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EP3639289A2 - Dispositif et procédé pour l'ionisation d'un analyte ainsi que dispositif et procédé pour l'analyse d'un analyte ionisé - Google Patents

Dispositif et procédé pour l'ionisation d'un analyte ainsi que dispositif et procédé pour l'analyse d'un analyte ionisé

Info

Publication number
EP3639289A2
EP3639289A2 EP18750480.8A EP18750480A EP3639289A2 EP 3639289 A2 EP3639289 A2 EP 3639289A2 EP 18750480 A EP18750480 A EP 18750480A EP 3639289 A2 EP3639289 A2 EP 3639289A2
Authority
EP
European Patent Office
Prior art keywords
electrode
analyte
ionization device
discharge
ionization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18750480.8A
Other languages
German (de)
English (en)
Inventor
Jan-Christoph WOLF
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Plasmion GmbH
Original Assignee
Plasmion GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Plasmion GmbH filed Critical Plasmion GmbH
Publication of EP3639289A2 publication Critical patent/EP3639289A2/fr
Pending legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/10Ion sources; Ion guns
    • H01J49/105Ion sources; Ion guns using high-frequency excitation, e.g. microwave excitation, Inductively Coupled Plasma [ICP]
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J27/00Ion beam tubes
    • H01J27/02Ion sources; Ion guns
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/02Details
    • H01J37/04Arrangements of electrodes and associated parts for generating or controlling the discharge, e.g. electron-optical arrangement or ion-optical arrangement
    • H01J37/08Ion sources; Ion guns
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32Gas-filled discharge tubes
    • H01J37/32009Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32348Dielectric barrier discharge
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/0027Methods for using particle spectrometers
    • H01J49/0031Step by step routines describing the use of the apparatus
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05HPLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00Generating plasma; Handling plasma
    • H05H1/24Generating plasma
    • H05H1/2406Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes
    • H05H1/2443Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes the plasma fluid flowing through a dielectric tube
    • H05H1/245Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes the plasma fluid flowing through a dielectric tube the plasma being activated using internal electrodes

Definitions

  • the invention relates to the technical field of ionization of an analyte, especially the ionization or ionization of a substance in a carrier gas in preparation for its analysis.
  • Sample nozzle an ion supply tube, which leads to an analysis apparatus, and a tube for a dielectric barrier discharge are connected to a T-shaped tube.
  • the object of the invention is to provide a device by which in
  • Flow is a discharge gas and an analyte is ionizable and the analyte largely not or only to a small extent fragmented, to avoid a high constructional and equipment expense is applicable under ambient conditions and ensures a high sensitivity in a possible analysis of an ionized substance.
  • the invention can achieve flow-through ionization of an analyte, especially for analysis.
  • a so-called "soft" ionization can be used, the molecules largely not destroyed or fragmented, but by protonation and
  • the invention provides highly efficient ionization devices (with associated method) and an analysis device (with associated method), which are used in combination with
  • Mass spectrometry or ion mobility spectrometry can provide a highly sensitive "electronic nose" (in an analytical method) that allows for direct chemical analysis of molecules in the gas phase.
  • chromatographic methods also include direct screening analyzes, e.g. direct pesticide analysis on fruit or vegetable surfaces.
  • the technique can be used to detect toxic compounds or warfare agents. Especially with chemical warfare agents a very high sensitivity is necessary, since this even in the smallest concentrations too
  • Another related application is forensics or security controls (narcotic or explosive wipe tests).
  • a combination with sample pre-enrichment systems such as SPME is also possible.
  • the method can be used for medical "point of care” diagnostics (eg biomarker analysis in breath or in combination with SPME for hazardous substances and prohibition substances in blood, urine, etc.).
  • flow ionization generally simplifies sampling ("sucking in", analogous to the human nose) during analysis, which is useful for rapid analysis applications or screening analyzes, e.g. important in industrial process control.
  • composition of the surrounding atmosphere (humidity, etc.).
  • additional compounds dopants
  • gas compositions a reduction or increase of the ionization efficiency and / or fragmentation can be achieved.
  • the latter is particularly useful for portable applications, since portable systems can not generate characteristic fragments that are used to identify the substances.
  • the invention allows a miniaturization of analyzers and can be combined with portable systems, which significantly increases their sensitivity. For this purpose, a battery or battery operation is possible. Normally, no consumables (except electrical energy) are needed and analysis can be done in less than 100 ms.
  • the miniaturization and design of the invention may combine with other existing ionization techniques (e.g., ESI, APCI, etc.), allowing for the simultaneous detection of different analytes, such as the parallel ionization of very polar and non-polar species.
  • a further embodiment of the ionization device comprises the introduction of so-called "dopant" substances (such as in chemical ionization) before or after the
  • An ionization device for ionizing an analyte comprises an inlet, an outlet, a first electrode, a second electrode, a dielectric element and a charge carrier filter. Therein are the first electrode, the second electrode and that
  • the dielectric element arranged so that between the first electrode and the second Electrode can be formed by applying an electrical voltage, a dielectric barrier discharge in a discharge region in the iontechnischsvoriques.
  • the analyte can flow into the ionization device via the inlet.
  • the analyte can flow through the discharge region and flow out of the ionization device via the outlet.
  • the charge carrier filter is arranged in front of the outlet of the ionization device.
  • the carrier filter is configured to filter or select ions or charged particles based on their charge type.
  • the charge carrier filter is preferably arranged downstream of the discharge region.
  • the charge carrier filter can be designed such that a magnetic field can be generated.
  • the magnetic field allows ions or charged particles to be filtered or selected based on their charge type.
  • the charge carrier filter can also be a grid, especially a grid with an electrical potential or a grid, against which an electrical potential is applied. In turn, the grid may be used to filter or select ions or charged particles based on their charge type.
  • the ionization device may comprise a first portion and a second portion.
  • the first section may comprise the inlet as the first inlet, wherein the first inlet can be flowed through by a discharge gas.
  • the second section may comprise a second inlet through which an analyte can flow.
  • the first section can be connected to the second section in a flow-through manner.
  • the discharge region may be in the first section of the ionization device.
  • the analyte does not directly flow through the discharge region, but the discharge gas flows through the discharge region where it is ionized and when the ionized discharge gas is contacted with the non-ionized analyte within the ionization device, at least a portion of the charges of the ionized discharge gas become transmit the analyte so that it is ionized. This results in a particularly gentle ionization for the analyte, with only a very low fragmentation of the analyte is expected to.
  • the distance between the first electrode and the second electrode of the ionization device may be less than 20 mm, preferably less than 10 mm, more preferably less than 5 mm, and most preferably less than 2 mm.
  • the distance describes the smallest distance between the first electrode and the second electrode. So the distance between a point of the first electrode and a point of the second electrode with the lowest length value.
  • the first electrode may abut the outer side of the dielectric member.
  • the first electrode may be formed as a layer on or on the outer side of the dielectric member.
  • Electrode discharges can be avoided, which can occur even at a (very) small distance (for example, gas inclusions) of the first electrode to the dielectric element.
  • the first electrode may be applied as a layer by a drying or hardening liquid or suspension, for example by a metal paint.
  • the layer may also be deposited by a transition from a gas phase to the solid phase on the outside of the dielectric element. This can be achieved, for example, by sputtering, CVD or PVD, or other layering techniques.
  • One of the ionization devices can be operated in one process. Therein, the analyte is introduced into the ionization device, the analyte in the
  • Ionization device is ionized, especially by a dielectric barrier discharge in the discharge region and the ionized analyte is discharged from the ionization device via the outlet.
  • a discharge gas can be introduced into the ionization device and ionized in the discharge region.
  • the analyte can be introduced into the ionization device and the analyte can be brought into contact with the ionized discharge gas in the ionization device so that an ionization of the analyte is carried out in the ionization device.
  • the pressure in the ionization apparatus may be greater than 40 kPa, preferably greater than 60 kPa, and more preferably greater than 80 kPa. Particularly preferred is the pressure in the ionization device substantially atmospheric pressure.
  • the substantially atmospheric pressure may allow for variation from the atmospheric pressure of 10% above the atmospheric pressure or 10% below the atmospheric pressure.
  • the voltage may be at most 20 kV, preferably at most 10 kV, more preferably at most 5 kV, and most preferably between 1 kV and 3 kV.
  • the dielectric barrier discharge can be effected by unipolar high voltage pulses.
  • the pulse duration may be at most 1 ⁇ , preferably at most 500 ns, and most preferably between 100 ns and 350 ns.
  • the high voltage pulses may have a frequency of at most 100 GHz, preferably at most 100 MHz, more preferably at most 500 kHz, and most preferably between 1 kHz and 100 kHz.
  • the first and second electrodes can be supplied with a sinusoidal voltage.
  • the sine voltage of one of the electrodes can be shifted by half a period duration with respect to the other of the two electrodes.
  • Another ionization device for ionizing an analyte comprises an inlet, an outlet, a first electrode, a second electrode and a dielectric element.
  • the first electrode, the second electrode and the dielectric element are arranged therein such that a dielectric barrier discharge in one of them is achieved by an electrical voltage applied between the first electrode and the second electrode
  • Discharge region can be formed in the ionization device.
  • the dielectric element has an outer side, wherein the first and the second electrode are arranged on the outer side of the dielectric element.
  • the ionization device may comprise a capillary having an inlet.
  • the capillary can be arranged at least in sections inside the dielectric element.
  • the analyte can be flowed into the capillary via the inlet and a discharge gas can be flowed in via the inlet of the ionization device.
  • the distance between the first electrode and the second electrode may be less than 20 mm, preferably less than 10 mm, more preferably less than 5 mm, and most preferably less than 2 mm.
  • the distance is the smallest distance between the first electrode and the second electrode, the smallest distance being determined as the length between a point of the first electrode and a point of the second electrode having the lowest value.
  • first and second electrodes or both the first electrode and the second electrode may abut on the outside of the dielectric element.
  • the first electrode and / or the second electrode is formed as a layer, wherein the layer is applied by a drying or hardening liquid or suspension or is applied by a transition from a vapor phase to a solid phase. This has the above-described advantage of avoiding parasitic discharges.
  • one of the ionization devices may be operated.
  • the method comprises introducing an analyte into the ionization device, ionizing the analyte in the ionization device, preferably by a dielectric barrier discharge in the discharge region, and applying the ionized analyte from the ionization device across the outlet.
  • a discharge gas may be introduced into the ionization device via the inlet, the discharge gas in the discharge region may be ionized, and the analyte introduced via an inlet of a capillary or the inlet of the capillary.
  • the analyte may be contacted with the ionized discharge gas in the ionization device, thereby performing ionization of the analyte.
  • the pressure in the ionization apparatus may be greater than 40 kPa, preferably greater than 60 kPa, and more preferably greater than 80 kPa. Particularly preferred is the pressure in the ionization device substantially atmospheric pressure.
  • the substantially atmospheric pressure may allow for variation from the atmospheric pressure of 10% above the atmospheric pressure or 10% below the atmospheric pressure.
  • the voltage may be at most 20 kV, preferably at most 10 kV, more preferably at most 5 kV, and most preferably between 1 kV and 3 kV.
  • the dielectric barrier discharge can be effected by unipolar high voltage pulses.
  • the pulse duration may be at most 1 ⁇ , preferably at most 500 ns, and most preferably between 100 ns and 350 ns.
  • the high voltage pulses may have a frequency of at most 100 GHz, preferably at most 100 MHz, more preferably at most 500 kHz, and most preferably between 1 kHz and 100 kHz.
  • the first and second electrodes can be supplied with a sinusoidal voltage.
  • the sine voltage of one of the electrodes can be shifted by half a period duration with respect to the other of the two electrodes.
  • Another ionization device for ionizing an analyte comprises an inlet, an outlet, a first electrode, a second electrode and a dielectric element.
  • the first electrode, the second electrode and the dielectric element are arranged therein such that a dielectric barrier discharge in one of them is achieved by an electrical voltage applied between the first electrode and the second electrode
  • Discharge region can be formed in the ionization device. At least one of the first and second electrodes is not formed completely circumferentially or circumferentially interrupted.
  • At least one of the first and second electrodes is arranged on an outer side of the, preferably through-flow, dielectric element arranged not completely circumferentially or circumferentially interrupted.
  • the circumferential view can be understood in the circumferential direction in a cylindrical coordinate system, wherein the axial direction of the cylindrical coordinate system parallel to the axis of the dielectric element and / or parallel to the (intended) flow direction in the
  • At least one of the first and second electrodes in a plane perpendicular to a flow direction through the ionization device is not completely circulating or circumferentially interrupted.
  • the embodiment according to the invention forms one or more strongly localized plasma discharges (discharge regions). This does not mean the entire
  • Analyte flow through the plasma discharge flows, but also through areas in which there is no plasma discharge (no discharge area).
  • the undesired fragmentation of the analyte can be reduced by direct interaction with the discharge.
  • the length of the discharge gap can be adapted as extension of the discharge areas to the required application (from localized discharge points, up to a several cm long discharge gap in the axial direction), whereby the number and density of the reactive species and thus the fragmentation and the sensitivity the respective analysis application can be adapted and optimized.
  • the first electrode may be disposed on an outside of the dielectric member.
  • the first electrode may be formed, at least in sections, in a spiral or helical (generally also helical) design.
  • the spiral or helical section has at least one complete (360 degrees) winding, preferably the section has at least five complete windings.
  • the first electrode may comprise at least two sub-electrodes, wherein the at least two sub-electrodes are circumferentially spaced, especially in the plane perpendicular to the flow direction.
  • the sub-electrodes can each have a line with a
  • the first electrode comprises at least 4 partial electrodes.
  • the sub-electrodes may be circumferentially arranged uniformly, so that in each case the same distance between the sub-electrodes in the circumferential direction and the interruption between each two sub-electrodes is the same.
  • the sub-electrodes may be configured circular or rod-shaped.
  • the second electrode may be disposed at least portion-wise in the dielectric member.
  • the first electrode may be arranged outside the dielectric element.
  • the first electrode, the second electrode and the dielectric element may be arranged to each other such that by applying an electrical voltage between the first electrode and the second electrode, a dielectric barrier discharge in at least two axially in the flow direction and / or circumferentially, especially in a plane perpendicular to the flow direction, spaced discharge areas in the
  • the distance between the first electrode and the second electrode of the ionization device may be less than 20 mm, preferably less than 10 mm, more preferably less than 5 mm, and most preferably less than 2 mm.
  • the distance describes the smallest distance between the first electrode and the second electrode. So the distance between a point of the first electrode and a point of the second electrode with the lowest length value.
  • the first electrode may abut the outer side of the dielectric member. Specifically, the first electrode may be formed as a layer on or on the outer side of the dielectric member. By applying or depositing the electrode as a layer, parasitic discharges of the electrode can be avoided, which can occur even at a (very) small distance (for example, gas inclusions) of the first electrode to the dielectric element.
  • the first electrode may be applied as a layer by a drying or hardening liquid or suspension, for example by a metal paint.
  • the layer may also be deposited by a transition from a gas phase to the solid phase on the outside of the dielectric element. This can be achieved, for example, by sputtering, CVD or PVD, or other layering techniques.
  • One of the ionization devices can be operated in one process.
  • Method comprises the steps of introducing an analyte into the
  • the ionizing device ionizing the analyte in the ionization device and applying the ionized analyte from the ionization device via the outlet.
  • the analyte is released by a dielectric barrier discharge in the
  • the pressure in the ionization apparatus may be greater than 40 kPa, preferably greater than 60 kPa, and more preferably greater than 80 kPa. More preferably, the pressure in the ionization apparatus is substantially atmospheric pressure. The substantially atmospheric pressure may allow for variation from the atmospheric pressure of 10% above the atmospheric pressure or 10% below the atmospheric pressure.
  • the voltage may be at most 20 kV, preferably at most 10 kV, more preferably at most 5 kV, and most preferably between 1 kV and 3 kV.
  • the dielectric barrier discharge can be effected by unipolar high voltage pulses.
  • the pulse duration may be at most 1 ⁇ , preferably at most 500 ns, and most preferably between 100 ns and 350 ns.
  • the high voltage pulses may have a frequency of at most 100 GHz, preferably at most 100 MHz, more preferably at most 500 kHz, and most preferably between 1 kHz and 100 kHz.
  • the first and second electrodes can be supplied with a sinusoidal voltage.
  • the sine voltage of one of the electrodes can be shifted by half a period duration with respect to the other of the two electrodes.
  • Another ionization device for ionizing an analyte comprises an inlet, an outlet, a first electrode, a second electrode and a dielectric element.
  • the first electrode, the second electrode and the dielectric element are arranged relative to one another such that a dielectric barrier discharge in one
  • Discharge region in the ionization device can be formed by applying an electrical voltage between the first electrode and the second electrode.
  • the first and second electrodes are arranged displaceable relative to one another.
  • the electrodes can be controllably arranged relative to each other displaceable, in particular, the electrodes can be displaced by a controllable electric motor relative to each other.
  • the first electrode and / or the second electrode can be configured, at least in sections, in a spiral or helical manner.
  • the second electrode may be arranged at least in sections in the dielectric element.
  • the first electrode is preferably arranged outside the dielectric element.
  • the displaceability of the first and second electrodes relative to one another is preferably given in the flow direction or counter to the flow direction by the ionization device.
  • At least one of the first and or second electrodes may have at least one winding.
  • the distance between the first electrode and the second electrode of the ionization device may be less than 20 mm, preferably less than 10 mm, more preferably less than 5 mm, and most preferably less than 2 mm.
  • the distance describes the smallest distance between the first electrode and the second electrode. So the distance between a point of the first electrode and a point of the second electrode with the lowest length value.
  • the first electrode is slidably disposed relative to the dielectric member.
  • the second electrode may be relative to the dielectric element
  • One of the ionization devices can be operated in one process. Therein, the analyte is introduced into the ionization device, the analyte in the
  • ionization device is ionized, preferably by a dielectric barrier discharge in the discharge region, and the ionized analyte is discharged from the ionization device via the outlet.
  • the pressure in the ionization apparatus may be greater than 40 kPa, preferably greater than 60 kPa, and more preferably greater than 80 kPa. More preferably, the pressure in the ionization apparatus is substantially atmospheric pressure.
  • the substantially atmospheric pressure may vary with atmospheric pressure Allow 10% above atmospheric pressure or 10% below atmospheric pressure.
  • the voltage may be at most 20 kV, preferably at most 10 kV, more preferably at most 5 kV, and most preferably between 1 kV and 3 kV.
  • the dielectric barrier discharge can be effected by unipolar high voltage pulses.
  • the pulse duration may be at most 1 ⁇ , preferably at most 500 ns, and most preferably between 100 ns and 350 ns.
  • the high voltage pulses may have a frequency of at most 100 GHz, preferably at most 100 MHz, more preferably at most 500 kHz, and most preferably between 1 kHz and 100 kHz.
  • the first and second electrodes can be supplied with a sinusoidal voltage.
  • the sine voltage of one of the electrodes can be shifted by half a period duration with respect to the other of the two electrodes.
  • An analysis device for analyzing an ionized analyte comprises a
  • the ionization device comprises an inlet, an outlet, a first electrode, a second electrode and a dielectric element.
  • the first electrode, the second electrode and the dielectric member are arranged to each other so that a dielectric barrier discharge can be formed in a discharge region between the first electrode and the second electrode by applying an electric voltage between the first electrode and the second electrode.
  • the ionization device is connected to the analysis unit.
  • the compound is designed such that an analyte ionized in the ionization device or
  • (different) ionized analytes can pass from the outlet of the ionization directly into the analysis unit. There is a gap in between the outlet of the ionization device and the first electrode or the discharge region
  • the distance is less than 50 mm, or the outlet of the ionization device and the first electrode overlap in the flow direction (x direction).
  • connection of the ionization device with the analysis unit is designed so that the analyte or the analytes after (first) ionization by a
  • reactive impact with a reactive species can not react further, eg by charge transfer reactions. Both ionization and subsequent reactions depend on the impact frequency of the molecules. This can be influenced by temperature and pressure.
  • the inventive design is an ionization with kinetic
  • Atmospheric pressure ionization methods occur, effectively suppressed. This not only ionizes more analytes than before, but also quantifies them safely in complex mixtures.
  • the ionized analyte can enter a vacuum chamber of the analysis unit.
  • a vacuum chamber can prevail a pressure which is below the ambient pressure, in particular below the pressure in the ionticiansvorraum.
  • a pressure gradient can prevail between the ionization device and the vacuum chamber of the analysis unit.
  • the pressure gradient is at least 20 kPa, more preferably at least 50 kPa.
  • the distance between the outlet of the ionization device and the first electrode may be adjustable.
  • the outlet of the ionization device may be designed to be displaceable relative to the first electrode.
  • a taper of the cross-section of the ionization device or an aperture in the flow direction (x direction) may be arranged in front of the outlet of the ionization device.
  • the first electrode is arranged on the taper or aperture.
  • the first electrode may be disposed on an outer side of the dielectric member or abut on the outer side.
  • the second electrode may be arranged at least in sections in the dielectric element.
  • Ionleitersvorraum may be less than 20 mm, preferably less than 10 mm, still more preferably less than 5 mm, and most preferably less than 2 mm.
  • the distance is the smallest distance between the first electrode and the second electrode. So it is the distance that has the lowest length value between a point of the first electrode and a point of the second electrode.
  • the distance between the outlet of the ionization device and the first electrode may be less than 40 mm, preferably less than 30 mm, more preferably less than 20 mm, even more preferably less than 10 mm, most preferably less than 5 mm. This in the flow direction (x-direction).
  • the analysis unit may be a mass spectrometer or an ion mobility spectrometer.
  • the outlet of the ionization device may have a smaller cross-sectional area than the inlet of the ionization device.
  • One of the analyzers can be used in a method of analyzing an analyte.
  • the method comprises the steps of introducing an analyte into the ionization device, ionizing the analyte, preferably by a dielectric barrier discharge in the discharge region, applying the ionized analyte from the ionization device via the outlet to the analysis unit, and analyzing the analyte in the analysis unit.
  • the pressure in the ionization apparatus may be greater than 40 kPa, preferably greater than 60 kPa, and more preferably greater than 80 kPa. More preferably, the pressure in the ionization apparatus is substantially atmospheric pressure.
  • the substantially atmospheric pressure may allow for variation from the atmospheric pressure of 10% above the atmospheric pressure or 10% below the atmospheric pressure.
  • the voltage may be at most 20 kV, preferably at most 10 kV, more preferably at most 5 kV, and most preferably between 1 kV and 3 kV.
  • the dielectric barrier discharge can be effected by unipolar high voltage pulses.
  • the pulse duration may be at most 1 ⁇ , preferably at most 500 ns, and most preferably between 100 ns and 350 ns.
  • the high voltage pulses may have a frequency of at most 100 GHz, preferably at most 100 MHz, more preferably at most 500 kHz, and most preferably between 1 kHz and 100 kHz.
  • the first and second electrodes can be supplied with a sinusoidal voltage.
  • the sine voltage of one of the electrodes can be shifted by half a period duration with respect to the other of the two electrodes.
  • a further analysis device for analyzing an ionized analyte may comprise an ionization device and an analysis unit.
  • the ionization device comprises an inlet, an outlet, a first electrode, a second electrode and a dielectric element.
  • the first electrode, the second electrode and the dielectric element are arranged relative to each other such that by applying an electrical voltage between the first electrode and the second electrode, a dielectric
  • Barrier discharge can be formed in a discharge area.
  • Ionization device is connected to the analysis unit so that one in the
  • the ionization device is designed and connected to the analysis unit such that a distance between the discharge region and the analysis unit can be flowed through by the analyte in less than 1 s.
  • the distance of the discharge (the discharge area) to the analysis device can be dimensioned such that the ionization time or residence time, which is determined by the
  • permeable volumes from the onset of plasma discharge (discharge area) and flow rate, prior to analysis or inhibition of ionization (e.g., by introduction in vacuum), is less than 1 second, preferably less than 500 milliseconds
  • the flowable volume comprises the distance between the discharge area or the start of the plasma discharge and the analysis or the inhibition of the
  • Ionization e.g., by vacuum
  • the flow-through cross-section does not have to be constant over the flow-through distance.
  • the spacing of the assembly of reactive species (e.g., in a discharge gas) and analyte relative to the analysis unit may be such that the ionization time
  • reaction time of the analytes with reactive species which can be traversed by the Volume starting from the first contact time of the analyte molecules with the reactive species formed by the plasma discharge and the flow rate yields less than 1 s, preferably less than 500 ms, more preferably less, prior to analysis or inhibition of ionization (eg, by introduction in a vacuum) than 200 ms, still
  • the combination of reactive species and analyte can be done directly in the discharge or later (downstream). Ionization of the analyte occurs at the first local collision of the analyte with the reactive species.
  • the analysis unit may comprise a vacuum chamber and the ionization device may be connected to the analysis unit such that the analyte can pass directly into the vacuum space of the analysis unit.
  • the ionization device can be connected to the analysis unit such that the distance between the discharge region and the vacuum chamber can be flowed through by the analyte in less than 1 s.
  • the vacuum chamber of the analysis unit can be flowed through in less than 500 ms, preferably in less than 200 ms, more preferably in less than 50 ms, most preferably in less than 20 ms.
  • Vacuum space of the analysis unit can at a flow through the
  • Ionization device of less than 20 L / min, preferably less than 10 L / min, more preferably less than 5 L / min, most preferably less than 2.5 L / min, flowed through by the analyte (S) in less than the respective upper time limit be.
  • a pressure gradient can prevail between the ionization device and the vacuum chamber of the analysis unit.
  • the pressure gradient is at least 20 kPa, more preferably at least 50 kPa.
  • the distance between the outlet of the ionization device and the first electrode may be adjustable.
  • the outlet of the ionization device may be designed to be displaceable relative to the first electrode.
  • a taper of the cross-section of the ionization device or an aperture in the flow direction (x direction) may be arranged in front of the outlet of the ionization device.
  • the first electrode is arranged on the taper or aperture.
  • the first electrode may be disposed on an outer side of the dielectric member or abut on the outer side.
  • the second electrode may be arranged at least in sections in the dielectric element.
  • Ionization device may be less than 20 mm, preferably less than 10 mm, more preferably less than 5 mm and most preferably less than 2 mm.
  • the distance is the smallest distance between the first electrode and the second electrode. So it is the distance that has the lowest length value between a point of the first electrode and a point of the second electrode.
  • the distance between the outlet of the ionization device and the first electrode may be less than 40 mm, preferably less than 30 mm, more preferably less than 20 mm, even more preferably less than 10 mm, most preferably less than 5 mm. This in the flow direction (x-direction).
  • the analysis unit may be a mass spectrometer or an ion mobility spectrometer.
  • the outlet of the ionization device may have a smaller cross-sectional area than the inlet of the ionization device.
  • One of the analyzers can be used in a method of analyzing an analyte.
  • the method comprises the steps of introducing an analyte into the ionization device, ionizing the analyte, preferably by a dielectric barrier discharge in the discharge region, applying the ionized analyte the ionization device via the outlet into the analysis unit and analyzing the analyte in the analysis unit.
  • the pressure in the ionization apparatus may be greater than 40 kPa, preferably greater than 60 kPa, and more preferably greater than 80 kPa. More preferably, the pressure in the ionization apparatus is substantially atmospheric pressure.
  • the substantially atmospheric pressure may allow for variation from the atmospheric pressure of 10% above the atmospheric pressure or 10% below the atmospheric pressure.
  • the voltage may be at most 20 kV, preferably at most 10 kV, more preferably at most 5 kV, and most preferably between 1 kV and 3 kV.
  • the dielectric barrier discharge can be effected by unipolar high voltage pulses.
  • the pulse duration may be at most 1 ⁇ , preferably at most 500 ns, and most preferably between 100 ns and 350 ns.
  • the high voltage pulses may have a frequency of at most 100 GHz, preferably at most 100 MHz, more preferably at most 500 kHz, and most preferably between 1 kHz and 100 kHz.
  • the first and second electrodes can be supplied with a sinusoidal voltage.
  • the sine voltage of one of the electrodes can be shifted by half a period duration with respect to the other of the two electrodes.
  • Another ionization device for ionizing an analyte includes a first inlet, a second inlet, an outlet, a first electrode, a second electrode and a dielectric element.
  • the first electrode, the second electrode, and the dielectric member are arranged to each other such that between the first electrode and the second electrode, a dielectric barrier discharge in a discharge region in the ionization device can be formed by applying an electric voltage between the first electrode and the second electrode ,
  • the first and second electrodes are arranged displaceable relative to one another.
  • the plasma By moving the electrode, the plasma can be formed closer or further away from a merger with the analyte. This allows different reactive components of the plasma to be reacted with the analyte, as the Plasma components have different lengths of life. This allows the ionization efficiency and fragmentation to be directly controlled since shorter-lived species are generally more reactive than long-lived species.
  • the second electrode may comprise an outwardly curved portion in the r direction.
  • the first electrode and / or the dielectric element may comprise an outwardly curved portion in the r direction.
  • the portion of the second electrode curved outward in the r direction and the portion of the first electrode and / or the dielectric element curved outward in the r direction can be configured correspondingly.
  • the respective arched section is designed to be substantially uniform.
  • the outwardly curved portion of the second electrode may be slidable in the outwardly r-directionally curved portion of the first electrode and / or the dielectric member.
  • the insurability of the second electrode relative to the first electrode and / or the dielectric element may be limited by the configuration of the curved portion of the first electrode and / or of the dielectric element.
  • the second electrode may be disposed at least portion-wise in the dielectric member.
  • the first electrode is preferably arranged outside the dielectric element.
  • the displaceability of the first and second electrodes relative to each other may be in
  • the distance can be none than 20 mm, preferably less than 10 mm, more preferably less than 5 mm and most preferably less than 2 mm.
  • the distance describes the smallest distance between the first electrode and the second electrode, the distance between a point of the first electrode and a point of the second electrode having the lowest length value.
  • the first electrode may be arranged immovable relative to the dielectric element.
  • the second electrode is slidably disposed relative to the dielectric member.
  • One of the ionization devices can be operated in one process.
  • the method comprises introducing an analyte into the ionization device, which Ionizing the analyte in the ionization device, preferably by a dielectric barrier discharge in the discharge region, and applying the ionized analyte from the ionization device across the outlet.
  • the pressure in the ionization apparatus may be greater than 40 kPa, preferably greater than 60 kPa, and more preferably greater than 80 kPa. More preferably, the pressure in the ionization apparatus is substantially atmospheric pressure.
  • the substantially atmospheric pressure may allow for variation from the atmospheric pressure of 10% above the atmospheric pressure or 10% below the atmospheric pressure.
  • the voltage may be at most 20 kV, preferably at most 10 kV, more preferably at most 5 kV, and most preferably between 1 kV and 3 kV.
  • the dielectric barrier discharge can be effected by unipolar high voltage pulses.
  • the pulse duration may be at most 1 ⁇ , preferably at most 500 ns, and most preferably between 100 ns and 350 ns.
  • the high voltage pulses may have a frequency of at most 100 GHz, preferably at most 100 MHz, more preferably at most 500 kHz, and most preferably between 1 kHz and 100 kHz.
  • the first and second electrodes can be supplied with a sinusoidal voltage.
  • the sine voltage of one of the electrodes can be shifted by half a period duration with respect to the other of the two electrodes.
  • the first and / or second electrode of the various embodiments of the disclosed ionization devices may be made of an electrically conductive material, such as metal.
  • the first and / or second electrode may comprise gold, silver or a metallic alloy (also in the form of a layer).
  • the first and / or second electrode of the different embodiments of the disclosed ionization devices can be configured as a (flow-through) hollow body, for example as a ring or hollow cylinder, optionally circumferentially interrupted.
  • the first electrode can be at least partially outside the dielectric element and the second electrode can be arranged at least in sections within the dielectric element.
  • the second electrode may be designed as a wire which is arranged concentrically or eccentrically at least in sections in the dielectric element.
  • Ionleitersvoriquesen may consist of a solid and in particular consist of a plastic (for example, PMMA or PP) or include this.
  • the dielectric element is made of quartz glass or comprises quartz glass.
  • the inlet of the ionization device may be open to the environment, and the discharge gas is the atmosphere surrounding the inlet, especially air.
  • Discharge gases are also usable, for example, the discharge gas may contain nitrogen, oxygen, methane, carbon dioxide, carbon monoxide or at least one noble gas or mixtures thereof.
  • the discharge gas may contain nitrogen, oxygen, methane, carbon dioxide, carbon monoxide or at least one noble gas or mixtures thereof.
  • Discharge gas is a dopant, which can be introduced as the discharge gas through the entrance of the ionization device or can be introduced via a further input into the ionization device, e.g. Methane, ethane, hydrogen, chlorobenzene or mixtures thereof or mixtures of various components.
  • the dielectric barrier discharge within the various embodiments of the ionization device may also be formed by applying a square or sawtooth voltage or by other AC forms known per se having a frequency of 100 GHz or less.
  • the dielectric barrier discharge within the various embodiments of the ionization device can also be formed by applying a DC voltage.
  • Iontechnischesvoriquesen comprise an ion mass filter.
  • the ion mass filter is isolated or selected from a particular ion or ions, based on their mass or mass-to-charge ratio.
  • An example of an ion mass filter is a quadrupole.
  • An ion mass filter can be used between the discharge region of an ionization device and the inlet of the
  • an analysis device By arranging an analysis unit on one of the various embodiments of the disclosed ionization devices, an analysis device can be formed.
  • the ionization device is directly (optionally via a short
  • a unit is preferably arranged which can carry out an analysis based on a molecular charge, for example mass spectrometers, ion mobility spectrometers or comparable devices.
  • At least one further ionizing device may be arranged in an analysis device, for example a device for carrying out electron impact ionization or electrospray ionization.
  • One of the disclosed ionization devices can be used in combination with a
  • Analysis unit as an analysis device as a handheld device (portable device) be configured.
  • One of the disclosed ionization devices can be used for flow through ionization.
  • FIG. 1 schematically shows an embodiment of an ionization device 10 having a first section 10a and a second section 10b.
  • FIG. 1a schematically shows an embodiment of an ionization device 10 having a first section 10a, a second section 10b and a grid 20 as a charge carrier filter.
  • FIG. 1b schematically shows an embodiment of an ionization device 10 having a first section 10a, a second section 10b and a magnet 21 as a charge carrier filter.
  • FIG. 2 shows schematically an embodiment of an ionization device 10 with a first and a second electrode (1, 2) on an outside 3a of a dielectric element 3.
  • FIG. 3 schematically shows an embodiment of an ionization device 10 with
  • FIG. 3 a schematically shows a section through the ionization device 10 of FIG. 3.
  • FIG. 3b schematically shows an embodiment of an ionization device 10 having a helical or helical first electrode 1.
  • FIG. 3 c schematically shows an embodiment of an ionization device 10
  • FIG. 4 shows schematically an embodiment of an ionization device 10 with first and second electrodes (1, 2) displaceable relative to one another in a first position.
  • FIG. 4a schematically shows an embodiment of an ionization device 10 with first and second electrodes (1, 2) which can be displaced relative to one another in a second position.
  • FIG. 5 schematically shows an embodiment of an analysis device 100 with adjustable distance D2 between a first electrode 1 and an outlet A of the ionization device 10.
  • FIG. 5 a schematically shows an embodiment of an analysis device 100
  • FIG. 6 shows schematically an embodiment of an ionization device 10 with an outwardly curved section 1a of the first electrode 1.
  • FIG. 1 shows an ionization device 10 with a first section 10a and a second section 10b.
  • the first section 10a includes an inlet E into which a discharge gas G can be introduced.
  • the first portion 10 a further includes a first electrode 1, a second electrode 2, and a dielectric member 3.
  • the dielectric member 3 is disposed between the first electrode and the second electrode 2.
  • the first electrode 1 is disposed on an outer side 3 a of the dielectric member 3.
  • a dielectric barrier discharge can be generated by applying an electrical voltage, wherein the discharge is primarily located in a discharge region 5.
  • Discharge area 5 and can be ionized in this area.
  • the distance D is shown in FIG. 1 as the shortest distance between the first and second electrodes 1, 2.
  • the first portion 10a is flowed through with the second portion 10b or
  • the second section 10b comprises an inlet E2, via which a sample or a sample substance or an analyte S can flow into the second section 10b.
  • the ionized analyte S and the (ionized) discharge gas G reach the ionization device 10.
  • the ionized analyte S can subsequently be analyzed.
  • the cross-section is tapered so that the cross-sectional area of the outlet is less than the cross-sectional area of the inlet E2.
  • the cross-sectional differences serve u.a. of the
  • the inlet E2 into which an analyte S can be introduced is typically open to the environment.
  • the ionization device 10 of FIG. 1a comprises a first section 10a and a second section 10b, the sections 10a, 10b being connected in a fluid-communicating manner.
  • a grid 20 as a charge carrier filter after (downstream) the discharge region 5 is arranged.
  • the grid 20 is connected to a voltage source (not shown in Figure la).
  • positively charged particles or negatively charged particles may pass through the grid 20 so that particles of the charge type (positively or negatively charged) that can not pass through the grid 20 are filtered. Examples of charged particles are ions and electrons.
  • the ionization device 10 shown in FIG. 1b is similar to the ionization device 10 of FIG. 1a, wherein a magnet 21 is arranged as the charge carrier filter instead of a grid 20, as in FIG. 1b.
  • the magnet 21 is disposed after (downstream) the discharge region 5 in the first portion 10 a of the ionization device 10.
  • the magnet 21 generates a magnetic field and allows passage of charged particles of a charge type (positive or negative).
  • FIG. 1b Another embodiment of an ionization device 10 is shown in FIG.
  • Ionization device 10 comprises a dielectric element 3 which is in the form of a
  • the dielectric element has an outside 3a. On the outside 3a, a first and a second electrode 1, 2 are arranged, which
  • a capillary 30 is arranged in the dielectric element 3.
  • the capillary 30 is concentric with the dielectric element 3 and has a hollow cylindrical shape.
  • a dielectric barrier discharge can be effected in a discharge region 5.
  • the discharge region is located primarily in a space between capillary 30 and dielectric element 3.
  • the arrangement of the capillary 30 and the dielectric element 3 results in an inlet EK into the capillary and an inlet E into the dielectric element 3.
  • a discharge gas G can be introduced into the ionization device 10 and via the inlet EK Analyte S are introduced into the ionization device 10.
  • the discharge gas G can flow through the discharge region 5 and thereby be ionized.
  • the longitudinal extent of the capillary 30 in the positive x-direction is less than that
  • the flow in the ionization apparatus 10 may be caused by a vacuum unit at the outlet A (not shown in Figure 2).
  • the inlet EK into the capillary 30 is preferably open to the environment.
  • a distance D is present, which results in the case of a constant cross section of the dielectric element 3 from the distance in the x direction.
  • FIGS. 3 and 3a An embodiment of an ionization device 10 with not completely circumferential or circumferentially interrupted electrode 1 is shown in FIGS. 3 and 3a.
  • the ionization device 10 comprises a first electrode 1, comprising a plurality of partial electrodes 1 a, 1 b,... 1 h, a second electrode 2 and a dielectric element 3 an outside 3a.
  • a first electrode 1 comprising a plurality of partial electrodes 1 a, 1 b,... 1 h
  • a second electrode 2 and a dielectric element 3 an outside 3a.
  • the sub-electrodes la, lb, ... lh a corresponding number of interruptions.
  • the sub-electrodes la, lb, ... lh can be used together with a control unit or a
  • a discharge gas G and an analyte S can be introduced into the ionization device via an inlet E and discharged from the ionization device 10 via an outlet A.
  • the second electrode 2 is designed here in a wire-like configuration, in other embodiments the second electrode can also be embodied as a (flow-through) hollow body, in particular
  • Discharge areas in the binary sense is not always completely possible, but can be primary discharge areas in which the main part of the discharge takes place, assign.
  • the sub-electrodes 1a, 1b,... 1h are circular in the embodiment of FIGS. 3 and 3a, in other embodiments the sub-electrodes may also be configured as rectangles, in particular squares.
  • a distance D between the first and second electrodes 1, 2 is given in FIG. 3 in the r-direction.
  • FIG. 3c The embodiment of an ionization device 10 in FIG. 3c is similar to FIG.
  • This ionization device 10 comprises a second electrode 2, a dielectric element 3 and a first electrode, which consists of a plurality of partial electrodes 1 a, 1 b,... 1 h, the partial electrodes 1 a, 1 b,... 1 h on an outer side 3 a of the dielectric element 3 present.
  • a discharge gas G and an analyte S can flow into an inlet A of the ionization device 10 and flow out of the ionization device 10 via an outlet A.
  • the first electrode 1 (partial electrodes la, lb, ... lh) is circumferentially interrupted or not completely formed circumferentially, as between the sub-electrodes la, lb, ... lh result in multiple interruptions or gaps.
  • a dielectric barrier discharge can be formed in a plurality of discharge regions 5a, 5b,... 5h.
  • the sub-electrodes la, lb, ... lh can be connected together to a control device or a control device.
  • the second electrode 2 is designed in the form of a wire and lies partially within the dielectric element 3.
  • the sub-electrodes la, lb, ... lh rod-shaped, wherein the sub-electrodes la, lb, ... lh have a greater length by at least five times (side length of the long sides) than their width (front sides).
  • Discharge regions 5a, 5b, ... 5h are formed over a greater axial length than in the application of shorter partial electrodes la, lb, ... lh.
  • Partial electrodes in the axial direction (x-direction) at least 5 mm.
  • the distance D between the first electrode 1 (partial electrodes 1 a, 1 b,... 1 h) and the second electrode 2 is constant over the axial length (x-direction) in the overlapping region of the electrodes 1, 2.
  • the sub-electrodes 1a, 1b,..., Lh of the ionization devices 10 have the same axial (x-direction) distance from the inlet E and the outlet A, ie they are at a same axial position
  • sub-electrodes may also be disposed axially offset (not the same axial position).
  • the ionization device 10 comprises a first electrode 1, a second electrode 2 and a dielectric element 3.
  • Ionleitersvoriques 10 are introduced and discharged via an outlet A.
  • the discharge gas G and the analyte S can flow through the ionization device in the flow direction R.
  • the first electrode 1 abuts on an outer side 3 a of the dielectric member 3 and is configured in a spiral or helical shape.
  • the first electrode 1 abuts on an outer side 3 a of the dielectric member 3 and is configured in a spiral or helical shape.
  • Windings shown in other embodiments may also at least one Winding be arranged. At least two windings, in particular at least five windings, are preferred.
  • the first electrode 1 in a plane perpendicular to the flow direction R is not completely circulating or circumferentially interrupted.
  • the first electrode is not shown cut in order to facilitate understanding, however, in a sectional view, the first electrode 1 would only be located as axially offset points outside the dielectric element 3 visible, noticeable.
  • the first electrode 1 Due to the helical or spiral configuration of the first electrode 1, the first electrode 1 is interrupted along a path outside the dielectric element 3 parallel to the flow direction R, or intermediate spaces (depending on the number of windings) are formed.
  • the second electrode 2 is wire-shaped.
  • the second electrode 2 lies partially or in sections in the dielectric element 3.
  • the discharge area 5 may be formed by the spiral or helical
  • Embodiment be interrupted along a path within the dielectric element 3 parallel to the flow direction R.
  • the discharge area 5 can by the
  • Flow direction R may be interrupted or not completely over an area in the plane bounded by the dielectric member 3, extend.
  • the ionization device 10 comprises a first electrode 1, a second electrode 2 and a dielectric element 3.
  • a capillary 30, which is arranged in sections in the dielectric element 3, is connected to the second electrode 2 connected and the second
  • Electrode 2 is located inside the dielectric element 3.
  • the capillary 30 has an inlet E into which a discharge gas G and an analyte S can be introduced into the ionization device 10. From an outlet A of
  • the discharge gas G and the analyte can be applied.
  • the capillary 30 may also be replaced by another element having dielectric properties.
  • the second electrode 2 is designed spirally or helically. Similar to the illustration in FIG. 3b, the second electrode 2 is not shown as a section in order to achieve a better understanding. In a sectional view as in FIGS. 4 and 4a, the second electrode 2 would be recognizable as axially offset points.
  • a dielectric barrier discharge can be formed when a voltage is applied between the electrodes 1, 2.
  • the first electrode 1 is located on an outer side 3 a of the dielectric member 3 such that the first electrode 1 can be displaced with respect to the dielectric member 3.
  • the second electrode 2 is not displaceable relative to the dielectric element 3, so that the first electrode 1 is displaceable relative to the second electrode 2.
  • FIGS. 4 and 4a Different positions of the first electrode 1 can be seen in FIGS. 4 and 4a. If the position of the first electrode 1 in FIG. 4 is considered, the first electrode 1 in FIG. 4 a is displaced counter to the flow direction R (in the negative x-direction). As a result of these different positions of the first electrode 1, the overlapping areas of the first and second electrodes 1, 2 are markedly different in the flow direction R (x-direction).
  • the overlapping area of the first and second electrodes 1, 2 in the flow direction R (x direction) is greater than for the position of the first electrode 1 of FIG.
  • the distance D between the first and second electrodes 1, 2 is the same in both positions (FIGS. 4 and 4a) of the first electrode 1.
  • FIG. 5 shows schematically an analysis device 100 with an ionization device 10 and an analysis unit 40. Therein, any disclosed ionization device 10 besides the one described for this embodiment can be used.
  • the ionization apparatus 10 includes a first electrode 1, a second electrode 2, and a dielectric member 3.
  • the first electrode 1 is arranged outside the dielectric element 3, and the second electrode 2 lies in sections inside the dielectric element 3.
  • the second electrode 2 comprises an inlet E, through which a discharge gas G and an analyte S can be introduced into the ionization device 10.
  • the first and second electrodes 1, 2 can be formed by applying a voltage of a dielectric barrier discharge in a discharge region 5.
  • the first and second electrodes 1, 2 have a distance D from each other.
  • the discharge region 5 can be traversed by the discharge gas G and the analyte S, whereby at least the analyte S is ionized.
  • an analysis unit 40 for example a mass spectrometer or a
  • the ionized analyte S is analyzed (qualitatively and / or quantitatively).
  • Discharge region 5 in or after which the analyte S is ionized, and the
  • Analysis unit 40 is a distance D2, preferably parallel to the flow direction R.
  • the distance D2 is adjustable, in particular, the positions of the first electrode 1 and the second electrode 2 relative to each other remains the same when the distance D2 is changed.
  • the adjustability or variability of the distance D2 can be configured in a manner known per se.
  • the ionized analyte S with the (ionized) discharge gas G flows through the distance D2 until it is analyzed.
  • chemical and / or physical processes can take place, which can change the ionization state of the analyte S.
  • the optimal distance D2 can be different, so that it is advantageously adjustable for different analytes S.
  • FIG. 5a shows an analysis device 100 in a further embodiment.
  • Analysis device 100 comprises an ionization device 10 and an analysis unit 40 with a vacuum chamber 41.
  • the ionization device 10 any disclosed ionization device 10 besides that described by way of example for this embodiment may be used.
  • the ionization apparatus 10 includes a first electrode 1, a second electrode 2, and a dielectric member 3 having an outside 3a.
  • the ionization device 10 has an inlet E, via which a discharge gas G and an analyte S can be introduced into the ionization device 10, and an outlet A, which is connected directly to the vacuum chamber 41 of the analysis unit 40.
  • a dielectric barrier discharge may be formed by applying a voltage between the first and second electrodes 1, 2 in a discharge region 5.
  • the pressure in the ionization device 10 is greater than the pressure in the vacuum chamber 41, so that a pressure gradient ⁇ results between the ionization device and the vacuum chamber 41. Due to the pressure gradient ⁇ , the discharge gas G and the analyte S flow into the vacuum space 41 of the analysis unit 40, in which the ionized analyte S can be analyzed (qualitatively and / or quantitatively).
  • the (flow-through) cross section of the ionization device 10 tapers in
  • the cross-sectional reduction of the outlet A may also be realized by a diaphragm.
  • the first electrode 1 is arranged in the region of the taper, specifically on the outside 3a of the dielectric element 3 in the region of the taper.
  • a distance D2 lies between the first electrode 1 and the outlet A in the flow direction R or in the x direction, wherein the distance D2 may be considered in other embodiments between the second electrode 2 and the outlet A of the ionization device, when the second electrode in Flow direction R or in the x direction closer to the outlet A is located.
  • the first electrode 1 may include the outlet A of the ionization device in FIG.
  • Flow direction R or in the x-direction also overlap, or the second electrode 2, the outlet A of the iontechnischsvoriques in the flow direction R or in the x-direction overlap when located closer to the outlet A of the ionization device than the first electrode 1.
  • the distance D2 is less than 50 mm.
  • the discharge region 5 results in a dielectric barrier discharge in the flow direction R or in the x direction near the outlet A and partly in the outlet A.
  • the ionization apparatus 10 includes a first electrode 1, a second electrode 2, and a dielectric member 3 having an outside 3a.
  • a dielectric barrier discharge in different discharge regions 5 can be formed by applying a voltage.
  • the first electrode 1 abuts against the outside 3a of the dielectric member 3 and has a portion la outwardly curved in the r-direction, which portion corresponds to or is uniformly formed with a portion 3a of the dielectric member curved toward the outside in the r direction.
  • the dielectric element 3 has an inlet E3 through which a discharge gas G can flow into the ionization device.
  • the second electrode 2 has an inlet E, through which an analyte S into the
  • the second electrode has an outwardly curved portion 2a or a thickened portion, which is partially disposed in the curved portion 3a of the dielectric member.
  • the second electrode 2 is displaceable relative to the first electrode 1 and the dielectric element 3, especially in the flow direction R or in the x direction. By a displacement of the second electrode 2 relative to the first electrode 1, different results
  • Usual diameters of the discharge paths are between 0.05 mm and 2 mm, wherein the diameter does not have to be constant over the entire discharge path.
  • Analysis unit is typically between 0.005 L / min and 5 L / min.
  • the ratio of discharge gas G to analyte S is usually between 0.1: 1 - 100: 1.
  • the diameter of the sample inlet E is typically between 0.2 mm and 3 mm.
  • a residence time to the analyzer or vacuum inlet (at approximate atmospheric pressure of 80 kPa) is less than 20 ms when kinetically controlled ionization is desired.
  • the residence time can be up to 10 s.
  • the residence time is the time that one or more analytes spend between the discharge region or the first (in the direction of flow, for example with ionized discharge gas) encountering reactive species and analysis or introduction into a vacuum.
  • the time is dependent on the geometric configuration of an ionization device and its arrangement to form an analysis unit or a vacuum chamber and the volume flows of discharge gas G, analyte or analyte S and optionally a dopant.
  • each ionization device can be combined with other embodiments.
  • each ionization device may be provided with one disclosed herein
  • the first and second electrodes can be arranged on the outside of the dielectric element, in each ionization device, the first and / or second electrode can not be designed to be completely circulating or circulating, in each ionization device the first and / or second In each ionization device, the first and second electrodes may be arranged to be displaceable relative to one another; in each ionization device, the first and / or second electrode and / or in each ionization device, the first and / or second electrode and / or the dielectric element to be curved outwards.
  • an analysis device can be formed in that the respective ionization device is connected to an analysis unit, if appropriate directly.
  • Each analyzer may have a spacing between the first electrode and the outlet of the ionization device of less than 50 mm and / or be configured and connected to an analysis unit such that a distance between a discharge region or a first meeting of reactive species with an analyte or more analytes and an analysis unit or a vacuum chamber can be flowed through by one or more analytes in less than 1 s.
  • the ionization can each be operated as flow ionization.

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Abstract

L'invention concerne un dispositif d'ionisation 10 pour l'ionisation d'un analyte S, présentant une entrée E, une sortie A, une première électrode 1, une deuxième électrode 2 et un élément diélectrique 3. La première électrode 1, la deuxième électrode 2 et l'élément diélectrique 3 sont disposés les uns par rapport aux autres de manière telle que par l'application d'une tension électrique entre la première électrode 1 et la deuxième électrode 2, une décharge de barrière diélectrique peut être formée dans une zone de décharge 5 dans le dispositif d'ionisation 10. La première électrode et la deuxième électrode 1, 2 sont disposées de manière coulissante ou mobile l'une par rapport à l'autre.
EP18750480.8A 2017-06-16 2018-06-15 Dispositif et procédé pour l'ionisation d'un analyte ainsi que dispositif et procédé pour l'analyse d'un analyte ionisé Pending EP3639289A2 (fr)

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US11201045B2 (en) 2017-06-16 2021-12-14 Plasmion Gmbh Apparatus and method for ionizing an analyte, and apparatus and method for analysing an ionized analyte
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US11621155B2 (en) * 2021-07-29 2023-04-04 Bayspec, Inc. Multi-modal ionization for mass spectrometry
CN114664636B (zh) * 2022-03-04 2023-03-24 苏州大学 基于介质阻挡放电的空气逆流式离子源

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