EP3639289A2

EP3639289A2 - Apparatus and method for ionizing an analyte, and apparatus and method for analysing an ionized analyte

Info

Publication number: EP3639289A2
Application number: EP18750480.8A
Authority: EP
Inventors: Jan-Christoph WOLF
Original assignee: Plasmion GmbH
Current assignee: Plasmion GmbH
Priority date: 2017-06-16
Filing date: 2018-06-15
Publication date: 2020-04-22
Also published as: WO2018229724A3; US20220102129A1; US11923184B2; WO2018229724A2; US20210151309A1; US11201045B2

Abstract

Disclosed is an ionization apparatus 10 for ionizing an analyte S, comprising an inlet E, an outlet A, a first electrode 1, a second electrode 2 and a dielectric element 3. The first electrode 1, second electrode 2 and the dielectric element 3 are arranged in relation to one another such that a dielectric barrier discharge can form in a discharge region 5 in the ionization apparatus 10 by the application of an electric voltage between the first electrode 1 and the second electrode 2. The first and second electrodes 1, 2 can be shifted or moved in relation to one another.

Description

Apparatus and method for ionizing an analyte and apparatus and method for analyzing an ionized analyte

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.

Various dielectric barrier discharge ionization devices known in the art are known in various ionization processes. After ionizing an analyte, it can be analyzed.

From US 2012 02 92 526 AI an ionization device is known in which a

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.

However, the prior art devices and methods often have relatively low sensitivity, fragment the analyte (making spectra created by subsequent analysis difficult to interpret), and are structurally expensive.

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 object is achieved by a lonisierungsvorrichtung according to claims 1, 14, 26, 38, 81 and by a method according to claims 8, 19, 31, 48, 89 and by an analysis device according to claims 54, 71 and by a method according to the

Claims 65, 76.

The invention can achieve flow-through ionization of an analyte, especially for analysis. In this case, a so-called "soft" ionization can be used, the molecules largely not destroyed or fragmented, but by protonation and

Charge transfer recombination leads to quasimolecular ions. Especially in connection with (high-resolution) mass spectrometry, this allows a direct identification of the substance via its elemental composition. By the invention Configuration of the ionization devices and the ionization method as well as the analysis device and the analysis method, a very high sensitivity in the low Femto- to Attogrambereich can be achieved in a subsequent analysis.

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.

Applications for this are in addition to classic combinations with

chromatographic methods (GC, HPLC, Nano-LC) also include direct screening analyzes, e.g. direct pesticide analysis on fruit or vegetable surfaces.

Military or civil defense, 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

lethal poisoning.

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.).

The possibility of 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.

In addition, the hitherto existing problem of effective transfer of charged particles at atmospheric pressure into vacuum (analysis) is solved. Due to the mutual repulsion of the charged particles, currently used atmospheric pressure ionization processes (for example, ESI, HESI, APCI, DART, DESI, LTP) lose large parts of the ions formed without being lost. The formation of ions directly in or at the inlet ensures effective transfer of the charged particles for analysis and thus high sensitivity. Chemical analyzes usually need to be conducted not only qualitatively but quantitatively. Due to the problem of an "open" connection of the ionization with the analyzer, as with existing methods, the quantification can be easily disturbed by external influences (draft, impurity diffusion, etc.). This results in the problem of incorrect or incorrect analysis results. Through flow ionization, the connection between ionization and analyzer is closed and thus solves the described problem in quantification.

Existing plasma-based ionization processes or ionization processes at quasi-atmospheric pressure do not allow introduction of the analyte into the discharge gas, since the analyte is destroyed in the discharge. By forming a very "soft" plasma with little or no fragmentation, this problem can be solved.

The degree of fragmentation that occurs depends partly on the efficiency of the system

Composition of the surrounding atmosphere (humidity, etc.). Thus, by a suitable choice of additional compounds (dopants) or 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.

Furthermore, 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. In addition, 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

Ionisationsvorrichtung, for the purpose of selectivity or sensitivity increase.

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

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 ionisierungsvorrichtung. 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.

Through the targeted selection (filtering) of reactive species, a defined and easier to interpret or calculate ionization can be carried out. In addition, this ionization by means of selected Reactandionen allows quantification of the analyte species due to specific reaction coefficients, even without intrinsic

Calibration. Also, unwanted ionization side reactions with very reactive or oxidizing species can be avoided, which in turn leads to more easily interpretable and more meaningful measurement results in an optional subsequent analysis.

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. In this case, 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.

In such an embodiment, 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.

In particular, 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 applying the electrode as a layer can parasitic

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.

Via the inlet as the first inlet, a discharge gas can be introduced into the ionization device and ionized in the discharge region. Via one or the second inlet, 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.

Between the first electrode and the second electrode may be applied an electrical voltage for generating a dielectric barrier discharge. 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 με, 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. In this case, 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.

As a result, a miniaturization of the ionization source can be made possible in particular with a simultaneously optimized flow profile, which offers advantages for the subsequent analysis, for example with portable devices. In addition, by the separation of the plasma gas flow from the analyte gas flow, a suppression undesirable

Fragmentation creations, which by the electrical discharge during the

Plasma formation can be effectively suppressed. 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. In the

Ionisierungsvorrichtung the streams of the discharge gas and the analyte can be merge.

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.

Specifically, 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.

One of the first and second electrodes or both the first electrode and the second electrode may abut on the outside of the dielectric element. Preferably, 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.

In one method, 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.

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.

In particular, 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

Ionisierungsvorrichtung can be understood. In particular, 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.

This means that in one complete revolution of the circumference (circumferential direction in cylindrical coordinates) of the first and / or second electrode, especially in the plane which is perpendicular to the flow direction, at least one interruption can be formed.

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 (discharge area) 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. In addition, 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. Preferably, 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

Be connected control unit.

Preferably, 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. Preferably, 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

Ionisierungsvorrichtung is bildbar.

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. The

Method comprises the steps of introducing an analyte into the

ionizing device, ionizing the analyte in the ionization device and applying the ionized analyte from the ionization device via the outlet. Preferably, the analyte is released by a dielectric barrier discharge in the

Discharge area or the discharge areas ionized. 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.

Another ionization device for ionizing an analyte comprises an inlet, an outlet, a first electrode, a second electrode and a dielectric element. In this case, 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.

Due to the displaceability of the electrodes, the expansion of the plasma (the

Extent of the discharge region) and thus the number of reactive species or the reaction space to the respective analysis, in particular to the respective analyte, adapted, which allows an adjustable lonisationseffizienz or fragmentation, whereby the ion source to the respective subsequent optional

Analysis task (eg high or low sensitivity) can be adjusted. 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. In particular, 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.

Preferably, the first electrode is slidably disposed relative to the dielectric member. The second electrode may be relative to the dielectric element

be arranged immovable.

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.

An analysis device for analyzing an ionized analyte comprises a

Ionisierungsvorrichtung 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 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

Flow direction (x-direction). 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).

The connection of the ionization device with the analysis unit is designed so that the analyte or the analytes after (first) ionization by a

so-called reactive impact with a reactive species, which was formed in the plasma, 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

Product control achieved. This means that the analysis of the ionized analyte (s) occurs so fast that the inherently thermodynamic

Equilibrium is not reached or adjusting the equilibrium, e.g. by introducing the ionized analyte (s) into a vacuum. As a result, suppression effects and competing reactions, such as those usually associated with

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. In the vacuum chamber can prevail a pressure which is below the ambient pressure, in particular below the pressure in the ionisierungsvorrichtung.

A pressure gradient can prevail between the ionization device and the vacuum chamber of the analysis unit. Preferably, 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. Preferably, 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.

The distance between the first electrode and the second electrode of

Ionisierungsvorrichtung 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. Specifically, 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 dielectric barrier discharge can be effected by unipolar high voltage pulses. The pulse duration may be at most 1 με, 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.

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. The

Ionization device is connected to the analysis unit so that one in the

ionizing analyte or (various) analytes from the outlet of the ionization device can get directly into the analysis unit. 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

more preferably less than 200 ms, even more preferably less than 50 ms, and most preferably less than 20 ms.

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) and the cross-section through which it flows. 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

more preferably less than 50 ms and most preferably less than 20 ms.

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.

These mostly metastable plasma species are usually by optical

(spectroscopic) methods are detected, since they have characteristic emissions or

Have absorption lines. Thereby, a discharge area or a discharge can be located.

The embodiment according to the invention once again achieves ionization with kinetic product control, which brings about the effects and advantages described above.

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. In particular, 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 distance between the discharge area and the analysis unit or the

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.

The distance between the discharge area and the analysis unit or the

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. Preferably, 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 distance between the first electrode and the second electrode of

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. Specifically, 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 analysis unit may be a mass spectrometer or an ion mobility spectrometer.

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.

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. Therein, 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.

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. In this case, 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.

In this case, 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

Be given flow direction or against the flow direction.

Between the first electrode and the second electrode of the ionization device, 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. Preferably, 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. Preferably, 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.

Generally, 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. In particular, 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. In the various embodiments of the disclosed ionization devices, 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.

In the various embodiments of the disclosed ionization devices, the second electrode may be designed as a wire which is arranged concentrically or eccentrically at least in sections in the dielectric element.

The dielectric element of the various embodiments of the disclosed

Ionisierungsvorrichtungen may consist of a solid and in particular consist of a plastic (for example, PMMA or PP) or include this. In particular, the dielectric element is made of quartz glass or comprises quartz glass. Likewise suitable are various ceramics or ceramic composite materials, for example corundum.

In the various embodiments of the disclosed ionization devices, the inlet of the ionization device may be open to the environment, and the discharge gas is the atmosphere surrounding the inlet, especially air. Other

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. In the discharge area, in addition to

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.

Generally, the various embodiments of the disclosed

Ionisierungsvorrichtungen comprise an ion mass filter. Through a

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

Ionization.

By arranging an analysis unit on one of the various embodiments of the disclosed ionization devices, an analysis device can be formed. Preferably, the ionization device is directly (optionally via a short

Intermediate element) connected to the analysis unit. As an analysis unit, 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.

Preferably, in addition to an ionization device, 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.

The embodiments of the invention are illustrated by way of example and not shown in a manner in which limitations of the figures are transferred or read into the claims.

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

Partial electrodes la, lb, ... of the first electrode 1.

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

Partial electrodes la, lb, ... of the first electrode 1 and a section of this embodiment.

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

a more detailed representation of the distance D2 between a first electrode 1 and an outlet A of the ionization device 10th

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. Between the first electrode 1 and the second electrode 2, a dielectric barrier discharge can be generated by applying an electrical voltage, wherein the discharge is primarily located in a discharge region 5.

When the discharge gas G via the inlet E in the first portion 10 a of

Ionisierungsvorrichtung 10 flows, the discharge gas flows through the G

Discharge area 5 and can be ionized in this area.

There is a distance D between the first electrode 1 and the second electrode 2. 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

connected in a fluid-communicating manner so that the (ionized) discharge gas G can flow from the first section 10a into the second section 10b. 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.

In the region of the second section 10b of the ionization device, in which the ionized discharge gas G flowing out of the first section 10a and the analyte S in FIG Are contacted, at least a portion of the charges of the ionized discharge gas G is passed to the analyte S and thereby the analyte S ionized.

Via an outlet A in the second section 10b of the ionization device 10, the ionized analyte S and the (ionized) discharge gas G reach the ionization device 10. The ionized analyte S can subsequently be analyzed.

In the area of the outlet A in the second section 10b of the ionization device 10, 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

Pressure control, since the flow through the ionisierungsvorrichtung 10 is typically caused by a pressure gradient. In this case, the pressure outside the outlet A is lower than the pressure outside the inlets E, E2 and in the ionization device 10. This negative pressure can be reduced by a vacuum unit, e.g. a pump connected to outlet A can be reached (not shown in FIG. 1).

The inlet E2 into which an analyte S can be introduced is typically open to the environment.

Similar to the embodiment of an ionization device 10 shown in FIG. 1, 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.

In addition to the features and operation of those shown in FIG

Ionisierungsvorrichtung 10, in the first portion 10a of the ionization device 10, 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). Depending on the wiring of the grid 20, 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). 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

Hollow cylinder is designed. The dielectric element has an outside 3a. On the outside 3a, a first and a second electrode 1, 2 are arranged, which

are designed in a hollow cylindrical shape. In the dielectric element 3, a capillary 30 is arranged. The capillary 30 is concentric with the dielectric element 3 and has a hollow cylindrical shape. Between the first and second electrodes 1, 2, 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. Via the inlet E, 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

Lengthwise extension of the dielectric element 3 in the positive x-direction, so that after (downstream) the analyte S has passed through an outlet AK of the capillary 30, the currents of the ionized discharge gas G and the analyte S are merged and the ionized discharge gas G at least part of its charge can be transferred to the analyte S, so that the analyte S is ionized. The ionized analyte S can flow out of the ionization device 10 through the outlet A.

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.

Between the first and second electrodes 1, 2, 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.

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. In the circumferential direction (see Figure 3a) results between 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

Be connected control device. 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

hollow cylindrical, be configured.

Between the second electrode 2 and the sub-electrodes 1a, 1b,... 1h of the first electrode 1, by applying a voltage, a dielectric barrier discharge in a plurality of discharge regions 5a, 5b,... 5h, which in a plane perpendicular to a flow direction R are interrupted by the ionization device 10 circumferentially formed. The skilled person is aware that a clearly defined demarcation of

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.

The embodiment of an ionization device 10 in FIG. 3c is similar to FIG

Embodiment of Figures 3 and 3a.

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. Between the sub-electrodes la, lb, ... lh and the second electrode 2, by applying a voltage, a dielectric barrier discharge can be formed in a plurality of discharge regions 5a, 5b,... 5h. For the delimitation of discharge areas, the above statements apply to the embodiment of Figure 3 and 3a. 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.

In this embodiment, 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).

Due to the rod-shaped configuration of the sub-electrodes la, lb, ... lh, the

Discharge regions 5a, 5b, ... 5h are formed over a greater axial length than in the application of shorter partial electrodes la, lb, ... lh. Preferably, the length of the

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.

In the embodiments of FIGS. 3, 3a and 3c, 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 In other embodiments of ionization devices 10, sub-electrodes may also be disposed axially offset (not the same axial position).

In a further embodiment of an ionization device 10, illustrated in FIG. 3 b, the ionization device 10 comprises a first electrode 1, a second electrode 2 and a dielectric element 3.

Via an inlet E, a discharge gas G and an analyte S in the

Ionisierungsvorrichtung 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. In this embodiment, several

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.

Due to the helical or spiral configuration of the first electrode 1, the first electrode 1 in a plane perpendicular to the flow direction R is not completely circulating or circumferentially interrupted. In FIG. 3b, 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.

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.

Between the first electrode 1 and the second electrode 2, by applying a voltage, a dielectric barrier discharge can be formed in a discharge region 5. 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

helical or helical configuration in a plane perpendicular to

Flow direction R may be interrupted or not completely over an area in the plane bounded by the dielectric member 3, extend.

In a further embodiment of an ionization device 10 of FIGS. 4 and 4 a, 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

Ionisierungsvorrichtung 10, 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.

Between the first electrode 1 and the second electrode 2, 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.

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).

For the position of the first electrode 1 of FIG. 4, 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.

This results in an adaptability of the volume of the discharge region 5, which is traversed by the analyte S to be ionized, so that an adaptability of the ionization conditions to the analyte S is given and the sensitivity of a later analysis can be increased.

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.

Figure 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.

Between 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. To an outlet of the ionization device 10 is an analysis unit 40, for example a mass spectrometer or a

ion mobility spectrometer, connected. In the analyzer, the ionized analyte S is analyzed (qualitatively and / or quantitatively).

Between the end of the first electrode 1 (in the positive x-direction) with the

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.

Depending on the spatial dimensions of the ionization device 10 and the volume flow flowing through it, there is a time in which the ionized analyte S with the (ionized) discharge gas G flows through the distance D2 until it is analyzed. Within this time, chemical and / or physical processes can take place, which can change the ionization state of the analyte S. For different analytes 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. The

Analysis device 100 comprises an ionization device 10 and an analysis unit 40 with a vacuum chamber 41. As 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.

In other embodiments, between which a transition piece or a

Be arranged transition line.

Between the first and second electrodes 1, 2, a dielectric barrier discharge may be formed by applying a voltage between the first and second electrodes 1, 2 in a discharge region 5.

There is a distance D between the first electrode 1 and the second electrode 2.

The pressure in the ionization device 10 is greater than the pressure in the vacuum chamber 41, so that a pressure gradient Δρ results between the ionization device and the vacuum chamber 41. Due to the pressure gradient Δρ, 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

Flow direction R to the outlet A of the ionization device 10 so that the inlet E has a larger cross-sectional area than the outlet A. In other embodiments, 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 ionisierungsvorrichtung 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.

In particular, the distance D2 is less than 50 mm.

As a result, 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.

Another embodiment of an ionization device 10 is shown in FIG. The ionization apparatus 10 includes a first electrode 1, a second electrode 2, and a dielectric member 3 having an outside 3a.

Between the first and second electrodes 1, 2, 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.

There is a distance D between the first electrode 1 and the second electrode 2.

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

Positions of the discharge area 5, wherein Figure 6 shows one of the possible positions.

When a discharge gas G flows into the inlet E3 of the dielectric member 3 and through the discharge region 5, the ionized discharge gas G is further extended

until the ionized discharge gas with the analyte entering the inlet E of the second electrode 2 has flowed into contact and deliver at least a portion of its charges to the analyte S in order to ionize the analyte. By the

Possibility of changing the length of the distance (corresponding to otherwise equal conditions of a change in the time duration), which must put the ionized discharge gas G back to contact with the analyte S to be ionized, results in an improved adaptability of the ionization device 10 to different analytes S, since chemical and / or physical processes may alter the ionized discharge gas G as a function of time.

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. The total flow, discharge gas G and analyte S and optionally a dopant in the

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. Generally, 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. For a thermodynamically (kinetically) controlled ionization, 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.

The various features of the embodiments of the disclosed

Ionization devices can be combined with other embodiments. In particular, each ionization device may be provided with one disclosed herein

In each ionization device, 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.

With each ionization device, 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.

Claims

Claims ...

An ionization device (10) for ionizing an analyte (S), comprising an inlet (E), an outlet (A), a first electrode (1), a second electrode (2) and a dielectric element (3)

(a) the first electrode (1), the second electrode (2) and the dielectric

Element (3) are arranged to each other such that by applying an electrical voltage between the first electrode (1) and the second electrode (2) a dielectric barrier discharge in a

Discharge region (5) in the ionisierungsvorrichtung (10) is bildbar;

(B) the first and second electrodes (1, 2) are arranged relative to each other displaceable or movable.

2. Ionisierungsvorrichtung according to claim 1, wherein the first and / or second electrode (1, 2) is configured at least partially spirally or helically.

3. Ionisierungsvorrichtung according to any one of claims 1 or 2, wherein the second

Electrode (2) is at least partially disposed in the dielectric element (3), and in particular the first electrode (1) outside the

dielectric element (3) is arranged.

4. Ionisierungsvorrichtung according to any one of claims 1 to 3, wherein the first and

second electrode (1, 2) relative to each other in the flow direction (R) or against the flow direction (R) are displaceable.

5. lonisierungsvorrichtung according to any one of claims 1 to 4, wherein the first and / or second electrode (1, 2) comprises or comprise at least one winding.

6. Ionisierungsvorrichtung according to any one of claims 1 to 5, wherein the distance (D), in particular the smallest distance between the first electrode (1) and the second electrode (2) is less than 20 mm, preferably less than 10 mm, more preferably less than 5 mm, and most preferably less than 2 mm.

The ionization device according to any one of claims 1 to 6, wherein the first electrode (1) is slidably disposed relative to the dielectric member (3), and preferably the second electrode (2) is disposed immovably relative to the dielectric member (3).

A method of operating an ionization apparatus (10) according to any one of claims 1 to 7, comprising the steps of:

(a) introducing an analyte (S) into the ionization device (10);

(b) ionizing the analyte (S) in the ionization device (10), in particular by a dielectric barrier discharge in the discharge region (5);

(c) applying the ionized analyte (S) from the ionization device (10) via the outlet (A).

The method of claim 8, wherein the pressure in the ionization device (10) is greater than 40 kPa, preferably greater than 60 kPa, more preferably greater than 80 kPa, and most preferably substantially atmospheric pressure.

10. The method according to any one of claims 8 or 9, wherein between the first

Electrode (1) and the second electrode (2) a voltage of at most 20 kV, preferably at most 10 kV, more preferably at most 5 kV, and most preferably between 1 kV and 3 kV, is applied to produce a dielectric

Barrier discharge.

11. The method according to any one of claims 8 to 10, wherein the dielectric

Barrier discharge is effected by unipolar high voltage pulses, preferably having a pulse duration of at most 1 ε, more preferably of at most 500 ns, and most preferably with a duration between 100 ns and 350 ns.

12. The method of claim 11, wherein the high voltage pulses 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.

13. The method according to any one of claims 8 to 12, wherein the first and second electrodes (1, 2) is supplied with a sine voltage, wherein the sine voltages of an electrode (1, 2) preferably by half a period compared to the other electrode (1, 2) is shifted.

An ionization device (10) for ionizing an analyte (S), comprising an inlet (E), an outlet (A), a first electrode (1), a second electrode (2), a dielectric element (3) and a charge carrier filter (20, 21), where

(a) the first electrode (1), the second electrode (2) and the dielectric

Element (3) are arranged to each other, that by applying a voltage between the first electrode (1) and the second electrode (2) a dielectric barrier discharge in one

Discharge region (5) in the ionisierungsvorrichtung (10) is bildbar;

(b) the analyte (S) via the inlet (E) into the ionization device (10)

is inflowable, the discharge region (5) of the analyte (S) can be flowed through and the analyte (S) via the outlet (A) from the ionisierungsvorrichtung (10) can be flowed out;

(C) the charge carrier filter (20, 21) before the outlet (A) of

Ionisierungsvorrichtung (10) is arranged and configured to filter ions or charged particles based on their charge.

15. Ionization device according to claim 14, wherein a magnetic field can be generated by the charge carrier filter (20, 21) (21) or the charge carrier filter (20, 21) is a grid (20), in particular with an electrical potential.

16. ionization device according to any one of claims 14 or 15, wherein the

Ionisierungsvorrichtung comprises a first portion (10 a) and a second portion (10 b), wherein the first portion (10 a) via the inlet (E) as the first inlet of a discharge gas (G) is flowed through, the second portion (10 b) via a second Inlet (E2) of the analyte (S) is flowed through and the first portion (10a) with the second portion (10b) is flow-through, and wherein the discharge region (5) in the first portion (10a) of

Ionisierungsvorrichtung lies.

17. lonisierungsvorrichtung according to any one of claims 14 to 16, wherein the distance (D), in particular the smallest distance between the first electrode (1) and the second electrode (2) is less than 20 mm, preferably less than 10 mm, more preferably less than 5 mm, and most preferably less than 2 mm.

18. lonisierungsvorrichtung according to any one of claims 14 to 17, wherein the first

Electrode (1) on the outer side (3a) of the dielectric element (3) and is preferably formed as a layer which is applied by a drying or curing liquid or suspension or applied by a transition from a vapor phase to a solid phase.

A method of operating an ionization apparatus (10) according to any one of claims 1 to 5, comprising the steps of: (a) introducing an analyte (S) into the ionization device (10);

20. The method of claim 19, wherein a discharge gas (G) is introduced into the ionization device (10) via the (first) inlet (E), the discharge gas (G) is ionized in the discharge region (5), the analyte (S) introducing the second inlet (E2) and bringing the analyte (S) into contact with the ionized discharge gas (G) in the ionization device (10) so that ionization of the analyte (S) is performed.

21. The method according to any one of claims 19 or 20, wherein the pressure in the

Ionisierungsvorrichtung (10), greater than 40 kPa, preferably greater than 60 kPa, more preferably greater than 80 kPa, and most preferably substantially

atmospheric pressure is.

22. The method according to any one of claims 19 to 21, wherein between the first

Barrier discharge.

23. The method according to any one of claims 19 to 22, wherein the dielectric

Barrier discharge is effected by unipolar high voltage pulses, preferably having a pulse duration of at most 1 5, more preferably of at most 500 ns, and most preferably with a duration between 100 ns and 350 ns.

24. The method of claim 23, wherein the high voltage pulses 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.

25. The method according to any one of claims 19 to 24, wherein the first and second electrodes (1, 2) is supplied with a sine voltage, wherein the sine voltages of an electrode (1, 2) preferably by half a period duration compared to the other electrode (1, 2) is shifted.

(a) the first electrode (1), the second electrode (2) and the dielectric

Discharge region (5) in the ionisierungsvorrichtung (10) is bildbar;

(b) the dielectric member (3) has an outside (3a), and the first electrode (1) and the second electrode (2) are disposed on the outside (3a) of the dielectric member (3).

27. lonisierungsvorrichtung according to claim 26, with a capillary (30) having an inlet (EK), wherein the capillary (30) at least in sections inside the

dielectric element (3) is arranged.

28. lonization device according to any one of claims 26 or 27, wherein the analyte (S) via the inlet (EK) in the capillary (30) can be flowed in and a discharge gas (G) through the inlet (E) of the ionisierungsvorrichtung (10) can be flowed , and the streams of the discharge gas (G) and the analyte (S) in the ionization device (10) are merge.

29. lonization device according to one of claims 26 to 28, wherein the distance (D), in particular the smallest distance between the first electrode (1) and the second electrode (2) is less than 20 mm, preferably less than 10 mm, more preferably less than 5 mm, and most preferably less than 2 mm.

30. ionization device according to any one of claims 26 to 29, wherein the first

Electrode (1) and / or the second electrode (2) on the outside (3) of the

dielectric element (3) and is preferably formed as a layer which is applied by a drying or curing liquid or suspension or applied by a transition from a vapor phase to a solid phase.

A method of operating an ionization apparatus (10) according to any one of claims 13 to 17, comprising the steps of:

(a) introducing an analyte (S) into the ionization device (10); (b) ionizing the analyte (S) in the ionization device (10), in particular by a dielectric barrier discharge in the discharge region (5);

32. The method according to claim 31, wherein a discharge gas (G) is introduced via the inlet (E) into the ionization device (10), the discharge gas (G) in the

Discharge region (5) is ionized, the analyte (S) via a second inlet or the inlet (EK) of a capillary (30) is introduced and the analyte (S) with the ionized discharge gas (G) in the ionisierungsvorrichtung (10) is brought into contact, so that an ionization of the analyte (S) is performed.

33. The method according to any one of claims 31 or 32, wherein the pressure in the

atmospheric pressure is.

34. The method according to any one of claims 31 to 33, wherein between the first

Barrier discharge.

35. The method according to any one of claims 31 to 34, wherein the dielectric

36. The method of claim 35, wherein the high voltage pulses 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.

37. Method according to one of claims 31 to 36, wherein the first and second electrodes (1, 2) are supplied with a sine voltage, wherein the sine voltages of one electrode (1, 2) are preferably half a period longer than the other electrode (1, 2). 2) is shifted.

An ionization device (10) for ionizing an analyte (S), having an inlet (E), an outlet (A), a first electrode (1), a second electrode (2) and a dielectric element (3)

(a) the first electrode (1), the second electrode (2) and the dielectric

Discharge region (5) in the ionisierungsvorrichtung (10) is bildbar;

(b) wherein at least one of the first and second electrodes (1, 2) is not

is formed completely circumferentially or circumferentially interrupted, in particular in a plane perpendicular to a flow direction (R) through the ionisierungsvorrichtung (10).

39. ionization device according to claim 38, wherein the first electrode (1) on an outer side (3a) of the dielectric element (3) is arranged.

40. Ionisierungsvorrichtung according to claim 38 or 39, wherein the first electrode (1) is at least partially formed spirally or helically, and in particular has at least one winding.

41. Ionisierungsvorrichtung according to any one of claims 38 or 39, wherein the first

Electrode (1) at least two partial electrodes (la, lb, ...), which in the plane perpendicular to the flow direction (R) circumferentially spaced ().

42. Ionisierungsvorrichtung according to claim 41, wherein the at least two partial electrodes (la, lb, ...) are arranged distributed circumferentially evenly.

43. Ionisierungsvorrichtung according to any one of claims 41 or 42, wherein the at least two partial electrodes (la, lb, ...) are configured circular or rod-shaped.

44. lonisierungsvorrichtung according to any one of claims 38 to 43, wherein the second

dielectric element (3) is arranged.

45. Ionisierungsvorrichtung according to any one of claims 38 to 44, wherein the first

Electrode (1), the second electrode (2) and the dielectric element (3) are arranged to each other, that by applying an electrical voltage between the first electrode (1) and the second electrode (2) a dielectric barrier discharge in at least two discharge regions (5a, 5b, ...) spaced axially in the flow direction () and / or circumferentially in a plane perpendicular to the flow direction (R) the ionization device (10) is bildbar.

46. Ionisierungsvorrichtung according to any one of claims 38 to 45, wherein the distance (D), in particular the smallest distance between the first electrode (1) and the second electrode (2) is less than 20 mm, preferably less than 10 mm, more preferably less than 5 mm, and most preferably less than 2 mm.

47. lonisierungsvorrichtung according to any one of claims 38 to 46, wherein the first

Electrode (1) or at least one of the sub-electrodes (la, lb, ...) on the outer side (3a) of the dielectric element (3) is applied and is preferably formed as a layer which is applied by a drying or curing liquid or suspension or is applied by a transition from a vapor phase to a solid phase.

48. A method of operating an ionization device (10) according to any one of claims 25 to 34, comprising the steps:

(a) introducing an analyte (S) into the ionization device (10);

(b) ionizing the analyte (S) in the ionization device (10), in particular by a dielectric barrier discharge in the discharge region (5) or the discharge regions (5a, 5b, ...);

49. The method of claim 48, wherein the pressure in the ionization device (10) is greater than 40 kPa, preferably greater than 60 kPa, more preferably greater than 80 kPa, and most preferably substantially atmospheric pressure.

50. The method according to any one of claims 48 or 49, wherein between the first

Barrier discharge.

51. The method according to any one of claims 48 to 50, wherein the dielectric

Barrier discharge is caused by unipolar high voltage pulses, preferably with a pulse duration of at most 1 5, more preferably of at most 500 ns, and most preferably of a duration between 100 ns and 350 ns.

52. The method of claim 51, wherein the high voltage pulses 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.

53. Method according to one of claims 48 to 52, wherein the first and second electrodes (1, 2) are supplied with a sine voltage, wherein the sine voltages of one electrode (1, 2) are preferably half a period longer than the other electrode (1, 2). 2) is shifted.

54. Analysis device (100) for the analysis of an ionized analyte (S), with a

Ionisierungsvorrichtung (10) and an analysis unit (40), wherein

(a) the ionization device (10) comprises an inlet (E), an outlet (A), a first electrode (1), a second electrode (2) and a dielectric element (3), and the first electrode (1) second electrode (2) and the dielectric element (3) are arranged to each other such that by applying an electrical voltage between the first electrode (1) and the second electrode (2) a dielectric barrier discharge in a

Discharge area (5) is bildbar;

(b) the ionization device (10) is connected to the analysis unit (40) in such a way that an analyte (S) ionized in the ionization device (10) from the outlet (A) of the ionization device (10) passes directly into the analysis unit (40) can;

(c) the distance (D2) in the flow direction (R) (x-direction) between the outlet (A) of the ionization device (10) and the first electrode (1) is less than 50 mm or the outlet (A) of the ionization device (10) and the first electrode (1) in the flow direction (R) (x direction) overlap.

55. The analyzer of claim 54, wherein the ionized analyte (S) into a

Vacuum space (41) of the analysis unit (40) can pass, in which the pressure is below the ambient pressure.

56. An analysis device according to any one of claims 54 or 55, wherein between the ionization device (10) and a / the vacuum chamber (41) of the

Analysis unit (40) a pressure gradient (Δρ) prevails.

57. Analysis device according to one of claims 54 to 56, wherein the distance (D2) between the outlet (A) of the ionization device (10) and the first electrode (1) is adjustable.

58. Analysis device according to one of claims 54 to 57, wherein upstream of the outlet (A) in the flow direction (R) (x-direction) a taper of the cross section of the ionization device (10) or a diaphragm arranged, in particular the first electrode (1) the taper or aperture is arranged.

59. The analyzer of any one of claims 54 to 58, wherein the first electrode

(1) is disposed on an outer side (3a) of the dielectric member (3).

60. The analyzer of any one of claims 54 to 59, wherein the second electrode

(2) is arranged at least in sections in the dielectric element (3).

61. Analysis device according to one of claims 54 to 60, wherein the distance (D), in particular the smallest distance, between the first electrode (1) and the second electrode (2) is less than 20 mm, preferably less than 10 mm, more preferably less than 5 mm, and most preferably less than 2 mm.

62. The analyzer according to one of claims 54 to 61, wherein the distance (D2) between the outlet (A) of the ionization device and the first electrode (1), less than 40 mm, preferably less than 30 mm, particularly preferably less than

20 mm, more preferably less than 10 mm, most preferably less than 5 mm.

63. The analyzer of any one of claims 54 to 62, wherein the analyzer unit (40) is a mass spectrometer.

64. An analyzer according to any one of claims 54 to 63, wherein the outlet (A) of the ionization device (10) has a smaller cross-sectional area than the inlet (E) of the ionization device (10).

65. A method of analyzing an analyte (S) with the analyzer of any of claims 54 to 64, comprising the steps of:

(a) introducing an analyte (S) into the ionization device (10);

(b) ionizing the analyte (S), in particular by a dielectric

Barrier discharge in the discharge area (5); (c) applying the ionized analyte (S) from the ionization device (10) to the analysis unit (40) via the outlet (A);

(d) analyzing the analyte (S) in the analysis unit (40).

66. The method of claim 65, wherein the pressure in the ionization apparatus (10) is greater than 40 kPa, preferably greater than 60 kPa, more preferably greater than 80 kPa, and most preferably substantially atmospheric pressure.

67. The method according to any one of claims 65 or 66, wherein between the first

Barrier discharge.

68. The method according to any one of claims 65 to 67, wherein the dielectric

Barrier discharge is effected by unipolar high-voltage pulses, preferably having a pulse duration of at most 1 με, more preferably of at most 500 ns, and most preferably with a duration between 100 ns and 350 ns.

69. The method of claim 68, wherein the high voltage pulses 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.

70. Method according to one of claims 65 to 69, wherein the first and second electrodes (1, 2) are supplied with a sine voltage, wherein the sine voltages of one electrode (1, 2) are preferably half a period longer than the other electrode (1, 2). 2) is shifted.

71. Analysis device (100) for analyzing an ionized analyte (S), with a

Ionisierungsvorrichtung (10) and an analysis unit (40), wherein

Discharge area (5) is bildbar; (b) the ionization device (10) is connected to the analysis unit (40) in such a way that an analyte (S) ionized in the ionization device (10) from the outlet (A) of the ionization device (10) passes directly into the analysis unit (40) can;

(C) the ionization device (10) is designed and so with the

Analysis unit (40) is connected, that a distance between the discharge region (5) and the analysis unit (40) in less than 1 s of the analyte (S) is flowed through.

72. The analysis device according to claim 71, wherein the analysis unit (40) has a

Vacuum space (41) and the ionisierungsvorrichtung (10) is connected to the analysis unit (40) that the analyst (S) can go directly into the vacuum chamber (41) of the analysis unit (40) and, in particular, is connected so that the distance between the discharge region (5) and the vacuum chamber (41) can be traversed by the analyte (S) in less than 1 s.

73. The analyzer according to claim 71 or 72, wherein the distance between the discharge area (5) and the analysis unit (40) or the vacuum space (41) of the analysis unit (40) 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 can be flowed through.

74. An analysis device according to any one of claims 71 to 73, wherein the distance

between the discharge area (5) and the analysis unit (40) or the

Vacuum space (41) of the analysis unit (40) at a flow rate through the ionization device (10) 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, can be flowed through by the analyte (S) in less than the upper limit of time.

75. An analysis device according to any one of claims 71 to 74 having one or more of the features of claims 55 to 64 without their back references.

76. A method of analyzing an analyte (S) with the analyzer of any one of claims 71 to 75, comprising the steps of:

(a) introducing an analyte (S) into the ionization device (10);

(b) ionizing the analyte (S), in particular by a dielectric

(d) analyzing the analyte (S) in the analysis unit (40).

77. The method of claim 76, wherein the pressure in the ionization device (10) is greater than 40 kPa, preferably greater than 60 kPa, more preferably greater than 80 kPa, and most preferably substantially atmospheric pressure.

78. The method according to any one of claims 76 or 77, wherein the dielectric

Barrier discharge is effected by unipolar high voltage pulses, preferably having a pulse duration of at most 1 5, more preferably of at most 500 ns, and most preferably having a duration between 100 ns and 350 ns, in particular the high voltage pulses 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.

79. The method according to any one of claims 76 to 78, wherein between the first

Barrier discharge.

80. The method according to any one of claims 76 to 79, wherein the first and second electrodes (1, 2) is supplied with a sine voltage, wherein the sine voltages of an electrode (1, 2) preferably by half a period compared to the other electrode (1, 2) is shifted.

81. Ionization device (10) for ionizing an analyte (S), having a first inlet (E), a second inlet (E3), an outlet (A), a first electrode (1), a second electrode (2) and a dielectric element (3), wherein

(a) the first electrode (1), the second electrode (2) and the dielectric

Discharge region (5) in the ionisierungsvorrichtung (10) is bildbar;

(B) the first and second electrodes (1, 2) relative to each other displaceable

are arranged.

82. Ionisierungsvorrichtung according to claim 81, wherein the second electrode (2) comprises a curved outward in the r-direction portion (2a).

83. Ionisierungsvorrichtung according to claim 82, wherein the first electrode (1) and / or the dielectric element (3) comprises a curved outward in the r-direction portion (la, 3a), in particular the curved outward in the r-direction portion (2a) of the second electrode (2) and the outwardly curved in the r-direction portion (la, 3a) of the first electrode (1) and / or the dielectric element (3) are configured correspondingly.

84. ionization device according to claim 83, wherein the outward in the r-direction

curved portion (2a) of the second electrode (2) in the outwardly in the r-direction curved portion (la, 3a) of the first electrode (1) and / or the dielectric member (3) is displaceable.

85. An ionization device according to any one of claims 81 to 84, wherein the second

dielectric element (3) is arranged.

86. Ionisierungsvorrichtung according to any one of claims 81 to 85, wherein the first and second electrodes (1, 2) relative to each other in the flow direction (R) or against the flow direction (R) are displaceable.

87. Ionisierungsvorrichtung according to any one of claims 81 to 86, wherein the distance (D), in particular the smallest distance between the first electrode (1) and the second electrode (2) is less than 20 mm, preferably less than 10 mm, more preferably less than 5 mm, and most preferably less than 2 mm.

88. ionization device according to any one of claims 81 to 87, wherein the first

Electrode (1) is arranged immovably relative to the dielectric element (3), and preferably the second electrode (2) is arranged displaceably relative to the dielectric element (3).

89. A method of operating an ionization apparatus (10) according to any one of claims 81 to 88, comprising the steps of:

90. The method of claim 89, wherein the pressure in the ionization device (10) is greater than 40 kPa, preferably greater than 60 kPa, more preferably greater than 80 kPa, and most preferably substantially atmospheric pressure.

91. The method according to any one of claims 89 or 90, wherein between the first

Barrier discharge.

92. The method according to any one of claims 89 to 91, wherein the dielectric

93. The method of claim 92, wherein the high voltage pulses 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.

94. The method according to any one of claims 89 to 93, wherein the first and second electrodes (1, 2) is supplied with a sine voltage, wherein the sine voltages of an electrode (1, 2) preferably by half a period compared to the other electrode (1, 2) is shifted.