方式中，本发明提出的大气压接口装置主要包括接口端板1、密封装置3以及具有真空腔体4的壳体2。
如图2所示，在本实施方式中，接口端板1上开设有通孔10。通孔10包括锥孔部100以及柱孔部101，其中，开设有锥孔部100的一表面为接口端板1的外表面，开设有柱孔部102的另一表面为接口端板1的内表面。具体来说，锥孔部100呈圆锥筒形，其孔径较大一端开口于接口端板1的外表面，且对应于密封装置3。柱孔部101呈圆柱筒形，其一端开口于接口端板1的内表面，其另一端连接于锥孔部100的孔径较小的一端，接口端板1的内表面即其固定于壳体2端壁20的表面。锥孔部100的中心线与柱孔部101的中心线重合。
此外，接口端板1的开设通孔10处的厚度优选为5至30mm。锥孔部100的最大孔径优选为1至10mm，柱孔部101的孔径优选为100至1000μm，锥孔部100与柱孔部101的孔深比优选为1：10至10：1，以上有关接口端板1、锥孔部100以及柱孔部101各部分尺寸并不唯一，可根据实际需要以及接口端板1等结构的时间尺寸灵活选择。在本实施方式中，接口端板1开设通孔10处的厚度为12mm，即通孔10的整体孔深为12mm，其中锥孔部100的最大孔径为5mm，锥孔部100的最小孔径即柱孔部101的孔径为500μm，并且锥孔部100与柱孔部101的孔深比为2：1，即锥孔部100孔深为8mm，柱孔部101孔深为4mm。
如图1所示，密封装置3设于接口端板1外表面一侧且可开闭地密封通孔10。密封装置3包括伸缩杆30以及驱动其伸缩的驱动机构31，伸缩杆30一端部固定有密封头 32且与通孔10位置对应。密封头32对应通孔10的部分呈半球形，伸缩杆30伸出时，密封头32密封于通孔10。在本实施方式中，密封装置3为电磁阀，具体可优选为改造后的电磁夹管阀，但并不以此为限。
如图1所示，在本实施方式中，密封头32固定于伸缩杆30的一端部，即密封头32固定于伸缩杆30伸出电磁阀的端部。密封头32靠近通孔10的部分呈半球形，半球形的密封头32可以使其对通孔10的密封效果达到最佳。进一步地，密封头32相对远离通孔10的部分呈圆柱形，但并不以此为限。
此外，在本实施方式中，密封头32的材质为聚醚醚酮(polyetheretherketone，简称PEEK)，但并不以此为限，其材质还可选择聚四氟乙烯或金属铝等。
如图1所示，在本实施方式中，壳体2界定一真空腔体4。壳体2的一端壁20上开设有开口200。接口端板1固定于端壁20的外表面，具体来说，接口端板1的内表面固定于端壁20的外表面。柱孔部101经由开口200与真空腔体4连通，即通孔10与真空腔体4连通。在本实施方式中，接口端板1的材质为不锈钢，亦可选择其他具有较高的抗腐蚀及耐磨损的的材料，以用于检测腐蚀性样品，使其适用性更加广泛。此外，接口端板1还可选用其他材质，例如铝材等，但并不以此为限。另外，接口端板1可选用现有结构，例如连接法兰，亦不以此为限。
质谱仪实施方式
如图1所示，本发明提出的质谱仪的一实施方式。在本实施方式中，本发明提出的质谱仪包括本发明提出的大气压接口装置、设于其壳体2外的离子源5以及设于其真空腔体4内的质量分析器6与检测器7。
在本实施方式中，如图1所示，离子源5选用大气压化学离子源(Atmospheric Pressure Chemical Ionization，简称APCI)，适用于气态挥发性样品，然而离子源5的种类并不唯一，亦可根据不同的待测样品选用其他种类，例如还可选用納升级电喷雾离子源(Nano-Electron Spray Ionization，简称Nano-ESI)等，适用于液态样品，但并不以此为限。此外，离子源5的数目并不唯一，即可利用多个离子源5同时通过通孔10向质量分析器6释放离子样品，用以增强质谱仪谱图的谱峰强度。
如图1所示，在本实施方式中，质量分析器6选用离子阱，且进一步优选为矩形线性离子阱，然而离子阱的种类并不唯一，亦可根据不同的待测样品或其他条件选用其他种类。或者在离子阱前并联其他离子导引装置，如离子透镜，离子漏斗，四级杆等。其中，离子阱两端分别设有离子阱前电极板60以及离子阱后电极板61，离子阱前电极板60上开设有 开孔600。密封装置3的伸缩杆30伸出时，其端部的密封头32密封通孔10，伸缩杆30缩回时，离子源5释放离子样品依次穿过通孔10以及开孔600进入离子阱。
进一步地，在本实施方式中，离子源5的释放离子一端与接口端板1之间的距离为3mm，且该距离可优选为1至10mm，但并不以此为限。并且，通孔10与开孔600的位置对应，且两者之间的距离开孔为2mm，且该距离可优选为1至5mm，但并不以此为限。
另外，在本实施方式中，如图1所示，质谱仪还包括真空泵系统8，用以保持真空腔室4的真空状态。具体来说，真空泵系统8可选用传统结构，例如带有控制板的涡轮真空泵，其与真空腔室4连通。由于在离子样品进样时，真空腔室4中都会进入微量气体，因此可在每次检测后，利用密封装置3将通孔10密封，之后再利用真空泵系统8对真空腔室4抽真空，以保持其真空度达到要求数值。较佳地，真空腔室4的真空度应保持在10-3Torr以下，在本实施方式中，以达到10-5Torr为宜，但并不以此为限。
在利用本发明提出的质谱仪对样品进行质谱分析时，离子源5对待测样品离子化并放出样品离子。这些样品离子依次穿过锥孔部100以及柱孔部101进入真空腔室7，样品离子进入真空腔室7后穿过离子阱前电极板60上的开孔600后进入质量分析器6中，质量分析器6对这些样品离子根据质荷比的不同进行分离并依次进入检测器7中进行检查，最后得出质谱图像。
以下通过五个本发明的使用例，即利用本发明提出的质谱仪对样品进行质谱分析，进一步对本发明相较于现有质谱仪器的优点进行阐述，仅作为说明与示例性的，并不作为对本发明的限制。
质谱仪使用例1
在本使用例中，待测样品为避蚊胺(N,N-Diethyl-3-methyl benzoyl amide，简称DEET)，对DEET样品的离子化方式选择APCI，即本发明的质谱仪中的离子源5选用APCI离子源。利用本发明的质谱仪得到的质谱图像如图3所示(图3至图7中，lon intensity为离子源释放离子的离子强度，m/z为质子数与电荷数的比值，即质荷比)。
质谱仪使用例2
在本使用例中，待测样品为具腐蚀性的罗丹明B(Rhodamine B，又称玫瑰红B)，其浓度为2ppm，对罗丹明B样品的离子化方式选择Nano-ESI，即本发明的质谱仪中的离子源5选用Nano-ESI离子源。利用本发明的质谱仪得到的质谱图像如图4所示。
质谱仪使用例3
在本使用例中，待测样品仍为罗丹明B，且其浓度为2ppm，对罗丹明B样品的离子化方式选择Nano-ESI，即本发明的质谱仪中的离子源5选用Nano-ESI离子源5，并且在本使用例中，本发明采用两个Nano-ESI离子源同时放出罗丹明B样品离子。利用本发明的质谱仪得到的质谱图像如图5所示。
质谱仪使用例4
在本使用例中，待测样品为多聚物PEG，其浓度为100ppm，对PEG样品的离子化方式选择Nano-ESI，即本发明的质谱仪中的离子源5选用Nano-ESI离子源。利用本发明的质谱仪得到的质谱图像如图6所示。
质谱仪使用例5
在本使用例中，待测样品为肽段MRFA(Met-Arg-Phe-Ala)，其浓度为20ppm，对MRFA样品的离子化方式选择Nano-ESI，即本发明的质谱仪中的离子源5选用Nano-ESI离子源。利用本发明的质谱仪得到的质谱图像如图7所示。
如图3至图7所示，通过以上五个使用例可以发现，本发明提出的质谱仪作为非连续进样大气压接口的质谱设备，其大气压接口装置以及例如电磁阀的驱动机构等部件不会出现老化现象，且有一定的耐腐蚀性，保证了每次进样的一致性。另外，经过连续测试，该质谱仪的工作的重复性较好。通过第三使用例及其质谱图像图5还可以发现，当本发明提出的质谱仪对测试样品同时采用多个离子源5进行离子化时，可显著增大谱峰的强度。
工业实用性
本发明提出的大气压接口装置以及质谱仪具有以下工业实用性：该大气压接口装置避免了使用容易老化的硅橡胶管作为其进样通道，不会出现硅橡胶管老化变粘，进而导致的进样不均甚至无法进样的情况。通孔的锥孔部以及柱孔部的结构设计，保证了离子传输速率。另外，通孔的锥孔部结构可以同时接收多个离子源释放的离子，增大谱峰的强度。该大气压接口装置的通孔可通过密封装置进行密封，保证了真空腔室的真空密封性。该质谱仪易于制造，具有广阔的应用前景。
虽已参照几个典型实施例描述了本发明的大气压接口装置以及质谱仪，但应理解所用的术语是说明和示例性的，而非限制性的。由于本发明能够以多种形式具体实施而不脱离其构思或实质，因此上述实施例不限于任何前述的细节，而应在随附权利要求所限定的构思和范围内广泛地解释，故落入权利要求或其等效范围内的全部变化和改型都应为随附权利要求涵盖。

Claims (15)

  1. 一种大气压接口装置，其特征在于，所述大气压接口装置包括：
    接口端板(1)，所述接口端板(1)上开设有通孔(10)，所述通孔(10)包括：
    锥孔部(100)，呈圆锥筒形，其孔径较大一端开口于所述接口端板(1)的一表面且对应于所述密封装置(3)；以及
    柱孔部(101)，呈圆柱筒形，其一端开口于所述接口端板(1)的另一表面，其另一端连接于所述锥孔部(100)的孔径较小的一端，所述锥孔部(100)的中心线与所述柱孔部(101)的中心线重合；以及
    密封装置(3)，设于所述接口端板(1)外侧且可开闭地密封所述通孔(10)。
  2. 根据权利要求1所述的大气压接口装置，其特征在于，所述接口端板(1)的开设所述通孔(10)处的厚度为5至30mm。
  3. 根据权利要求1所述的大气压接口装置，其特征在于，所述锥孔部(100)的最大孔径为1至10mm，所述柱孔部(101)的孔径为100至1000μm，所述锥孔部(100)与柱孔部(101)的孔深比为1:10至10:1。
  4. 根据权利要求1所述的大气压接口装置，其特征在于，所述接口端板(1)的材质为不锈钢。
  5. 根据权利要求1所述的大气压接口装置，其特征在于，所述密封装置(3)包括伸缩杆(30)以及驱动所述伸缩杆(30)伸缩的驱动机构(31)，所述伸缩杆(30)一端部固定有密封头(32)且与所述通孔(10)位置对应，所述伸缩杆(30)伸出时，所述密封头(32)密封所述通孔(10)。
  6. 根据权利要求5所述的大气压接口装置，其特征在于，所述密封头(32)对应所述通孔(10)的部分呈半球形。
  7. 根据权利要求6所述的大气压接口装置，其特征在于，所述密封头(32)的远离所述通孔(10)的部分呈圆柱形。
  8. 根据权利要求5所述的大气压接口装置，其特征在于，所述密封头(32)的材质为聚四氟乙烯或者聚醚醚酮。
  9. 根据权利要求1至8中任意一项所述的大气压接口装置，其特征在于，所述大气压接口装置还包括具有真空腔体(4)的壳体(2)，所述壳体(2)的一端壁(20)上开设有开口(200)，所述接口端板(1)的开设有所述柱孔部(101)的表面固定于所述端壁(20)的外表面，所述柱孔部(101)经由所述开口(200)与真空腔体(4)连通。
  10. 一种质谱仪，包括离子源(5)、质量分析器(6)、检测器(7)以及大气压接口装置，其特征在于，所述大气压接口装置为权利要求9所述的大气压接口装置，所述离子源(5)设于所述壳体(2)外，所述质量分析器(6)与所述检测器(7)设于所述真空腔体(4)内。
  11. 根据权利要求10所述的质谱仪，其特征在于，所述离子源(5)放出离子一端与接口端板(1)之间距离为1至10mm。
  12. 根据权利要求10所述的质谱仪，其特征在于，所述质量分析器(6)为离子阱，所述离子阱两端分别设有离子阱前电极板(60)以及离子阱后电极板(61)，所述离子阱前电极板(60)上开设有开孔(600)。
  13. 根据权利要求12所述的质谱仪，其特征在于，所述通孔(10)与所述开孔(600)的位置对应。
  14. 根据权利要求12所述的质谱仪，其特征在于，所述开孔(600)与所述通孔(10)之间距离为1至5mm。
  15. 根据权利要求10所述的质谱仪，其特征在于，所述质谱仪还包括真空泵系统(8)，用以对所述真空腔室(4)抽真空。
PCT/CN2015/073158 2014-05-21 2015-02-16 大气压接口装置以及质谱仪 WO2015176567A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410216421.8 2014-05-21
CN201410216421.8A CN105097411B (zh) 2014-05-21 2014-05-21 大气压接口装置以及质谱仪

Publications (1)

Publication Number Publication Date
WO2015176567A1 true WO2015176567A1 (zh) 2015-11-26

Family

ID=54553392

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/073158 WO2015176567A1 (zh) 2014-05-21 2015-02-16 大气压接口装置以及质谱仪

Country Status (2)

Country Link
CN (1) CN105097411B (zh)
WO (1) WO2015176567A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105789020B (zh) * 2016-04-28 2017-07-28 清华大学深圳研究生院 用于质谱仪的脉冲进样装置及质谱设备
CN108962718B (zh) * 2018-07-12 2020-08-18 镇江市爱威尔电子有限公司 一种质谱仪的进出样装置
CN112834676A (zh) * 2020-12-31 2021-05-25 杭州谱育科技发展有限公司 质谱和色谱的接口装置及安装方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2200818Y (zh) * 1994-06-13 1995-06-14 山东大学 可调式粒子束雾化器
CN102339720A (zh) * 2011-09-26 2012-02-01 中国科学院化学研究所 一种大气压下进样离子源装置
CN102393418A (zh) * 2011-09-23 2012-03-28 聚光科技(杭州)股份有限公司 一种应用于质谱分析的进样装置及方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2160235B1 (en) * 2007-06-01 2016-11-30 Purdue Research Foundation Discontinuous atmospheric pressure interface
CN102820201B (zh) * 2012-09-02 2015-06-17 王利兵 同轴嵌套型多模式离子源
CN102800553B (zh) * 2012-09-02 2015-07-29 王利兵 一种气相液相色谱-电子轰击电喷雾双重离子源飞行时间质谱系统
CN103094050B (zh) * 2013-01-08 2016-03-23 中国科学院化学研究所 一种灵敏的辉光放电直接离子化方法及其装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2200818Y (zh) * 1994-06-13 1995-06-14 山东大学 可调式粒子束雾化器
CN102393418A (zh) * 2011-09-23 2012-03-28 聚光科技(杭州)股份有限公司 一种应用于质谱分析的进样装置及方法
CN102339720A (zh) * 2011-09-26 2012-02-01 中国科学院化学研究所 一种大气压下进样离子源装置

Also Published As

Publication number Publication date
CN105097411B (zh) 2017-05-10
CN105097411A (zh) 2015-11-25

Similar Documents

Publication Publication Date Title
US10325764B2 (en) Automated beam check
JP5604165B2 (ja) 質量分析装置
EP3069375B1 (en) Concentric apci surface ionization ion source, ion guide, and method of use
US8859957B2 (en) Systems and methods for sample analysis
US9129786B2 (en) Systems and methods for analyzing a sample
US9076638B2 (en) Mass spectrometer method and mass spectrometer
WO2015055128A1 (zh) 一种大气压接口的离子源系统以及质谱仪
US10629424B2 (en) Low temperature plasma probe with auxiliary heated gas jet
GB2519853A (en) Automated beam check
US9881781B2 (en) Optimized multiple reaction monitoring or single ion recording method
WO2015176567A1 (zh) 大气压接口装置以及质谱仪
JP6768938B2 (ja) イオン衝突断面積を決定するための分離後の移動度分析器および方法
US9779924B2 (en) Mass spectrometer
JP2015115202A (ja) 質量分析方法
CN110137071A (zh) 分体式过程质谱仪
WO2017041361A1 (zh) 紫外光电离中性丢失分子的质谱装置及其操作方法
CN108493091B (zh) 一种高电子利用率低能电离装置、质谱系统及方法
US20170076929A1 (en) Multi-Dimensional Ion Separation
US6518581B1 (en) Apparatus for control of gas flow into a mass spectrometer using a series of small orifices
US9524859B2 (en) Pulsed ion beam source for electrospray mass spectrometry
CN207676876U (zh) 一种离子阱再电离的质谱仪
RU2640393C2 (ru) Способ анализа примесей в жидкостях или газах при их микроканальном истечении в вакуум под воздействием сверхзвукового газового потока, содержащего ионы и метастабильно возбуждённые атомы, с формированием и транспортировкой анализируемых ионов в радиочастотной линейной ловушке, сопряжённой с масс-анализатором
Wang et al. Development of dual-photoionization ion trap mass spectrometry and its application for direct analysis of VOCs in fruit aroma
CN104282528A (zh) 一种用于中性电喷雾紫外单光子电离源
Lieszkovszky Mass Analysis and Partial Pressure Measurements

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15795326

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15795326

Country of ref document: EP

Kind code of ref document: A1