+

WO1998007505A1 - Procede et appareil perfectionnant l'analyse par electropulverisation - Google Patents

Procede et appareil perfectionnant l'analyse par electropulverisation Download PDF

Info

Publication number
WO1998007505A1
WO1998007505A1 PCT/US1996/013701 US9613701W WO9807505A1 WO 1998007505 A1 WO1998007505 A1 WO 1998007505A1 US 9613701 W US9613701 W US 9613701W WO 9807505 A1 WO9807505 A1 WO 9807505A1
Authority
WO
WIPO (PCT)
Prior art keywords
chamber
pressure
jet
liquid
wall
Prior art date
Application number
PCT/US1996/013701
Other languages
English (en)
Inventor
Edward W. Sheehan
Original Assignee
Sheehan Edward W
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 Sheehan Edward W filed Critical Sheehan Edward W
Priority to PCT/US1996/013701 priority Critical patent/WO1998007505A1/fr
Publication of WO1998007505A1 publication Critical patent/WO1998007505A1/fr

Links

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
    • H01J49/165—Electrospray ionisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0431—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for liquid samples
    • H01J49/044—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for liquid samples with means for preventing droplets from entering the analyzer; Desolvation of droplets

Definitions

  • Electrospray-ion spray A comparison of mechanisms and performance.
  • This invention relates to a method and apparatus for electrospraying solutions of chemical species for detection in gas phase ion detectors from liquid solutions, particularly chemical species that are separated and detected with liquid chromatography-mass spectrometry.
  • Region D The highly charged droplets in Region D are generally evaporated with dry gas 5 or heat 9 to produce further breakup of the liquid and formation of gas phase ionic species.
  • ions are emitted directly from the apex of the cone instead of a jet, particularly with liquid metal emittors.
  • Cone-jet aerosol sources have been utilized for a number of applications; including, mass spectrometry sample introduction and ionization, 5 11 particle generation, 12 and thruster technology, 13 and liquid metal ion sources. 10 The operation of cone-jet source of aerosols has been demonstrated at atmospheric 1 17 and at reduced pressure. 10,18
  • ES ion sources are operated at atmospheric pressure because of the efficient heat transfer at these pressures to the charged droplets which results in the evaporation of the primary droplets and concomitantly causes efficient ion production.
  • atmospheric pressure only a fraction of the ions produced are actually sampled into the low pressure detectors because of the difficulty of focusing and sampling ions through small sampling apertures to reduced pressures. Larger apertures are sometimes used to improve sampling efficiencies; however, these require more costly and/or higher capacity pumping on the vacuum system to maintain acceptable detector operating pressures.
  • Another limitation of atmospheric pressure ES operation is the threshold of electrical discharge across the gap between the high electrical potential capillary and the counterelectrode. This threshold is generally a function of capillary and counterelectrode spacing and geometry, surrounding gas composition, and pressure.
  • the operating voltages are limited by the discharge threshold due to partial or complete degradation of the electrospray process during an electrical discharge. Discharges generally present a greater limitation while operating atmospheric pressure ES sources in the negative ion mode. 19,20
  • Practioners of EHD minimize the problem of freezing and boiling by dissolving there analyte in a non-volatile solvent, such as glycerine, and introducing sample into a vacuum chamber at reduced flow rates (nanoliters/min).
  • a non-volatile solvent such as glycerine
  • Some low pressure ES devices included various lenses for controlling the ions (not droplets) downstream from ES needle. 346 18
  • Prior related art can be divided into four (4) groups:
  • low pressure electrospray with a focusing means for directing the aerosol into low pressure detectors (such as, references 3 and 6);
  • Mahoney and coworkers 6 addresses declustering downstream from the spray but does not effectively deal with the evaporation of droplets produced at low pressure.
  • Platzer 22 addresses the problem of solvent declustering and wide kinetic energy spread at low pressures by directly spraying from low pressures through a heated tube into a higher pressure ionization region.
  • the art of Platzer fails to address the inherent instability of the primary electrospray process, freezing and boiling in a vacuum; and the wide angular and spatial dispersion of the spray.
  • the primary outcome of failing to address the low pressure spray stability will result in significant losses of analyte and droplets on the walls of their first chamber and the heated transfer tube. Although, they may collect some of the spray through the tube by virtue of large cross sectional diameters, they will still have irreproducible and unstable signal resulting from the unstable spray processes.
  • the object of the current invention is to overcome the aforementioned limitations of both atmospheric pressure and low pressure operations of electrospray.
  • Electrospray-ion spray A comparison of mechanisms and performance.
  • Luttgens U., Dulcks, T., Rollgen, F.W. Surface Science 1992, 266, 197-203. Field induced disintegration ofglycerol solutions under vacuum and atmospheric pressure conditions studied by optical microscopy and mass spectrometry.
  • the current invention is intended to overcome many of the aforementioned limitations of conventional atmospheric pressure electrospray and low pressure electrohydrodynamic (EHD) devices by physically separating the primary aerosol generation process from the secondary aerosol and ion generation processes and discretely optimizing both.
  • the primary process of cone-jet formation is controlled by thermal and electrostatic means to facilitate the formation of a directionally stable liquid cone-jet. Once a stable cone-jet is formed, the jet and resulting droplets are introduced into a evaporation region where the secondary aerosol is generated and the ion generating processes take place.
  • a liquid solution is introduced through a needle, held at high electrical potential, into a first chamber maintained at reduced pressure to produce a stable electrospray cone-jet.
  • the product of this primary process is intended to be a highly charged liquid jet and droplets from an electrospray source directed on the axis of a countereclectrode (see Figure 1).
  • other devices used in low pressure ES systems are typically operated to produce ions directly from the primary cone. 43,46
  • the pressure in the first chamber of the present device is maintained below the pressure at which electrical discharge occurs, typically less than 0.1 Torr. Ancillary heating of the tube may be required in the first chamber to prevent freezing of the liquid from evaporative cooling.
  • the liquid cone-jet in the present device is stabilized by the electrostatic lens surrounding the capillary resulting in a constant (in time) conical geometry with a constant (in space) axial direction associated with the liquid jet.
  • the liquid jet under influence of surface tension will break into droplets that will continue in the axial direction of the jet.
  • the present invention takes advantage of the extremely small axial cross-section of the liquid jet and droplets and their high axial velocity, to sample all of this jet of liquid across a high pressure gradient through a small cross sectional aperture into a higher pressure region.
  • the aperture size is selected for efficient transfer of liquid through the aperture and in order to maintain pressure requirements in both the first chamber (to prevent discharge) and the second chamber (to desolvate, breakup ion clusters, form ions, react species, and focus ions).
  • a key aspect of the present method of ion generation is the precise alignment of the liquid jet with the sampling aperture located in the wall of the first chamber leading into the second chamber. This alignment allows virtually all analyte in solution to be introduced into the second chamber.
  • the alignment of the jet may be accomplished with either mechanical translational adjustment, and/or electrostatic or magnetic steering.
  • the stability of the cone- jet is also dependent upon the geometry and spatial relationship of the stabilizing electrode; and the stability of the liquid flow.
  • the extent of evaporation in the second chamber is regulated by a controlled heat supply, the gas composition, gas pressure and the geometry of the region.
  • the density of charges on the surface of the droplet increases, driving the highly charged droplets to the limit of charging, sometimes called the "Rayleigh limit". 25
  • the primary droplets deform and emit secondary droplets, ion clusters, or ions.
  • the secondary droplets undergo further evaporation and a subsequent emission of droplets, ion clusters and ions.
  • the ions that leave the droplets may be highly solvated or clustered.
  • ions and/or ion clusters with the residual background gas(es) or other ions in this higher pressure region will be sufficiently energetic to decluster the adducts and leave intact gas phase molecular ions formed from the electrospray process.
  • These ions can then be focused, analyzed, and detected by conventional means, such as a mass spectrometer.
  • mass spectrometers include, (but are not limited to) time-of-flight, ion traps, fourier transform, quadrupole, magnetic sector, and tandem instruments.
  • the second chamber affords a degree of isolation of the ion generation processes from the primary droplet charging process, alternative operating conditions are compatible with the present device.
  • the second chamber can be pressurized with helium (a highly conductive gas) to induce efficient desoivation.
  • This gas results in a gas discharge when used with conventional electrospray devices, at atmospheric pressure.
  • high energy sources such as, dc and rf discharges, to augment both desoivation, ionization processes, and fragmentation.
  • the second chamber could also serve as a reaction chamber for a variety of processes, as a collector or trap of selected ions for storage and/or subsequent analyze (e.g. quadrupole trap, potential well trap).
  • the restriction of the total mass flow into the vacuum system with the present devise significantly reduces the system pumping requirements when compared to conventional ES devices.
  • the production of a stable cone-jet at reduced pressures minimizes the problems associated with gas discharge in atmospheric pressure modes of operation, particularly in negative ion mode.
  • the collection of virtually the entire primary aerosol into a higher pressure region allows efficient ion production and declustering and eliminates problems associated with other low pressure ES devices, such as, spatial and directional instabilities and cluster formation. Since ion production occurs in close proximity to the mass analyzer or other gas phase ion detectors, the transport losses compared with atmospheric ES operation are not as significant. Description of the Preferred Embodiments.
  • a preferred embodiment of the invention which may be [but is not limited to] the effluent from a liquid chromatograph, flows within tube 17 in the direction of the arrow and all or a portion of the liquid is caused to flow out of capillary tube 10. Excess liquid flows out of splitter tube 16 in a flow splitter configuration.
  • Insulator tube 15 joins onto tee 14 and is composed of an electrically insulating material. Insulator tube 15 is of sufficient length, internal diameter, and total resistance to maintain an electrical potential difference between the high voltage power supply and the liquid chromatograph, which is at ground.
  • Tee 14 is composed of electrically conducting material, usually stainless steel.
  • Tee 14 is connected to a high voltage power supply which can be regulated in terms of voltage, current, a combination of current and voltage, and possibly modulated. Tee 14 may be kept at several thousand volts, but is not limited to this.
  • the portion of the liquid that flows through capillary tube 10 also flows into vacuum chamber 1 , through a vacuum seal 13 composed of an electrically insulating material, such as glass, or lexan, which also provides mechanical support for capillary tube 10.
  • Capillary tube 10 may be composed of an insulating or metallic material.
  • Electrode 11 is located coaxially to the capillary tube 10.
  • electrode 11 is a coaxial cylindrical tube but not limited to this specific geometry (e.g., plate(s), quadrupole, octopole).
  • Coaxial cylindrical tube 11 is composed of electrically conducting material, usually stainless steel.
  • Coaxial cylindrical tube 11 is also at a high electrical potential which is adjustable to maintain a stable axial spray.
  • Adjuster 12 is affixed to both tubes 10 and 11 and allows mechanical alignment of these tubes relative to one another and relative to the entrance lens 21.
  • FIG 3 is an expanded view of the cone-jet region of the preferred embodiment.
  • Liquid cone 76 emerges from the tip 9 of the capillary tube 10 and forms a liquid jet 19 moving in the direction of entrance lens 21.
  • the alignment of the liquid jet 19 with exit or pinhole aperture 28 is performed with adjuster 12 to ensure the liquid flows into chamber 2.
  • the second chamber 2 is separated from chamber 1 by means of an entrance lens 21 and skimmer lens 22.
  • an additional focusing lens 20 Inside chamber 2 is an additional focusing lens 20. All three lens are made of metal and serve as focusing lens for ions and charged particles.
  • Entrance lens 21 is isolated from focusing lens 20 by insulator 23 and in turn, focusing lens 20 is isolated from chamber 2 by insulator 27.
  • Skimmer lens 22 is isolated from chamber 2 by insulator 24.
  • the housing of chamber 2 is made of metal and serves as a focusing lens for ions and charged particles contained in chamber 2. The volume, length and geometry is chosen to minimize surface losses of analyte and maximize transport of ions.
  • a conductive gas such as nitrogen or helium but not limited to such gases, is added to chamber 2 through gas tube 52 from a gas supply source 50 in sufficient quantity to maintain chamber 2 at a pressure greater than either chambers 1 or 3.
  • Gas tube 52 enters chamber 1 through vacuum feedthrough 53 and is electrically isolated from gas inlet tube 55 by means of an electrically insulating union 54.
  • Electrically insulating union 54 is composed of a gas impermeable electrically insulating material such as glass, or ceramic but not limited to this specific material.
  • Gas inlet tube 55 then joins chamber 2.
  • Gas tube 52 and gas inlet tube 55 are made of a material impermeable to gas such as metal, but not limited to this specific material.
  • Gas may be removed from chamber 2 through pump out line 72 .
  • This pump out line 72 is pumped by a mechanical pump (not shown) to maintain an effective pressure in chamber 2 greater than either chambers 1 or 3.
  • Pump out line 72 enters chamber 1 through vacuum feedthrough 73 and is electrically isolated from gas outlet tube 75 by an electrical insulating union 74.
  • Electrically insulating union 74 is composed of a gas impermeable electrically insulating material such as glass, or ceramic but not limited to this specific material.
  • Gas outlet tube 75 then joins chamber 2.
  • Pump out line 72 and gas outlet tube 75 are made of a material impermeable to gas such as metal, but not limited to this specific material.
  • the flow, pressure and composition of gas(es) into chamber 2 are controlled by a combination of the gas manifold (not shown), gas inlet valve 51 , gas outlet valve 71 , and sizes of apertures 28 and 29.
  • Chamber 2 is heated by a heater cartridge 26 imbedded in the chamber wall 25, and a thermocouple (not shown) attached to the chamber indicates the temperature and couples to a temperature controller to adjust the heater power to maintain the desired temperature.
  • Skimmer lens 22 is electrically isolated from the chamber 2 so that a potential can be applied to cause ions to drift toward lens 22 and thus increase the fraction of ions that exit through aperture or pinhole aperture 29 of said skimmer lens 22.
  • the ions exit from chamber 2 into associated ion optics (planar lens 30, planar entrance lens 33, extractor lens 38) used for focusing ions into the mass analyzer 34.
  • a quadrupole mass filter is shown to be the mass analyzer.
  • the mass analyzer is located in vacuum chamber 3 which must be maintained at 10 5 torr or below for normal operation.
  • An isolator wall 37 divides chambers 1 and 3 and contains a planar entrance lens 33. Planar entrance lens 33 is electrically isolated from isolator wall 37.
  • Chamber 3 is evacuated through pumping port 61. In this differently pumped embodiment, higher pressures and associated gas loads can be accommodated in chamber 1 while still maintaining normal operating pressures in chamber 3.
  • Figure 4 illustrates a second embodiment of the invention where chamber 2, mass analyzer 34 and associated ion optics (planar lens 30, extractor lens 38) all reside inside the same chamber, chamber 1.
  • Chamber 1 is a region of high vacuum, evacuated through pumping port 60.
  • a larger pump would be required to evacuate chamber 1 through pumping port 60 to maintain a normal operating pressure of 10 '5 torr or below if the same size apertures (28 and 29) for entrance lens 21 and skimmer lens 22 are used in this said second embodiment.
  • a third embodiment of the invention is a variation of the second embodiment, where apertures 28 and 29 for entrance lens 21 and skimmer lens 22 are smaller than those used in either the first or second embodiments.
  • the pressure in chamber 1 could be maintained at normal operating pressure for the mass analyzer with a similar pump use in said first embodiment (a differentially pumped system).
  • the planar lens 30 focuses ions directly into the mass analyzer 34 rather than through planar entrance lens 33.
  • FIGURE 1 is a schematic diagram of the regions (Region A: Needle, Region B: Cone, Region C: Jet, Region D: Plume) associated with electrospray aerosol generation and ionization.
  • FIGURE 2 is a schematic cross-sectional diagram of the present invention with a differentially pumped vacuum system in a liquid chromatography mass spectrometer implementation.
  • FIGURE 3 is a detailed cross-sectional diagram of a preferred embodiment of the invention showing an expanded view of the capillary tube, the cone-jet in chamber 1 being steered through an entrance lens into the higher pressure chamber, chamber 2.
  • FIGURE 4 is a detailed cross-sectional diagram of an alternative vacuum configuration for the present device.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

La présente invention concerne un perfectionnement de procédé d'ionisation par électropulvérisation et une source d'ions permettant de réduire la charge de gaz total sur le système de dépression et d'améliorer la production d'ions et les rendements d'obtention. La source d'ions, destinée à l'analyse des ions de phase gazeuse de constituants dissous dans une solution liquide, comporte une aiguille (10) tenue à un potentiel électrique élevé. Le flux de solution considérée, en passant par ce potentiel et en pénétrant dans une première chambre (1) maintenue à pression réduite, forme un jet conique de liquide à charge élevée. Dans la première chambre, ce jet de liquide à charge élevée est dirigé dans l'axe d'un orifice de façon à pénétrer dans une seconde chambre (2) maintenue à une pression supérieure à la celle de la première chambre. Pour faciliter la désolvatation des gouttelettes de solution issues de la fragmentation du jet à charge élevée, cette seconde chambre est chauffée et pressurisée, ce qui fait que le procédé d'ionisation par électropulvérisation aboutit à une production d'ions de phase gazeuse.
PCT/US1996/013701 1996-08-21 1996-08-21 Procede et appareil perfectionnant l'analyse par electropulverisation WO1998007505A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US1996/013701 WO1998007505A1 (fr) 1996-08-21 1996-08-21 Procede et appareil perfectionnant l'analyse par electropulverisation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1996/013701 WO1998007505A1 (fr) 1996-08-21 1996-08-21 Procede et appareil perfectionnant l'analyse par electropulverisation

Publications (1)

Publication Number Publication Date
WO1998007505A1 true WO1998007505A1 (fr) 1998-02-26

Family

ID=22255661

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/013701 WO1998007505A1 (fr) 1996-08-21 1996-08-21 Procede et appareil perfectionnant l'analyse par electropulverisation

Country Status (1)

Country Link
WO (1) WO1998007505A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000019193A1 (fr) * 1998-09-28 2000-04-06 Varian Inc Dispositif d'electronebulisation a courant divergent pour spectrometrie de masse
US6949740B1 (en) 2002-09-13 2005-09-27 Edward William Sheehan Laminated lens for introducing gas-phase ions into the vacuum systems of mass spectrometers
US7569812B1 (en) 2003-05-30 2009-08-04 Science Applications International Corporation Remote reagent ion generator
US7568401B1 (en) 2005-06-20 2009-08-04 Science Applications International Corporation Sample tube holder
US7576322B2 (en) 2005-11-08 2009-08-18 Science Applications International Corporation Non-contact detector system with plasma ion source
US7586092B1 (en) 2005-05-05 2009-09-08 Science Applications International Corporation Method and device for non-contact sampling and detection
US7671344B2 (en) 2007-08-31 2010-03-02 Battelle Memorial Institute Low pressure electrospray ionization system and process for effective transmission of ions
US7960711B1 (en) 2007-01-22 2011-06-14 Chem-Space Associates, Inc. Field-free electrospray nebulizer
US8173960B2 (en) 2007-08-31 2012-05-08 Battelle Memorial Institute Low pressure electrospray ionization system and process for effective transmission of ions
US8180203B2 (en) * 2004-02-13 2012-05-15 Gl Sciences Incorporated Direct heating tube and method of heating fluid using same
CN105097412A (zh) * 2014-05-08 2015-11-25 岛津分析技术研发（上海）有限公司 一种质量校准物离子化与引入装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4607163A (en) * 1983-12-19 1986-08-19 Jeol Ltd. Device for coupling a liquid chromatograph and a mass spectrometer
US5015845A (en) * 1990-06-01 1991-05-14 Vestec Corporation Electrospray method for mass spectrometry
US5162650A (en) * 1991-01-25 1992-11-10 Finnigan Corporation Method and apparatus for multi-stage particle separation with gas addition for a mass spectrometer
US5245186A (en) * 1991-11-18 1993-09-14 The Rockefeller University Electrospray ion source for mass spectrometry
US5349186A (en) * 1993-06-25 1994-09-20 The Governors Of The University Of Alberta Electrospray interface for mass spectrometer and method of supplying analyte to a mass spectrometer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4607163A (en) * 1983-12-19 1986-08-19 Jeol Ltd. Device for coupling a liquid chromatograph and a mass spectrometer
US5015845A (en) * 1990-06-01 1991-05-14 Vestec Corporation Electrospray method for mass spectrometry
US5162650A (en) * 1991-01-25 1992-11-10 Finnigan Corporation Method and apparatus for multi-stage particle separation with gas addition for a mass spectrometer
US5245186A (en) * 1991-11-18 1993-09-14 The Rockefeller University Electrospray ion source for mass spectrometry
US5349186A (en) * 1993-06-25 1994-09-20 The Governors Of The University Of Alberta Electrospray interface for mass spectrometer and method of supplying analyte to a mass spectrometer

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000019193A1 (fr) * 1998-09-28 2000-04-06 Varian Inc Dispositif d'electronebulisation a courant divergent pour spectrometrie de masse
US6949740B1 (en) 2002-09-13 2005-09-27 Edward William Sheehan Laminated lens for introducing gas-phase ions into the vacuum systems of mass spectrometers
US7569812B1 (en) 2003-05-30 2009-08-04 Science Applications International Corporation Remote reagent ion generator
US8180203B2 (en) * 2004-02-13 2012-05-15 Gl Sciences Incorporated Direct heating tube and method of heating fluid using same
US7586092B1 (en) 2005-05-05 2009-09-08 Science Applications International Corporation Method and device for non-contact sampling and detection
US7568401B1 (en) 2005-06-20 2009-08-04 Science Applications International Corporation Sample tube holder
US7576322B2 (en) 2005-11-08 2009-08-18 Science Applications International Corporation Non-contact detector system with plasma ion source
US7960711B1 (en) 2007-01-22 2011-06-14 Chem-Space Associates, Inc. Field-free electrospray nebulizer
US7671344B2 (en) 2007-08-31 2010-03-02 Battelle Memorial Institute Low pressure electrospray ionization system and process for effective transmission of ions
US8173960B2 (en) 2007-08-31 2012-05-08 Battelle Memorial Institute Low pressure electrospray ionization system and process for effective transmission of ions
CN105097412A (zh) * 2014-05-08 2015-11-25 岛津分析技术研发（上海）有限公司 一种质量校准物离子化与引入装置

Similar Documents

Publication Publication Date Title
US5838002A (en) Method and apparatus for improved electrospray analysis
US6278111B1 (en) Electrospray for chemical analysis
US4531056A (en) Method and apparatus for the mass spectrometric analysis of solutions
US5756994A (en) Electrospray and atmospheric pressure chemical ionization mass spectrometer and ion source
US4999493A (en) Electrospray ionization interface and method for mass spectrometry
US7002146B2 (en) Ion sampling for APPI mass spectrometry
EP1507282B1 (fr) Source d' ions multimode.
JP4178110B2 (ja) 質量分析装置
EP0644796B1 (fr) Interface ionique a pression atmospherique pour un analyseur de masses
US6646257B1 (en) Multimode ionization source
EP0161744B1 (fr) Spectromètre de masses
US6649907B2 (en) Charge reduction electrospray ionization ion source
US6586731B1 (en) High intensity ion source apparatus for mass spectrometry
US5663560A (en) Method and apparatus for mass analysis of solution sample
JP2778689B2 (ja) 放電イオン化質量分析計
JPH07288099A (ja) 電気噴霧形成のための絶縁された針装置
JPH07239319A (ja) 液体クロマトグラフィー／質量分析計装置
US20030062474A1 (en) Electrospray ion source for mass spectrometry with atmospheric pressure desolvating capabilities
WO1998007505A1 (fr) Procede et appareil perfectionnant l'analyse par electropulverisation
US5633496A (en) Mass spectrometry apparatus
US7365315B2 (en) Method and apparatus for ionization via interaction with metastable species
JPH06215729A (ja) 質量分析計
JP2000100375A (ja) 質量分析計及びその静電レンズ
JPH1164289A (ja) 液体クロマトグラフ質量分析装置

Legal Events

Date Code Title Description
AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载