CN107946166A - Mass spectrograph and the method that the information on sample is measured using mass spectrograph - Google Patents

Mass spectrograph and the method that the information on sample is measured using mass spectrograph Download PDF

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Publication number
CN107946166A
CN107946166A CN201711304468.XA CN201711304468A CN107946166A CN 107946166 A CN107946166 A CN 107946166A CN 201711304468 A CN201711304468 A CN 201711304468A CN 107946166 A CN107946166 A CN 107946166A
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China
Prior art keywords
ion
mass spectrograph
mass
detector
electrode
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Granted
Application number
CN201711304468.XA
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Chinese (zh)
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CN107946166B (en
Inventor
安德鲁·J·巴特费伊-萨博
克里斯多佛·D·布朗
迈克尔·乔宾
凯文·J·诺普
叶夫根尼·克雷洛夫
斯科特·米勒
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908 Devices Inc
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908 Devices Inc
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Priority to CN201711304468.XA priority Critical patent/CN107946166B/en
Publication of CN107946166A publication Critical patent/CN107946166A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/0013Miniaturised spectrometers, e.g. having smaller than usual scale, integrated conventional components
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/24Vacuum systems, e.g. maintaining desired pressures

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)

Abstract

Disclose mass spectrograph and using method of the mass spectrograph measurement on the information of sample.Mass spectrograph includes ion gun, ion trap, ion detector and pressure regulation system, wherein, during mass spectrograph is run, pressure regulation system be configured in ion gun, ion trap and ion detector at least two in maintain air pressure between 100mTorr and 100Torr, and ion detector is configured and detects ion according to the mass-to-charge ratio of the ion by ion gun generation.

Description

Mass spectrograph and the method that the information on sample is measured using mass spectrograph
It is on December 31st, 2012 applying date that the application, which is, Application No. 201280078246X, entitled " mass spectrum The division Shen of the application of instrument and the method (original name is known as compact mass spectrograph) that the information on sample is measured using mass spectrograph " Please.
Technical field
This disclosure relates to the identification using mass spectroscopy.
Background technology
Mass spectrograph is widely used in the detection of chemical substance.In typical mass spectrograph, molecule or particle are excited or ionize, this A little species that are excited often are decomposed to form the ion of smaller quality or react to form other characteristic ions with other species.Ion shape It can be interpreted into pattern by Systems Operator to be inferred to the identity of compound.
The content of the invention
Generally speaking, in a first aspect, disclosure characterization includes ion gun, ion trap, ion detector and air pressure adjustment The mass spectrograph of system, wherein, during mass spectrograph is run, pressure regulation system is configured in ion gun, ion trap and ion inspection The air pressure between 100mTorr and 100Torr is maintained at least two surveyed in device, and ion detector is configured basis Ion is detected by the mass-to-charge ratio of the ion of ion gun generation.
Mass spectrometric embodiment can include any one or more in following features.
During operation, pressure regulation system can be configured in ion trap and ion detector and maintain 100mTorr Air pressure between 100Torr.During operation, pressure regulation system can be configured in ion gun and ion trap and maintain Air pressure between 100mTorr and 100Torr.During operation, pressure regulation system can be configured in ion gun and ion inspection The air pressure maintained between 100mTorr and 100Torr is surveyed in device.During operation, pressure regulation system can be configured in from The air pressure between 100mTorr and 100Torr is maintained in component, ion trap and ion detector.
Ion gun can include glow discharge ionization source.Ion gun can include capacitive discharge ionization source.Ion gun can With including medium barrier discharge ionization source.
Pressure regulation system can include air pump, it is configured in control ion gun, ion trap and ion detector extremely Air pressure two few.Mass spectrograph can include controller, it is configured activation air pump to control ion gun, ion trap and ion to examine Survey at least two air pressure in device.Air pump can include vortex pump.
During operation, pressure regulation system can be configured in ion gun, ion trap and ion detector at least The air pressure between 500mTorr and 10Torr is maintained in two.During operation, pressure regulation system can be configured in from In component, ion trap and ion detector at least two in maintain measures of dispersion be less than 10Torr air pressure.During operation, gas Pressure regulating system can be configured in the air pressure for maintaining measures of dispersion to be less than 10Torr in ion gun, ion trap and ion detector. During operation, pressure regulation system can be configured in ion gun, ion trap and ion detector at least two in tie up Hold identical air pressure.During operation, pressure regulation system can be configured in ion gun, ion trap and ion detector and tie up Hold identical air pressure.
Mass spectrograph can include:Gas circuit, wherein, ion gun, ion trap and ion detector are connected to gas circuit;And gas Entrance, it is connected to gas circuit and is arranged such that during operation, and gas to be analysed particle is introduced into by gas access Gas circuit, and in gas circuit gas to be analysed particle pressure between 100mTorr and 100Torr.Gas access can through with Put so that during operation, including the gas particle mixture of gas to be analysed particle and atmospheric gas particle is inhaled into gas Body entrance, and the mixture of gas particle is not filtered before gas circuit is introduced to remove atmospheric gas particle.
Mass spectrograph can include the sample gas inlet for being connected to gas circuit, and be connected to the buffer gas entrance of gas circuit, Wherein, sample gas inlet and buffer gas entrance are arranged such that during mass spectrometric operation:Gas to be analysed grain Son is introduced in gas circuit by sample gas inlet;Buffer gas particle is introduced in gas circuit by buffer gas entrance; And the combination pressure of gas to be analysed particle and buffer gas particle is between 100mTorr and 100Torr in gas circuit. Buffer gas particle can include nitrogen molecule and/or Inert gas molecule.
Ion gun and ion trap can be closed in the shell including the first multiple electrodes, and mass spectrograph can also wrap The support base of the second multiple electrodes of characterization is included, the second multiple electrodes, which are configured, is releasably engaged the first multiple electrodes so that Shell can repeat to be connected and disconnected from from support base.Mass spectrograph can include attachment means, it is configured when the first multiple electrodes Support base is secured the housing to when engaging the second multiple electrodes.Attachment means can be included in clamping device and cam at least One.
First multiple electrodes can include pin, and the second multiple electrodes can include being configured the pipe for accommodating the pin Seat.
Ion detector can be closed inside the shell.Pressure regulation system can include pump, and the pump can be sealed Close inside the shell.
Support base can include the voltage source for being couple to a electric contact more than second, and be connected to the control of voltage source Device, wherein, when cage connection is to support base, controller is also connected to ion gun and ion trap.During operation, controller At least one air pressure that can be configured in definite ion gun, ion trap and ion detector, and by activating air pressure tune Section system control pressure.
Mass spectrometric full-size can be less than 35cm.Mass spectrometric gross mass can be less than 4.5kg.
In any combinations, in due course, mass spectrometric embodiment is additionally may included in other features disclosed herein Any one.
On the other hand, disclosure characterizing method, this method include:Examined in mass spectrometric ion gun, ion trap and ion Maintain air pressure between 100mTorr and 100Torr at least two surveyed in device, and according to by ion gun generate from The mass-to-charge ratio detection ion of son.
The embodiment of this method can include any one or more in following features.
This method can be included in the gas maintained in ion trap and ion detector between 100mTorr and 100Torr Pressure.This method can be included in the air pressure maintained in ion gun and ion trap between 100mTorr and 100Torr.This method can To be included in the air pressure maintained in ion gun and ion detector between 100mTorr and 100Torr.This method can include The air pressure between 100mTorr and 100Torr is maintained in ion gun, ion trap and ion detector.This method can include In ion gun, ion trap and ion detector at least two in maintain air pressure between 500mTorr and 10Torr.Should Method can be included in the gas for maintaining measures of dispersion to be less than 10Torr at least two in ion gun, ion trap and ion detector Pressure.This method can be included in the air pressure for maintaining measures of dispersion to be less than 10Torr in ion gun, ion trap and ion detector.The party Method can be included in ion gun, ion trap and ion detector at least two in maintain identical air pressure.This method can be with It is included in ion gun, ion trap and ion detector and maintains identical air pressure.
This method can include:The gas particle that will be analyzed by gas access introduces connection ion gun, ion trap In the gas circuit of ion detector so that in gas circuit the pressure of gas to be analysed particle 100mTorr and 100Torr it Between.This method can include:The mixture of gas particle is introduced connection ion gun, ion trap and ion by gas access to examine Survey in the gas circuit of device, wherein, the mixture of gas particle includes gas to be analysed particle and atmospheric gas particle, and gas The mixture of body particle is not filtered before gas circuit is introduced into remove atmospheric gas particle.
This method can include:The gas particle that will be analyzed by sample gas inlet introduce connection ion gun, from In the gas circuit of sub- trap and ion detector, and buffer gas particle is introduced into gas circuit by buffer gas entrance, wherein, gas The combination pressure of gas to be analysed particle and buffer gas particle is between 100mTorr and 100Torr in road.Buffer gas Body particle can include nitrogen molecule and/or Inert gas molecule.
In any combinations, in due course, the embodiment of this method is additionally may included in other features disclosed herein Any one.
On the other hand, disclosure characterization mass spectrograph, the mass spectrograph include:The support base of the first multiple electrodes is characterized, And the pluggable module of the second multiple electrodes of characterization.Wherein, pluggable module is configured by making a electric connector more than second and A electric connector more than one is engaged to be releasably connected to support base, also, ion of the pluggable module including being connected to gas circuit Trap.
Mass spectrometric embodiment can include any one or more in following features.
Pluggable module can include the ion trap for being connected to gas circuit.Second multiple electrodes can include pin, and first Multiple electrodes can include being configured the tube socket for accommodating the pin.
Support base includes the first attachment means, and pluggable module includes being configured the engaged with the first attachment structure Two attachment means.
First and second attachment means can be arranged such that pluggable module can only be releasably connected in one direction Support base.One in first and second attachment means can include asymmetric extended element, and the first and second attachments Another in mechanism can include being configured the groove for accommodating the extended element.At least one in first and second attachment means It is a to include flexible seal member.In first and second attachment means it is at least one can include clamping device and cam in It is at least one.
Mass spectrograph can include the gas access for being connected to gas circuit.Mass spectrograph can include the ion for being attached to support base Detector.Pluggable module can include the ion detector for being connected to gas circuit.Ion detector can be positioned in support base On so that when pluggable module is connected to support base, ion detector is connected to gas circuit.
Mass spectrograph can include the pump for being attached to support base.Pluggable module can include the pump for being connected to gas circuit.Pump can To be positioned in support base so that when pluggable module is connected to support base, which is connected to gas circuit.Pump can include Vortex pump.
Ion gun can include glow discharge ionization source and/or capacitive discharge ionization source.
Mass spectrograph can include the ion detector for being connected to gas circuit, and be attached to support base and be connected to ion trap Controller.During mass spectrograph is run, controller can be configured the ion generated using detector detection by ion gun, really The fixed relevant information of identity with tested measured ion, and show the information using output interface.
Mass spectrograph can include be connected to gas circuit and be configured by the pressure of gas particle maintain from 100mTorr to The pump of the scope of 100Torr.Mass spectrograph can include the controller for being connected to ion trap and pump, wherein, in the operation mass spectrograph phase Between, controller can be configured the pressure of the gas particle in definite gas circuit, and activate the pump so that the pressure of gas particle to be tieed up Hold in the scope from 100mTorr to 100Torr.
The pump can be configured the scope maintained the pressure of gas particle from 100mTorr to 100Torr.
Mass spectrograph can include the seal bootr around support base and pluggable module, which includes neighbouring pluggable module The opening of placement, to allow mass spectrometric user to be connected and disconnected from pluggable module from support base by the opening.Mass spectrograph can With including covering, when disposing the covering, it seals the opening in the seal bootr.Covering can include collapsible door. Covering can include can be from the cover piece that seal bootr is pulled down completely.
Mass spectrometric full-size can be less than 35cm.Mass spectrometric gross mass can be less than 4.5kg.
In any combinations, in due course, mass spectrometric embodiment is additionally may included in other features disclosed herein Any one.
On the other hand, disclosure characterization spectrometer system, the system include any of mass spectrograph disclosed herein, These first pluggable modules of mass-spectroscopic characterization, and one or more additional pluggable modules, wherein, each add pluggable module bag Ion trap and the 3rd multiple electrodes are included, and each adds pluggable module and is configured by making the 3rd multiple electrodes and more than first Electrode engagement is releasably connected to support base.
The embodiment of system can include any one or more in following features.
At least one in additional pluggable module can include with the ion trap in the first pluggable module it is substantially similar from Sub- trap.
First pluggable module can include ion gun, and at least one in additional pluggable module can include and first The different ion gun of the ion gun of pluggable module.For example, the ion gun of the first pluggable module can include glow discharge ionization source, And in additional pluggable module it is at least one can include the ionization source different from glow discharge ionization source (for example, electron spray Ionization source, medium barrier discharge ionization source, and/or capacitance discharge ionization source).
At least one in additional pluggable module can include the ion trap different from the ion trap in the first pluggable module. The diameter of the ion trap of first pluggable module can be different from the diameter of at least one ion trap in additional pluggable module.Separately Selection of land or additionally, the shape of cross section of the ion trap of the first pluggable module can with it is at least one in additional pluggable module The shape of cross section of ion trap is different.
First pluggable module can include ion detector, and the ion that can each include in additional pluggable module is examined Device is surveyed, and the ion detector of the first pluggable module can be with least one ion detector in additional pluggable module not Together.
At least one surface of first pluggable module can include first coating, and at least one in additional pluggable module A at least one surface can include the second coating different from first coating.
In any combinations, in due course, the embodiment of the system is additionally may included in other features disclosed herein Any one.
On the other hand, disclosure characterization mass spectrograph, the mass spectrograph include support base, are installed to the ion of support base Source, is installed to the ion trap of support base, is installed to the ion detector of support base, and is installed to support base and passes through Support base is electrically connected to the electric supply of ion gun, ion trap and ion detector, wherein, when running mass spectrograph, electric power Power supply is configured to ion gun, ion trap and ion detector and provides electric power.
Mass spectrometric embodiment can include any one or more in following features.
Mass spectrometric full-size can be less than 35cm.Mass spectrometric gross mass can be less than 4.5kg.
Mass spectrograph can include being installed to support base and the air pressure adjustment of electric supply is electrically connected to by support base System, wherein, when running mass spectrograph, electric supply is configured to pressure regulation system and provides electric power.Mass spectrograph can include It is installed to support base and ion gun, ion trap, ion detector and pressure regulation system is electrically connected to by support base Controller.Ion gun, ion trap and ion detector may be connected to gas circuit, and during mass spectrograph is run, air pressure tune Section system can be configured the air pressure in gas circuit is maintained from 100mTorr to 100Torr in the range of (for example, from In the range of 500mTorr to 10Torr).Pressure regulation system can include vortex pump.
Support base can include printed circuit board (PCB).
Mass spectrograph can include the gas access for being connected to gas circuit, wherein, gas access is arranged such that in operation mass spectrum During instrument, the mixture of gas particle is introduced into gas circuit by gas access, which includes gas to be analysed grain Son and atmospheric gas particle, and the mixture of gas particle is introduced into gas circuit in the case of no filtered atmospheric gas particle In.Gas access can include the valve for being electrically connected to controller, and during mass spectrograph is run, controller can be configured in The mixture of gas particle is introduced into gas circuit by the interval time of at least 30 seconds by gas access.
During mass spectrograph is run, controller can be configured using ion detector detection by ion gun generate from Son, and the duty cycle of ion gun is adjusted based on the ion detected.Controller can be configured to be generated by adjusting ion gun The time interval of ion adjusts the duty cycle of ion gun.Controller can be configured is applied to ion source electrode by adjusting At least one in the duration and amplitude of current potential adjusts the duty cycle of ion gun.
During mass spectrograph is run, controller can be configured the relevant information of identity determined with tested measured ion, and And show the information using output interface.
Ion gun can include glow discharge ionization source and/or medium barrier discharge ionization source.
In any combinations, in due course, mass spectrometric embodiment is additionally may included in other features disclosed herein Any one.
On the other hand, disclosure characterization mass spectrograph, the mass spectrograph include:Be connected to the ion gun of gas circuit, ion trap and Detector;It is connected to gas circuit and characterizes the gas access of valve;The pressure regulating system for the air pressure being configured in control gas circuit;And The controller of valve, ion gun, ion trap and detector is connected to, wherein, during mass spectrometric operation, pressure regulating system warp Air pressure in gas circuit is maintained above 100mTorr by configuration, and controller is configured:(a) activation valve is with by gas particle Mixture introduces gas circuit, wherein, mixture includes gas to be analysed particle and atmospheric gas particle, and wherein, gas The mixture of particle is introduced into the case of no filtered atmospheric gas particle;(b) active ions sources is with from being analyzed Gas particle generates ion;And (c) activation detector is with according to the mass-to-charge ratio of ion detection ion.
Mass spectrometric embodiment can include any one or more in following features.
Atmospheric gas particle can include at least one of nitrogen particle and oxygen particles.Pressure regulating system can be through Air pressure in gas circuit is maintained above 500mTorr (for example, being more than 1Torr) by configuration.Controller can be configured activation valve with Within the time of at least 10 seconds (for example, within the time of at least 30 seconds, within the time of at least 1 minute, at least 2 minutes In time) mixture of gas particle is continually introduced into gas circuit.
Mass spectrograph can include:Shell, it closes ion gun and ion trap, and characterizes and be connected to ion gun and ion trap First multiple electrodes;And the support base of the second multiple electrodes of characterization, the second multiple electrodes are configured more than first electricity of engagement Pole, wherein, which forms the pluggable module for being configured and being releasably connected to support base.Controller may be coupled to support Base portion.
Mass spectrometric full-size can be less than 35cm.Mass spectrometric gross mass can be less than 4.5kg.
During operation, controller can be configured the duty cycle based on detected ion-select electrode ion gun.For example, Controller can be configured adjusting ion gun so that ion is in 10 seconds or the duration of longer time (for example, the duration For 30 seconds or longer, the duration was 1 minute or longer, and the duration is 2 minutes or longer) from gas to be analysed particle Produce.
In any combinations, in due course, mass spectrometric embodiment is additionally may included in other features disclosed herein Any one.
On the other hand, disclosure characterizing method, including:The mixture of gas particle is introduced into mass spectrometric gas circuit, Wherein, which includes gas to be analysed particle and atmospheric gas particle, and wherein, the mixture of gas particle exists Do not have to be introduced into the case of filtered atmospheric gas particle;The air pressure in gas circuit is set to be maintained above 100mTorr;Use connection Ion is generated to the ion gun of gas circuit from gas to be analysed particle;And the detector for being connected to gas circuit is used according to ion Mass-to-charge ratio detects ion.
The embodiment of this method can include any one or more in following features.
Atmospheric gas particle can include at least one of nitrogen particle and oxygen particles.
This method can include the air pressure in gas circuit being maintained above 500mTorr (for example, being more than 1Torr).This method (for example, within least 30 seconds time, within the time of at least 2 minutes) can be included in the time of at least 10 seconds by gas The mixture of particle is continually introduced into gas circuit.This method can include adjusting ion gun so that ion is at 10 seconds or for more time Duration in (for example, the duration is 30 seconds or longer, the duration is 2 minutes or longer) from gas to be analysed Particle produces.
In any combinations, in due course, the embodiment of this method is additionally may included in other features disclosed herein Any one.
On the other hand, disclosure characterization mass spectrograph, it includes ion gun, ion trap, ion detector, characterization Single Mechanical The pressure regulating system of pump, and the controller of ion gun, ion trap and ion detector is connected to, Single Mechanical pump is configured The air pressure in ion gun, ion trap and ion detector is controlled, wherein, Single Mechanical pump is in the frequency fortune less than 6000 turns per minute Row is with control pressure, and wherein, and during mass spectrograph is run, controller is configured active ions detector with according to by ion The mass-to-charge ratio of the ion of source generation detects ion.
Mass spectrometric embodiment can include any one or more in following features.
Single Mechanical pump can include vortex pump.Single Mechanical pump can be run in the frequency less than 4000 turns per minute to control Air pressure.
During mass spectrograph is run, Single Mechanical pump can be at least two in ion gun, ion trap and ion detector In maintain air pressure between 100mTorr and 100Torr.During mass spectrograph is run, Single Mechanical pump can ion gun, from In sub- trap and ion detector at least two in maintain air pressure between 500mTorr and 10Torr.In the operation mass spectrograph phase Between, Single Mechanical pump can maintain common air pressure at least two in ion gun, ion trap and ion detector.In operation matter During spectrometer, it is 10mTorr or smaller that Single Mechanical pump can maintain measures of dispersion in ion gun, ion trap and ion detector Air pressure.
Controller may be coupled to pump, and during mass spectrograph is run, controller can be configured the frequency of control pump. During mass spectrograph is run, controller is configured the ion generated using ion detector detection by ion gun, and based on detection To ion adjust the frequency of pump.
Ion gun can include glow discharge ionization source, medium barrier discharge ionization source and/or capacitive discharge ionization source.
Mass spectrograph can include:Shell, it closes ion gun and ion trap, and characterizes and be connected to ion gun and ion trap First multiple electrodes;And the support base of the second multiple electrodes of characterization, the second multiple electrodes are configured more than first electricity of engagement Pole, wherein, which is to be configured the pluggable module for being releasably connected to support base.Shell can close pump.Controller It can be installed in support base.Support base can include printed circuit board (PCB).Electronic processors can pass through support base It is electrically connected to ion gun and ion trap.
Mass spectrometric full-size can be less than 35cm.Mass spectrometric gross mass is less than 4.5kg.
In any combinations, in due course, mass spectrometric embodiment is additionally may included in other features disclosed herein Any one.
On the other hand, disclosure characterizing method, it includes:Using Single Mechanical pump control mass spectrograph in ion gun, from Air pressure in sub- trap and ion detector, and detect what is generated by ion gun using ion detector according to the mass-to-charge ratio of ion Ion, wherein, the frequency being included in using Single Mechanical pump control pressure less than 6000 turns per minute runs the pump with control pressure.
The embodiment of this method can include any one or more in following features.
The frequency operation that this method can be included in less than 4000 turns per minute is pumped with control pressure.This method can include In ion gun, ion trap and ion detector at least two in maintain air pressure (example between 100mTorr and 100Torr Such as, between 500mTorr and 10Torr).
This method can be included in ion gun, ion trap and ion detector at least two in maintain common air pressure. This method can be included in the air pressure that difference 10mTorr or less amount are maintained in ion gun, ion trap and ion detector.
This method can include the frequency that pump is adjusted based on the ion (for example, based on the abundance for detecting ion) detected Rate.
In any combinations, in due course, the embodiment of this method is additionally may included in other features disclosed herein Any one.
On the other hand, the disclosure characterization mass spectrograph, it include ion gun, ion trap, ion detector, user interface and The controller of ion gun, ion trap, ion detector and user interface is connected to, wherein, during mass spectrograph is run, controller The ion generated using ion detector detection by ion gun is configured, determines the chemical name associated with the ion measured, And chemical name is shown on a user interface, and wherein, user interface includes control, control after chemical name is being shown When part is activated by a user, which promotes controller to show the frequency spectrum for measuring ion on a user interface.
Mass spectrometric embodiment can include any one or more in following features.
The frequency spectrum that display measures ion includes the abundance that measures ion of the display as the function of the mass-to-charge ratio of ion.Control It can include at least one of region of button, switch and touch-screen display.During mass spectrograph is run, controller may be used also The harm associated with measuring ion is shown on a user interface to be configured.
Ion gun can include in glow discharge ionization source, capacitive discharge ionization source and medium barrier discharge ionization source It is at least one.
During mass spectrograph is run, controller can be arranged such that the frequency spectrum for measuring ion is not shown until control quilt Activation.
Ion detector can include Faraday detector.
Mass spectrograph can include pressure regulating system, wherein, during mass spectrograph is run, pressure regulating system is configured in Maintained in ion trap and ion detector between 100mTorr and 100Torr (for example, between 500mTorr and 10Torr) Air pressure.
Pressure regulating system can include vortex pump.
Mass spectrograph can include:Pluggable module, it characterizes ion gun and ion trap and is connected to ion gun and ion trap The first multiple electrodes;And the support base of characterization voltage source and the second multiple electrodes, the second multiple electrodes are configured engagement First multiple electrodes, wherein, which, which is configured, is releasably connected to support base.
Pluggable module can include ion detector.Pluggable module can include pressure regulating system.
Mass spectrograph can include shell, the shell seal pluggable module and support base, and characterize an opening, and the opening is adjacent Nearly pluggable module placement, is configured to allow pluggable module to be inserted into by the opening to be releasably connected to support base.
Mass spectrometric full-size can be less than 35cm.Mass spectrometric gross mass can be less than 4.5kg.
In any combinations, in due course, mass spectrometric embodiment is additionally may included in other features disclosed herein Any one.
On the other hand, disclosure characterization mass spectrograph, including:Ion gun, ion trap, ion detector, user interface with And the controller of the ion gun, ion trap, ion detector and user interface is connected to, wherein, user interface includes can be by Mass spectrometric user is activated to a kind of control at least two states, wherein, during mass spectrograph is run, controller is through matching somebody with somebody Put using ion detector to detect the ion generated by ion gun, determine the chemical name associated with measuring ion, and: If control is activated into first state, chemical name is shown on a user interface;And if control is activated into second State, then show the frequency spectrum for measuring ion on a user interface.
Mass spectrometric embodiment can include any one or more in following features.
If control is activated into the second state, controller can also be configured and show chemical name on a user interface Claim.The frequency spectrum that display measures ion can include the abundance that measures ion of the display as the function of the mass-to-charge ratio of ion.Control It can include at least one of region of button, switch and touch-screen display.
Ion gun can include glow discharge ionization source, capacitive discharge ionization source and/or medium barrier discharge ionization source At least one of.
Mass spectrograph can include the pressure regulating system for being connected to controller, wherein, during mass spectrograph is run, pressure tune Section system, which is configured in ion trap and ion detector, to be maintained between 100mTorr and 100Torr (for example, in 500mTorr Between 10Torr) air pressure.Pressure regulating system can include vortex pump.
Mass spectrograph can include:Pluggable module, it includes ion gun and ion trap, and is connected to ion gun and ion trap The first multiple electrodes;And the support base including voltage source and the second multiple electrodes, the second multiple electrodes are configured engagement First multiple electrodes, wherein, which, which is configured, is releasably connected to support base.Pluggable module can include ion Detector and/or pressure regulating system.
Mass spectrograph can include shell, the shell seal pluggable module and support base, and characterize an opening, and the opening is adjacent Nearly pluggable module placement, and be configured to allow pluggable module to be inserted into by the opening to be releasably connected to support base.
Mass spectrometric full-size can be less than 35cm.Mass spectrometric gross mass can be less than 4.5kg.
In any combinations, in due course, mass spectrometric embodiment is additionally may included in other features disclosed herein Any one.
On the other hand, disclosure characterization mass spectrograph, it includes:Ion gun, ion trap, ion detector, sample inlet And pressure regulating system, wherein, ion gun, ion trap, ion detector, sample inlet and pressure regulating system are connected to gas Road, and wherein, during mass spectrograph is run, gas particle is only introduced in gas circuit by sample inlet, and pressure adjusts system System is configured and maintains the air pressure in gas circuit between 100mTorr and 100Torr, and ion detector be configured according to from Son mass-to-charge ratio come detect by gas particle ion gun generation ion.
Mass spectrometric embodiment can include any one or more in following features.
Pressure regulating system can be configured and maintain air pressure between 500mTorr and 10Torr.Pressure regulating system can Air pressure is maintained on 500mTorr with being configured.
Ion gun can include in glow discharge ionization source, capacitive discharge ionization source and medium barrier discharge ionization source It is at least one.
Mass spectrometric full-size can be less than 35cm.Mass spectrometric gross mass can be less than 4.5kg.
Pressure regulating system can include vortex pump.
Sample inlet can be arranged such that the gas particle being introduced in gas circuit includes gas to be analysed particle With atmospheric gas particle.
Mass spectrograph can include being connected to the valve of sample inlet and being connected to the controller of valve, wherein, in operation mass spectrum During instrument, controller can be configured by sample inlet within the time of at least 30 seconds (for example, the time of at least 1 minute, extremely Time 2 minutes few) gas particle is continually introduced into gas circuit.
Mass spectrograph can include being connected to the controller of ion gun, wherein, during mass spectrograph is run, controller can be through Configuration adjustment is applied to the current potential of ion gun so that ion within the time of at least 30 seconds (for example, the time of at least 1 minute, extremely Time 2 minutes few) continuously generated from the gas particle of ion gun.
Mass spectrograph can include:Pluggable module, it characterizes ion gun and ion trap and is connected to ion gun and ion trap The first multiple electrodes;And the support base of characterization voltage source and the second multiple electrodes, the second multiple electrodes are configured engagement First multiple electrodes, wherein, which, which is configured, is releasably connected to support base.Pluggable module can include pressure Regulating system.
Mass spectrograph can include shell, the shell seal pluggable module and support base, and characterize an opening, and the opening is adjacent Nearly pluggable module placement, and be configured to allow pluggable module to be inserted into by the opening to be releasably connected to support base.
Pressure regulating system can include Single Mechanical and pump, wherein, during mass spectrograph is run, Single Mechanical pump is configured in every The frequency of 6000 turns of minute or smaller is run to maintain the air pressure in gas circuit.
In any combinations, in due course, mass spectrometric embodiment is additionally may included in other features disclosed herein Any one.
On the other hand, disclosure characterizing method, it can include:By single gas access by the mixture of gas particle It is introduced into mass spectrometric gas circuit, wherein, the mixture of gas particle only includes gas to be analysed particle and atmospheric gas grain Son;Air pressure in gas circuit is maintained between 100mTorr and 100Torr;And detected according to the mass-to-charge ratio of ion from being divided The ion of the gas particle generation of analysis.
The embodiment of this method can include any one or more in following features.
This method can include maintaining air pressure between 500mTorr and 10Torr.This method can include tieing up air pressure Hold on 500mTorr.
This method can be included in the time of at least 30 seconds (for example, within the time of at least 1 minute, at least 2 minutes Time in) mixture of gas particle is continually introduced into gas circuit by single gas access.
This method can include:Adjust the current potential being applied on mass spectrometric ion gun so that ion was at least 30 seconds (for example, within least 1 minute time, within the time of at least 2 minutes) is continuous from gas to be analysed particle in time Generation.
This method can be included in 6000 turns per minute or the frequency operation Single Mechanical of smaller is pumped to maintain the gas in gas circuit Pressure.
In any combinations, in due course, the embodiment of this method is additionally may included in other features disclosed herein Any one.
On the other hand, disclosure characterization mass spectrograph, it includes:The ion gun of exit electrodes is characterized, passes through outlet electricity Pole, ion leave ion gun;The ion trap of the inlet electrode of the neighbouring exit electrodes placement of characterization;Ion detector;And pressure Regulating system, wherein:Exit electrodes include defining one or more apertures of the shape of cross section of exit electrodes, and entrance electricity Pole includes defining one or more apertures of the shape of cross section of inlet electrode;The shape of cross sections of exit electrodes it is substantially matching enter The shape of cross section of mouth electrode;And during mass spectrograph is run, pressure regulating system is configured to be maintained at least in an ion trap The air pressure of 100mTorr, and ion detector is configured according to the mass-to-charge ratio of ion to detect the ion generated by ion gun.
Mass spectrometric embodiment can include any one or more in following features.
Ion trap can include one or more ion chambers, which defines the cross section shape of ion trap Shape, and the shape of cross section of ion trap can be with the shape of cross section of substantially matching inlet electrode.
One or more apertures of exit electrodes can include the multiple apertures arranged with rectangle or square matrix.Outlet electricity One or more apertures of pole can include the multiple apertures arranged with hexagonal matrix.One or more apertures of exit electrodes It can include the aperture with rectangular cross-sectional shape.One or more apertures of exit electrodes can include having spiral transversal The aperture of face shape.One or more apertures of exit electrodes can include the aperture with serpentine cross sectional face shape.Outlet electricity One or more apertures of pole can include 4 or more than 4 apertures (for example, 8 or more than 8 apertures, 24 or more than 24 A aperture, 100 or more than 100 apertures).One or more apertures of exit electrodes can be included with serpentine pattern arrangement Multiple apertures.
Mass spectrograph can include being connected to the exit electrodes of ion gun and the voltage source of first electrode, and be connected to voltage The controller in source, wherein, during mass spectrograph is run, controller can be configured by applying to first electrode and exit electrodes Different current potentials runs ion gun, the common earthing potential of different potential references in one kind at least two patterns. In first mode at least two patterns, controller, which can be configured to first electrode and exit electrodes, applies current potential, makes First electrode is obtained relative to common earthing potential in positive potential, and in the second mode at least two patterns, controller It can be configured to first electrode and second electrode and apply current potential so that first electrode relative to being grounded in negative potential jointly.
Mass spectrograph can include the user interface that control may be selected in characterization, this may be selected control and is arranged such that when the control It is activated when running mass spectrograph, controller changes the operational mode of ion gun.
Ion gun can include glow discharge ionization source.
Mass spectrograph can include being connected to the detector of controller, wherein, during mass spectrograph is run, controller can be through Configuration is detected by the ion of ion gun generation using ion detector, and is applied to the first electricity based on the ion-select electrode measured Pole and the current potential of exit electrodes, to control ion gun to continuously generate the duration of ion.During mass spectrograph is run, ion gun Ion can be generated in the multiple ionization cycles for defining ion source frequency, it is each to ionize the cycle and include the of generation ion One time interval, and the second time interval of ion is not generated, the first and second time intervals define duty cycle, and control Device can be configured duty cycle adjustment to the value between 1% and 40% (for example, the value between 1% and 20%, 1% With the value between 10%).
During mass spectrograph is run, controller can be configured determines ion gun should when clear based on the ion measured Reason, by the duty cycle adjustment of ion gun to the value between 50% and 90%, and run the ion gun time of at least 30 seconds with Clear up ion gun.
Pressure regulating system can be configured and maintain in an ion trap between 100mTorr and 100Torr (for example, Between 500mTorr and 10Torr) air pressure.
Mass spectrometric full-size can be less than 35cm.Mass spectrometric gross mass can be less than 4.5kg.
In any combinations, in due course, mass spectrometric embodiment is additionally may included in other features disclosed herein Any one.
On the other hand, disclosure characterization mass spectrograph, it includes:Ion gun, ion trap, ion detector, pressure are adjusted System, is connected to the voltage source of ion gun, ion trap, ion detector and pressure regulating system, and be connected to ion gun, from The controller of sub- trap, ion detector and voltage source, wherein, during mass spectrograph is run, controller is configured active ions source With from gas particle generate ion, active ions detector with detect by ion gun generate ion, and based on measure from Son adjusts mass spectrometric resolution ratio.
Mass spectrometric embodiment can include any one or more in following features.
Controller may be coupled to pressure regulating system and be configured by activation pressure regulating system to change ion gun Resolution ratio is adjusted with least one air pressure in ion trap.Controller can be configured by activation pressure regulating system with At least one air pressure in ion gun and ion trap is reduced to increase resolution ratio.
Controller can be configured to be repeated to apply current potential to spray from trap using voltage source to the central electrode of ion trap Ion, the repetition of current potential apply the repetition rate for defining current potential, and adjusts resolution ratio by varying the repetition rate of current potential. Controller can be configured increases resolution ratio by increasing the repetition rate of current potential.
Controller can be configured the maximum amplitude of the current potential for the central electrode that ion trap is applied to by varying voltage source To adjust resolution ratio.
Controller can be configured applies axial potential difference using voltage source between the electrode of the opposed end of ion trap, And adjust resolution ratio by varying the amplitude of axial potential difference.Controller can be configured by increasing axial potential difference Amplitude increases resolution ratio.
Controller can be configured repeats to apply potential difference to generate ion using voltage source between the electrode of ion gun, The repetition of current potential applies the repetition rate for defining ion gun, and adjusts resolution ratio by varying the repetition rate of ion gun. Controller, which can be configured, makes the repetition rate of ion gun and the repetition rate of the current potential for the central electrode for being applied to ion trap same Step.
Controller can be configured:Application potential difference is repeated between the electrode of ion gun using voltage source, wherein, current potential Repetition apply the repetition time for defining ion gun, and the repetition time is included between the electrode of ion gun and applies potential difference First time interval, and not between the electrode of ion gun apply potential difference the second time interval;And pass through adjusting The duty cycle of ion gun adjusts resolution ratio, wherein, duty cycle corresponds to ratio of the first time interval to the repetition time.Control Device can be configured increases resolution ratio by reducing the duty cycle of ion gun.
Mass spectrograph can include gas circuit, wherein, ion gun, ion trap, ion detector and pressure regulating system are connected to The gas circuit;And buffer gas entrance, it is connected to gas circuit, and characterizes the valve for being connected to controller, wherein, controller is through matching somebody with somebody Put and control the valve to adjust the speed for the buffer gas particle being introduced into by buffer gas entrance in gas circuit, so as to adjust resolution Rate.Controller can be configured increase buffer gas particle and be introduced into the speed in gas circuit to increase resolution ratio.
During mass spectrograph is run, controller can be configured:Reconditioning ion gun with from gas particle generate ion, Active ions detector is to detect the ion generated by ion gun, and based on the mass spectrometric resolution ratio of ion-select electrode measured, directly Reach threshold value to mass spectrometric resolution ratio;Active ions detector when mass spectrometric resolution ratio is at least big as threshold value to examine Survey the ion from gas particle generation;Determine to close based on the ion measured when mass spectrometric resolution ratio is at least big as threshold value In the information of gas particle identity;And information is shown on a user interface.The information can include the chemical name of gas particle Title and/or the information on the harm associated with gas particle and/or the letter on the corresponding material classification of gas particle Breath.
During mass spectrograph is run, controller can be configured adjusting voltage source so that only when resolution ratio reaches threshold value, Current potential is applied to the central electrode of ion trap.
During mass spectrograph is run, pressure regulating system can be configured in ion gun, ion trap and ion detector At least two in maintain between 100mTorr and 100Torr the air pressure of (for example, between 500mTorr and 10Torr).
Mass spectrograph can include:Pluggable module, it characterizes ion gun, ion trap and detector, and be connected to ion gun, First multiple electrodes of ion trap and detector;And the support base of the second multiple electrodes of characterization, the second multiple electrodes are through matching somebody with somebody The first multiple electrodes of engagement are put, wherein, voltage source and controller are installed in support base, and wherein, the pluggable module It is configured and is releasably connected to support base.
Mass spectrometric full-size can be less than 35cm.Mass spectrometric gross mass can be less than 4.5kg.
In any combinations, in due course, mass spectrometric embodiment is additionally may included in other features disclosed herein Any one.
On the other hand, disclosure characterizing method, it includes:Gas particle is introduced into mass spectrometric ion gun, from gas Body particle generates ion, and ion is detected using mass spectrometric detector, and based on mass spectrometric point of the ion-select electrode measured Resolution.
The embodiment of this method can include any one or more in following features.
Adjust at least one middle change air pressure that resolution ratio can be included in ion gun and ion trap.This method can wrap Include by reducing at least one air pressure in ion gun and ion trap to increase resolution ratio.
This method can include repeating to apply current potential to spray ion, the weight of current potential from trap to the central electrode of ion trap It is multiple apply the repetition rate for defining current potential, and adjust resolution ratio by varying the repetition rate of current potential.This method can wrap Include increases resolution ratio by increasing the repetition rate of current potential.This method can include by varying the center for being applied to ion trap The maximum amplitude of the current potential of electrode adjusts resolution ratio.
This method, which can be included between the electrode of the opposed end of ion trap, applies axial potential difference, and by varying The amplitude of axial potential difference adjusts resolution ratio.This method can include differentiating to increase by increasing the amplitude of axial potential difference Rate.
This method repeats to apply potential difference to generate ion between being included in the electrode of ion gun, and the repetition of current potential is applied Reorder the repetition rate of adopted ion gun, and resolution ratio is adjusted by varying the repetition rate of ion gun.This method can wrap The repetition rate for including the repetition rate for making ion gun and being applied to the current potential of the central electrode of ion trap is synchronous.
This method can include:Repeat to apply potential difference between the electrode of ion gun, wherein, the repetition of current potential, which applies, to be determined The repetition time of adopted ion gun, and the repetition time be included between the first time applied potential difference between the electrode of ion gun Every, and not between the electrode of ion gun apply potential difference the second time interval;And by the duty for adjusting ion gun Than adjusting resolution ratio, wherein, duty cycle corresponds to first time interval and the ratio of repetition time.This method can include logical Cross and reduce the duty cycle of ion gun and increase resolution ratio.
This method can include adjusting buffer gas particle and be introduced into the speed in mass spectrometric gas circuit to adjust resolution ratio. This method can include increase buffer gas particle and be introduced into the speed in gas circuit to increase resolution ratio.
This method can include:Reconditioning ion gun from gas particle to generate ion, and active ions detector is to examine The ion generated by ion gun is surveyed, and based on the mass spectrometric resolution ratio of ion-select electrode measured, until mass spectrometric resolution ratio reaches To threshold value;What active ions detector was generated with being detected when mass spectrometric resolution ratio is at least big as threshold value from gas particle Ion;Letter on gas particle identity is determined based on the ion measured when mass spectrometric resolution ratio is at least big as threshold value Breath;And information is shown on a user interface.The information can include gas particle chemical name and/or on gas grain The information of the associated harm of son and/or the information on the corresponding material classification of gas particle.
This method can include applying current potential to the central electrode of ion trap only when resolution ratio reaches threshold value.
This method can be included in ion gun, ion trap and ion detector at least two in maintain 100mTorr The air pressure of (for example, between 500mTorr and 10Torr) between 100Torr.
In any combinations, in due course, the embodiment of this method is additionally may included in other features disclosed herein Any one.
On the other hand, disclosure characterization mass spectrograph, it includes:Ion gun, ion trap, ion detector, characterizes unit The pressure regulation system of tool pump, and the controller of ion gun, ion trap and ion detector is connected to, wherein, in operation matter During spectrometer, pressure regulation system be configured in ion gun, ion trap and ion detector at least two in maintain Air pressure between 100mTorr and 100Torr, and controller is configured active ions detector with the mass-to-charge ratio according to ion To detect the ion generated by ion gun, and wherein, Single Mechanical pump is run in the frequency less than 6000 turns per minute to maintain Air pressure.
Mass spectrometric embodiment can include one or more of following features.During operation, pressure regulation system The air pressure maintained in ion trap and ion detector between 100mTorr and 100Torr can be configured in.During operation, Pressure regulation system can be configured in the air pressure maintained in ion gun and ion trap between 100mTorr and 100Torr. During operation, pressure regulation system can be configured in ion gun, ion trap and ion detector maintain 100mTorr with Air pressure between 100Torr.
Single Mechanical pump can be vortex pump.
During operation, pressure regulation system can be configured in ion gun, ion trap and ion detector at least The air pressure for maintaining measures of dispersion to be less than 10Torr in two.During operation, pressure regulation system can be configured in ion gun, from The air pressure for maintaining measures of dispersion to be less than 10Torr in sub- trap and ion detector.During operation, pressure regulation system can through with Put and identical air pressure is maintained at least two in ion gun, ion trap and ion detector.
Mass spectrograph can include:Gas circuit, wherein, ion gun, ion trap, ion detector and pressure regulation system are connected to Gas circuit;And gas access, it is connected to gas circuit and is arranged such that during mass spectrograph is run, gas to be analysed particle Gas circuit is introduced into by gas access, and the total gas pressure in gas circuit is between 100mTorr and 100Torr.Gas access can be with It is arranged such that during mass spectrograph is run, including the mixing of the gas particle of gas to be analysed particle and atmospheric gas particle Thing is inhaled into gas access, wherein, the mixture of gas particle is not filtered before gas circuit is introduced to remove atmospheric gas grain Son.
Mass spectrograph can include gas circuit, wherein, ion gun, ion trap, ion detector and pressure regulation system are connected to Gas circuit;It is connected to the sample gas inlet of gas circuit;And the buffer gas entrance of gas circuit is connected to, wherein, sample gas inlet It is arranged such that with buffer gas entrance during mass spectrograph is run:Gas to be analysed particle passes through sample gas inlet quilt It is incorporated into gas circuit, buffer gas particle is introduced in gas circuit by buffer gas entrance, and to be analyzed in gas circuit The combination pressure of gas particle and buffer gas particle is between 100mTorr and 100Torr.Buffer gas particle can include At least one of nitrogen molecule and Inert gas molecule.
Mass spectrograph can include:Pluggable module, it characterizes ion gun and ion trap and is connected to ion gun and ion trap The first multiple electrodes;And the support base of the second multiple electrodes of characterization, the second multiple electrodes, which are configured, to be releasably engaged First multiple electrodes so that the pluggable module may be coupled to support base and be disconnected from it.Mass spectrograph can include attachment machine Structure, it is configured is fixed to support base when the first multiple electrodes engage the second multiple electrodes by pluggable module.More than first Electrode can include pin, and the second multiple electrodes can include being configured the tube socket for accommodating the pin.
Pluggable module can include ion detector, and the first multiple electrodes may be coupled to ion detector.It can insert Module can include mechanical pump.
Mass spectrograph can include voltage source, wherein, voltage source and controller are attached to support base and are connected to second Multiple electrodes.
Support base can include printed circuit board (PCB).When pluggable module is connected to support base, controller can connect To ion gun and ion trap.
Single Mechanical pump can be run with control pressure in the frequency less than 4000 turns per minute.
Mass spectrometric full-size can be less than 35cm.Mass spectrometric gross mass can be less than 4.5kg.
In any combinations, in due course, mass spectrometric embodiment is additionally may included in other features disclosed herein Any one.
On the other hand, disclosure characterizing method, it includes:Use the list run in the frequency less than 6000 turns per minute Mechanical pump to maintain the air pressure at least two in mass spectrometric ion gun, ion trap and ion detector, and according to from Son mass-to-charge ratio come detect by ion gun generate ion, wherein, at least two in ion gun, ion trap and ion detector In air pressure maintain between 100mTorr and 100Torr.
The embodiment of this method can include any one or more in following features.
Air pressure in ion gun and ion trap can be maintained between 100mTorr and 100Torr.Ion trap and ion inspection The air pressure surveyed in device can be maintained between 100mTorr and 100Torr.This method can be included in ion gun, ion trap and from In sub- detector at least two in maintain measures of dispersion be less than 10Torr air pressure.This method can be included in ion gun, ion Identical air pressure is maintained in trap and ion detector.
This method can include:The mixture of gas particle is introduced into connection ion gun, ion trap and ion detector In gas circuit, wherein, the mixture of gas particle includes gas to be analysed particle and atmospheric gas particle, and gas particle Mixture do not filtered before gas circuit is introduced into remove atmospheric gas particle.
The frequency that this method can be included in less than 4000 turns per minute runs mechanical pump with control pressure.
In any combinations, in due course, the embodiment of this method is additionally may included in other features disclosed herein Any one.
Unless specifically stated otherwise, all technical and scientific terms used herein has the ordinary skill of disclosure fields The normally understood equivalent of personnel.Although similar or be equivalent to method described herein and material and can also be used for this theme Embodiment practice or experiment, but suitable method and material will be described herein below.All publications for being mentioned above, Patent application, patent and other bibliography are fully incorporated herein by quoting.In the case of a conflict, will be with this specification Based on (including definition).In addition, the material, method and example are only exemplary, it is not intended to limit.
One or more embodiments of the detail illustrate in attached drawing and following embodiment.From the specific implementation Mode, drawings and claims, other feature and advantage will be apparent.
Brief description of the drawings
Figure 1A is the mass spectrometric schematic diagram of compact.
Figure 1B is the cross-sectional view of mass spectrometric embodiment.
Fig. 1 C are the cross-sectional views of mass spectrometric another embodiment.
Fig. 1 D are the mass spectrometric schematic diagrames for the component for having mounted to support base.
Fig. 1 E are the mass spectrometric schematic diagrames for having pluggable module.
Fig. 1 F are the schematic diagrames for mass spectrometric module to be connected to the attachment means of support base.
Fig. 2A and 2B is the schematic diagram of glow discharge ion source.
Fig. 2 C-2H are the schematic diagrames for showing to have the electrode of foraminate ion gun.
Fig. 2 I are applied to the curve map of the bias potential of the electrode of ion gun.
Fig. 2 J are applied to the electrode of ion gun to clear up the curve map of the bias potential of ion gun.
Fig. 2 K are the schematic diagrames of capacitive discharge ion gun.
Fig. 3 A are the cross-sectional views of the embodiment of ion trap.
Fig. 3 B are the schematic diagrames of another embodiment of ion trap.
Fig. 3 C are the cross-sectional views of the ion trap of Fig. 3 B.
Fig. 4 A are the schematic diagrames of voltage source.
Fig. 4 B are the curve maps for not amplifying modulated signal shown for ion trap.
Fig. 4 C are the curve maps for showing the revise signal for ion trap.
Fig. 4 D are the curve maps for showing reference carrier.
Fig. 4 E are the curve maps for showing the amplification modulated signal for ion trap.
Fig. 4 F are the curve maps for the resonance circuit for showing the signal for enlarged drawing 4E.
Fig. 5 A are the perspective views of the embodiment of Faraday cup charged particle detector.
Fig. 5 B are the schematic diagrames of the Faraday cup detector of Fig. 5 A.
Fig. 5 C are the schematic diagrames of another embodiment of Faraday cup detector.
Fig. 5 D are the schematic diagrames of the matrix of Faraday cup detector.
Fig. 6 A are the schematic diagrames for the pressure regulation sub-systems for characterizing vortex pump.
Fig. 6 B are the schematic diagrames of vortex pump flange.
Fig. 7 A are the mass spectrometric perspective views of compact.
Fig. 7 B and 7C are the cross-sectional views of the mass spectrometric embodiment of compact.
Fig. 8 A are shown for measuring the Information in Mass Spectra of sample and showing the flow chart of the series of steps of information.
Fig. 8 B are the schematic diagrames of the mass spectrometric embodiment of compact.
Fig. 8 C are shown for measuring Information in Mass Spectra and adjusting the flow chart of the series of steps of mass spectrometric configuration.
Same reference numbers label in each drawing represents identical element.
Embodiment
I is generally outlined
Mass spectrograph for chemical substance identification is typically the large complicated instrument for consuming suitable power.This quasi-instrument is often It is excessively heavy so that be difficult to carry, and therefore be limited in can be substantially in the environment of held stationary for its application.It is in addition, traditional Mass spectrograph is typically expensive and needs well-trained operator to interpret the ion that instrument produces to form the frequency spectrum of pattern to push away Break and the identity of analyzed chemical substance.
To obtain high sensitivity and resolution ratio, traditional mass spectrometer is various usually using working at low pressure through design Different components.For example, traditional ion detector such as electron multiplier cannot efficient work in the pressure about on 10mTorr Make.As another example, the thermionic emitter in conventional ion source also best-fit under the pressure less than 10mTorr Work, and generally can not even be used when there is the oxygen concentration of appropriateness.In addition, traditional mass spectrometer generally includes quality analysis Instrument, which, which has to be specifically designed, is only used in the pressure less than 10mTorr and specifically in the pressure of microtorr scope The geometry run under power.As a result, traditional mass spectrograph is not only to be configured as running under low pressure, and due to tradition Mass spectrograph used in component, they cannot generally also run under the air pressure of higher.The air pressure of higher may destroy biography Unite mass spectrometric some components.In the case of less obvious, some components may be difficult to run in more hyperbar, or very Difference operation is so that mass spectrograph can no longer gather useful Information in Mass Spectra.As a result, the mass spectrograph with significantly different configuration and component Need to run under high pressure (for example, pressure more than 100mTorr).
To realize low pressure, traditional mass spectrometer generally includes a series of pumps for evacuating mass spectrograph internal capacity.For example, pass The mass spectrograph of system can include quick the thick of internal system pressure that reduce and pump, and internal pressure is further decreased to microtorr value Turbomolecular pump.Turbo-molecular pump volume is big and consumes suitable power.But, this is only the secondary important of traditional mass spectrometer Consider;Main important consideration is to realize high-resolution when measuring mass spectrum.By using the foregoing component run under low pressure, pass System mass spectrograph can generally realize 0.1 atomic mass unit (amu) or more preferable resolution ratio.
Compared with bulky traditional mass spectrometer, compact mass spectrograph disclosed herein is through designing low-power consumption, high-efficiency operation. To realize low power operation, compact mass spectrograph disclosed herein does not include turbomachinery or the vacuum pump of other power consumptions.On the contrary Compact mass spectrograph only usually is included in the Single Mechanical pump of low-frequency operation, this substantially reduces power consumption.
By using the pump of smaller, compact mass spectrograph disclosed herein is usually in the pressure of 100mTorr to 100Torr In the range of run, this is substantially than the operating pressure scope higher of traditional mass spectrometer.Traditional mass spectrometer can not be changed at these more Run under high pressure, because the component (for example, electron multiplier, thermionic emitter and ion trap) in traditional instrument is no It can be run in the pressure limit that compact mass spectrograph disclosed herein is run.In addition, traditional mass spectrometer generally can not be changed to Run under the internal pressure of higher, because such device would generally produce measurement mass spectrum excessively poor resolution ratio when so doing. The purpose of such device is used because the mass spectrum for obtaining highest possible resolution ratio is typically for we, few reasons remove change device To provide worse resolution ratio.
But, compact mass spectrograph disclosed herein provides a user and the different types of information of traditional mass spectrometer.Specifically Ground, compact mass spectrograph disclosed herein are normally reported title and the relevant harm of the material of such as analyzed chemical substance Information and/or the material belong to the information of classification.Compact mass spectrograph disclosed herein can also report such as material yes or no Specific objective material.In general, the mass spectrum recorded is not shown to user, except non-user activates the control for causing mass spectrum to show.Knot Fruit, unlike traditional mass spectrometer, compact mass spectrograph disclosed herein need not obtain the mass spectrum with highest possible resolution ratio.Instead And as long as the mass spectrum quality obtained is not high enough to information of the definite report to user, it is key further to increase resolution ratio Can standard.
It is public herein by running at lower resolutions (in general, resolution ratio of the mass spectrum between 1amu and 10amu obtains) The compact mass spectrograph opened consumes significantly less power than traditional mass spectrograph.For example, compact mass spectrograph disclosed herein Characterize minitype ion trap, its in the pressure Effec-tive Function from 100mTorr to 100Torr to separate the ion of different mass-to-charge ratioes, and The power less more than conventional mass analysis instrument such as ion trap is consumed at the same time, because the size of its reduction.For example, with cylinder The size of shape ion trap is reduced, and is applied to trap to separate the reduction of the maximum voltage of ion, and applies alive frequency increase.Knot Fruit, the size of inductor and/or resonator in power circuit are reduced, and for generate maximum voltage other The size and power consumption demand of component are also reduced.
In addition, compact mass-spectroscopic characterization high-effect ionic source such as glow discharge ionization source and/or capacitance disclosed herein Property discharge ionization source, the thermionic emitter that such as can be generally found relative to ion gun in traditional mass spectrometer, this is further Reduce power consumption.Efficient low-power consumption detector such as Faraday detector is used in compact mass spectrograph disclosed herein, rather than Use the more power consumption electron multiplier being present in traditional mass spectrometer.Due to these low-power consumption components, compact disclosed herein Mass spectrograph Effec-tive Function and the electrical power for consuming relatively small amount.They can be by the power supply based on battery of standard (for example, lithium Ion battery) power supply, and it is easy to carry due to hand-held shape.
Because traditional mass spectrograph directly provides high resolution mass spec to user, it is generally not suitable for without specialized training Application of the personnel to material motion scan.Specifically, for the site safety scanning on transport hub such as airport and railway station Application, traditional mass spectrograph is not practical solution.Compact need to transport less relatively on the contrary, such application is benefited from the contrary Row power and the mass spectrograph that the information easily interpreted by the personnel without advanced training is provided, as described above.It is compact, inexpensive Mass spectrograph be also useful for various other applications.For example, such device can use in the lab it is unknown to provide The Rapid identification of chemical compound.Since its cost is low, occupying little space, laboratory can provide private mass spectrograph to worker, Reduce or eliminate the needs in the mass spectroscopy device planning application time of concentration.Compact mass spectrograph can be also used in such as medical diagnosis Test is included in the clinical application set with individuals patients' house.Thus interpretation can be easy to by performing the technician of this class testing The information that class mass spectrograph provides, to provide feedback in real time to others, and also carries to medical facilities, doctor and other health cares For the quick fresh information of business.
The compact low-power consumption mass spectrograph of disclosure characterization provides a user various information, includes the chemicals of mass spectrograph scanning The identification of matter and/or associated background information, including related material belong to classification information (for example, acid, alkali, strong oxidizer, Explosive, nitro compound), the information related with the harm that the material is associated, and safety recommendation and/or information.The matter Spectrometer is run under the air pressure inside than traditional mass spectrometer higher.By running under high pressures, relative to traditional mass spectrum Instrument, the mass spectrometric size of compact and power consumption are decreased obviously.Moreover, even if mass spectrograph is run under high pressures, it is mass spectrometric Resolution ratio is enough precise Identification and the quantization for allowing various chemical substances.
Figure 1A is the schematic diagram of the embodiment of compact mass spectrograph 100.Mass spectrograph 100 includes ion gun 102, ion trap 104, voltage source 106, controller 108, detector 118, pressure regulation sub-systems 120, and sample inlet 124.Sample inlet 124 include valve 129.Alternatively, mass spectrograph 100 includes buffering source of the gas 150.The component of mass spectrograph 100 is sealed in shell 122. Controller 108 includes electronic processors 110, user interface 112, storage unit 114, display 116, and communication interface 117.
Controller 108 via control line 127a-127g be connected respectively to ion gun 102, ion trap 104, detector 118, Pressure regulation sub-systems 120, voltage source 106, valve 129 and optional buffering source of the gas 150.Control line 127a-127g allows to control Each component that device 108 (for example, electronic processors 110 in controller 108) processed is connected to it sends operation order.It is such Order can include for example active ions source 102, ion trap 104, detector 118, pressure regulation sub-systems 120, valve 129 and Buffer the signal of source of the gas 150.Activating the order of the various parts of mass spectrograph 100 can be included to voltage source 106 with first to component Part applies the instruction of current potential.For example, being active ions source 102, controller 108 can be sent to voltage source 106 to ion gun 102 In electrode apply current potential instruction.As another example, it is active ions trap 104, controller 108 can be to voltage source 106 Send the instruction that the electrode into ion trap 104 applies current potential.As further example, it is activation detector 118, controller 108 detecting elements that can be sent to voltage source 106 into detector 118 apply the instruction of current potential.Controller 108 can also be sent out Activation pressure is sent to adjust the signal (for example, by voltage source 106) of subsystem 120, to control all parts in mass spectrograph 100 In air pressure, and send signal to valve 129 (for example, passing through voltage source 106) to allow gas particle to pass through sample inlet 124 Into mass spectrograph 100.
In addition, controller 108 can receive signal by control line 127a-127g from each component of mass spectrograph 100.Example Such as, such signal can include adjusting subsystem on ion gun 102 and/or ion trap 104 and/or detector 118 and/or pressure The information of the operation characteristic of system 120.Controller 108 can also receive the information of the ion detected by detector 118.Information can be with Including the gas current measured by detector 118, it is related with the abundance of the ion with specific mass-to-charge ratio.The information can be with Be included in specific ion abundance be applied to when being measured by detector 118 ion trap 104 electrode specific voltage information.It is special Surely the voltage applied is related with the particular value of the mass-to-charge ratio of ion.It is related to the abundance messages surveyed by information of voltage, control Device 108 can be determined as the abundance of the ion of the function of mass-to-charge ratio, and can be in the form of mass spectrographic using display 116 This existing information.
Voltage source 106 is connected respectively to ion gun 102, ion trap 104, detector 118, pressure via control line 126a-e Adjust subsystem 120 and controller 108.Each offer electricity of the voltage source 106 by control line 126a-e into these components Position and electric power.Voltage source 106, which is established, corresponds to the electrically grounded reference potential that opposite voltage is 0 volt.Voltage source 106 is applied to matter This earthing potential of the potential reference of all parts of spectrometer 100.In general, voltage source 106 is configured to mass spectrograph 100 Component, which applies, to be positive current potential relative to reference ground potential and is negative current potential.By to these components (for example, to each component Electrode) apply the current potentials of distinct symbols, the electric field of distinct symbols can generate in each component, this causes ion in not Tongfang To movement.Therefore, by applying suitable current potential to the component of mass spectrograph 100, controller 108 (passing through voltage source 106) can be with Control the movement of ion in mass spectrograph 100.
Ion gun 102, ion trap 104 and detector 118 are connected so that the inner passage for gas particle and ion I.e. gas circuit 128 extends between these components.Sample inlet 124 and pressure regulation sub-systems 120 are also coupled to gas circuit 128. If it exists, optionally buffering source of the gas 150 is also connected to gas circuit 128.The part of gas circuit 128 schematically illustrates in figure ia. In general, gas particle and ion are moved in any direction of gas circuit 128, and moving direction can pass through mass spectrograph 100 Configuration control.For example, suitable current potential is applied by the electrode into ion gun 102 and ion trap 104, in ion gun The ion generated in 102 can be directed to flow into ion trap 104 from ion gun 102.
Figure 1B shows the schematic partial cross-sectional view of mass spectrograph 100.As shown in Figure 1B, 130 coupling of delivery outlet of ion gun 102 It is connected to the input hole 132 of ion trap 104.In addition, the delivery outlet 134 of ion trap 104 is couple to the input hole 136 of detector 118. As a result, ion and gas particle can be in any direction flowings between ion gun 102, ion trap 104 and detector 118. During running mass spectrograph 100, operating pressure adjust subsystem 120 with by the air pressure drop in gas circuit 128 low to less than atmospheric pressure Value.As a result, gas to be analysed particle enters from the environment (for example, environment in the outside of shell 122) around mass spectrograph 100 Sample inlet 124 is simultaneously moved into gas circuit 128.The gas particle for entering ion gun 102 by gas circuit 128 passes through 102 quilt of ion gun Ionization.Ion is diffused into ion trap 104 from ion gun 102, and ion is in an ion trap by when voltage source 106 is to ion trap 104 electrode applies the electric field capture that suitable potential is formed.
The circulation in ion trap 14 of captured ion.Ion, under the control of controller 108, voltage source are circulated for analysis 106 change the amplitude of the radio frequency capture field for the one or more electrodes for being applied to ion trap 104.The change of amplitude repeats, So as to define the frequency sweep of ion trap 104.When changing the amplitude of field, the ion with specific mass-to-charge ratio fall outside track and Some are sprayed from ion trap 104.The ion of ejection is detected by detector 118, and the information on measuring ion is sent to Controller 108 (for example, the gas current that detector 118 measures, and it is applied to ion trap when measuring specific ion electric current 104 specific voltage).
Although sample inlet 124 disposes in figs. 1 a and 1b so that the environment of gas particle from the outside of shell 122 enter from Sub- trap 104, but, it is more common that sample inlet 124 can also be positioned in other positions.For example, Fig. 1 C show mass spectrograph 100 schematic partial cross-sectional view, wherein, sample inlet 124 be placed so that gas particle from the environment of the outside of shell 122 into Enter ion gun 102.In addition to the configuration shown in Fig. 1 C, if the position of sample inlet 124 allows gas particle from shell The environment of 122 outsides enters gas circuit 128, and sample inlet 124 can usually be placed in any position along gas circuit 128.
In general, communication interface 117 can be wired or wireless communication interface (or both all).Connect by communication Mouthfuls 117, controller 108 can be configured communicate with various devices, the device including remote computer, mobile phone with And monitoring and security scanner.Communication interface 117, which can be configured on various networks, sends and receives data, various network bags Include but be not limited to Ethernet, wireless WiFi nets, Cellular Networks and bluetooth wireless network.Controller 108 can use communication interface 117 with Remote-control device communication is to obtain various information, and various information include the operation of mass spectrograph 100 and configuration is set, and related sense is emerging The information of interesting material, the information include the mass spectrographic record of known substance, the harm associated with particulate material, substances of interest The classification belonged to, and/or the spectral signature of known substance.This information can be used to analyze sample measurement by controller 108.Control Device 108 processed can also send information to remote-control device, and the predetermined substance which includes being measured by mass spectrograph 100 is (for example, dangerous And/or explosive) alarm information.
Mass spectrograph disclosed herein is not only compact but also can low power operation.It is various to realize compact size and low power operation Mass spectrometry components, including ion gun 102, ion trap 104, detector 118, pressure regulation sub-systems 120 and voltage source 106 are through son It is thin to design and configure so that space requirement and power consumption to be minimized.In traditional mass spectrometer, low internal operation pressure is used for realization Vacuum pump (for example, 1x10-3Torr or less) it is not only big but also consume considerable amount of electrical power.For example, to reach such pressure, pass A series of two or more pumps of mass spectrograph generally use of system, the pump are included internal system pressure from the fast prompt drop of atmospheric pressure It is low slightly to be pumped to about 0.1-10Torr, and by internal system pressure from 10Torr be reduced to one of expected internal operation pressure or Multiple turbomolecular pumps.Thick pump and turbomolecular pump both of which are the mechanical pumps for needing considerable amount of electric power to run.Thick pump (its Can include such as pump based on piston) generally produce obvious mechanical oscillation.Turbomolecular pump usually rushes vibration and machinery It is sensitive to hit, and since high rotating speed can produce the effect similar to gyroscope.As a result, traditional mass spectrograph includes being enough completely The power supply of sufficient vacuum pump power consumption demand, and ensure these pump remain on interrupter (for example, vibration and/or rotate every Disembark structure).When traditional mass spectrograph even may be required in operation, turbomolecular pump is immovable, because of that doing to produce Destroy the mechanical oscillation of these pumps.As a result, the combination for the vacuum pump and power supply of traditional mass spectrometer causes traditional mass spectrometer to become Greatly, it is heavy and be difficult to move.
On the contrary, spectrometer system disclosed herein and method are compact, moveable and realize low power operation.These are special Property part realized by removing for traditional mass spectrometer is common turbomolecular pump, thick pump and other big machineries pump.Replace For these mammoth pumps, small low-consumption Single Mechanical pump is used to control the air pressure in spectrometer system.It is disclosed herein to be used for mass spectrum Single Mechanical pump in instrument system cannot reach pressure low as conventional turbine molecular pump.As a result, system disclosed herein exists Than being run under the air pressure inside of traditional mass spectrometer higher.
Such as explain in detail below, caused by various mechanism are such as collided between broadening of spectral lines and molecular fragment Charge-exchange, run usually reduces mass spectrometric resolution ratio under high pressures.As it is used herein, " resolution ratio " defines For at the full width at half maximum (FWHM) of institute's mass metering peak value (FWHM).Specific mass spectrometric resolution ratio is by measuring from 100 to 125amu's The FWHM of all peak values occurred in mass charge ratio range, and resolution ratio is selected as corresponding to the maximum FWHM of single peak to determine (for example, being excluded corresponding to the spike width of the tight spacing collection of two or more peak values).To determine resolution ratio, can use With known mass spectrographic chemical substance such as toluene.
Although can decline in the mass spectrometric resolution ratio of higher pressure operation, mass spectrograph disclosed herein, which is configured, to be made The resolution ratio that must be reduced does not jeopardize mass spectrometric validity.Specifically, mass spectrograph disclosed herein is arranged such that when interested Chemical substance when being scanned using mass spectrograph, mass spectrograph is to information of the user report in relation to material identity, rather than such as in tradition The quality parsing spectrum of common molecular ion in mass spectrograph.In certain embodiments, in mass spectrograph disclosed herein Algorithm can compare the information of surveyed fragment ion pattern and known fragment pattern with the identity of definite such as substances of interest Information, the one or more compounds categories for endangering information and/or substances of interest and belonging to of related substances of interest.In spy Determine in embodiment, which can include determining that the expert system of the information of the identity in relation to substances of interest.For example, numeral filter Ripple device can be used for the special characteristic surveyed in spectrum for searching for substances of interest, and based on existence or non-existence institute in spectrum Feature is stated, material can be accredited as corresponding to specific objective material or not correspond to target substance.
When controller 108 performs Such analysis, can pass through by running reduced resolution ratio under high pressures System disclosed herein compensates.That is if can carry out it is reliable corresponding between surveyed fragment pattern and reference information, Then due to the low resolution of high-voltage operation be for mass spectrometric user disclosed herein do not have it is influential.Therefore, i.e., Mass spectrograph disclosed herein is set to be run under the pressure than traditional mass spectrometer higher, they are such as safe in various applications Scanning, medical diagnosis and lab analysis are still useful, and in such applications, concern is primarily with substances of interest by user Identification rather than detailed inspection material fragment ion pattern, and wherein, the advanced instruction that user can interpret without mass spectrum Practice.
Pumped by using single small-sized machine, mass spectrometric weight, size and power consumption disclosed herein are relative to traditional matter Spectrometer is greatly reduced.Therefore, mass spectrograph disclosed herein generally includes pressure regulation sub-systems 120, it characterizes small-sized machine pump, And the mechanical pump is configured (for example, the air pressure in gas circuit 128, and is connected to the ion gun of gas circuit 128 by air pressure inside 102nd, the air pressure in ion trap 104 and detector 118) maintain between 100mTorr and 100Torr (for example, in 100mTorr Between 500mTorr, between 500mTorr and 100Torr, between 500mTorr and 10Torr, 500mTorr with Between 5Torr, between 100mTorr and 1Torr).In certain embodiments, be configured will be public herein for pressure regulation sub-systems Air pressure inside in the mass spectrograph opened is maintained (for example, more than 500mTorr, more than 1Torr, to be exceeded more than 100mTorr 10Torr, more than 20Torr).
In aforementioned pressure, mass spectrograph disclosed herein detects ion in 10amu or more preferable resolution ratio.For example, some In embodiment, mass spectrometric resolution ratio disclosed herein as above it is measured be 10amu or more preferable resolution ratio (for example, 8amu or more preferable, 6amu or more preferable, 5amu or more preferable, 4amu or more preferable, 3amu or more preferable, 2amu or more preferable, 1amu or more It is good).In general, any one of these resolution ratio can be realized using mass spectrograph disclosed herein under any aforementioned pressure.
In addition to pump, pressure regulation sub-systems 120 can include various other components.In certain embodiments, pressure Adjusting subsystem 120 includes one or more pressure sensors.One or more pressure sensors can be configured measurement pressure Adjust the air pressure in the fluid line such as gas circuit 128 that subsystem 120 is connected.Measuring for air pressure can be sent to pressure tune Pump and/or controller 108 in sub-system 120, and can show on display 116.In a particular embodiment, pressure Adjust the other elements that subsystem 120 can include being used for fluid processing, such as one or more valves, aperture, seal and/or Fluid line.
To ensure pressure regulation sub-systems Effec-tive Function to control the internal pressure in mass spectrograph disclosed herein, mass spectrograph Internal volume (for example, the volume pumped by pressure regulation sub-systems) substantially subtract relative to the internal volume of traditional mass spectrometer It is small.The internal volume of reduction adds the benefit for reducing mass spectrometric overall dimensions disclosed herein so that the mass spectrograph is tight Gather, portable and user being capable of one-handed performance.
As shown in figs. ib and 1 c, mass spectrometric internal volume disclosed herein includes ion gun 102, ion trap 104 and inspection Survey the internal volume in the region between device 118 and these components.It is more common of, mass spectrometric internal volume disclosed herein Corresponding to gas circuit 128 volume-that is, all connection spaces that gas particle and ion can circulate in mass spectrograph 100 Volume.In certain embodiments, the internal volume of mass spectrograph 100 is 10cm3Or smaller is (for example, 7.0cm3Or smaller, 5.0cm3 Or smaller, 4.0cm3Or smaller, 3.0cm3Or smaller, 2.5cm3Or smaller, 2.0cm3Or smaller, 1.5cm3Or smaller, 1.0cm3 Or smaller).
In certain embodiments, mass spectrograph disclosed herein is completely integrated in single support base.Fig. 1 D are mass spectrographs The schematic diagram of 100 embodiment, wherein, all components of mass spectrograph 100 are integrated into single support base 140.Such as Fig. 1 D It is shown, each it is installed on support base in ion gun 102, ion trap 104, detector 118, controller 108 and voltage source 106 On 140 and it is electrically connected to support base 140.Support base 140 is printed circuit board (PCB), and is included in each portion of mass spectrograph 100 The control line extended between part.Thus, for example, voltage source 106 by the control line that is integrated into support base 140 (for example, control Line 126a-e processed) to ion gun 102, ion trap 104, detector 118, controller 108 and pressure regulation sub-systems 120 provide electricity Power.It is in addition, each logical in ion gun 102, ion trap 104, detector 118, pressure regulation sub-systems 120 and voltage source 106 Cross the control line (for example, control line 127a-e) being integrated into support base 140 and be connected to controller 108 so that controller 108 Electric signal can be received by each transmission electric signal of the support base 140 into these components and thus.
In integrated offer some important advantages of the single support base such as on printed circuit board (PCB).Support base 140 provides The stabilized platform of the component of mass spectrograph 100, it is ensured that each component is stablized and reliably installed, and reduces the thick place of mass spectrograph 100 The possibility that each component is damaged during reason.In addition, the system that all components simplify mass spectrograph 100 is installed in single support base Technique is made, because support base 140 provides the reproducible template that various parts are disposed and connected each other.In addition, by supporting All control lines are integrated on base portion so that both electric power and control signal are sent between the components by support base 140, respectively The integrality of electrical connection between component is maintained-and such connection is than the respective conductive lines shape by extending between the components Into connection it is less easy to wear and/or broken string.
In addition, each component by integrating mass spectrograph 100 in single support base, mass spectrograph 100 has compact outer Shape.Specifically, support base 140 full-size (for example, maximum linear in support base 140 between any two point away from From) can be 25cm or smaller (for example, 20cm or smaller, 15cm or smaller, 10cm or smaller, 8cm or smaller, 7cm or more It is small, 6cm or smaller).
As shown in figure iD, support base 140 using installation pin 145 through being installed on shell 122.In some embodiments In, installation pin 145 through design make support base 140 (and being installed to each component of support base 140) and mechanical shock every From.For example, installation pin 145 can include impact absorbing material (for example, flexible material such as soft rubber) so that support base 140 isolate with mechanical shock.As another example, the insulating washer or partition formed from impact absorbing material can be positioned in So that support base 140 is isolated with mechanical shock between support base 140 and shell 122.
In certain embodiments, mass spectrograph disclosed herein include inserting, alternative module, multiple system units are integrated Into the module.Fig. 1 E are the schematic diagrames of the embodiment of mass spectrograph 100, mass spectrograph 100 includes inserting, alternative module 148 with And it is configured the support base 140 for receiving module 148.In ion gun 102, ion trap 104, detector 118 and sample inlet 124 Each be integrated into module 148.
Module 148 also includes the outwardly extending multiple electrodes 142 of slave module.In module 148, electrode 142 is connected to Each component in module, for example, being connected to ion gun 102, ion trap 104 and detector 118.
It also show support base 140 (for example, printed circuit board (PCB)), controller 108, voltage source 106 and pressure in Fig. 1 E Subsystem 120 is adjusted to be installed in the support base 140.Support base 140 includes multiple electrodes 144, it, which is configured, to release Put engagement and depart from the electrode 142 of module 148.In certain embodiments, for example, electrode 142 is pin, and electrode 144 is It is configured the tube socket of accommodate electrod 142.Alternatively, electrode 144 can be pin, and electrode 142 can be configured receiving The tube socket of the pin.It is aligned by the electrode 142 of module 148 with the counter electrode 144 of support base, module 148 can pass through The direction shown in arrow in fig. ie applies force to be connected to support base 140 so that module 148 can be releasably attached Disconnected to support base 140 or from support base 140.By in the direction applying power opposite with the arrow, module 148 can be with Depart from from support base 140.
The electrode 144 of support base 140 may be coupled to controller 108 and voltage source 106, as referring to figure 1E.When in electricity When connection is established between pole 142 and electrode 144, controller 108 can be sent to/from each component being integrated into module 148 With reception signal, discussed as mentioned above for control line 127.In addition, voltage source 106 can be to being integrated into module 148 Each component provides electric power, is discussed as mentioned above for control line 126.
The pressure regulation sub-systems 120 for being installed to support base 140 are connected to manifold 121 via conduit 123.Including one Or the manifold 121 of multiple apertures 125 is positioned in support base 140 so that when module 148 is connected to support base 140, Fluidly connecting for sealing is established between manifold 121 and module 148.Specifically, the aperture 125 in manifold 121 and module 148 In respective apertures between establish and fluidly connect and (do not show in fig. ie).Aperture in module 148 can ion gun 102, Formed in the wall of ion trap 104 and/or detector 118.When establishing sealing and fluidly connecting, by manifold 121 by gas particle Module is pumped out, pressure regulation sub-systems 120 can be with the air pressure in each component of control module 148.
The other configurations of module 148 are also possible.In certain embodiments, for example, detector 118 is not module 148 A part, but be changed to be installed to support base 140.In such configuration, detector 118 is positioned in support base 140 On so that when module 148 is connected to support base 140, the fluid of sealing is established between ion trap 104 and detector 118 Connection.Establishing sealing and fluidly connecting allows the circulation ion in ion trap 104 to spray from trap and detected using detector 118, And also allow pressure regulation sub-systems 120 maintained in detector 118 reduce air pressure (for example, 100mTorr with Between 100Torr).
In a particular embodiment, pressure regulation sub-systems 120 can be integrated into module 148.For example, pressure regulator The gas circuit 128 that system 120 can be attached to the downside of ion trap 104 and be directly connected in module 148.Pressure regulation sub-systems 120 are also electrically connected to the electrode 142 of module 148.When module 148 is connected to support base 140, pressure regulation sub-systems 120 Electric signal can be sent and received to/from controller 108 and voltage source 106 by electrode 142.
The modular arrangements of the mass spectrograph 100 shown in fig. ie provide some advantages.For example, in operation mass spectrograph 100 Period, particular elements can analyte residual contaminations.For example, analyte residual can adhere to the wall of ion trap 104, ion trap is reduced 104 can separate the efficiency of ion, and pollute the analyte of other materials.By the way that ion trap 104 is integrated into module 148, If ion trap 104 is contaminated, whole module 148 can be replaced easily and quickly at the scene, it is ensured that mass spectrograph 100 can be quick Back to operating status, aforesaid operations can be also carried out even if deconditioned user.Equally, if ion gun 102 or detector 118 are contaminated or are failed, and module 148 can be replaced easily so that mass spectrograph 100 returns to fortune by the user of mass spectrograph 100 OK.
The modular arrangements shown in fig. ie also ensure that mass spectrograph 100 keeps compact and easy to carry.In some implementations In example, for example, the full-size (for example, maximum linear distance in module 148 between any two point) of module 148 is 10cm Or smaller (for example, 9cm or smaller, 8cm or smaller, 7cm or smaller, 6cm or smaller, 5cm or smaller, 4cm or smaller, 3cm or Smaller, 2cm or smaller, 1cm or smaller).
The module 148 of function is reduced (for example, being adhered to the inner wall of ion gun 102, ion trap 104 and/or detector 118 Analyte particle pollution module) can regenerate and return to use.In certain embodiments, to make module 148 return normally Operation, the module can be heated when it is installed in mass spectrograph 100.Heating can use be installed in support base 140 Heating element 127 complete.As referring to figure 1E, heating element 127 is positioned in support base 140 so that when module 148 When being connected to support base 140, heating element 127 contacts one or more of each component of module 148 (for example, ion gun 102nd, ion trap 104 and detector 118).
By guiding voltage source 106 to apply suitable current potential to heating element 127, controller 108 can be configured activation Heating element 127.The beginning of heating and the temperature of heating and duration can be controlled by the user of mass spectrograph 100, example Such as, it is input to by activating the control on display 116 and/or setting user configuration in storage unit 114.In particular implementation In example, it is appropriate that controller 108, which can be configured and automatically determine the regeneration of module 148,.For example, controller 108 can monitor Measure gas current in a period of time, and if gas current in special time (for example, 1 it is small when or more, 5 it is small when Or more, 10 it is small when or more, 24 it is small when or more, 2 days or more, 5 days or more, 10 days or more) decrease beyond threshold value Amount (for example, 25% or more, 50% or more, 60% or more, 70% or more), then, 108 determining module of controller 148 regeneration is necessary.
Although in fig. ie, heating element 127 is installed in support base 140, other configurations are also possible.Some In embodiment, for example, heating element 147 is a part for module 148, and it can be attached so that it directly contacts module 148 Each component part or all of (for example, ion gun 102, ion trap 104, and detector 118).
In a particular embodiment, module 148 can be removed from mass spectrograph 100 for regeneration.For example, work as 148 table of module Revealing reduced function (for example, being determined by the user of mass spectrograph 100, or uses above-mentioned standard automatically true by controller 108 It is fixed) when, module 148 can be removed and heated from mass spectrograph 100 to recover its normal operating condition.Heating can pass through various sides Formula is completed, this is included in general baking oven heats.In certain embodiments, mass spectrograph 100 can include special insertion heating Device, it includes being configured the slit for accommodating module 148.When module is inserted into slit and heater is activated, module quilt Heat to recover its function.
Although ion gun 102, ion trap 104 and detector 118 are usually configured the various chemical substances of detection and identification, It is that in a particular embodiment, these components can be used for the material for detecting particular category through specific change.In certain embodiments, Ion gun 102 can be through being configured specifically for predetermined substance.For example, can to the electrode of ion gun 102 apply different potentials with Positive or negative ion is generated from gas particle.In addition, the amplitude for being applied to the current potential of the electrode of ion gun 102 can change to control The efficiency of predetermined substance ionization processed.In general, different ionization affinity is had according to chemical constitution, different material.It is logical The polarity and potential difference between each electrode of ion gun 102 are overregulated, the ionization of various materials can be controlled carefully.
In a particular embodiment, ion trap 104 can be through being configured specifically for predetermined substance.For example, ion trap 104 is interior Portion's size (for example, inside diameter) chosen can be conducive to the capture and detection with the ion of higher mass-to-charge ratio.
In certain embodiments, the inside in one or more of ion gun 102, ion trap 104 and detector 118 Air pressure chosen can be conducive to softer or harder ionization mechanism, or the generation of positive or negative ion.In addition, it is applied to ion gun 102 and ion trap 104 each electrode current potential amplitude and polarity chosen can be conducive to specific ionization mechanism.As above begged for Opinion, different material has different ionization affinity, and can ionize (example than other modes more efficient way with one kind Such as, according to a mechanism).Current potential by each electrode for adjusting air pressure and being applied in mass spectrograph 100, the mass spectrograph can fit In specifically detecting various materials and various types of other material.In addition, by adjust ion trap 104 geometry and/ Or the current potential of its electrode is applied to, the quality window of ion trap 104 can be selected (for example, may remain in following in ion trap 104 The scope of the mass-to-charge ratio of ion in loop orbit).
In a particular embodiment, ion gun 102 can include the certain types of electricity for being altered for specific type of material From device.For example, the electricity ionized based on glow discharge ionization, electrospray ionization mass spectrum ionization, capacitive discharge ionization, medium barrier discharge It can be used in from any ionization source of source and other electro-dissociator types disclosed herein in ion gun 102.
In certain embodiments, detector 118 can be used for certain types of Detection task through specific change.For example, inspection It can be any one or more in detector disclosed herein to survey device 118.Detector can be in concrete configuration for example with square Formation formula is arranged, has multiple detecting elements, such as will then have to the multiple Faraday cup detectors discussed, and/or detecting There is any arrangement in device 118.In addition to being altered for detection predetermined substance, detector 118 can also be altered for Certain types of ion gun and ion trap.For example, the arrangement and type of detecting element in detector 118 can be with chosen correspondences Arrangement in the ion chamber in ion trap 104, specifically, wherein, ion trap 104 specifically includes multiple ion chambers.
In a particular embodiment, (for example, ion gun 102 and/or ion trap 104 and/or detector 118) module 148 One or more interior surfaces can include one or more coatings and/or surface treatment.The coating and/or surface treatment can It is suitable for application-specific, including the certain types of material of detection, is run in specific air pressure range, and/or in specific application Current potential is run.The example that can be used for change for the coating and surface treatment of predetermined substance and/or the module 148 of application includes Teflon(more common of, fluorocarbon polymer coating), the surface of anodized, nickel, chromium.
The miscellaneous part of module 148 can also be adapted to detect for predetermined substance or classification material.For example, sample inlet 124 can With equipped with filter (for example, the filter 706 in Fig. 7 B, it will be discussed in chapters and sections below) its be configured selectivity only permit Perhaps the material of particular category enters mass spectrograph 100, or equally, compared with other passages, delays certain material to enter mass spectrograph. In some embodiments, for example, filter can include HEPA filters (or filter of similar type), it enters from into sample The flow of the gas particle of mouth 124 removes solid-state, the particle such as grit of micron size.In a particular embodiment, filter can With including molecular sieve type filter, it removes vapor from the flow for the gas particle for entering sample inlet 124.Both types Filter not filtered atmospheric gas particle (for example, nitrogen molecular and oxygen molecule), and be changed to allow atmospheric gas particle to pass through simultaneously Into the gas circuit 128 of mass spectrograph 100.Filter-do not remove such as or the filtering of filtered atmospheric gas particle are mentioned in the disclosure In the case of device 706, it should be understood that the filter allows at least 95% or more of the atmospheric gas particle for meeting the filter Pass through.
Therefore, in certain embodiments, mass spectrograph 100 can include multiple replaceable modules 148.Certain module can be Identical, and (for example, in the case of pollution) can be replaced directly with one another.Other modules can be configured for different Operational mode.For example, multiple replaceable modules 148, which can be configured, detects different classes of material.Operate the use of mass spectrograph 100 Family can select suitable module to be used for the material of particular category, and can be inserted into chosen module before analysis is started In support base 140.To analyze different classes of material, user can depart from the first module from support base 140, select new mould New module is simultaneously inserted into support base 140 by block.As a result, each component of mass spectrograph 100 is used for being reconfigured at for various different applications It is quick and categorical.Module can also be through being configured specifically for different types of measure (for example, using different ionization Method, is applied to different capture and/or the injection current potentials of each electrode of ion trap 104, and/or different detection methods).It is general next Say, can each include any feature disclosed herein in multiple replaceable modules 148.Therefore, certain module can be based on Ion gun and it is different, certain module can be based on ion trap and it is different, and certain module can based on detector and it is different.It is special Cover half block can be different from each other based on the more than one component in these components.
In certain embodiments, one or more attachment means can be used for module 148 being fixed to support base 140. With reference to Fig. 1 F, module 148 includes the first attachment means 195, it is attached in the form of extension in support base 140 with second Mechanism 197 engages.In certain embodiments, extension 195 can be positioned in support base 140, and complementary attachment Mechanism is included in module 148.In certain embodiments, attachment means 195 can be and attachment means 197 are rotatable engages Cam, for example, attachment means 197 include being configured the groove for accommodating cam.In a particular embodiment, by flexible material such as rubber One or more seals 193 (for example, O rings, gasket, and/or other seals) that glue and/or silicone are formed can be placed With the connection between seal modules 148 and support base 140.
In a particular embodiment, attachment means 195 and 197 can be by keying so that module 148 can only be in single direction It is connected to support base 140.Keying attachment means have the advantages that to prevent user from installing module 148 in incorrect direction.
In some embodiments it is possible to use other attachment means.For example, support base 140 and/or module 148 can With the clamping device 199 including module 148 to be fixed to support base 140.One or more clamping devices can be used.Separately Outside, in addition to other attachment means, it can also use clamping device.
In following chapter, the different components of mass spectrograph 100 are will be discussed in detail, and also mass spectrograph 100 will be discussed not Same operational mode.
II ion guns
In general, ion gun 102 is configured generation electronics and/or ion.In ion gun 102 from gas to be analysed In the case that particle directly generates ion, by being applied to the suitable potential of ion gun 192 and ion trap 104, ion then from Ion gun 102 is transmitted to ion trap 104.According to the amplitude of the current potential for the electrode for being applied to ion gun 102 and polarity and will quilt The chemical constitution of the gas particle of analysis, the ion generated by ion gun 102 can be positive or negative ions.In some embodiments In, the electronics and/or ion that are generated by ion gun 102 can be collided with the neural gas particles to be analyzed with from gas grain Son generation ion.During operation ion gun 102, according to the chemical constitution of gas to be analysed particle and ion gun 102 Operating parameter, various ionization mechanism can occur in ion gun 102 at the same time.
By being run under the air pressure inside than traditional mass spectrometer higher, compact mass spectrograph disclosed herein can use Various ion guns.Specifically, ion gun that is small and needing relatively appropriate amount of electrical power operation can be used in mass spectrograph 100 In.In certain embodiments, for example, ion gun 102 can be glow discharge ionization (GDI) source.In a particular embodiment, ion Source 102 can be capacitive discharge ion gun.
The size of quantity of power and ion gun according to needed for operation, the ion gun of various other types can also be used in mass spectrum In instrument 100.For example, other ion guns being suitable for use in mass spectrograph 100 include medium barrier discharge ion gun and thermion is put Penetrate source.As further example, the ion gun based on electron spray ionisation (ESI) can be used in mass spectrograph 100.Such source can be with Including but not limited to using desorption electrospray ionization (DESI), secondary ion electron spray ionisation (SESI), extraction electron spray ionisation (EESI) spray with paper and ionize the source of (PSI).As another example, the ion gun based on laser desorption ionisation (LDI) can be used In mass spectrograph 100.Such source can include but is not limited to the laser desorption ionisation (ELDI) and matrix using electron spray auxiliary The source of the laser desorption ionisation (MALDI) of auxiliary.Further, based on technology such as air solid analysis probe (ASAP), solution Inhale atmospheric chemical ionization (DAPCI), desorption atmospheric photoionization (DAPPI) and sound wave spraying ionize the ion gun of (SSI) can be with In mass spectrograph 100.Ion gun based on nanofiber array (for example, carbon nanofiber arrays) is suitable for use of.It is foregoing Other aspect and feature of ion gun and other examples of the ion gun suitable for mass spectrograph 100 are for example in following publications Disclosed in, the full content of each publication is incorporated herein by reference:Alberici et al. exists Anal.Bioanal.Chem.398:" the Ambient mass spectrometry delivered in 265-294 (2010): bringing MS into the‘real world’”Chem.bringing MS into the‘real world’”; Harris et al. is in Anal Chem.83:" the Ambient Sampling/Ion Mass delivered in 4508-4538 (2011) Spectrometry:Applications and Current Trends”;And Chen et al. is in IEEE Trans.Electron Devices 58(7):" the AMicro Ionizer for delivered in 2149-2158 (2011) Portable Mass Spectrometers using Double-gated Isolated Vertically Aligned Carbon Nanofiber Arrays”。
GDI sources are used in mass spectrograph 100 and are particularly advantageous, because they are compact and be suitable for transporting under low-power OK.Glow discharge just only but occurs when these sufficient sources of air pressure are enlivened.In general, for example, GDI is only limited to about Run under the air pressure of 200mTorr and the above.Under the air pressure less than 200mTorr, it is difficult to keep stable glow discharge. As a result, GDI is not used in the traditional mass spectrograph run under the air pressure of 1mTorr or smaller.But, it is because disclosed herein Mass spectrograph is run under the air pressure usually between 100mTorr and 100Torr, it is possible to uses GDI sources.
Fig. 2A shows the example in GDI sources 200, it includes preceding electrode 210 and rear electrode 220.Two electrodes 210 and 220 with Shell 122 forms GDI rooms 230 together.In certain embodiments, GDI sources 200 can also encase the shell of the electrode in source. For example, in the embodiment shown in fig. 2b, GDI rooms 230 have independent shell 232, it encases electrode 210 and 220.Shell 232 are fixed or are installed via retaining element 250 (for example, clamping device, screw, threaded fastener or other types fastener) To shell 122.
As shown in Figure 2 A and 2B, preceding electrode 210 has aperture 202, and gas to be analysed particle is entered by the aperture GDI rooms 230.As used in this article, term " gas particle " refers to the atom of gaseous state, molecule or as independent community Existing aggregation gas molecule.If for example, the material to be analyzed is organic compound, then, the gas particle of the material It is the gas phase single molecule of the material.
Aperture 202 is surround by insulation tube 204.In Figures 2 A and 2 B, aperture 202 is connected to 124 (not shown) of sample inlet, So that due to the pressure differential between the air of the outside of mass spectrograph 100 and GDI rooms 230, gas to be analysed particle is inhaled into In GDI rooms 230.In addition to gas to be analysed particle, atmospheric gas particle is also due to pressure differential is inhaled into GDI rooms 230 In.As used in this article, term " atmospheric gas particle " refers to gas atom, the molecule in air, such as oxygen and Nitrogen molecule.
In certain embodiments, gas particle in addition can be introduced into GDI sources 200 to help to generate electronics in source And/or ion.For example, explained as mentioned above for Figure 1A, mass spectrograph 100 can include the buffering gas for being connected to gas circuit 128 Source 150.Buffer gas particle from buffering source of the gas 150 can be introduced directly into GDI sources 200, or can be introduced into gas circuit 128 another part is neutralized and is diffused into GDI sources 200.Buffer gas particle can include nitrogen molecular and/or intert-gas atoms (for example, He, Ne, Ar, Kr, Xe).Partial buffer gas particle can be ionized by electrode 210 and 220.
Including the gas particle of gas to be analysed particle and atmospheric gas particle alternatively, in certain embodiments, Mixture be only the gas particle being introduced into GDI rooms 230.In such embodiments, only gas to be analysed particle It can be ionized in GDI rooms 230.In certain embodiments, gas to be analysed particle and the atmospheric gas particle permitted Both can be ionized in GDI rooms 230.
The center of electrode 210 before although aperture 202 is positioned in Figures 2 A and 2 B, more generally useful, aperture 202 can With the diverse location being positioned in GDI sources 200.For example, the sample that is connected to that aperture 202 can be positioned in GDI rooms 230 enters In the side wall of mouth 124.In addition, as described earlier, in certain embodiments, sample inlet 124 could be arranged so that will Analyzed gas particle is taken directly in another component of each component of mass spectrograph 100, such as ion trap 104 or detector 118.When gas particle is inhaled into different from the component of ion gun 102, gas particle is diffused into ion gun by gas circuit 128 In 102.Alternatively or additionally, when gas to be analysed particle is taken directly in component such as ion trap 104, ion gun 102 can generate the then ion and/or electronics with gas to be analysed particle encounter in ion trap 104, so that from ion Gas particle in trap directly generates ion.
Therefore, according to gas to be analysed particle, somewhere (for example, position of sample inlet 124) is introduced into matter Spectrometer 100, ion can be from the gas particle generations in various diverse locations.Ion generation can occur directly in ion gun In 102, and the ion generated can be passed by applying suitable current potential to ion gun 102 and the electrode of ion trap 104 It is sent in ion trap 104.Ion generation can also occur in ion trap 104, when charged particle is such as given birth to by ion gun 102 Into ion (for example, buffer gas ion) and electronics enter ion trap 104 when, itself and gas to be analysed particle encounter. Ion generation can occur in multiple local (for example, in ion guns 102 and ion trap 104), the ion of all generations at the same time Finally it is captured in ion trap 104.Although interested gas of the main concentrated ion out of ion gun 102 is discussed in this section Particle directly generates, but each side disclosed herein and feature are also generally applicable to ion from the miscellaneous part of mass spectrograph 100 In gas particle interested secondary generation.
A variety of spacing can be used between electrode 210 and electrode 220.In general, generate the efficiency of ion by A number of factors determines, the potential difference being included between electrode 210 and 220, the air pressure in GDI sources 200, between electrode 210 and 220 Distance 234, and be ionized the chemical constitution of gas particle.In general, distance 234 is relatively small to ensure that GDI sources 200 keep tight Gather.In certain embodiments, for example, the distance between electrode 210 and 220 234 be 1.5cm or smaller (for example, 1cm or smaller, 0.75cm or smaller, 0.5cm or smaller, 0.25cm or smaller, 0.1cm or smaller).
Air pressure in GDI rooms 230 is usually adjusted by pressure regulating system 120.In certain embodiments, GDI rooms 230 In air pressure it is roughly the same with the air pressure in ion trap 104 and/or detector 118.In certain embodiments, in GDI rooms 230 Air pressure is different from the air pressure in ion trap 104 and/or detector 118.In general, the air pressure in GDI rooms 230 is 100Torr or more Small (for example, 50Torr or smaller, 20Torr or smaller, 10Torr or smaller, 5Torr or smaller, 1Torr or smaller, 0.5Torr or smaller) and/or 100mTorr or bigger (for example, 200mTorr or bigger, 300mTorr or bigger, 500mTorr Or bigger, 1Torr or bigger, 10Torr or bigger, 20Torr or bigger).
During operation, when by the voltage source 106 under the control of controller 108 preceding electrode 210 with after electrode 220 it Between when applying voltage difference, the self-holding glow discharge (or plasma) of the generation of GDI sources 200.In certain embodiments, voltage difference can Be 200V or higher (for example, 300V or higher, 400V or higher, 500V or higher, 600V or higher, 700V or higher, 800V or higher) to keep glow discharge.As discussed above, detector 118 detects the ion generated by GDI sources 200, and And the potential difference between electrode 210 and 220 can be adjusted by controller 108 to control the speed of the ion generated by GDI sources 200 Rate.
In certain embodiments, GDI sources 200 are directly installed in support base 140, and electrode 210 and 220 passes through branch Support group portion 140 is directly connected to voltage source 106, as shown in figure iD.In certain embodiments, GDI sources 200 form module 148 A part, and electrode 210 and 220 is connected to the electrode 142 of module 148, as referring to figure 1E.When module 148 is inserted into branch support group When in portion 140, electrode 210 and 220 is connected to voltage source 106 by the electrode 144 of bonding electrodes 142.
By applying the current potential of the earthing potential opposed polarity with being established by voltage source 106, GDI sources 200 can be configured In different ionization mode operations.For example, during typical case's operation in GDI sources 200, the small part of gas particle is due to random process (for example, thermalizing collision) is in GDI rooms 230 by initial ionization.In certain embodiments, electrode 210 and rear electricity before current potential is applied to Pole 220 so that preceding electrode 210 serves as cathode and rear electrode 220 serves as anode.In this configuration, it is raw in GDI rooms 230 Into cation due to indoor electric field be driven to before electrode 210.Anion and electronics are driven to rear electrode 220.Electronics and from Son can be collided with other gas particles, generate greater amount of ion.Anion and/or electronics are exited by rear electrode 220 GDI rooms 230.
In certain embodiments, suitable potential is applied to preceding electrode 210 and rear electrode 220 so that preceding electrode 210 serves as sun Pole and rear electrode 220 serve as cathode.In this configuration, the positive charged ions generated in GDI rooms 230 pass through rear electrode 220 leave the room.Positive charged ions can be collided with other gas particles, generate greater amount of ion.
In certain embodiments, user interface 112 can include allowing a kind of in the above-mentioned ionization pattern of user's selection Control.The selection of appropriate ionization pattern can depend on the property for the material to be analyzed by mass spectrograph 100.Cucumber is more efficient Ionize and be selected so that rear electrode 220 serves as cathode for cation, and operational mode.Generated just in this mode operation Ion exits GDI sources 200 by rear electrode 220.Alternatively, the more efficient ionization of Cucumber is anion, and operational mode It is selected so that rear electrode 220 serves as anode.GDI is exited by rear electrode 220 in the anion that this mode operation is generated Source 200.In general, controller 108 is configured the gas current that monitoring is measured by detector 118, and is based on gas current Select the suitable operational mode in GDI sources.Alternatively or additionally, the user of mass spectrograph 100 can use shows in user interface 114 Suitable operational mode is selected in the control shown or the storage unit 114 by the way that suitable configurations to be set to input mass spectrograph 100.
Generated in ion and by any operational mode after rear electrode 220 leaves GDI rooms 230, ion passes through end cap electricity Pole 304 enters in ion trap 104.In general, rear electrode 220 can include one or more apertures 240.The number of aperture 240 Amount and their shape of cross section are usually selected to form the relatively uniform ion space distribution for inciding endcap electrode 304. When the ion generated in GDI rooms 230 leaves the room by one or more of rear electrode 220 aperture 240, due to collision and Space charge interacts, and each mutual space of ion is scattered.As a result, leave the overall space point of each ion in GDI sources 200 Cloth is diverging.By selecting the suitable quantity aperture 240 with certain cross sectional, the sky of the ion in GDI sources 200 is left Between be distributed and can be controlled so that the distribution overlaps or is filled in all apertures 292 formed in endcap electrode 304.Some In embodiment, additional ion optical element (for example, ion lens) can be positioned in rear electrode 220 and endcap electrode 304 Between further to manipulate the spatial distribution for the ion gushed out from GDI sources 200.But, the spy in compact ion source disclosed herein Other advantage is to obtain suitable ion distribution without the add ons between rear electrode 220 and endcap electrode 304.
In certain embodiments, rear electrode 220 includes single hole 240.The shape of cross section of aperture 240 can be circular, side Shape, rectangle, or can more commonly correspond to regular or irregular n sides polygon.In certain embodiments, aperture 240 Shape of cross section can be irregular.
In certain embodiments, rear electrode 220 includes more than one aperture 240.In general, rear electrode 220 can wrap Include any amount of aperture (for example, 2 or more, 4 or more, 8 or more, 16 or more, 24 or more, 48 A or more, 64 or more, 100 or more, 200 or more, 300 or more, 500 or more), between aperture Interval can be any amount, it is assumed that in the case that electrode 220 fully keeps mechanically stable after when being used in GDI sources 200.Figure 2C-2H shows each embodiment of rear electrode 220, and each embodiment has different apertures 240.As shown in Fig. 2 C-2H, rear electricity Pole 220 usually can be circular, rectangle or any other shape.
Fig. 2 C show the rear electrode 220 with circular aperture array 242.Although showing 25 apertures 242 in fig. 2 c, It is more generally useful, there may be any amount of aperture 242.In addition, although aperture 242 has circular cross sectional shape, More generally useful, the aperture 242 with any regular or irregular shape of cross section can be used.With varying cross-section shape Aperture can also be used in single electrode 220 in.In general, the size of the opening formed by aperture 242 can be according to need To select, and different size of aperture 242 can reside in after list in electrode 220.In general, formed in rear electrode 220 Aperture quantity and aperture size control through electrode gas pressure drop.Therefore, aperture size and quantity can also be chosen Select to realize during operation mass spectrograph 100 through the specific objective pressure drop of rear electrode 220.
The exemplary embodiment of the rear electrode 220 with opening 243,244,245 and 246 is also shown respectively in Fig. 2 D-2G. In Fig. 2 D-2G, opening 243,244,245 and 246 can be formed by slit (for example, continuous opening) or in rear electrode 220 A series of and keyhole formations being spaced apart.As shown in Fig. 2 D-2G, opening 243,244,245 and 246 can be arranged to form Linear aperture array, Concentric circle array, serpentine pathway and spiral channel.But, the embodiment shown in Fig. 2 D-2G is only shown Example property.More generally, the arrangement of various aperture with varying cross-section shapes and sizes can be used in rear electrode In 220.
Fig. 2 H show the embodiment of the rear electrode 220 for the hexagonal array for including aperture 247.Six sides shown in Fig. 2 H Shape array and the square or rectangular array shown in fig. 2 c are showing for the regular array of orifices that can be formed in rear electrode 220 Example.But more generally, various Different Rule array of orifices can be used in rear electrode 220, such as (but not limited to) circular Array and radiation array.
As shown in Figure 2 A and 2B, the endcap electrode 304 of ion trap 104 can also include one or more apertures 294.At certain In a little embodiments, endcap electrode 304 includes the shape of cross section with circular, square, rectangle or other n sides polygonal shapes Single hole 294.In certain embodiments, aperture has irregular shape of cross section.
More generally, endcap electrode 304 can include multiple apertures 294.Specific aperture class is selected for endcap electrode 304 The small pore type and its arrangement and Standard General of type are similar with type, arrangement and the standard discussed above for rear electrode 220. Therefore, it is discussed above to be equally applicable to form aperture 294 in endcap electrode 304.
As shown in Figure 2 A and 2B, the spaced apart a certain amount of 244 of rear electrode 220 and endcap electrode 304.Between these electrodes Spacing allow the ion gushed out from rear electrode 220 space divergence be filled in what is formed in endcap electrode 304 as homogeneously as possible Aperture 294.To further improve the uniform filling of aperture 294, in certain embodiments, the aperture formed in rear electrode 220 240 pattern can be with the pattern match of the formation aperture 294 in endcap electrode 304.
More specifically, as shown in the example in Fig. 2 H, it is electric after the pattern definition of the aperture 247 formed in rear electrode 220 The shape of cross section of pole 220.Equally, the cross section of the pattern definition endcap electrode 304 of the aperture formed in endcap electrode 304 Shape.In certain embodiments, the shape of cross section of rear electrode 220 and endcap electrode 304 is substantially matching.As in this paper institutes Use, the relative position for the aperture that " substantially matching " means to be formed in rear electrode 220 and formed in endcap electrode 304 The relative position of aperture at least 70% or more is identical.For each aperture, its position correspondence is in the position of its mass centre Put.
In certain embodiments, the pattern actual match of the aperture 240 formed in rear electrode 220 is in endcap electrode 304 The pattern of the aperture 294 of middle formation, i.e. have one-to-one relationship between each aperture.In general, with rear electrode 220 and end The distance between the increase of the aperture matching degree of lid electrode 304, rear electrode 220 and endcap electrode 304 244 can reduce, because Ion to gush out from rear electrode 220 evenly fills the aperture 294 in endcap electrode 304.When the aperture essence between each electrode When really or almost accurately matching, distance 244 can even be reduced to zero, and (that is, rear electrode 220, which can be placed, to be directly adjacent to hold Lid electrode 304) so that 200 highly compact of GDI sources.In addition, with matched degree increase between each aperture, by reduce from Son impacts the quantity of the part of endcap electrode 304 between aperture, and the quantity into the ion of aperture 294 can reach maximum Value.As a result, the ion collection efficiency of ion trap 104 can increase.In addition, the ion generated by increasing ion gun 102 exists The efficiency collected in ion trap 104, relative to single hole electrode and/or with the electrode for mismatching aperture, rear electrode 220 and end cap The overall dimensions of electrode 304 can reduce.
In certain embodiments, rear electrode 220 and endcap electrode 304 can be formed as discrete component, and in GDI rooms The ion formed in 230 the element can be directly entered in ion trap 104 with approach.In such embodiments, the rear electrode of combination It can include single hole as described above or porous with endcap electrode.
In addition, in certain embodiments, the endcap electrode of ion trap 104 can serve as 210 He of preceding electrode in GDI sources 200 Electrode 220 afterwards.As will be discussed in detail below, ion trap 104 includes two endcap electrodes being placed on the opposite face of trap 304 and 306.By applying suitable current potential (for example, preceding electrode 210 as referenced above and the institute of rear electrode 220 to these electrodes State), endcap electrode 304 can fill front electrode 210, and endcap electrode 306 can serve as rear electrode 220.Therefore, at these In embodiment, ion trap 104 also functions as glow discharge ion source 102.
Various operational modes can be used for generating charged particle in GDI sources 200.For example, in certain embodiments, use Continuous operation mode.Fig. 2 I include curve map 260, it shows that constant bias voltage 262 is applied to the preceding electrode 210 in GDI sources 200 The embodiment of continuous operation mode between rear electrode 220.In this mode, charged particle is continuously given birth in ion gun Into.
In certain embodiments, GDI sources 200 are configured pulsing operation.Fig. 2 I include curve map 270, it shows biased electrical Position 272 is applied to the embodiment of the pulse mode operation of duration 274 between preceding electrode 210 and rear electrode 220.Bias potential 272 repetition applies the repetition rate for defining pulsing operation, it corresponds to the inverse of time interval 276 between continuous impulse.One As for, during bias potential 272 is applied to electrode, the duration of time interval 276 can be significantly greater than the time 274 Duration (for example, about 100 times).In certain embodiments, for example, the duration 274 can be about 0.1ms, with timely Between interval 276 can be about 10ms.More generally, the duration 274 can be 5ms or less (for example, 4ms or less, 3ms or less, 2ms or less, 1ms or less, 0.8ms or less, 0.6ms or less, 0.5ms or less, 0.4ms or more It is few, 0.3ms or less, 0.2ms or less, 0.1ms or less, 0.05ms or less, 0.03ms or less) and time interval 276 can be 50ms or less (for example, 40ms or less, 30ms or less, 20ms or less, 10ms or less, 5ms or more It is few).
When bias potential 272 is applied to electrode, ion generates within the duration of time 274.In some embodiments In, the sequential of the pulsed bias current potential 272 during pulse mode is run can be with the modulation for generating high pressure RF signals 482 Signal 412 is synchronous, and high pressure RF signals 482 are applied to the central electrode of ion trap 104, as will then have to be discussed in detail.Fig. 2 J In curve map 280 be for generate be applied to ion trap 104 central electrode RF signals 482 modulated signal 412 song Line.Comparative graph 280 and curve map 270, when pulsed bias current potential 272 is applied to the electrode in GDI sources 200, modulated signal 412 are disconnected.During this time interval, ion generates in GDI sources 200.Then, bias potential 272 is closed, and is adjusted Current potential 282 processed is switched on.During time interval 284, ion is captured and stablizes in ion trap 104.Then, between the time During 286, the amplitude of the current potential of the central electrode of ion trap 104 is applied to by increase, the ion that is captured is from ion trap 104 Spray into detector 118.
Pulse mode operation can have the advantages that several.For example, repetition rate and the duration of pulsed bias current potential 272 And/or amplitude is suitable for the amount of existing gas to be analysed particle and the air pressure in ion trap 104.In general, control The gas current that the monitoring of device 108 processed is measured by detector 118, and the amplitude based on gas current, controller 108 can be adjusted The section one or more parameters associated with pulse mode operation.
In certain embodiments, for example, controller 108 can adjust the amplitude of bias potential 272.Increasing bias potential can To increase the speed that ion is produced in GDI sources 200.
In certain embodiments, controller 108 can adjust the repetition rate of bias potential 272.For some interested Analyte, increase repetition rate can increase in GDI sources 200 produce ion speed.For other analytes, reduce weight Complex frequency can increase the speed that ion is produced in GDI sources 200.Controller 108 can be configured and adjust in an adaptive way Repetition rate is saved, until the speed that ion is generated in GDI sources 200 reaches desired value.
In certain embodiments, controller 108 can be configured the duty cycle for adjusting GDI sources 200.Reference curve Figure 27 0, The duty cycle in GDI sources 200 refers to ratio of the duration to total time interval 276 for applying the time 274 of bias potential 272. Controller 108 can be configured the duty cycle for adjusting GDI sources 200.For example, duty cycle can be reduced to reduce in GDI sources 200 The middle speed for producing ion.The speed of ion is produced by reducing, the signal-to-noise ratio of measured ion signal can be improved, and can To eliminate undesired ghost peak (for example, when the ion that measurement source 200 is disconnected, since what is produced by GDI sources 200 is not intended to The peak value of charged particle).Alternatively, duty cycle can be increased to increase the speed that ion is produced in GDI sources 200.
In certain embodiments, controller 108 can be configured adjusts (the example between 1% and 50% by the value of duty cycle Such as, between 1% and 40%, between 1% and 30%, between 1% and 20%, between 1% and 10%).
Pulse mode operation another important advantage is that when not needed, such as when source 200 has generated ion, apply Bias potential between electrode 210 and 220 can be disconnected.In the most of time of the duty cycle in source 200, biasing is disconnected Current potential can cause to run significantly reducing for the power needed for mass spectrograph.
In addition, pulse mode operation avoids the use for the door or shield being placed between GDI sources 200 and detector 118.Disappear Suitable space can be saved except the door and shield that are generally used in traditional mass spectrometer and further reduces operation mass spectrograph 100 institute The quantity of power needed.
In certain embodiments, the service condition in GDI sources 200 can be checked using the calibration process of automation.For example, User can activate the calibration process that one or more known reference samples are continually analysed.The detection of ghost peak (that is, should not be Peak value present in measurement frequency spectrum) it can indicate that GDI sources 200 are contaminated.For example, any one in electrode 210 and 220 can be by Viscous particle or detritus insertion there may be ghost peak detection.In some calibration processes, no sample is injected into, and ghost peak exists Compare and detected under the background of mass spectrograph noise.What whether GDI sources 200 needed to be replaced determines that calibration result can be based on, such as Quantity and size based on the ghost peak detected.
For ease of replacing, in certain embodiments, ion gun 102 can be configured as the miscellaneous part with mass spectrograph 100 Different standalone modules.For example, as shown in Figure 2 B, GDI sources 200 may be implemented as by discharge retaining element 250 easily from The miscellaneous part of mass spectrograph 100 or the separate modular pulled down from shell 122.Alternatively, can be configured can for electrode 210 and 220 Independently removed from GDI rooms 230.Removing for electrode 210 and 220 can be adjacent to electrode position for example, by removing to be integrated into Lid in shell 122 is realized.When lid is removed from shell 122, exposed electrode can be removed from GDI rooms 230.
In certain embodiments, GDI sources 200 can be cleaned, rather than be replaced.For example, GDI sources 200 can pass through Apply to electrode 210 and 220 corresponding to the bias potential of inverse duty cycle to clear up.Fig. 2 J show the curve map 263 of inverse duty cycle, Wherein, it is inverse bias potential 264 quilt during scale removal process relative to the pulse mode bias potential shown in curve map 270 It is applied to electrode 210 and 220.What most of duty cycles applied is constant DC current potentials, and only by the brief electrical of duration 274 Potential drop is interrupted.These potential drops are repeated with time interval 276.Without wishing to be bound by theory, it is believed that quick voltage change is easy to Remove the viscous particle being embedded in electrode 210 and 220.Once it is determined that GDI sources 200 are cleaned (for example, using above-mentioned calibration Process), GDI sources 200 can be switched to the normal operation (for example, pulse mode operation) for generating ion.
In certain embodiments, controller 108 can be configured by the value of the duty cycle during cleaning adjust 50% with Between 100% (for example, between 50% and 90%, between 50% and 80%, between 50% and 70%, 50% with Between 60%).Inverse duty cycle can be applied in 5s or longer total time (for example, 10s or longer, 20s or longer, 30s or more It is long, 40s or longer, 50s or longer, 1 minute or longer, 2 minutes or longer, 3 minutes or longer, 5 minutes or longer).
The electrode in other methods cleaning GDI sources 200 can also be used, if they are contaminated.In some embodiments In, cleaning gas can be sprayed into GDI rooms 230 to promote the viscous particle on clearing electrode 210 and 220.Suitable cleaning gas Body can include such as inert gas.In addition, in certain embodiments, the electrode cleaning in GDI sources 200 can also be by heating electricity Pole 210 and 220 becomes easier to.In certain embodiments, electrode 210 and 220 can remove and suitable from GDI rooms 230 Cleared up in cleaning liquid.
Whether the measurement discussed above around ghost peak is contaminated with definite GDI sources 200.More generally, except ghost peak is examined Alternative solution beyond survey or as ghost peak detection, can also use other methods.For example, controller 108 can be configured prison Survey measurement of the detector 118 to gas current.If the ion signal that detector 118 measures flickers or suddenly change is (for example, jump Jump declines) exceed threshold quantity, or if average detected ion/electronic signal has been declined to less than specific threshold, then, control It is desirable that device 108, which can automatically determine the cleaning in GDI sources 200 or replacement,.
A variety of materials can be used in ion gun 102 being formed the electrode 210 and 220 in electrode, including GDI sources 200. In some embodiments, the electrode of ion gun 102 can be made from the material of such as copper, aluminium, silver, nickel, gold and/or stainless steel.One As for, it is not easy to the material for adsorbing viscous particle be it is favourable, from such material formed electrode usually seldom need frequently Cleaning is replaced.
The use discussed above for surrounding GDI sources 200 in mass spectrograph 100.But, above-mentioned feature, design standard, algorithm and Aspect is equally applicable to the other types ion gun that can be used in mass spectrograph 100, and such as capacitive discharge source and thermion are put Penetrate source.Specifically, capacitive discharge source is suitable for the opposite hyperbar of operation mass spectrograph 100 very well.Therefore, description above Suitable for such source.For example, Fig. 2 K show the example for including the capacitive discharge source 265 of 266 array of ionization source.Inserting in Fig. 2 K Single ionization source 266 is illustrated, its conducting wire 268 with conducting wire 267 and coating insulator.When bias potential is applied by voltage source 106 When being added to conducting wire 267, plasma discharge occurs from each source in source 266.The ion generated by capacitive discharge source 265 Into in ion trap 104, ion is captured and selectively sprays herein to be used to detect.The additional aspect in capacitive discharge source and spy Sign is for example disclosed in United States Patent (USP) No.7274015, the full content of the patent is incorporated herein by reference.
Due to use that is compact, being spaced closely together electrode, the overall dimensions of ion gun 102 can be with very little.Ion gun 102 is most Large scale refers to the maximum linear distance between any 2 points on ion gun.In certain embodiments, for example, ion gun 102 Full-size be 8.0cm or smaller (for example, 6.0cm or smaller, 5.0cm or smaller, 4.0cm or smaller, 3.0cm or smaller, 2.0cm or smaller, 1.0cm or smaller).
III ion traps
As previous section I is described, it is captured by the ion that ion gun 102 generates in ion trap 104, the ion Circulated under the influence of the electric field formed by applying current potential to the electrode of ion trap 104.Receiving from controller 108 After control signal, voltage source 106 applies current potential to the electrode of ion trap 104.It is used for make circulation ion be sprayed from ion trap 104 Detection, for controller 108 to 106 transmission of control signals of voltage source, this promotes voltage source 106 to modulate radio frequency (RF) in ion trap 104 The amplitude of field.The modulation of the amplitude of RF promotes the circulation ion in ion trap 104 to come off from track and exits ion trap 104, The detector 118 being detected into them.
As explained in previous section I, to ensure that mass spectrograph 100 is compact and consuming the electricity of relatively small amount during operation Power, mass spectrograph 100 are pumped to adjust its air pressure inside only in pressure regulation sub-systems 120 using single gadget.As a result, matter Spectrometer 100 is run under the air pressure inside of the internal pressure higher in than traditional mass spectrometer.To ensure to be drawn into mass spectrograph 100 Gas particle is by the fast electric analysis of variance, much smaller than the internal volume of traditional mass spectrometer of the internal volume of mass spectrograph 100.Pass through Reduce the internal volume of mass spectrograph 100, gas particle can be quickly drawn into mass spectrograph 100 by pressure regulation sub-systems 120. In addition, by ensuring the fast electric analysis of variance, the user of mass spectrograph 100 can quickly obtain the information on predetermined substance.Matter The smaller internal volume of spectrometer 100 has added the advantages of smaller internal surface area for being easy to pollution during operation.Traditional matter Spectrometer uses various different quality analyzers, and many of which has the larger internal volume for operationally maintaining low pressure, And/or a large amount of power are consumed during operation.For example, some mass spectrographs use linear quadrupole mass filter, since it is in axis The extension in direction thus there is larger internal volume, this allows mass filter and big charge storage capacity.Some traditional mass spectrometers Using magnetic sector mass filter, this is generally also larger and can consume a large amount of power to generate the magnetic field of mass filter.Traditional matter Spectrometer can also use hyperbolic type ion trap, it can also be difficult to manufacture with big internal volume.
With aforementioned conventional ion trap technology on the contrary, mass spectrograph disclosed herein is used to catch using compact, cylindrical ion trap Obtain and analyze ion.Fig. 3 A are the cross-sectional views of the embodiment of ion trap 104.Ion trap 304 includes cylindrical center electricity Pole 302, two endcap electrodes 304 and 306, and two insulation spacers 308 and 310.Electrode 302,304 and 306 respectively via Control line 312/314 and 316 is connected to voltage source 106.Voltage source 106 is connected to controller 108 via control line 127e, control Device 108 transmits signal via control line 127e to voltage source 106, and command voltage source 106 applies electricity to the electrode of ion trap 104 Position.
During operation, ion trap 104 is entered by the aperture 320 in electrode 304 by the ion that ion gun 102 generates. Voltage source 106 applies current potential to form axial field (for example, symmetrical around axis 318) in ion trap 104 to electrode 304 and 306. Ion is axially limited between electrode 304 and 306 by axial field, it is ensured that ion by the aperture 320 in electrode 306 or does not pass through Aperture 322 leaves ion trap.Voltage source 106 also applies current potential to central electrode 302 and is radially constrained with being generated in ion trap 104 .Radial field radially constrains ion in the inner aperture of electrode 302.
Both axial field and radial field are present in ion trap 104, and ion circulates in trap.The track of each ion is several What determines by a number of factors, including the geometry of electrode 302,304 and 306, be applied to electrode current potential amplitude and symbol and from The mass-to-charge ratio of son.By varying the amplitude for the current potential for being applied to central electrode 302, the ion of specific mass-to-charge ratio will be out of trap 104 Track drop out and trap exited by electrode 306 and enter detector 118.Therefore, the ion of different mass-to-charge ratioes is analyzed for selectivity, Voltage source 106 (under the control of controller 108) changes the amplitude for the current potential for being applied to electrode 302 in a stepwise fashion.With The amplitude for applying current potential changes, and the ion of different mass-to-charge ratioes is sprayed from ion trap 104 and detected by detector 118.
Electrode 302,304 and 306 in ion trap 104 is usually by conductive material such as stainless steel, aluminium or other metal shapes Into.Gasket 308 and 310 is usually by insulating materials such as ceramics, teflon(for example, fluorinated polymeric material), rubber are each Kind plastics are made.
Can have in endcap electrode 304 and 306, in central electrode 302 and the central opening in gasket 308 and 310 There are identical diameter and/or shape or different diameters and/or shape.For example, in the embodiment shown in figure 3 a, in electrode 302 and gasket 308 and 310 in central opening there is circular cross sectional shape and diameter c0.And 304 He of endcap electrode 306 have shape of cross section for circular and a diameter of c2<c0Central opening.As shown in Figure 3A, the opening in electrode and gasket Axially aligned with axis 318 so that when electrode and gasket are assembled into sandwich, the opening in electrode and gasket forms logical Cross 104 axially extending opening of ion trap.
In general, the diameter c of the central opening in electrode 3020It can select to work as from ion to realize as needed Specific objective resolution capability when the selectivity of trap 104 sprays ion and also control the general internal volume of mass spectrograph 100.At certain In a little embodiments, c0About 0.6mm or bigger (for example, 0.8mm or bigger, 1.0mm or bigger, 1.2mm or bigger, 1.4mm or Bigger, 1.6mm or bigger, 1.8mm or bigger).The diameter c of central opening in endcap electrode 304 and 3062Can also basis Need to select to realize the specific objective resolution capability when spraying ion from ion trap 104 and ensure to not being ejected The appropriate limitation of ion.In certain embodiments, c2About 0.25mm or bigger (for example, 0.35mm or bigger, 0.45mm or more Greatly, 0.55mm or bigger, 0.65mm or bigger, 0.75mm or bigger).
The axial length c of electrode 302 and the combined openings in gasket 308 and 3101Can also select as needed with Ensure that appropriate ion limits and realizes the specific objective resolution capability when ion is sprayed from ion trap 104.In some implementations In example, c1About 0.6mm or bigger (for example, 0.8mm or bigger, 1.0mm or bigger, 1.2mm or bigger, 1.4mm or bigger, 1.6mm or bigger, 1.8mm or bigger).
Rule of thumb have determined that and work as c0And c1It is selected such that c1/c0During more than 0.83, the resolution capability of mass spectrograph 100 is more Greatly.Therefore, in certain embodiments, c0And c1It is selected such that c1/c0Value be 0.8 or bigger (for example, 0.9 or bigger, 1.0 Or bigger, 1.1 or bigger, 1.2 or bigger, 1.4 or bigger, 1.6 or bigger).
Due to the relative small size of ion trap 104, if the quantity for the ion that can be captured at the same time in the ion trap 104 by Dry factor limitation.One such factor is the space charge interaction between ion.Increase with the density of captured ion, The average headway of captured circulation ion reduces.With ion (can be any of positive charge or negative electrical charge) be forced it is close Together, the amplitude increase of the repulsive force of captured ion.
To overcome the limitation of amount of ions that can be interior while captured in ion trap 104 and increasing the appearance of mass spectrograph 100 Amount, in certain embodiments, mass spectrograph 100 can include the ion trap with multiple rooms.Fig. 3 B show to have with hexagon battle array Arrange the schematic diagram of the ion trap 104 of multiple ion chambers 330 of arrangement.Each room 330 is with identical with the ion trap 104 in Fig. 3 A Mode works, and including two endcap electrodes and cylindrical center electrode.Endcap electrode 304 and endcap electrode 306 A part is shown in figure 3b.Endcap electrode 304 is connected to voltage source 106 by tie point 334, and endcap electrode 306 leads to Cross tie point 332 and be connected to voltage source 106.
Fig. 3 C are cross-sectional views of Fig. 3 B along section line A-A.It shows five ion chambers declined along section line A-A It is each in 330.Voltage source 106 is connected to central electrode 302 via single connection point (not showing in fig. 3 c).As a result, pass through Apply suitable current potential to electrode 302, voltage source 106 (under the control of controller 108) can be caught at the same time in each room 330 Ion is obtained, and the ion of selected mass-to-charge ratio is sprayed from each room 330.
In certain embodiments, the quantity of 104 intermediate ion room 330 of ion trap can be with forming in endcap electrode 304 The quantity Matching of aperture.As described in chapters and sections II, endcap electrode 304 can generally include one or more apertures.Work as end cap When electrode 304 includes multiple apertures, ion trap 104 can also include multiple ion chambers 330 so that the shape in endcap electrode 304 Into each aperture correspond to different ion chambers 330.In this way, the ion of generation can lead in ion gun 102 Ion trap 104 is crossed efficiently to collect and capture in ion chamber 330.As described above, the use of multiple rooms reduces captured ion Between space charge interaction, add the capture ability of ion trap 104.In general, the position of ion chamber 330 and horizontal stroke Cross sectional shape can be identical with the arrangement and shape of the aperture 240 and 294 discussed in chapters and sections II.
As an example, with reference to figure 3B, endcap electrode 304 includes the multiple apertures arranged with hexagonal array.In electrode 304 Each aperture of middle formation is matched with corresponding ion chamber 330, and therefore, and ion chamber 330 is also arranged with hexagonal array.
In certain embodiments, the quantity of ion chamber 330, arrangement and/or shape of cross section not with endcap electrode 304 The arrangement matching of aperture.For example, endcap electrode 304 can only include the aperture 294 of one or a small amount of, and ion trap 304 can be with Including multiple ion chambers 330.Because using the capture ability of multiple ion chambers 330 increase ion trap 104, multiple ion chambers are used Multiple advantages can be provided, even if arrangement of the arrangement of ion chamber not with the aperture in endcap electrode 304 matches.
The supplementary features of ion trap 104 are in such as United States Patent (USP) No.6469298 in United States Patent (USP) No.6762406 in the U.S. Disclosed in patent No.6933498, the full content of above-mentioned each patent is incorporated herein by reference.
IV voltage sources
Voltage source 106 provides fortune based on the signal that controller 108 transmits on control line 127e to the component of mass spectrograph 100 Row power and current potential.As above discussed in chapters and sections I, mass spectrometric major advantage disclosed herein be its compact size and The power consumption significantly reduced relative to traditional mass spectrometer.Although mass spectrograph 100 can usually be run with various voltage sources, if Voltage source 106 is efficient source, and the power consumption for reducing mass spectrograph 100 as much as possible is favourable.
But, size is not only small but also can generate the efficient voltage source of the voltage for the component for being enough to drive mass spectrograph 100 and does not allow It is commercially available.Fig. 4 A show the schematic diagram of the embodiment of efficient voltage source 106, it is configured offer and is applied to ion trap 104 Central electrode 302 high pressure RF signals 482.During operation, voltage source 106 can amplify the voltage received from power supply 440, The waveform for changing high pressure RF signals 482 at the same time is measured with being suitable for specific mass spectrograph.
The design of power supply 106 allows mass spectrograph 100 to be imitated in the whole different scanning stage of high pressure RF signals 482 with high power Rate is run.In each stage, power efficiency is defined as ratio of the input electric power to electromotive power output.In some embodiments In, the efficiency of power supply 106 in all stages of voltage amplification can be 40% or higher (for example, 50% or higher, 60% or more Height, 70% or higher, 80% or higher, 90% or higher).On the contrary, traditional power amplifier (put by emitter follower or A classes Big device) usually there is maximal efficiency in highest amplifying stage, but there is the efficiency being decreased obviously in relatively low amplifying stage.Therefore, pass System power amplifier is probably poorly efficient and unsuitable to needing the application that scanning voltage amplifies.
In addition to Effec-tive Function, voltage source 106 allows relatively low power supply (for example, battery) to provide activation mass spectrograph 100 All parts needed for electric power and current potential.As a result, mass spectrograph 100 has compact shape and lighter than traditional mass spectrometer.
With reference to figure 4A, voltage source 106 includes proportional-integral-differential (PID) control loop 420, and switch mode power 430 can The linear regulator 450 of choosing, class-D amplifier 460, and resonance circuit 480.In certain embodiments, voltage source 106 is each Component can be integrated into a module, which can be inserted into support base 140.If this allows voltage source 106 It is defective, easily replaced with other module.Alternatively, in certain embodiments, any or more component of voltage source 106 can be with Standalone module is implemented as, and can be individually replaced.In certain embodiments, some or all component can be mounted directly to Support base 140.The each component shown in Figure 4 A is relatively low cost and usually commercially available, this permission voltage source 106 are manufactured with the effective means of cost.
During operation, pid control circuit 420 receives modulated signal 412, the generator from modulation signal generator 410 It can be or can not be the component of voltage source 106.Fig. 4 B show the example of modulated signal 412, wherein, the amplitude change of signal (that is, envelope) is illustrated as the function of time.The envelope of modulated signal 412 is approximate with the envelope for exporting high pressure RF signals 482 related. Based on modulated signal 412, pid control circuit 420 respectively to switch mode power 430 and linear regulator 450 (if there is Words) send control signal 422 and 424.
Switch mode power 430, which is configured, receives the input power signal 442 from power supply 440, which can include electricity Pond (for example, lithium ion, lighium polymer, ni-Cd or Ni-MH battery).The voltage provided by power supply 440 is usually in 0.5V and about 13V Between.As an example, voltage can be about 7.2V.Switch mode power 430 is based on control signal 422 and amplifies input power signal 442, so as to produce modulated voltage signal 432, which is sent to linear regulator 450 (if present).Modulation electricity The example of pressure signal 432 is shown in figure 4 c.Modulated voltage signal 432 usually has the amplitude between 0V and about 25V.
In certain embodiments, switch mode power 430 includes being used for the switch regulator of highly efficient power amplification.In the runtime Between, input power signal 442 can be less than, greater than or equal to output voltage signal 432.When power supply 440 is battery, this is special Sign is particularly advantageous.Unlike linear power supply, switch mode power 430 (it is nonlinear amplifier) can be in different magnifying states Between dissipation little power or non-dissipated power when switching, so as to cause high power to be changed.Further, since the inside transformation of smaller Device size and weight, switch mode power 430 are usually more more compact than conventional linear power supply and lighter.
Linear regulator 450 is optional to be included in voltage source 106.If linear regulator 150 is not deposited in voltage source 106 , then, the voltage signal 432 of change is sent directly to class-D amplifier 460 from switch mode power 430.Alternatively, when linear In the presence of adjuster 450 is in voltage source 106, linear regulator 150 receives modulated voltage signal 432 from switch mode power 430 Control signal 424 is received with from pid control circuit 420.
Linear regulator 450 serves irregular in the voltage signal 432 of filtering change.From linear regulator The voltage signal 442 of 450 filtering is received by D amplifiers 442.In general, linear regulator 450 includes low dropout voltage regulator, its In, constant low pressure drop may insure that the whole efficiency of voltage source 106 is only slightly decreased due to the presence of linear regulator 450. In certain embodiments, the control signal 424 received by linear regulator 450 is used for the envelope of output voltage signal 442 more It is changed to the mass spectrum for being adapted to measurement predetermined substance.
Benchmark wave producer 470 is optional to be included in voltage source 106.If it does, benchmark wave producer 470 is put to D classes Big device 460 provides reference wave signal 472.In general, reference wave signal 472 has in radio-frequency region (for example, from about 0.1MHz To about 50MHz) frequency.For example, in certain embodiments, reference wave signal 472 can have 1MHz or higher (, 2MHz or Higher, 4MHz or higher, 6MHz or higher, 8MHz or higher, 15MHz or higher, 30MHz or higher) frequency.
Fig. 4 D show the example of reference wave signal 472.In fig. 4d, reference wave signal 472 is square wave.But, it is more general Everywhere, benchmark wave producer 470 can generate the reference wave signal 472 of various different waves.In certain embodiments, for example, Reference wave signal 472 can correspond to any of triangular wave, sine wave or nearly sine wave.
Class-D amplifier 460 receives reference wave signal 472 (if benchmark wave producer 470 exists) and the voltage letter of filtering Both numbers 442 (or voltage signals 432 of change, if linear regulator 450 is not present), and generated from these input signals The RF signals 462 of modulation.Fig. 4 E show the example of modulated rf signal 462.In this illustration, the time interval of signal 462 is About 10ms.The amplitude of signal 462 changes between 0V and about 30V.The frequency of carrier wave and reference wave signal 472 in RF signals 462 Frequency it is identical or approximately the same.Voltage signal of the envelope (for example, being represented by the dotted line in Fig. 4 E) of RF signals 462 with filtering The envelope of 442 (or voltage signals 432 of change) is identical or approximately the same.
Fig. 4 F show the schematic diagram of the embodiment of class-D amplifier 460.Class-D amplifier 460 includes a pair of transistor 441. In class-D amplifier 460, the envelope tune for the voltage signal 442 (or voltage signal 432 of change) that reference wave signal 472 is filtered Make to generate RF signals 462.
RF signals 462 are received by resonance circuit 480, which also schematically illustrates in Fig. 4 F.Resonance circuit 480 includes electricity Sensor 486 and capacitor 488.In certain embodiments, the position of inductor 486 and capacitor 488 can be relative in Fig. 4 F In the place-exchange that shows.The inductance value of the inductor 486 and capacitance of capacitor 488 is conventionally selected to so that circuit 480 The substantially matching frequency in reference wave signal 472 of resonant frequency.
In certain embodiments, resonance circuit 480 have 60 or bigger (for example, 80 or bigger, 100 or bigger) Q because Number.When RF signals 462 are applied to resonance circuit 480, high pressure RF signals 482 generate on capacitor 488.In general, The waveform of high pressure RF signals 482 is identical or approximately the same with the waveform of RF signals 462, except the amplitude of high pressure RF signals 482 is bright Beyond the aobvious amplitude more than RF signals 462.For example, in certain embodiments, the maximum amplitudes of high pressure RF signals 482 be 100V or Higher (for example, 500V or higher, 1000V or higher, 1500V or higher, 2000V or higher).In general, resonance circuit 480 high Q factor allows to generate significantly threshold voltage in RF signals 482.
The combination of class-D amplifier 462 and resonance circuit 480 is favourable, there is several reasons, including low-power consumption and frequency tune Section.Another important advantage is, and the fact that pure sinusoid reference wave signal 472 are not required.On the contrary, 462 He of class-D amplifier The combination of resonance circuit 480 can use the reference wave signal with different wave.Specific waveforms such as square wave often can be with Fidelity than pure sinusoid waveform higher generates.As a result, the combination of class-D amplifier 462 and resonance circuit 480 allows with high stable Property reference wave signal operation.
Fig. 4 A are returned to, high pressure RF signals 482 can be monitored by optional signal monitor 490, which can be with It is present or not present in voltage source 106.Signal monitor 490 receives feedback signal 484 from resonance circuit 480, which leads to It is often the relatively low amplitude value copy of high pressure RF signals 482.Although feedback signal 484 usually has than 482 smaller of high pressure RF signals Amplitude, but in all the points, the amplitude of feedback signal 484 is usually directly proportional to the amplitude of high pressure RF signals 482.
The feedback signal received by signal monitor 490 from resonance circuit can be sent to PID as control signal 492 Control loop 420 and/or benchmark wave producer 470.Based on control signal 492, pid control circuit 420 can be to switching regulator electricity Source 430 and linear regulator 450 send modified control signal 422 and 424, with optimize the waveform of high pressure RF signals 482 and Amplitude.For example, pid control circuit 420 can change the envelope of modified voltage signal 432 based on control signal 492, so that Make the amplitude maximum of high pressure RF signals 482.
In certain embodiments, the resonant frequency of resonance circuit 480 can not be accurate with the frequency of reference wave signal 472 Match somebody with somebody.For example, this is possible, because the inductance value of inductor 486 and/or the capacitance of capacitor 488 are inaccurate.This Outside, the capacitance of the inductance of inductor 486 and/or capacitor 488 can change with the time.This is possible, if for example, Class-D amplifier 460 deforms the output frequency of RF signals 462 so that the frequency of RF signals 462 no longer with reference signal ripple 472 Frequency matching.The possible potential efficiency for reducing voltage source 106 of this mismatch, because resonance circuit 480 is no longer RF signals 462 effective resonator.
It can implement several technologies to compensate this mismatch.In certain embodiments, in monitoring and controlling signal 492, The frequency of reference wave signal 472 can be scanned by benchmark wave producer 470.Benchmark wave producer 470 can be by reference wave signal 472 choice of optimal frequency is the frequency for the amplitude maximum for making control signal 492.
In certain embodiments, the capacitance of capacitor 488 can change in resonance circuit 480, which capacitance determined Value makes the amplitude maximum of control signal 492.For this purpose, capacitor 488 can be variable condenser.
Can directly it implement in hardware, software or both for compensating the unmatched aforementioned techniques of frequency.For example, control Device 108, which can be configured, performs the one or more in these methods to compensate frequency mismatch.Controller 108 can be configured Automatically and/or these methods are continually performed with the matching of constantly optimization frequency.Alternatively, controller 108 can be configured only When receiving instruction from user, for example, performing these methods when the control on user's activated user interface 112.When by controlling Device 108 perform when, it is disclosed herein be used for compensate the unmatched technology of frequency usually 5 minutes or shorter (for example, 3 minutes or Shorter, 2 minutes or shorter, 1 minute or shorter) time in complete.
High pressure RF signals 482 are applied to ion trap 104 (for example, central electrode 302 of ion trap 104) with selective spray Go out captured ion to detect for detector 118.In addition to other factors, the mass-to-charge ratio that can be analyzed using ion trap 104 Scope additionally depend on the profiles (for example, envelope and maximum amplitude) of RF signals 482.It is special by varying these of RF signals 482 Sign, voltage source 106 can select the scope of analyzed mass-to-charge ratio (under the control of controller 108).
In certain embodiments, voltage source 106 can include multiple benchmark wave producers 470 and/or multiple resonance circuits 480.During operation, the combination of special datum wave producer 470 and particular resonance circuit 480 can be selected by controller 108 To generate using suitable high pressure RF signal 482 of the ion trap 104 for analyzing specific mass charge ratio range.To change analyzed matter lotus The scope of ratio, controller 108 select different benchmark wave producer 470 and/or resonance circuit 480.
V detectors
Detector 118 is configured the charged particle that ion trap 104 is left in detection.Charged particle can be cation, bear from Son, electronics or these combination.
Different detectors in extensive range can be used in mass spectrograph 100.Fig. 5 A show the detection for including Faraday cup 500 The embodiment of device 118.Faraday cup 500 has round base portion 502 and cylindrical side wall 504.In general, Faraday cup 500 Shape and geometry can be altered to optimization mass spectrograph 100 sensitivity and resolution ratio.
For example, base portion 502 can have a various shape of cross sections, including square, rectangle, ellipse, circle or it is any its He rule or irregular shape.Base portion 502 for example can be flat or curved.
Fig. 5 B show the side view of Faraday cup 500.In certain embodiments, the length 506 of side wall 504 can be 20mm Or shorter (for example, 10mm or shorter, 5mm or shorter, 2mm or shorter, 1mm or shorter, or even 0mm).In general, length 506 can select according to various criterion, including keep the compactedness of mass spectrograph 100, there is provided the institute during charged particle is detected The selectivity needed, and resolution ratio.In certain embodiments, side wall 504 meets the shape of cross section of base portion 502.But more Generally, side wall 504 is not required the shape for meeting base portion 502, and can have the various of the shape for being different from base portion 502 Shape of cross section.Moreover, side wall 504 needs not be the shape of cylinder.In certain embodiments, for example, side wall 504 can be with Axis direction along Faraday cup 500 is curve.
In general, Faraday cup 500 can be relatively small.The full-size of Faraday cup 500 is taken up an official post corresponding to cup Maximum linear distance between what 2 points.In certain embodiments, for example, the ultimate range of Faraday cup 500 is 30mm or more Small (for example, 20mm or smaller, 10mm or smaller, 5mm or smaller, 3mm or smaller).
In general, the thickness of base portion 502 and/or the thickness of side wall 504 are selected to ensure that effective detection of charged particle. In some embodiments, for example, the thickness of base portion 502 and/or side wall 504 be 5mm or smaller (for example, 3mm or smaller, 2mm or more It is small, 1mm or smaller).
The side wall 504 and base portion 502 of Faraday cup 500 are usually formed from one or more of metals.Autofrettage can be applied Drawing the glass 500 of metal includes such as copper, aluminium and silver.In certain embodiments, Faraday cup 500 can in base portion 502 and/or There is one or more layers coating on the surface of side wall 504.Coating can be formed from the material of such as copper, aluminium, silver and gold.
During operation mass spectrograph 100, when charged particle is sprayed from ion trap 104, charged particle can drift about or add Speed is into Faraday cup 500.Once in Faraday cup 500, charged particle be captured on the surface of Faraday cup 500 (for example, The surface of base portion 502 and/or side wall 504).Electricity is generated by the charged particle of any one capture in base portion 502 or side wall 504 Stream, the electric current are measured (for example, by circuit in detector 118) and report to controller 108.If charged particle be from Son, measured electric current are gas currents, and its amplitude and the abundance cost ratio of measured ion.
To obtain the mass spectrum of analyte, the amplitude for being applied to the current potential of the central electrode 302 of ion trap 104 is changed (example Such as, variable amplitude signal, high pressure RF signals 482 are applied in) to spray the ion of specific mass-to-charge ratio from the selectivity of ion trap 104. Each change for the amplitude corresponding to different mass-to-charge ratioes, uses corresponding to the gas current of the ejection ion of selected mass-to-charge ratio Faraday cup 500 measures.The measurement gas current-it corresponds to mass spectrum-become with the current potential for being applied to electrode 302 is reported To controller 108.In certain embodiments, controller 108 based on the algorithm for ion trap 104 and/or calibration information by institute The voltage conversion of application is for the algorithm of ion trap 104 and/or the specific mass-to-charge ratio of calibration information.
Charged particle by endcap electrode 306 from ion trap 104 ejection after, by detector 118 and endcap electrode Electric field is formed between 306, charged particle can be accelerated to hit detector 118.In certain embodiments, in detector 118 In the case of including Faraday cup 500, for example, the conductive surface of Faraday cup 500 is maintained at the ground connection established by voltage source 106 Current potential, and positive potential is applied to endcap electrode 306.By the current potential of these applications, cation is arranged from endcap electrode 306 Denounce the ground connection conductive surface of Faraday cup 500.In addition, the electronics for flowing through endcap electrode 306 is attracted to endcap electrode 306, And Faraday cup 500 is not therefore struck against.Therefore, this configuration causes improved signal-to-noise ratio.More generally, configured at this In, Faraday cup 500 can be the current potential different from ground connection, as long as it is in the current potential lower than endcap electrode 306.
In certain embodiments, it is desired to detect negatively charged particle (for example, anion and/or electronics).For detection Such particle, Faraday cup 500 is by the voltage than 306 higher of endcap electrode is biased negatively charged particle is attracted to Faraday cup 500。
In certain embodiments, detector 118 can include Faraday cup 500, it has two separated by insulating regions A region.Different bias potentials can be applied in by each region.For example, Fig. 5 C show Faraday cup 500, it, which has, is insulated Two conductive regions 510 and 520 that region 530 separates.By the way that endcap electrode 306 is grounded and is applied respectively to region 510 and 520 Add positive and negative bias voltage, region 510, which can detect negatively charged particle and region 520, can detect positively charged particle.It is this Configuration can provide additional information during mass spectrum is measured, because positive charged ions and electronegative ion can be detected at the same time. Alternatively, by applying one in bias potential active region 510 and 520 first, and another region, band are then activated The measurement of carbonium and electronegative ion can carry out in order.Alternatively, in certain embodiments, detector 118 can Including two Faraday cups 500, to be used to detect positively charged wherein different bias voltages is applied to each Faraday cup 500 Ion and electronegative ion.
In certain embodiments, detector 118 can be fixed directly to shell 122.For example, Fig. 5 C show shell 122, It includes the one or more electrodes 550 and 552 for contacting Faraday cup 500.Alternatively, in certain embodiments, one or more A electrode 550 and 552 can be attached directly to Faraday cup 500.In certain embodiments, an electrode can be used for biasing Faraday cup 500, and another electrode can be used for the electric current that measurement is generated by Faraday cup 500.Alternatively, in some implementations In example, identical electrodes can be used to apply bias voltage and measure electric current.
In certain embodiments, shell 122 can be arranged such that detector 118 is easily mounted or removes.For example, such as Shown in Fig. 5 C, shell 122 includes opening, and Faraday cup 500 can be by clamping element 540 (for example, screw or other fasteners) It is firm to be installed and retained in wherein.This is particularly advantageous when Faraday cup 500 is damaged or contaminated, and shown Faraday cup is broken Damage contaminated can be determined during mass-spectrometer measurement as described above by detecting plasma peak value.Contaminated farad It can be replaced by removing cup 500 from the opening in shell 122, and refill-unit is installed for glass 500.Contaminated faraday Cup can be with spot repair or cleaning.For example, Faraday cup 500 can toast in drying,portable oven so that 500 surface of Faraday cup On viscous particle be evaporated.Faraday cup through cleaning can be turned back in shell 122.This replaceability allows mass spectrograph 100 minimum downtime, even if mass spectrometric particular elements are contaminated.In certain embodiments, contaminated Faraday cup 500 can clear up (for example, applying high current by base portion 502 and side wall 504) by heating, while Faraday cup is still pacified In shell 122.Subsystem can be adjusted by pressure from the dye particle of getting dirty of the surface of base portion 502 and/or side wall 504 release System 120 removes.
In certain embodiments, Faraday cup 500 may be implemented as inserting, the component of replaceable module 148, such as in chapter Save described in I.In modular arrangements, Faraday cup 500 can be formed as the groove in the plate of such as conductive material.The plate can To be directly attached to another component of module 148, such as ion trap 104 so that aperture and groove pair in endcap electrode 306 Standard, and the ion sprayed from ion trap 104 is directly entered Faraday cup.Module with different Faraday cup diameters can be used In the selective enumeration method for providing different type analyte.
Fig. 5 D show detector 118, it includes the array of farad electricity cup detector 500, it can be or can not be list Piece is formed.Detector array can be favourable, for example, when ion trap 104 includes the array of ion chamber 330.Endcap electrode 306 can include multiple apertures 560 for be directed at each ion chamber so that the ion sprayed from each room is through small holes 560 In one.In an aperture in through small holes 560, ion incidence to one in 500 array of Faraday cup detector On cup.This method sprayed based on array and detect ion can substantially increase the efficiency that detection sprays ion.In such as Fig. 5 D In shown array geometry, the size of each Faraday cup 500 can meet each aperture formed in endcap electrode 306 560 size.
In certain embodiments, the repulsion grid of biasing or magnetic field can be placed in before Faraday cup 500 or prevent Secondary charges corpuscular radiation, this can make the measurement distortion of the particle sprayed from ion trap 104.Alternatively, in certain embodiments, SE secondary emission from Faraday cup 500 can be used for detection and spray ion.
Although discussion above surrounds low power operation and the Faraday cup detector of compact size, more generally, respectively Other detectors of kind can be used in mass spectrograph 100.For example, other suitable detectors include electron multiplier, photomultiplier transit Pipe detector, scintillation detector, picture current detector, Daly detector, fluorescence-based detector, and incident band electrochondria Other detectors (that is, the detector using electric charge to photon transduction mechanism) that son generation photon and photon are then detected.
VI pressure regulation sub-systems
Pressure regulation sub-systems 120 generally be configured adjust gas circuit 128 in air pressure, gas circuit 128 include ion gun 102, The internal volume of ion trap 104 and detector 118.As described in chapters and sections I, run the period of mass spectrograph 100, pressure tune above Sub-system 120 by the air pressure in mass spectrograph 100 maintain 100mTorr or bigger (for example, 200mTorr or bigger, 500mTorr or bigger, 700mTorr or bigger, 1Torr or bigger, 2Torr or bigger, 5Torr or bigger, 10Torr or more Greatly), and/or 100Torr or smaller (for example, 80Torr or smaller, 60Torr or smaller, 50Torr or smaller, 40Torr or more It is small, 30Torr or smaller, 20Torr or bigger).
In certain embodiments, the air pressure in some components of mass spectrograph 100 is maintained at by pressure regulation sub-systems 120 In the range of stating.For example, pressure regulation sub-systems 120 can be by ion gun 102 and/or ion trap 104 and/or detector 118 Air pressure be maintained between 100mTorr and 100Torr (for example, between 100mTorr and 10Torr, 200mTorr with Between 10Torr, between 500mTorr and 10Torr, between 500mTorr and 50Torr, in 500mTorr and 100Torr Between).In certain embodiments, the air pressure at least two in ion gun 102, ion trap 104 and detector 118 is phase With.In certain embodiments, the air pressure in all three components is identical.
In certain embodiments, the air pressure phase at least two in ion gun 102, ion trap 104 and detector 118 To a small amount of different.For example, pressure regulation sub-systems 120 can by ion gun 102, ion trap 104 and detector 118 at least The air pressure of two keep 100mTorr or smaller (for example, 50mTorr or smaller, 40mTorr or smaller, 30mTorr or smaller, 20mTorr or smaller, 10mTorr or smaller, 5mTorr or smaller, 1mTorr or smaller) difference.In certain embodiments, In all three of ion gun 102, ion trap 104 and detector 118 air pressure difference 100mTorr or smaller (for example, 50mTorr or smaller, 40mTorr or smaller, 30mTorr or smaller, 20mTorr or smaller, 10mTorr or smaller, 5mTorr Or smaller, 1mTorr or smaller).
As shown in Figure 6A, pressure regulation sub-systems 120 can include vortex pump 600, and, with pump receptacle 606, it is carried for it One or more alternating vortex flange 602 and 604.Relative track movement capture gas and liquid between vortex flange 602 and 604 Body, causes pump action.In certain embodiments, vortex flange 604 can be fixed, and vortex flange 602 prejudicially presses rail Road moves, and with rotation or does not rotate.In certain embodiments, both deviation pivot movements of vortex flange 602 and 604. Fig. 6 B show the schematic diagram of vortex flange 602.The example of vortex flange geometry includes but is not limited to involute, Archimedes's spiral shell Rotation and Mixing Curve.
The track motion of vortex flange 602 and 604 allows vortex pump 600 to only generate a small amount of vibration and low during operation Noise.Therefore, vortex pump 600 can be directly coupled to ion trap 104, and not have the unfavorable of introducing essence during mass-spectrometer measurement Influence.Further to reduce vibration coupling, the vortex flange 602 of orbital motion can be with simple mass block come balanced.Cause There is a small amount of moving component for vortex pump and only generate minimal amount of vibration, the reliability of such pump is usually very high.
Vortex pump 600 is generally dimensionally compact, and very light weight.In certain embodiments, for example, vortex pump The 600 full-size maximum linear distance of any point-to-point transmission (for example, on vortex pump 600) be less than 10cm (for example, be less than 8cm, Less than 6cm, less than 5cm, less than 4cm, less than 3cm, less than 2cm).In certain embodiments, the weight of vortex pump 600 is less than 1.0kg (for example, being less than 0.8kg, less than 0.7kg, less than 0.6kg, less than 0.5kg, less than 0.4kg, less than 0.3kg, is less than 0.2kg)。
The small size and weight of vortex pump 600 allow it to be merged in various configurations in mass spectrograph 100.In some embodiments In, for example, as seen in figs. 1D and 1E, vortex pump 600 (part as pressure regulation sub-systems 120) can be mounted directly to Support base 140 (for example, printed circuit board (PCB)).In certain embodiments, vortex pump 600 is (as pressure regulation sub-systems 120 A part) it may be implemented as inserting, the component of replaceable module 148, and other portions of module 148 can be directly attached to One or more of part, such as ion gun 102, ion trap 104 and/or detector 118.
Fig. 6 A show to be mounted directly to the vortex pump 600 of printed circuit board (PCB) 608.Pump intake 610 is directly connected to manifold 121 Pump intake 620.Vortex pump 600 is fixed to plate 608 by tightening member 630 and retaining element 632, tightening member 630 and solid Determine element 632 can be positioned in the location interval 1cm of pump intake 610 and 620 or bigger (for example, 2cm or bigger, 3cm or Bigger, 4cm or bigger) position so that reduce pump 600 and plate 608 between vibration couple.Alternatively, instead of pump 600 with It is directly connected between manifold 121, in certain embodiments, conduit (for example, flexible and rigid pipe) can connect pump intake 610 It is connected to pump intake 620.
The vortex pump being suitable for use in pressure regulation sub-systems 120 can be from such as Agilent technology company (Jia Lifuni The Santa Clara in sub- state) buy.In addition to vortex pump, other pumps can be also used in pressure regulation sub-systems 120.Appropriate pump Example includes diaphragm pump, diaphragm pump and Roots blower pump.
Some advantages relative to the pumping scheme in traditional mass spectrometer are provided using small simple and mechanical pump.Specifically Ground, usually using multiple pumps, at least one in the pump runs traditional mass spectrometer in high speed.Transported in high speed The mechanical oscillation in mass spectrometric miscellaneous part are coupled in capable big machinery pump generation, so as to be generated in metrical information bad Noise.In addition, even if taking measures the component for isolating such vibration, interrupter usually increases mass spectrometric size, sometimes It is increased relatively large.In addition, the mammoth pump in high frequency operation consumes substantial amounts of electrical power.Therefore, traditional mass spectrometer includes being used for Meet the large-scale power supply of these requirements, this further increases the size of this quasi-instrument.
On the contrary, Single Mechanical pump such as vortex pump can be used in mass spectrograph disclosed herein, with each portion of control system Air pressure in part.By running mechanical pump, the mechanical coupling being vibrated into mass spectrometric miscellaneous part in relatively low speed Conjunction can be much less or eliminate.In addition, by low speed run, pump consumption quantity of power it is small can to its appropriate requirement To be met by voltage source 106.
It is empirically determined in certain embodiments, by being less than 6000 turns (for example, per minute be less than 5000 per minute It is turn, per minute to be less than 4000 turns, per minute to be less than 3000 turns, per minute to be less than 2000 turns) frequency operation Single Mechanical pump, the pump The expectation air pressure in mass spectrograph 100 can be kept, and at the same time, its power consumption requirements can be met by voltage source 106.
VII shells
As described in chapters and sections I, mass spectrograph 100 includes shell 122, its closed mass spectrometric component.Fig. 7 A show shell The schematic diagram of 122 embodiment.Sample inlet 124 is integrated into shell 122 and is configured introduces gas circuit 128 by gas particle In.It is integrated into shell 122 and also has display 116 and user interface 112.
In certain embodiments, display 116 is passive or active liquid crystal or light emitting diode (LED) display.At certain In a little embodiments, display 116 is touch-screen display.Controller 108 is connected to display 116, and can use display The user of device 116 to mass spectrograph 100 shows various information.Shown information can include for example on being scanned by mass spectrograph 100 One or more materials identity information.The information can also include mass spectrum (for example, as mass-to-charge ratio function by examining Survey the measurement result for the abundance of ions that device 118 detects).In addition, shown information can include joining for the operation of mass spectrograph 100 Number and information (for example, measured gas current, are applied to the voltage of the various parts of mass spectrograph 100, and installed in mass spectrograph The title and/or identity that current block 148 in 100 is associated, the police associated with the material identified by mass spectrograph 100 Accuse, and defined user runs the preference of mass spectrograph 100).The all user preferences as defined of information and operation setting can To be stored in storage unit 114 and be retrieved by controller 108 for showing.
In certain embodiments, as shown in Figure 7 A, user interface 112 includes a series of controls being integrated into shell 122. Button, sliding block, rocking bar, the switch control similar with other can be included by the user activated control of mass spectrograph 100. By the control of activated user interface 112, the user of mass spectrograph 100 can start various functions.For example, in some embodiments In, the activation of a control in the control starts the scanning of mass spectrograph 100, and during this period, mass spectrograph passes through sample inlet 124 suction samples (for example, gas particle), ion is generated from gas particle, and then uses ion trap 104 and detector 118 Capture and analyze ion.In certain embodiments, before new scanning is performed, the activation of a control in the control resets Mass spectrograph 100.In certain embodiments, mass spectrograph 100 includes the control for restarting mass spectrograph 100 when activated by the user (for example, change mass spectrograph 100 a component such as module 148 and/or be connected to sample inlet 124 filter it Afterwards).
When display 116 is touch-screen display, a part for user interface 112 even or all may be implemented as A series of touch screen controls on display 116.That is some or all of the control of user interface 112 can be expressed The touch sensitive area for the display 116 that display 116 is activated is contacted by finger for user.
As described in chapters and sections I, in certain embodiments, mass spectrograph 100 includes replaceable, pluggable module 148, it includes Ion gun 102, ion trap 104 and (alternatively) detector 118.When mass spectrograph 100 includes pluggable module 148, shell 122 can With including opening with allow user enter shell 122 inside with replacement module 148, without pulling down shell 122.Fig. 7 B are to include The viewgraph of cross-section of the mass spectrograph 100 of pluggable module 148.In figure 7b, shell 122 includes opening 702 and sealed opening 702 Partition plate 704.When module 148 is to be replaced, the user of mass spectrograph 100 can open partition plate 704 to expose in mass spectrograph 100 Portion.Partition plate 704 is placed so that it provides directly accessing to pluggable module 148, it is allowed to which user pulls out from support base 140 Module 148, and another module is installed in place, without pulling down shell 122.User then can be by fastening partition plate 704 again Secondary sealed opening 702.
In figure 7b, partition plate 704 is implemented in the form of collapsible door.But more common of, various partition plates can For the opening in sealing shell 122.For example, in certain embodiments, partition plate 704 may be implemented as can be from shell 122 Completely dismountable lid.
In general, mass spectrograph 100 can include various different sample inlets 124.For example, in some embodiments In, sample inlet 124 includes aperture, it is configured is directly sucked in gas circuit 128 by the gas particle of 100 surrounding environment of mass spectrograph In.Sample inlet 124 can include one or more filters 706.For example, in certain embodiments, filter 706 is HEPA Filter, and prevent dust and solids from entering mass spectrograph 100.In certain embodiments, filter 706 includes capture moisture The molecular screen material of son.
As discussed previously, traditional mass spectrometer is run under low air pressure inside.To keep low pressure, traditional mass spectrometer bag Include the one or more filters for being attached to sample inlet.These filters are selective, and filter out specific type of material Particle, such as atmospheric gas particle (for example, nitrogen molecular and/or oxygen molecule) is to prevent it from entering mass spectrograph.Filter may be used also To be used for the analyte of particular category, such as biomolecule through concrete modification, and other kinds of molecule can be filtered out.Knot Fruit, for the filter of traditional mass spectrometer, (it can include pinched valve, and be formed from the material of such as dimethyl silicone polymer Molecular filter, wherein, dimethyl silicone polymer allows the selectivity of material to transmit) filtering gas particle into becoming a mandarin with from the stream Remove certain types of particle.There is no such filter, traditional mass spectrometer cannot be run, because low air pressure inside cannot be kept, Also, it is admitted into the operation that mass spectrometric some particles will prevent some components.As an example, in traditional mass spectrometer Thermal ionization ion source is not run when there is the aerial oxygen of appropriate concentration.
There are some defects using predetermined substance filter in traditional mass spectrometer.For example, because filter is selectivity , a small amount of analyte may only be analyzed in the case of no change filter and/or service condition, this is pretty troublesome. Specifically, for mass spectrometric non-trained users, correct selective filter is selected to be reconfigured at for designated analysis thing Mass spectrograph is probably difficult.In addition, time delay is introduced for the filter in traditional mass spectrometer, because analyte particle is not Spread by filter moment.According to the selectivity of filter and the concentration of analyte, meet with first time of analyte with Sufficient amount of analyte ions by measure with generate Information in Mass Spectra time between introduce sizable delay.
But, mass spectrograph disclosed herein is run under high pressures, it is not necessary that including filter such as molecular filter with Keep the low pressure in mass spectrograph.By being transported in the case of the filter for the type that no use uses in traditional mass spectrometer OK, mass spectrograph disclosed herein can analyze larger number or different types of sample is reconfigured at without important, and can Faster to perform analysis.Moreover, because mass spectrometric component disclosed herein usually to atmospheric gas such as nitrogen and oxygen not Sensitivity, mass spectrograph can permit these gases together with the particle of analytes of interest analytes, this substantially increases analyze speed and reduces matter The service requirement of the miscellaneous part (for example, pumping load of pressure regulation sub-systems 120) of spectrometer.
Therefore, in general, the filter in mass spectrograph disclosed herein (for example, filter 706) do not filter into Enter the atmospheric gas particle (for example, nitrogen molecular and oxygen molecule) in the stream of the gas particle of sample inlet 124.Specifically, filter At least 95% or more the atmospheric gas particle that device 706 allows to meet with filter passes through.
Different types of filter 706 is interchangeable, and if they are dirty or invalid, can be by mass spectrograph 100 User replace.In certain embodiments, mass spectrograph 100 can include multiple filters 706, and user can be according to being divided The property for analysing sample selectively installs any one or more filters.
In certain embodiments, sample inlet 124, which can be configured, receives the directly incident material to be analyzed.Example Such as, filter 706 can be replaced by the sample incident mouth for being attached to sample inlet 124.During mass spectrograph 100 is used, lead to Cross sample incident mouth and incide the material of sample inlet 124 and be introduced into gas circuit 128, ionized by ion gun 102, and by ion trap 104 and detector 118 analyze.
In certain embodiments, mass spectrograph 100 can include being attached to shell 122 by different types of analyte introducing matter The various samples of spectrometer 100 introduce module.Sample introduces module 750 and schematically illustrates in fig. 7 c.Module 750 is attached to shell 122 so that the electrode 752 in shell 122 establishes the electrical connection of the counter electrode in module 750.Electrode 752 is connected to branch Controller 108 and voltage source 106 in support group portion 140.Voltage source 106 can supply electric power by electrode 752 to module 750, And controller 108 can transmit and receive signal to/from module 750.When module 750 is connected to shell 122 (for example, using Bolt or keying connection, or magnetic attachment means, or any of various other attachment means) when, voltage source 106 is supplied automatically Electric power is with active module 750.Once activation, module 750 reports its identity to controller 108, and controller 108 can be in display Information of the display on active module on 116.Controller 108 can retrieve configuration setting and other operations from storage unit 114 Parameter so that mass spectrograph 100 is configured the sample for automatically analyzing and being introduced by module 750.
In general, various samples introduce module and can be used together with mass spectrograph 100.For example, in certain embodiments, Module 750 is steam heat absorption module.In certain embodiments, module 750 is low-temperature plasma module.In some embodiments In, module 750 is electron spray ionisation module.These moulds each module in the block can interchangeably be used for mass spectrograph 100, with analysis Different samples in extensive range.
In addition to replaceable module 750, mass spectrograph 100 can also include various sensors.For example, in some embodiments In, mass spectrograph 100 can include the limit sensor 708 for being couple to controller 108.Limit sensor 708 detects mass spectrograph week Gas particle in collarette border, and report gas concentration to controller 108.During user runs mass spectrograph 100, controller 108 monitoring limit sensors 708 measure the time span and concentration of gas, and if exposure of the gas particle to user exceeds Threshold concentration or threshold time limit value, to user's display alarm (for example, via display 116).On threshold value exposure concentrations and The information of time limit value can be stored in such as storage unit 114, and be retrieved by controller 108.Mass spectrum can be used in Example limit sensor in instrument 100 include flammable/LEL gas sensors, photoionization sensor, electrochemical sensor and Temperature and moisture sensors.
In certain embodiments, mass spectrograph 100 can include explosion danger sensor 710.It is connected to the quick-fried of controller 108 Fried danger sensor 710 detects the presence of explosive substance near mass spectrograph 100.The threshold concentration of various explosive substances can store Retrieved in storage unit 114, and by controller 108.During operation mass spectrograph 100, when the one kind measured by sensor 710 Or the concentration of a variety of explosive substances, when exceeding threshold value, controller 108 can be shown via the user of display 116 to mass spectrograph 100 Show alarm information.In certain embodiments, alarm information can suggest that user stops using mass spectrograph 100, or in auxiliary shield Using to prevent to light one or more explosive substances in (for example, cage).The explosion danger that can be used for mass spectrograph 100 passes Sensor includes such as combustible sensor, which is purchased from MSA (Pennsylvania mossberry township) and RAE Systems (California Sheng Ruoze).
The shape of shell 122 is usually designed so that user can use either hand or two hand comfortable operations.It is general next Say, shell 122 there can be different shape in extensive range.But, due to selecting and being integrated with mass spectrograph 100 disclosed herein Component, shell 122 be typically it is compact.As shown in figs. 7 a-b, regardless of global shape, shell 122, which has, to be corresponded to The full-size a of any point-to-point transmission the longest straight line distance on outer surface of outer cover1.In certain embodiments, a1It is 35cm or smaller (for example, 30cm or smaller, 25cm or smaller, 20cm or smaller, 15cm or smaller, 10cm or smaller, 8cm or smaller, 6cm or Smaller, 4cm or smaller).
Further, since the selection of the component in mass spectrograph 100, the overall weight of mass spectrograph 100 is relative to traditional mass spectrometer It is decreased obviously.In certain embodiments, for example, the gross weight of mass spectrograph 100 be 4.5kg or more it is light (for example, 4.0kg or lighter, 3.0kg or lighter, 2.0kg or lighter, 1.5kg or lighter, 1.0kg or lighter, 0.5kg or lighter).
VIII operational modes
In general, mass spectrograph 100 is run according to a variety of operational modes.Fig. 8 A are shown in different operation moulds Be performed in formula with scan and analyze sample general step order flow chart 800.In first step 802, start sample Scanning.In certain embodiments, scanning the user by mass spectrograph 100.For example, mass spectrograph 100 can be configured to " one Keyed " mode operation, in this mode, user can start sample simply by the control in activated user interface 112 Scanning.Fig. 8 B show the embodiment of mass spectrograph 100, wherein, user interface 112 includes being used for the control 820 for starting scanning.Work as control When part 820 is activated by a user, the scanning of sample (being shown as gas particle 822 in the fig. 8b) is started.
In certain embodiments, controller 108 can automatically begin to scan based on one or more sensors reading.Example Such as, when mass spectrograph 100 includes limit sensor such as photoionization detector and/or LEL sensors, controller 108 can be with Monitor the signal of these sensors.If sensor indicates that potential material interested has been measured, for example, controller 108 can To start to scan.In general, different sensors class event in extensive range or situation can be automatically used for open by controller 108 Begin to scan.
In certain embodiments, mass spectrograph 100 can be configured runs in " continuous scanning " pattern.In mass spectrograph 100 It is placed in after continuous scan pattern, after Fixed Time Interval expires, scanning is repeated beginning.Time interval is matched somebody with somebody by user Put, and the value of time interval can be stored in storage unit 114 and be retrieved by controller 108.Therefore, in the step of Fig. 8 A In rapid 802, when mass spectrograph 100 is in continuous scan pattern, scan by the mass spectrograph.
After scanning has started, sample is introduced in mass spectrograph 100 in step 804.A variety of methods can be used In introducing the sample into mass spectrograph.In certain embodiments, in sample by gas particle (for example, the gas particle in Fig. 8 B 822) in the case of forming, 108 activation valve 129 of controller, opens the valve to permit gas particle into (example in mass spectrograph 100 Such as, into gas circuit 128).If sample inlet 124 includes filter 706, gas particle passes through filter, filter filter Except the dust in gas-particle flow and other solid-state materials.As disclosed above, pressure regulation sub-systems are by gas circuit 128 Air pressure is maintained at subatmospheric degree.As a result, when valve 129 is opened, gas particle 822 passes through gas circuit 128 and mass spectrograph Pressure differential between 100 surrounding environment is inhaled into sample inlet 124.Alternatively or additionally, pressure regulation sub-systems 120 can be with Gas particle is promoted to flow into mass spectrograph 100.
In certain embodiments, sample can be introduced into mass spectrograph 100 via direct incidence.As above in chapters and sections VII Disclosed in, mass spectrograph 100 can include the sample incident mouth for being connected to sample inlet 124.Sample incident mouth allows mass spectrum Sample is directly incident on sample inlet 124 for analysis by the user of instrument 100.Once incident, sample enters gas circuit 128.
In certain embodiments, the sample in partial ionization state can suck mass spectrograph 100 by electrostatic or electric power In.For example, applying suitable current potential by the electrode into mass spectrograph 100, charged particle can be accelerated into mass spectrograph 100 (for example, passing through sample inlet 124).
Next, in step 806, sample ionizes in ion gun 102.As disclosed above, sample inlet 124 can Diverse location along gas circuit 128 is positioned in the miscellaneous part relative to mass spectrograph 100.For example, in certain embodiments, sample Product entrance 124 is placed so that the gas particle being introduced into mass spectrograph 100 enters ion trap from sample inlet 124 first 104.In certain embodiments, sample inlet 124 is placed so that is introduced into the gas particle in mass spectrograph 100 first from sample Product entrance 124 enters ion gun 102.In certain embodiments, sample inlet 124 is placed so that gas particle is first from sample Product entrance 124 enters detector 118.Moreover, sample inlet 124 can be placed so that into the gas particle of mass spectrograph 100 Into the gas circuit 128 of the point between ion gun 102 and/or ion trap 104 and/or detector 118.
In sample (for example, gas particle 822) after the point along gas circuit 128 is introduced into mass spectrograph 100, some gas grains Son enters ion gun 102.If sample inlet 124 is not placed so that gas particle 822 is directly entered ion gun 102, then, The movement that gas particle 822 enters source 102 can be realized by spreading.Once in ion gun 102, controller 108 activates Ion gun 102 is with ionized gas particles, as disclosed in chapters and sections II.
Next, the ion generated in step 806 is captured in ion trap 104 in step 808.Such as in chapter above Save disclosed in II, ion is from ion gun 102 to the movement of ion trap 104 usually ion gun 102 and ion trap 104 Occur under the influence of the electric field of generation.Once in ion trap 104, ion is captured by the electric field in trap, and in central electrode Circulation in opening in 302, and circulated between endcap electrode 304 and 306.Electric field in ion trap 104 is in controller 108 Control under generated by voltage source 106, voltage source 106 applies suitable current potential to generate capture to electrode 302,304 and 306 .
In step 810, the circulation ion in ion trap 104 is selectively sprayed from the trap.As begged in chapters and sections III Opinion, the selectivity of ion from trap 104, which is ejected under the control of controller 108, to be occurred, and controller 108 is transmitted to voltage source 106 Signal is to change the amplitude for the RF voltages for being applied to central electrode 302.When the amplitude of current potential changes, in central electrode 302 The amplitude of the electric field of inside center also changes.In addition, when the amplitude of the field in central electrode 302 changes, there is specific matter lotus Cyclic track of the circulation ion of ratio out of central electrode 302 drops out, and passes through one or more of endcap electrode 306 aperture Sprayed from ion trap 104.Controller 108 is configured to be swept according to defined function (for example, linear amplitude is scanned) command voltage source 106 The amplitude for applying current potential is plunderred, is sprayed into the ion of specific mass-to-charge ratio in detector 118 from ion trap 104 with selectivity.Scan and apply The speed of power-up position can be automatically determined (for example, to realize the target resolution capability of mass spectrograph 100) by controller 108, and/or It can be set by the user of mass spectrograph 100.
In ion after the selectivity of ion trap 104 sprays, they are detected by detector 118 in step 812.Such as exist Disclosed in chapters and sections V, ion can be detected using a variety of detectors.For example, in certain embodiments, detector 118 include being used to detect the farad electricity cup for spraying ion.
For the current potential of the central electrode 302 by being applied in ion trap 104 amplitude come each mass-to-charge ratio of selection, inspection Survey the measurement of device 118 and the relevant electric current of abundance of the ion being measured with selected mass-to-charge ratio.Measured electric current is transmitted To controller 108.As a result, the information that controller 108 is received from detector 118 corresponds to the abundance for the ion measured, ion is rich Spend the function as ion mass-to-charge ratio.This information corresponds to the mass spectrum of sample.
More generally, controller 108 is configured detects ion according to the mass-to-charge ratio of ion, it means that controller 108 It is detected or received that detection to ion is related and the relevant signal of mass-to-charge ratio of with ion.In certain embodiments, controller 108 Detect ion or receive the information of the function directly as mass-to-charge ratio on ion.In certain embodiments, controller 108 is examined Measured ion or the information for receiving the function as another amount on ion, which can be all as applied to ion trap 104 Current potential is simultaneously related to the mass-to-charge ratio of ion.In all such embodiments, controller 108 detects ion according to mass-to-charge ratio.
In step 814, the information received from detector 118 is analyzed by controller 108.In general, to analyze the letter Breath, the mass spectrum and reference information of controller 108 (for example, electronic processors 110 in controller 108) comparative sample are with definite sample The mass spectrum of product indicates whether any of material.Reference information can be stored in such as storage unit 114, and by controlling Device 108 is retrieved to perform analysis.In certain embodiments, controller 108 can also be examined from the database for being stored in remote location Rope reference information.For example, controller 108 can obtain known substance using communication interface 117 and such database communication Mass spectrum, for analyzing the information measured by detector 118.
Analyzed by the information that detector 118 measures by controller 108 to determine the information on sample identity.If sample Product include multiple compounds, by comparing the metrical information and reference information of detector 118, controller 108 can determine on The information of all or part of identity of multiple compounds.
Controller 108 is configured the various information determined on sample identity.For example, in certain embodiments, the information Including the one or more in sample universal title, IUPAC titles, No. CAS, No. UN and/or its chemical formula.In some embodiments In, the information on sample identity includes whether belonging to the information of certain class material (for example, explosive, high energy material on the sample Material, fuel, oxidant, strong acid or alkali, noxious material).In certain embodiments, which can include on related to sample The harmfulness of connection, the information for handling code, safety warning and reporting procedures.In certain embodiments, which can include closing In the concentration of the sample measured by mass spectrograph or the information of grade.
In certain embodiments, which can include the instruction whether sample corresponds to target substance.For example, when scanning When starting in step 802, mass spectrograph can be placed in target pattern, in this mode, mass spectrograph by the user of mass spectrograph 100 Whether 100 scanning samples have identified any of target substance with specifically definite sample corresponding to a series of.Controller 108 can It is specific to be searched for using various data analysis techniques such as digital filtering and expert system in the Information in Mass Spectra measured Spectrum signature.For specific objective material, controller 108 may search for the specific mass spectral characteristic of characterization target substance, such as in spy Determine the peak value of mass-to-charge ratio.If the Information in Mass Spectra measured lacks certain spectrum signature, or if the information measured is any including that should not have The spectrum signature that thing occurs, then the information of the identity of sample on being determined by controller 108 can include sample not with mesh Mark the corresponding instruction of material.Controller 108 can be configured this type of information determined for multiple target compounds.
After the completion of sample analysis, controller 108 is shown on sample to user in step 816 using display 116 Information.Shown information depends on the operational mode of mass spectrograph 100 and the action of user.As disclosed in chapters and sections I, matter Spectrometer 100 is arranged such that the mass spectrograph can not be received people's use of the specialized training of mass spectrum interpretation.For without such Trained personnel, complete mass spectrum (for example, abundance of ions as the function of mass-to-charge ratio) often carry less implication.Knot Fruit, mass spectrograph 100 are arranged such that in step 816, do not show the sample mass spectrum measured to user.On the contrary, mass spectrograph 100 is only Some (or whole) information on sample identity definite in step 814 are shown to user.For without specialized training User, the information on sample identity are main.
In addition on the information of sample identity, controller 108 can also show other information.For example, in some realities Apply in example, mass spectrograph 100 can access (for example, being stored in storage unit 114, or can may have access to via communication interface 117 ) database of known danger material.If the information on the identity of sample is present in the database of hazardous material, then Controller 108 can show early warning information and/or additional information to user.The early warning information can include for example on sample The information of related harmfulness.Additional information can be contemplated that the action taken including such as user, including limitation user or its Other people exposures to the material, and other safety-related action.
In certain embodiments, mass spectrograph 100 is configured the mass spectrum for showing sample to user when control is activated.With reference to Fig. 8 B, user interface 112 include control 824, when the control is activated by a user, show the mass spectrum of sample on display 116. Control 824 allows the information that user's direct viewing by mass spectrum interpretation training is measured from detector 118.The information can be had , for example, when not obtaining the decisive matching between the Information in Mass Spectra and reference information measured.In addition, work as mass spectrograph 100 During with vitro analysis, for example, user can activate control 824 to attempt to be inferred to more detailed chemical informations, The splitting mechanism of such as specific ion.In certain embodiments, mass spectrograph 100 is configured only when control 824 is activated by a user Show the mass spectrum of sample, and/or after the information on the identity of sample has been shown.That is mass spectrograph 100 can through with Put so that in normal operation, detailed Information in Mass Spectra is not shown to user;Only control 824 is activated in user to wish to check this Shown in the case of details.
In certain embodiments, control 824, which can be configured, allows two kinds of different operational modes.For example, work as control 824 When being activated to first state by the user of mass spectrograph 100, on sample identity information analyze complete when on display 116 Shown to user.When control 824 is activated into the second state, display Information in Mass Spectra (for example, as mass-to-charge ratio function from Sub- abundance).Therefore, control 824 can have the form of two-way switch, it allows user to select it is expected during mass spectrograph is run Display mode information.In certain embodiments, when control 824 is activated into the second state, in addition to Information in Mass Spectra, matter Spectrometer 100 can also be configured information of the display on sample identity.
In step 818, the process shown in flow chart 800 terminates.If scanning is swashed by user in step 802 Control 820 live to start, then, before another scanning is started, mass spectrograph 100 waits control 820 to activate again.Alternatively, If mass spectrograph 100 is in continuous scan pattern, then, the time interval to be defined such as mass spectrograph 100, and then in the time After interval has passed, another scanning is automatically begun to, or wait another external trigger such as sensor signal.
As discussed previously, in general, mass spectrograph 100 without using filtered atmospheric gas particle filter.As a result, When analyte particle is introduced into mass spectrograph, atmospheric gas particle is also introduced into, so as to form gas grain in mass spectrograph 100 The mixture of son.Because mass spectrograph 100 is run under the pressure of the internal pressure higher in than traditional mass spectrometer, and because matter The component of spectrometer 100 is usually insensitive to atmospheric gas particle, and mass spectrograph disclosed herein can be used for can not with traditional mass spectrometer The mode of energy introduces analyte.Specifically, the particle of analyte can be by continuously sucking gas in analyte particle and air The mixture of particle is introduced into, so as to not filter any particle.In certain embodiments, mass spectrograph 100 can be configured logical Sample inlet 124 is crossed at least 10s (for example, at least 15s, at least 20s, at least 30s, at least 45s at least 1 minute, at least 1.5 Minute, at least 2 minutes, at least 3 minutes, at least 4 minutes, at least 5 minutes) or the interior mixture by gas particle of longer time It is continually introduced into gas circuit 128.
When analyte particle is continuously introduced into extended time interval, mass spectrograph 100 can also adjust ion gun 102 duty cycle so that ion gun 102 generates ion (for example, during analyte particle is introduced into extended time interval A part for whole time interval).As previously explained, the duty cycle of ion gun 102 usually can be adjusted (for example, logical Overregulate the duration 274 in Fig. 2 I) with the time interval of control generation ion.In certain embodiments, mass spectrograph 100 passes through The duty cycle of configuration adjustment ion gun 102 so that ion by ion gun 102 10s or longer (for example, 20s or longer, 30s or It is longer, 40s or longer, 50s or longer, 1 minute or longer, 1.5 minutes or longer, 2 minutes or longer, 3 minutes or longer, 4 Minute or it is longer, 5 minutes or longer) time in continuously generate.
As discussed above, mass spectrograph 100 had both realized that compactedness can usually be sent out further through removal in traditional mass spectrometer Existing some high power consumption components realize low power operation.Among these components, the turbomolecular pump of vacuum pump-especially not only again but also Consume a large amount of power.Mass spectrograph 100 does not include such pump, and as a result, not only lighter than traditional mass spectrometer consume substantially few work(again Rate.
By using pressure regulation sub-systems 120, internal pressure of the mass spectrograph 100 in than traditional mass spectrometer is obvious high Run under air pressure inside.In general, in the pressure of higher, due to various mechanism, including collision-induced line is broadening and ion in Charge of the electron exchanges, and mass spectrometric resolution ratio can degenerate.Therefore, it is the highest possible resolution mass spectrometric of acquisition, it is interior in mass spectrograph Portion's air pressure should keep as low as possible.
But as explained above, when the optimal probable value of mass spectrometric resolution ratio deteriorates, on the useful of sample Information, such as information on sample identity can be obtained and provided to user by measuring the mass spectrum of sample.Specifically, i.e., Make when mass spectrograph 100 is run under the air pressure inside than traditional mass spectrometer higher and therefore has worse point than traditional mass spectrometer During resolution, still it can realize enough accurate corresponding between the Information in Mass Spectra and reference information measured.
Because mass spectrograph 100 is run under the resolution ratio lower than traditional mass spectrometer, in certain embodiments, mass spectrograph 100 can also be configured the operations of some components of automatic adjusument further to reduce its overall power.Component self-adapting operation To realize the target resolution for the Information in Mass Spectra measured, or realize between Information in Mass Spectra and known substance or the reference information of condition It is any of corresponding enough.
Fig. 8 C show the flow chart 850 for including the series of steps of the self-adapting operation for mass spectrograph 100, and the step is real Measure corresponding enough between Information in Mass Spectra and known substance or the reference information of condition.Target resolution can be by mass spectrum The user of instrument 100 sets (for example, by user-defined setting, or by having measured the vision-based detection of Information in Mass Spectra), or Set automatically by controller 108.In first step 852, to start to scan with the same way disclosed in previous step 802. Next, in step 854, to be introduced the sample into the same way disclosed in previous step 804 in mass spectrograph 100.In step In rapid 856, sample particle is ionized to produce ion, as disclosed in previous step 806.
Then, in step 858, detected by the sample ions that ion gun 102 generates using detector 118.Step 858 It can be performed without active ions trap 104 and ion is sprayed with capture or selectivity.On the contrary, in step 858, by ion gun The ion of 102 generations is directly over the endcap electrode 304 and 306 of ion trap 104, and incides on detector 118.Voltage source 106 can be configured electrodes into ion gun 102 and detector 118 apply current potential with ion gun 102 and detector 118 it Between form electric field to promote the transmission of ion.
Next, in step 860, whether 108 threshold value gas current of controller is measured by detector 118.Threshold value Gas current can be the setting that the user of mass spectrograph 100 defines and/or user is adjusted.Alternatively, threshold value gas current can be with Measurement based on such as controller 108 to dark current and/or noise in detector 118 is automatically determined by mass spectrograph 100.If Threshold current is also not up to, the ionization of sample and the detection of sample ions continue to carry out in step 856 and 858.Alternatively, such as Fruit has reached threshold value gas current, and the active ions trap 104 and selectively spraying into ion in step 862 of controller 108 detects In device 118.The ion of penetrating is detected by detector 118, and Information in Mass Spectra is analyzed to try in step 864 by controller 108 Figure determines the information on sample identity.
As a part for the analysis in step 864, controller 108 can determine the sample Information in Mass Spectra source measured From known substance or the probability of condition.In step 866, controller 108, which compares, has determined that probability and threshold probability to determine matter The resolution ratio for analysing whether to be limited to mass spectrograph 100 of spectrum information.If probability is more than threshold value, then, controller 108 uses aobvious Show that device 116 shows the information (for example, the identity of sample and/or information on sample identity) on sample, and process exists Step 870 terminates.
But, if in step 866, probability is less than threshold probability value, then, the analysis of Information in Mass Spectra may be limited to The resolution ratio of mass spectrograph 100.To increase the resolution ratio of mass spectrograph 100, before control return to step 862, controller 108 is adaptive Mass spectrometric configuration should be adjusted.
Controller 108 be configured in a variety of ways regulating allocation to increase the resolution ratio of mass spectrograph 100.In some embodiments In, controller 108 is configured activation buffering source of the gas 150 so that buffer gas particle is introduced into gas circuit 128.The buffer gas of introducing Particle can include the atom of such as nitrogen molecular, hydrogen molecule or inert gas such as helium, neon, argon or krypton.Buffering source of the gas 150 can be with Include the replaceable cylinder of receiving buffer gas particle, and the valve of controller 108 is connected to via control line 127g, or it is slow Rush gas generator.Controller 108 can be configured activation buffering source of the gas 150 in valve so that buffer gas particle it is controlled Amount is released in gas circuit 128.Once being discharged into gas circuit 128, buffer gas particle is mixed with the ion generated by ion gun 102 Close, and promote capture and spray into ion selectivity in detector 118, so as to increase the resolution capability of mass spectrograph 100.
In certain embodiments, controller 108 reduces the air pressure inside in mass spectrograph 100 to increase point of mass spectrograph 100 Distinguish ability.To reduce air pressure inside, controller 108 adjusts subsystem 120 via control line 127d activation pressures.It is alternative or additional Ground, controller 108 can close valve 129 to reduce air pressure inside.In certain embodiments, valve 129 can be to account for specific The pulse mode of empty ratio is alternately opened and closed to reduce air pressure inside.In certain embodiments, mass spectrograph 100 can include more A sample inlet, and valve 129 can be turned off to sealed sample entrance 124, and another in small diameter sample inlet Online valve can be opened.By using different sample inlets to reduce the air pressure in mass spectrograph 100, rate of pumping does not become Change is necessary.The air pressure inside in mass spectrograph 100 is reduced, by reducing in ion gun 102, ion trap 104 and detector 118 Ion between collision frequency, increase mass spectrograph 100 resolution ratio.
In certain embodiments, to improve the resolution ratio of mass spectrograph 100, the increase of controller 108 is applied to central electrode 302 Potential change frequency.By the speed of reduction application potential change, the speed of the internal electric field change in electrode 302 also subtracts It is small.As a result, the selectivity increase that ion is sprayed from ion trap 104, so as to improve the resolution ratio of mass spectrograph 100.
In certain embodiments, controller 108, which is configured, changes axial electric field frequency in ion trap 104 or amplitude to change Become the resolution ratio of mass spectrograph 100.The injection border of ion trap can be shifted by changing the axial electric field in ion trap 104, so as to prolong Stretch or reduce mass spectrometric high quality scope and change the resolution capability and/or resolution ratio of mass spectrograph 100.
In certain embodiments, controller 108 is configured increases mass spectrograph 100 by varying the duty cycle of ion gun 102 Resolution ratio.Through Germicidal efficacy, the resolution ratio of mass spectrograph 100 can be improved by reducing ionization time.Therefore, with reference to the song in figure 2I Line chart 270, by reducing the duration 274 for the bias potential 272 for being applied to ion gun 102 (for example, reducing ion gun 102 Duty cycle), the resolution ratio of mass spectrograph 100 can be improved.
On the contrary, the resolution ratio for reducing mass spectrograph 100 is also useful in some cases.For example, with reference to the song in figure 2I Line chart 270 and 280, the duration 274 of the bias potential 272 of ion gun 102 is applied to by increase (for example, increase ion The duty cycle in source 102), and therefore reduce increase be applied to ion trap 104 electrode 302 current potential amplitude when it is lasting when Between (for example, the time interval 284 and 286 in curve map 280), the resolution ratio of mass spectrograph 100 is reduced, but mass spectrograph 100 sensitivity increase, so as to increase the signal-to-noise ratio of the Information in Mass Spectra measured using mass spectrograph 100.Increased sensitivity is trying It is particularly useful during the very low concentration of figure detection Cucumber.
In certain embodiments, controller 108 is configured is increasing the electrode 302 for being applied to ion trap 104 by increasing Current potential when duration (for example, time interval 286 in Fig. 2 I) increase the resolution ratio of mass spectrograph 100.Pass through increase Duration in scanning, circulation ion is more slowly sprayed from ion trap 104, so as to increase the resolution ratio for the Information in Mass Spectra measured.
In certain embodiments, controller 108 is configured is scanned by adjusting the amplitude of the current potential with being applied to electrode 302 Associated slope section changes the resolution ratio of mass spectrograph 100.As shown in the curve map 280 in Fig. 2 I, electrode 302 is applied to The amplitude of current potential increase generally according to linear ramp function.But, more generally, controller 108 can be configured root The amplitude of the current potential of electrode 302 is applied to according to different slope section increases.For example, slope section can be adjusted by controller 108 A series of section so that the current potential applied is represented according to different linear ramp section increases, each different slopes section The increased different rates of current potential.As another example, slope section can be adjusted so that be applied to the current potential of electrode 302 Amplitude is according to nonlinear function such as exponential function or polynomial function increase.
As discussed above, controller 108, which is configured, takes any of above-mentioned action or a variety of to change mass spectrum The resolution ratio of instrument 100.These orders acted are taken to be determined by mass spectrograph 100 or by user preference.For example, in some realities Apply in example, the user of mass spectrograph 100 can specify which of above-mentioned steps, and in what order, controller 108 is taken to increase Add the resolution ratio of mass spectrograph 100 and/or reduce its power consumption.User's selection can be stored in storage unit 114 as one group of preference In.Alternatively, in certain embodiments, the order for the action that controller 108 is taken can be forever encoded to controller 108 Logic in, or as it is immutable setting be stored in storage unit 114.
In certain embodiments, controller 108 can determine the order of action based on other considerations.For example, to ensure matter Spectrometer 100 as far as possible lack consumption of electric power, controller 108 taken raising mass spectrograph 100 resolution capability action it is suitable Sequence can be determined according to the increase of the power consumption as the result acted every time.Controller 108, which can match somebody with somebody, to be related to be disclosed above Each action how to increase the information of overall power, and appropriate sequence of movement can be selected based on power consumption information, caused The minimum increased action of power consumption occurs first.Alternatively, controller 108 can be configured measurement and the associated power consumption of each action Increase, and appropriate sequence of movement can be selected based on measured power consumption number.
Although in flow chart 850, the adjusting of the configuration to mass spectrograph 100 is corresponded to known based on the Information in Mass Spectra measured The probability of reference information, still, the adjusting of the configuration to mass spectrograph 100 can also be carried out based on other standards.In some realities Apply in example, for example, the configuration to mass spectrograph 100 adjust can the target resolution based on mass spectrograph 100 whether realized come Carry out.In step 864, controller 108 is based on the Information in Mass Spectra measured (for example, single in the measurement window based on mass spectrograph 100 The maximum FWHM of ion peak value) determine the true resolution of mass spectrograph 100.In step 866, true resolution is by controller 108 compared with the target resolution of mass spectrograph 100.If true resolution is less than target resolution, then, in step 872, Controller 108 adjusts the configuration of mass spectrograph 100 to improve mass spectrometric resolution ratio as discussed above.
Hardware, software and electron process
Any method and step, feature and/or attribute disclosed herein can be performed (for example, controller by controller 108 108 electronic processors 110) and/or one or more additional electron processors based on standard program technology executive program it is (all Such as computer or pre-programmed integrated circuit).This class method is through designing in programmable computation device or the integrated electricity being specifically designed Performed on road, each equipment includes processor, data-storage system (including memory and/or memory element), at least one deposits Storage device and at least one device, such as display or printer are shown.Program code is applied to input data to perform work( The output information for being applied to one or more output devices and can be generated.Each such computer program can with advanced procedures or Object-Oriented Programming Language or compilation or machine language are implemented.In addition, language can be compiling or interpretive language.It is each such Computer program can be stored on computer-readable recording medium (for example, CD-ROM or disk), when program is by computer During reading, the processor in computer can be promoted to perform and analyze and control function as described herein.
Other embodiment
In certain embodiments, mass spectrograph 100 is configured in more hyperbar, such as under the up to pressure of 1atm (for example, 760Torr) run.That is when mass spectrograph 100 detects ion according to the mass-to-charge ratio of ion, in ion gun 102, ion trap Air pressure inside in one or more of 104 and/or detector 118 between 100Torr and 760Torr (for example, 200Torr or more, 300Torr or more, 400Torr or more, 500Torr or more, 600Torr or more).
Some components disclosed herein are also applied for running under the pressure of up to 1atm (and even more high pressure).Example Such as, some ion guns disclosed herein such as glow discharge ion source can be in the case of no change or seldom change in height Run under up to the pressure of 1atm.In addition, certain form of detector such as Faraday detector (such as Faraday cup detector and Its array) it can also be run in the case of no change or seldom change under the up to pressure of 1atm.
Ion trap disclosed herein modified can be run under the up to pressure of 1atm.For example, with reference to figure 3A, be Run under the pressure of 1atm, the size c of ion trap 1040It should be reduced between 1.5 microns and 0.5 micron (for example, micro- 1.5 It is 1 micron approximate between 1.2 microns and 0.8 micron between 1.2 microns and 0.5 micron between rice and 0.7 micron).This Outside, to be run under the up to air pressure of 1atm, voltage source 106 modified can provide to ion trap 104 and scan voltage, the voltage GHz such as 1.0GHz or higher frequency (for example, 1.2GHz or higher, 1.4GHz or higher, 1.6GHz or higher, 2.0GHz or higher, 5.0GHz or higher or even more high) in the range of repeat.By to ion trap 104 and voltage source 106 These changes, mass spectrograph 100 can be run under the up to pressure of 1atm so that the use of pressure regulation sub-systems 120 is obvious Reduce.In certain embodiments, or even from mass spectrograph 100 pressure regulation sub-systems 120 are removed so that such as mass spectrograph 100 is nothing It is also possible to pump mass spectrograph.
Some embodiments have been described.It should be understood, however, that in the case of the spirit and scope without departing from the disclosure, It can carry out various changes.Therefore, other embodiment is within the scope of the claims.

Claims (10)

1. a kind of mass spectrograph, it includes:
Ion gun;
Ion trap;
Ion detector;And
Pressure regulation system,
Wherein, during the mass spectrograph is run:
The pressure regulation system is configured as at least two in the ion gun, the ion trap and the ion detector The air pressure between 100mTorr and 100Torr is maintained in a;And
The ion detector is configured as detecting the ion according to the mass-to-charge ratio of the ion generated by the ion gun.
2. mass spectrograph according to claim 1, wherein, during operation, the pressure regulation system is configured as in institute State the air pressure maintained in ion trap and the ion detector between 100mTorr and 100Torr.
3. mass spectrograph according to claim 1, wherein, during operation, the pressure regulation system is configured as in institute State the air pressure maintained in ion gun and the ion trap between 100mTorr and 100Torr.
4. mass spectrograph according to claim 1, wherein, during operation, the pressure regulation system is configured as in institute State the air pressure maintained in ion gun and the ion detector between 100mTorr and 100Torr.
5. mass spectrograph according to claim 1, wherein, during operation, the pressure regulation system is configured as in institute State the air pressure maintained in ion gun, the ion trap and the ion detector between 100mTorr and 100Torr.
6. mass spectrograph according to claim 1, wherein, the ion gun includes glow discharge ionization source.
7. mass spectrograph according to claim 1, wherein, the pressure regulation system includes air pump, and the air pump is configured Air pressure in described at least two in the ion gun, the ion trap and the ion detector in order to control.
8. mass spectrograph according to claim 7, further include controller, the controller be configured as activating the air pump with Control the air pressure in described at least two in the ion gun, the ion trap and the ion detector.
9. mass spectrograph according to claim 7, wherein, the air pump includes vortex pump.
10. mass spectrograph according to claim 1, wherein, during operation, the pressure regulation system is configured as in institute Maintained in stating described at least two in ion gun, the ion trap and the ion detector 500mTorr and 10Torr it Between air pressure.
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