WO1997026072A1 - Subatmospheric, variable pressure sample delivery chamber for electrospray ionization/mass spectrometry and other applications - Google Patents
Subatmospheric, variable pressure sample delivery chamber for electrospray ionization/mass spectrometry and other applications Download PDFInfo
- Publication number
- WO1997026072A1 WO1997026072A1 PCT/US1997/000733 US9700733W WO9726072A1 WO 1997026072 A1 WO1997026072 A1 WO 1997026072A1 US 9700733 W US9700733 W US 9700733W WO 9726072 A1 WO9726072 A1 WO 9726072A1
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- WIPO (PCT)
- Prior art keywords
- chamber
- sample
- delivery device
- sample delivery
- gas
- Prior art date
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Classifications
-
- 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
- H01J49/0445—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 introducing as a spray, a jet or an aerosol
- H01J49/045—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 introducing as a spray, a jet or an aerosol with means for using a nebulising gas, i.e. pneumatically assisted
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/447—Systems using electrophoresis
- G01N27/44704—Details; Accessories
- G01N27/44717—Arrangements for investigating the separated zones, e.g. localising zones
-
- 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
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N2030/285—Control of physical parameters of the fluid carrier electrically driven carrier
-
- 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
- G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
- G01N30/724—Nebulising, aerosol formation or ionisation
- G01N30/7266—Nebulising, aerosol formation or ionisation by electric field, e.g. electrospray
Definitions
- This invention relates to the introduction of a sample into an analytical device and particularly to the use of an electrospray process to introduce a sample into a mass spectrometer.
- Electrospray ionization a process in which a liquid is subjected to a strong electric field and is formed into a stream of small, charged droplets leading to sample ionization in the gas phase, is one of the most versatile ionization techniques for the investigation of macromolecules.
- the electrospray ionization process has recently found application as a means of producing ions for mass spectrometric analysis. (See, e.g., Smith et al . , Anal. Chem. 62 . :885, 1990; Mann, Organ. Mass Spec. 25.: 575, 1990; Henion et al . , U.S. Pat. No.
- electrospray ionization mass spectrometry is a widely used technique in biological, biochemical, pharmaceutical and medical research for studying complex biological samples containing species such as peptides, protein, carbohydrates or nucleic acids.
- the information on a sample that such an ESI-MS system can provide can be further enhanced by on-line combination with a microseparation technique, such as capillary electrophoresis, capillary electrochromatography or microcolumn liquid chromatography.
- a microseparation technique such as capillary electrophoresis, capillary electrochromatography or microcolumn liquid chromatography.
- the electrospray needle is typically placed 1 to 20 mm in front of the mass spectrometer entrance port or sampling orifice, which often is heated to assist in the desolvation process.
- the needle is usually at high potential and the mass spectrometer at or near ground, although the polarities can be reversed.
- Current trends are to use very small needle tips, metal coated drawn glass with internal diameters of 1-10 ⁇ m or even in the submicrometer range. This helps to utilize the sample more effectively by transferring the generated ions more efficiently to the mass spectrometer.
- a metalized glass micropipette is used as both the sample reservoir and electrospray needle. Extremely low sample flow rates (low nL/min) are generated by the electrospray action.
- microelectrospray (sometimes also called nanoelectrospray) seems to work very well for infusion studies, its use for coupling of capillary electrophoresis
- CE capillary to mass spectrometry is limited to very narrow separation capillaries with the electrospray interface operating in the sheathless mode.
- Coupling of a more standard (routinely used) larger bore (50-100 ⁇ m i.d.) CE capillary to a microelectrospray may require the use of a liquid junction type of interface with a flow of a supporting liquid solution, such as 1% acetic acid in 50% methanol. (See, Lee et al . , U.S. Pat. No. 4,994,165.)
- the use of a pump necessary for pumping of the spray solution through the electrospray needle, generates significant pressure at the junction point and can result in reverse liquid flow in the CE capillary.
- a subatmospheric, variable pressure sample delivery chamber which is useful as an electrospray ionization interface for a mass spectrometer.
- the sample delivery chamber of the invention is also useful without electrospray ionization for subatmospheric delivery of a sample, e.g., directly to a collection device contained within the chamber.
- Subatmospheric operating pressures of between 1 and 750 Torr are contemplated, with pressures between 50 and 700 Torr preferred.
- the invention generally features a sample delivery chamber that is configured for removal of gas to subatmospheric pressures.
- the chamber has an inlet port for introducing a gas into the chamber and an exit port for withdrawing gas from the chamber.
- the chamber also has a sample delivery device extending from outside the chamber into the chamber interior.
- the sample delivery device is a capillary tube, or a microchip containing a groove or channel through which a sample can be delivered.
- the exit end of the sample delivery device preferably has an inside diameter that is less than the average inside diameter of the sample passage through the device.
- the exit port of the chamber is configured for attachment to a mass spectrometer, or other analytical device, external to the chamber, and the exit end of the sample delivery device is aligned with the chamber exit port.
- the exit port of the chamber is coupled to a pump for gas removal, and a collection device, which is most preferably a movable system of collection capillaries but which could be a collection membrane, is positioned within the chamber and adjacent to the exit end of the sample delivery device.
- Control of the flow rate through the sample delivery device e.g., an electrospray needle, by pressure regulation at its exit end, as in the sample delivery chamber of the invention, eliminates the need for time consuming pressure balancing optimization at the sampling end, as required by certain prior art configurations.
- the sample delivery chamber of the invention also permits more precise directing of the electrospray generated ions into the sampling orifice of the mass spectrometer.
- Fig. la is a section through a side schematic view of one embodiment of the invention in which a subatmospheric, variable pressure sample delivery chamber, configured as an electrospray ionization mass spectrometer interface, is coupled to an electrophoresis capillary;
- Fig. lb is a perspective view of an alternative configuration for a sample delivery device for the embodiment of the invention shown in Fig. la;
- Fig. lc is an end view of the sample delivery device of Fig. lb;
- Fig. Id shows an air flow pattern formed in the operation of the embodiment of the invention of Fig. la;
- Fig. 2a is a UV trace of a mixture of peptides separated by capillary electrophoresis according to the embodiment of the invention shown in Fig. la, as monitored by a fiber optic detector;
- Fig. 2b is a total ion electropherogram and selected ion monitoring traces of the separated sample described in Fig. 2a;
- Fig. 3 is a graph showing a mass spectrometer ion signal plotted versus pressure in the sample delivery chamber of the embodiment of Fig. la;
- Fig. 4 is a section through a side schematic view of another embodiment of the invention.
- a subatmospheric electrospray interface device consists of a subatmospheric chamber (2) , which has an inlet port (4) , for introducing a gas into the chamber, and an exit port (6) , coupled to a sampling orifice
- An electrospray needle (10) extends from outside the chamber into the interior of the chamber through inlet port (4) .
- the inlet end (12) of electrospray needle (10) is capable of receiving a sample to be delivered into a mass spectrometer, and the electrospray tip (14) is aligned with the chamber exit port (6) .
- Electrospray needle (10) is preferably formed from a narrow (1-20 ⁇ i.d.) fused si-lica capillary, which can be metalized or left non-metalized. When desirable, the electrospray tip
- sampling end (12) of the electrospray needle is aligned with the exit end of an electrophoresis capillary
- an electrospray needle or sample delivery device could be formed from a fused silica microchip, as shown in Figs, lb and lc.
- a fused silica microchip (100) such as disclosed in U.S. Pat. Appl. Ser.
- Microchip (100) has one or more parallel sample delivery channels (102) , each channel having a sample delivery inlet opening (106) and an electrospray opening (108) .
- (100) surrounding electrospray opening (108) can optionally be coated with a non-wetting, hydrophobic material.
- Capillary electrophoresis can be carried out in the channels of the chip or the chip can serve solely as a sample delivery device, e.g., for a sample from an attached system.
- the flow rate through the electrospray needle is controlled by regulating the pressure in chamber (2) in the following manner.
- a vacuum gas pressure of less than 10 mTorr
- gas flow is initiated out of chamber (2) into mass spectrometer (9) via coupled chamber exit port (6) and sampling orifice (8) .
- Electrospray needle (10) is positioned in the stream of gas (air or any supporting gas such as nitrogen, SF 6 , etc.) entering the electrospray chamber through inlet port (4) via gas input tube (22) , which passes through a solid stabilization chamber lid (24) .
- Gas flow is regulated at input valve (20) , by controlling gas flow into chamber (2) via inlet port (4) , to achieve a gas pressure in chamber (2) of between 1-750 torr, the optimum pressure depending on the diameter of sampling - orifice (8) .
- the pressure in the chamber is monitored by a pressure monitor (26) .
- the ability to control the pressure in the electrospray chamber allows for fine control of the sample flow rate without the necessity of providing a pressure driven flow from the sampling end of the needle. Formation of the electrospray droplets at lower (subatmospheric) pressure also facilitates their better desolvation, allowing the use of a wide range of sizes of electrophoretic capillaries with or without electroosmotic flow.
- the internal volume of electrospray needle (10) should be comparable to or smaller than the volume of the bands in the separation capillary
- a 50 mm long, 20 ⁇ m i.d. electrospray needle has an internal volume of less than 16 nL while the volume of a typical zone in the 75 ⁇ m CE capillary is -20-50 nL.
- the pressure in the electrospray chamber should be in the range of 1 - 750 Torr.
- the size of the orifice (8) can be increased to improve sampling efficiency without loss of vacuum efficiency in the mass spectrometer.
- electrospray needle (10) and electrophoretic capillary (16) allows use of different compositions of the buffer for separation and electrospray ionization.
- a fiber-optic based detector cell (28) can be attached close to the exit end of the electrophoretic capillary.
- capillary electrophoresis/electrospray mass spectrometry can be carried out with only one high voltage power supply (30) , which is in contact with electrode buffer input reservoir (32) , as shown in Fig. la.
- a separate power supply is used for the electrospray interface itself and was believed to be necessary for electrospray ionization.
- a separate power supply is not required for the electrospray interface, since the CE high voltage power supply (30) always generates more current than is consumed by the electrospray process.
- a variable resistor (34) can be used for control of the electrospray needle potential.
- the CE power supply (30) would preferentially be operated in the constant current mode, assuring the desired electric field strength in the CE separation capillary.
- two power supplies could also be used with the subatmospheric electrospray interface of the invention.
- Capillary zone electrophoresis ESI-MS analysis of a peptide mixture was carried out according to the method of the invention described herein.
- the applied sample consisted of Peptide Calibration Set No. 148-2012 from Bio ⁇ Rad Laboratories, Inc., a mixture of bradykinin, angiotensin II, ⁇ -MSH, TRH, LHRH, bombesin, leu-enkephalin, met- enkephalin and oxytocin, at 50 ng/ml each.
- Capillary electrophoresis separation conditions were: [background electrolyte: 50 mM acetic acid; capillary: 75 ⁇ m id x 15 cm, inside wall coated with a hydrophilic polymer to prevent adsorption and electroosmosis; constant current: 6 ⁇ A (8 kV) ; hydrodynamic injection, 5 s/5 cm] .
- Electrospray injection for mass spectrometry was accomplished using a fused silica electrospray needle (25 ⁇ m id x 50 mm) . Pressure in the subatmospheric chamber: 600 Torr.
- Electrospray voltage ⁇ 1500 V generated by an electrophoresis power supply with a resistor of 250 MOhms . In Fig.
- Fig. 2a the UV trace of the separated peptides, as monitored by fiber optic detector (28) is presented, and the corresponding total ion electropherogram and selected ion monitoring traces are shown in Fig. 2b.
- the optimum pressure for subatmospheric sample delivery chamber operation to produce the maximum ion signal was determined by electrospray of a sample of bullfish angiotensin I at IO "5 M in 1.5% acetic acid and 50% methanol/H 2 0 via an ESI needle having a tip i.d. of 24 ⁇ m and o.d. of 50 ⁇ m.
- the electrospray potential was 2.24 kV. Referring to Fig.
- a plot of ion signal versus sample delivery chamber pressure shows a preferred operating range of 450-700 torr.
- the optimum pressure in the sample delivery chamber will depend on the gas intake capability of the mass spectrometer. This experiment was carried out using a mass spectrometer supplied by Finnigan Corporation (San Jose, CA) , which, as supplied by the manufacturer, has a sampling orifice of ⁇ 0.4 mm in diameter. Generally, the wider the opening of the mass spectrometer sampling orifice, the higher the gas intake and the lower the optimum operating pressure can be in the subatmospheric chamber. If the sampling orifice diameter is tripled, optimun results could be provided with an order of magnitude lower pressure in the subatmospheric pressure (- 50 Torr) .
- a subatmospheric sample delivery chamber is also useful for direct delivery of a sample to a collection device.
- a suitable system consists of a subatmospheric chamber (52) , which has an inlet port (54) , for introducing a gas into the chamber, and an exit port (56) , coupled to a pump for gas removal (58) .
- a sample delivery needle (60) extends from outside the chamber into the interior of the chamber.
- sample delivery needle (60) is aligned with the exit end (64) of an electrophoresis capillary (66) in an electrode buffer reservoir (68) .
- exit end (70) of sample delivery needle (60) is aligned with a collection capillary (72) in fraction collector (84) .
- Capillary electrophoresis is conducted in electrophoresis capillary (66) under a current established via high voltage power supply (76) , in contact with electrode buffer input reservoir (78) , and an optically controlled voltage divider (80) , in contact with electrode buffer output reservoir (68) .
- the fluid from the electrode buffer output reservoir (68) flows into sample delivery needle (60) at inlet end (62) and towards exit end (70) due to the pressure difference between the reservoir (68) and subatmospheric chamber (52) . This flow causes the ions exiting the outlet
- CE capillary (66) also to enter the sample delivery needle.
- the fractions are then collected at the exit end (70) into collection vials (capillaries) (72) of the fraction collector (74) .
- the pressure inside the subatmospheric chamber (52) is controlled by the pump (58) connected to the chamber outlet (56) and by the pressure regulator (82) connected to the chamber air inlet port (54) . This arrangement assures that the transport of ions and fluid inside the CE capillary (66) is not affected by the changes of the flow into the sample delivery needle (60) , which would occur if a positive pressure was applied at the electrode output buffer reservoir (68) .
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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CA 2243973 CA2243973A1 (en) | 1996-01-19 | 1997-01-17 | Subatmospheric, variable pressure sample delivery chamber for electrospray ionization/mass spectrometry and other applications |
EP97903835A EP0888169A4 (en) | 1996-01-19 | 1997-01-17 | Subatmospheric, variable pressure sample delivery chamber for electrospray ionization/mass spectrometry and other applications |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US1024296P | 1996-01-19 | 1996-01-19 | |
US60/010,242 | 1996-01-19 |
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WO1997026072A1 true WO1997026072A1 (en) | 1997-07-24 |
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PCT/US1997/000733 WO1997026072A1 (en) | 1996-01-19 | 1997-01-17 | Subatmospheric, variable pressure sample delivery chamber for electrospray ionization/mass spectrometry and other applications |
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EP (1) | EP0888169A4 (en) |
WO (1) | WO1997026072A1 (en) |
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- 1997-01-17 US US08/784,400 patent/US6068749A/en not_active Expired - Fee Related
- 1997-01-17 EP EP97903835A patent/EP0888169A4/en not_active Withdrawn
- 1997-01-17 WO PCT/US1997/000733 patent/WO1997026072A1/en not_active Application Discontinuation
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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WO1998053308A1 (en) * | 1997-05-23 | 1998-11-26 | Northeastern University | On-line liquid sample deposition interface for matrix assisted laser desorption ionization-time of flight (maldi-tof) mass spectroscopy |
US6674070B2 (en) | 1997-05-23 | 2004-01-06 | Northeastern University | On-line and off-line deposition of liquid samples for matrix assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectroscopy |
US6825463B2 (en) | 1997-05-23 | 2004-11-30 | Northeastern University | On-line and off-line deposition of liquid samples for matrix assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectroscopy |
US6175112B1 (en) | 1998-05-22 | 2001-01-16 | Northeastern University | On-line liquid sample deposition interface for matrix assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectroscopy |
US6459080B1 (en) | 1998-06-12 | 2002-10-01 | Agilent Technologies, Inc. | Miniaturized device for separating the constituents of a sample and delivering the constituents of the separated sample to a mass spectrometer |
EP1113850A1 (en) * | 1998-09-17 | 2001-07-11 | Advion BioSciences, Inc. | Integrated monolithic microfabricated electrospray and liquid chromatography system and method |
EP1113850A4 (en) * | 1998-09-17 | 2006-02-01 | Advion Biosciences Inc | Integrated monolithic microfabricated electrospray and liquid chromatography system and method |
Also Published As
Publication number | Publication date |
---|---|
US6068749A (en) | 2000-05-30 |
EP0888169A4 (en) | 2006-06-14 |
EP0888169A1 (en) | 1999-01-07 |
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