WO2004049384A2 - Miniaturized ion mobility spectrometer - Google Patents
Miniaturized ion mobility spectrometer Download PDFInfo
- Publication number
- WO2004049384A2 WO2004049384A2 PCT/EP2003/013128 EP0313128W WO2004049384A2 WO 2004049384 A2 WO2004049384 A2 WO 2004049384A2 EP 0313128 W EP0313128 W EP 0313128W WO 2004049384 A2 WO2004049384 A2 WO 2004049384A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas
- ion mobility
- drift
- mobility spectrometer
- adsorber material
- Prior art date
Links
- 239000000463 material Substances 0.000 claims abstract description 30
- 150000002500 ions Chemical class 0.000 claims description 36
- 238000004140 cleaning Methods 0.000 claims description 17
- 239000004744 fabric Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 abstract description 21
- 238000011144 upstream manufacturing Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 55
- 239000000126 substance Substances 0.000 description 7
- 239000012080 ambient air Substances 0.000 description 6
- 239000002575 chemical warfare agent Substances 0.000 description 6
- 239000012491 analyte Substances 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000003570 air Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011538 cleaning material Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009993 protective function Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
- H01J49/34—Dynamic spectrometers
- H01J49/40—Time-of-flight spectrometers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/622—Ion mobility spectrometry
Definitions
- the invention relates to a miniaturized ion mobility spectrometer with an ionization chamber with gas inlet and gas outlet, an ionization source and with a drift chamber with drift gas inlet, a gas cleaning device being connected upstream of the drift gas inlet.
- Ion mobility spectrometers are used, among other things, to detect traces (typically ng / L to pg / L range (pp ⁇ to ppt v range)) of gases in air or other carrier gases. They are particularly suitable for the detection of chemical warfare agents, explosives or drugs, but they also play a role in an increasing number of other areas of application. Such spectrometers have recently been miniaturized. While ion mobility spectrometers were initially known as table-top devices, portable spectrometers have been used in the last decade, the main components of which are so small that they fit on a palm, for example. This applies in particular to the heart pieces, the miniaturized drift tubes, which are now only a few centimeters long and have an outside diameter of approx. 1 cm.
- miniaturized spectrometers built as independent devices, are suitable, for example, for the detection of chemical warfare agents. They usually have a gas circuit and a sampling system. According operating a drift gas flows towards the carrier gas containing the analyte. This drift gas serves, among other things, to ensure that even if the grid is not ideally closed, at most neutral carrier gas molecules can get into the drift space of the ion mobility spectrometer.
- a basis for the operation of an ion mobility spectrometer is that only in the ionization space of an ion mobility spectrometer with, for example, a 63 Ni beta radiation source in various interaction processes, preferably by means of ion-molecule reactions, but also by means of charge reversal processes, charges of carrier gas Analyte molecules.
- there should be no analyte molecules in the drift space since otherwise these processes can also occur there and the starting point for the drift of the analyte ions is no longer determined solely by the position of the ion lattice, but could in principle start anywhere in the drift space. Such "smearing" of the geometric starting point thus reduces the resolution of the otherwise high-resolution spectrometer.
- the drift gas itself should ideally not have any contamination, in any case as little as possible, so that it is usually conducted in the gas mobility spectrometer in the gas circuit via an external cleaning stage, for example a cartridge filled with a suitable cleaning material, the each is significantly larger than a miniaturized drift tube itself.
- a person concerned with it is therefore usually equipped with a protective clothing as described above and additionally wears a prescribed, preferably miniaturized, ion mobility spectrometer, which is equipped with the necessary and much larger and heavier accessories than the miniaturized drift tube, for example a cleaning gas cartridge for the drift gas.
- the object of the invention is to significantly improve the wearing and usage properties of a miniaturized ion mobility spectrometer for a person wearing protective clothing.
- This object is achieved according to the invention with a miniaturized ion mobility spectrometer of the type described in the introduction in that the gas cleaning device is formed by at least one adsorber material integrated in a garment.
- the drift gas of the miniaturized ion mobility spectrometer is thus passed over the adsorber material embedded in the protective clothing and thus cleaned of any contamination.
- the operating time of the spectrometer is extended by the fact that a larger amount of adsorber material is usually contained in the clothing than in additional cartridges.
- monitoring the reliability of the protective function of the protective clothing also results as a further significant advantage, since a "smearing" of the spectrum, by transition from high-resolution to low-resolution mode, eliminates the often undesired breakthrough of a chemical in the adsorber material of the protective clothing and thus directly signals the reduction in the effectiveness or the failure of the protective clothing for the wearer.
- only the internal gas circuit for the drift gas is routed through the adsorber material of the garment; the spectrometer of any design itself is connected from the outside.
- protective clothing of this type has adsorber materials made of activated carbon or a molecular sieve or other gas cleaning materials in the usual way, it is preferably provided that the adsorber material consists of these materials.
- a change of protective clothing is therefore easy to carry out, because it is only about Hoses or the like.
- a connection of the adsorber material of the protective clothing to the gas circuit of the spectrometer is required.
- the gas outlet is connected to the adsorber material via a bypass. Only the necessary amount of drift gas then enters the cleaning cycle through the adsorber material of the protective clothing, while excess gas is emitted directly into the environment.
- the gas outlet opens into the adsorber material. Since the protective clothing itself is gas-permeable, gas which is returned to the drift space and emerges from the ion mobility spectrometer cannot then be released into the environment through the clothing itself.
- the gas inlet at the end facing away from the ionization space opens into the fabric of the garment outside the adsorber material.
- the gas inlet is therefore no longer in direct contact with the surroundings, the gas to be analyzed is then absorbed from the tissue, but in such a way that the adsorber material is not passed through.
- the ion mobility spec The trometer is then completely integrated into the clothing so that the ambient air first enters the fabric of the clothing and from there into the ion mobility spectrometer.
- Fig. 1 is a schematic diagram of a miniaturized ion mobility spectrometer according to the invention in a first embodiment and in
- FIG. 2 shows a second embodiment of an ion mobility spectrometer.
- An ion mobility spectrometer is usually tubular and initially has a tubular ionization chamber 5, in which an ionization source (not shown) is arranged.
- the ionization chamber 5 is provided with a gas inlet 1, indicated by an arrow, through which gas molecules to be analyzed enter the ionization chamber 5 from the environment.
- the ionization chamber 5 is separated from a drift chamber 6 by an ion grid or ion gate (not shown), at the other end of which a Faraday plate (not shown) is arranged.
- a gas outlet 2 is provided in the edge region of the ionization space 5 adjoining the ion grid.
- An electrical field is applied along the entire tubular ionization space 5 and drift space 6, which is not shown in detail.
- drift rings can be arranged in the usual way, which are also not shown.
- a drift gas inlet 3 is arranged at the end of the drift space 6.
- Gas for example from ambient air, with analytes is led through the gas inlet 1 into the ionization chamber 5 and is released again into the ambient air at the gas outlet 2.
- Part of the gas emerging from the gas outlet 2 is returned via a bypass 2a through a cleaning stage after the cleaning as a drift gas via the drift gas inlet 3 into the ion mobility spectrometer. This creates a cleaning gas circuit for the drift gas via the bypass 2a, the cleaning stage 4 to the drift gas inlet 3 and through the drift chamber 6 again to the bypass 2a.
- the cleaning stage 4 of an adsorber material 8 is formed in a garment 7, which consists for example of activated carbon or is formed by a molecular sieve.
- a garment 7 which consists for example of activated carbon or is formed by a molecular sieve.
- Such garments are known, for example, as military protective clothing and are used to provide protection against dangerous substances, for example poisons or chemical warfare agents.
- Ambient air can get into the fabric of the garment 7 and through the adsorber material 8 to the skin of the wearer, but is more or less cleaned as it passes through the adsorber material 8, depending on the degree of saturation of the adsorber material 8.
- air can pass through the clothing at 9 are returned to the environment.
- the drift gas cleaning circuit of the ion mobility spectrometer can thus be seen integrated in the protective clothing, so that additional cleaning cartridges or the like, which have to be carried by the wearer and have a not inconsiderable weight, can be completely dispensed with.
- the ion mobility spectrometer itself can be connected via the bypass 2a and the drift gas inlet 3 in a suitable manner to the adsorber material 8 of the garment, in the simplest way, for example by means of hoses.
- the ion mobility spectrometer according to the invention has the considerable further advantage that the cleaning effectiveness of his protective clothing is automatically displayed to the user, because if the adsorber material is too heavily loaded with foreign substances, the drift gas is no longer properly cleaned , which is immediately visible to a visible "smearing" of the spectrum, by switching from high-resolution to low-resolution mode, so that the wearer of the clothing is directly signaled the reduction in the effect of his protective clothing and can take appropriate measures.
- FIG. 2 shows a second embodiment in which, if the same parts are affected, the same reference numerals as in FIG. 1 are used.
- this variant in this variant there is no gas outlet 2 which opens into the surroundings. Rather, the now designated 2a gas outlet opens directly into the adsorber material 8 of the garment 7 or its fabric and part of the gas emerging from the ionization chamber 5 can be released to the environment via the garment 7 at 9, while a part is cleaned and cleaned by the Drift gas inlet 3 flows through.
- the gas inlet 1 is not connected directly to the environment, but rather to the fabric of the garment 7, so that the gas is absorbed via the fabric with analytes, but so that the adsorber material 8 is not is going through.
- the inlet point for the analyte is at 10 and the outlet at 9.
- the ion mobility spectrometer is thus integrated into the garment 7, so that ambient air penetrates into the ion mobility spectrometer at the point 10 and, without passing through the adsorber material 8, reaches the gas inlet 1, which now has no direct contact with the Ambient air has more.
- the gas exchange can thus be implemented at different points on the garment 7, provided that there is no gas conduction via the adsorber material 8.
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to a miniaturized ion mobility spectrometer comprising an ionization chamber with a gas inlet and gas outlet, and comprising an ionization source and a drift chamber with a drift gas inlet, and a gas purification device is connected upstream from said drift gas inlet. The aim of the invention is to significantly improve the wearability and usability for an individual wearing a protective garment. To this end, the invention provides that the gas purification device is formed from at least one adsorber material (8) integrated inside a garment (7).
Description
"Miniaturisiertes Ionenbeweglichkeitsspektrometer""Miniaturized ion mobility spectrometer"
Die Erfindung betrifft ein miniaturisiertes Ionenbeweg- lichkeitsspektrometer mit einem Ionisationsraum mit Gaseinlass und Gasauslass, einer Ionisationsquelle und mit einem Driftraum mit Driftgaseinlass, wobei dem Driftgas- einlass eine Gasreinigungseinrichtung vorgeschaltet ist.The invention relates to a miniaturized ion mobility spectrometer with an ionization chamber with gas inlet and gas outlet, an ionization source and with a drift chamber with drift gas inlet, a gas cleaning device being connected upstream of the drift gas inlet.
Ionenbeweglichkeitsspektrometer dienen unter anderem zur Detektion von Spuren (typischerweise ng/L bis pg/L-Be- reich (ppπ bis pptv-Bereich) ) von Gasen in Luft oder anderen Trägergasen. Sie sind insbesondere zur Detektion chemischer Kampfstoffe, von Sprengstoffen oder Drogen geeignet, spielen aber auch in immer mehr anderen Anwendungsgebieten eine Rolle. In letzter Zeit sind solche Spektrometer miniaturisiert worden. Waren lonenbeweglich- keitsspektrometer zunächst als Auftischgeräte bekannt, kamen im letzten Jahrzehnt tragbare Spektrometer zum Einsatz, deren Hauptkomponenten so klein sind, dass sie zum Beispiel auf einen Handteller passen. Dies trifft insbesondere auf die Herzstücke, die miniaturisierten Driftröhren, zu, die inzwischen nur wenige Zentimeter lang sind und Außendurchmesser von ca. 1 cm haben.Ion mobility spectrometers are used, among other things, to detect traces (typically ng / L to pg / L range (ppπ to ppt v range)) of gases in air or other carrier gases. They are particularly suitable for the detection of chemical warfare agents, explosives or drugs, but they also play a role in an increasing number of other areas of application. Such spectrometers have recently been miniaturized. While ion mobility spectrometers were initially known as table-top devices, portable spectrometers have been used in the last decade, the main components of which are so small that they fit on a palm, for example. This applies in particular to the heart pieces, the miniaturized drift tubes, which are now only a few centimeters long and have an outside diameter of approx. 1 cm.
Diese miniaturisierten, als selbständiges Gerät gebauten Spektrometer sind beispielsweise zur Detektion chemischer Kampfstoffe geeignet. Sie weisen in der Regel einen Gaskreislauf auf und ein Probenentnahmesystem. Betriebsgemäß
strömt dem den Analyten enthaltenden Trägergas ein Driftgas entgegen. Diese Driftgas dient unter anderem dazu, zu sichern, dass selbst bei nicht ideal geschlossenem Gitter höchstens neutrale Trägergasmoleküle in den Driftraum des Ionenbeweglichkeitspektrometers gelangen können. Eine Grundlage des Betriebes eines Ionenbeweglichkeitsspektro- meters ist es, dass nur im Ionisationsraum eines Ionenbeweglichkeitsspektrometers mit beispielsweise einer 63Ni- Beta-Strahlungsquelle bei verschiedenen Wechselwirkungs- prozessen, vorzugsweise durch Ionen-Molekül-Reaktionen, aber auch durch Umladungsprozesse, Ladungen von Trägergas- zu Analytmolekülen, übergehen. Insbesondere sollen sich im Driftraum keine Analytmoleküle aufhalten, da sonst auch dort diese Prozesse auftreten können und somit der Startpunkt für die Drift der Analytionen nicht mehr durch die Lage des Ionengitters allein bestimmt wird, sondern sie prinzipiell überall im Driftraum starten könnten. Solche "Verschmierungen" des geometrischen Startpunktes verringern damit die Auflösung der sonst hochauflösenden Spektrometer. Es versteht sich von selbst, dass das Driftgas selbst im Idealfall keine, in jedem Fall möglichst geringe Kontamination aufweisen soll, so dass es in den Ionenbeweglichkeitsspektrometern in der Regel im Gaskreislauf über eine externe Reinigungsstufe geführt wird, beispielsweise eine mit einem geeigneten Reinigungsmaterial gefüllte Patrone, die je-
doch deutlich größer ist als eine miniaturisierte Driftröhre selbst .These miniaturized spectrometers, built as independent devices, are suitable, for example, for the detection of chemical warfare agents. They usually have a gas circuit and a sampling system. According operating a drift gas flows towards the carrier gas containing the analyte. This drift gas serves, among other things, to ensure that even if the grid is not ideally closed, at most neutral carrier gas molecules can get into the drift space of the ion mobility spectrometer. A basis for the operation of an ion mobility spectrometer is that only in the ionization space of an ion mobility spectrometer with, for example, a 63 Ni beta radiation source in various interaction processes, preferably by means of ion-molecule reactions, but also by means of charge reversal processes, charges of carrier gas Analyte molecules. In particular, there should be no analyte molecules in the drift space, since otherwise these processes can also occur there and the starting point for the drift of the analyte ions is no longer determined solely by the position of the ion lattice, but could in principle start anywhere in the drift space. Such "smearing" of the geometric starting point thus reduces the resolution of the otherwise high-resolution spectrometer. It goes without saying that the drift gas itself should ideally not have any contamination, in any case as little as possible, so that it is usually conducted in the gas mobility spectrometer in the gas circuit via an external cleaning stage, for example a cartridge filled with a suitable cleaning material, the each is significantly larger than a miniaturized drift tube itself.
Insbesondere bei der Detektion chemischer Kampfstoffe oder vergleichbarer Stoffe, aber auch sonstiger giftiger oder krebserzeugender Stoffe, beispielsweise solche, die bei Bränden entstehen können, ist es üblich, dass die damit befassten Personen Schutzkleidung tragen. Solche Schutzkleidung für Menschen gegenüber Einflüssen von Chemikalien oder dergl. soll dabei häufig ein Eindringen über die Kleidung in Körpernähe, insbesondere in oder auf die Haut, ausschließen. Dabei sind zwangsläufig Kompromisse einzugehen, weil ein hermetischer Abschluss auch die Atmung über die Haut unterbinden würde. So sollen beispielsweise bei modernen militärischen Uniformen eingedrungene Chemikalien, insbesondere chemische Kampfstoffe, beispielsweise über Adsorbermaterial in einer Textilschicht oder zwischen einzelnen Schichten gebunden werden. Die Wirksamkeit der Schutzfunktion einer solchen Schutzkleidung läßt sich jedoch für den Träger nicht überprüfen, d.h., wenn die Schutzkleidung nach einer gewissen Zeit kontaminiert ist, tritt dieses Ereignis (Durchbruch durch Schutzkleidung) weitgehend ohne Vorwarnung ein.In particular when detecting chemical warfare agents or comparable substances, but also other toxic or carcinogenic substances, for example those that can arise during fires, it is common for the persons concerned to wear protective clothing. Such protective clothing for people against the effects of chemicals or the like is often intended to prevent penetration through clothing close to the body, in particular into or onto the skin. Compromises are inevitable, because a hermetic seal would also prevent breathing through the skin. For example, chemicals that have penetrated into modern military uniforms, in particular chemical warfare agents, are to be bound, for example, via adsorber material in a textile layer or between individual layers. However, the effectiveness of the protective function of such protective clothing cannot be checked for the wearer, i.e. if the protective clothing is contaminated after a certain time, this event (breakthrough through protective clothing) occurs largely without warning.
Während der Detektion chemischer Kampfstoffe oder dergl .
ist eine damit befasste Person somit üblicherweise mit einer vorbeschriebenen Schutzkleidung ausgerüstet und trägt zusätzlich ein vorbeschriebenes, vorzugsweise miniaturisiertes Ionenbeweglichkeitsspektrometer, das mit dem notwendigen und gegenüber der miniaturisierten Drift- röhre wesentlich größeren und schwereren Zubehör, beispielsweise einer Reinigungsgaspatrone für das Driftgas ausgerüstet ist.During the detection of chemical warfare agents or the like. a person concerned with it is therefore usually equipped with a protective clothing as described above and additionally wears a prescribed, preferably miniaturized, ion mobility spectrometer, which is equipped with the necessary and much larger and heavier accessories than the miniaturized drift tube, for example a cleaning gas cartridge for the drift gas.
Aufgabe der Erfindung ist es, die Trage- und Gebrauchseigenschaften eines miniaturisierten Ionenbeweglichkeits- spektrometers für eine eine Schutzkleidung tragende Person wesentlich zu verbessern.The object of the invention is to significantly improve the wearing and usage properties of a miniaturized ion mobility spectrometer for a person wearing protective clothing.
Diese Aufgabe wird mit einem miniaturisierten Ionenbeweg- lichkeitsspektrometer der eingangs bezeichneten Art erfindungsgemäß dadurch gelöst, dass die Gasreinigungseinrichtung von wenigstens einem in ein Kleidungsstück integrierten Adsorbermaterial gebildet ist.This object is achieved according to the invention with a miniaturized ion mobility spectrometer of the type described in the introduction in that the gas cleaning device is formed by at least one adsorber material integrated in a garment.
Erfindungsgemäß wird somit das Driftgas des miniaturisierten Ionenbeweglichkeitsspektrometers über das in die Schutzbekleidung eingebettete Adsorbermaterial geführt und so von evtl. Kontaminationen gereinigt. Damit müssen keine zusätzlichen Reinigungspatronen für das Driftgas des Ionenbeweglichkeitsspektrometers mitgeführt werden,
die einen wesentlichen Gewichtsanteil, beispielsweise bei tragbaren Spektrometern, ausmachen, der damit vollständig entfällt. Außerdem verlängert sich die Funktionsdauer des Spektrometers dadurch, dass in der Kleidung in der Regel eine größere Menge Adsorbermaterial untergebracht ist als in zusätzlichen Patronen. Neben dieser Verbesserung der Trageeigenschaften ergibt sich als wesentlicher weiterer Vorteil auch eine Überwachung der Zuverlässigkeit der Schutzfunktion der Schutzkleidung, denn durch eine "Ver- schmierung" des Spektrums, durch Übergang vom hochauflösenden in den niedrigauflösenden Modus, wird der häufig unerwünschte Durchbruch einer Chemikalie im Adsorbermaterial der Schutzkleidung angezeigt und damit die Verringerung der Wirkung oder der Ausfall der Schutzkleidung für den Träger direkt signalisiert. Erfindungsgemäß ist nur der interne Gaskreislauf für das Driftgas über das Adsorbermaterial des Kleidungsstückes geführt, das Spektrometer beliebiger Bauart selbst ist von außen angeschlossen.According to the invention, the drift gas of the miniaturized ion mobility spectrometer is thus passed over the adsorber material embedded in the protective clothing and thus cleaned of any contamination. This means that no additional cleaning cartridges for the drift gas of the ion mobility spectrometer need to be carried, which make up a significant proportion of the weight, for example in portable spectrometers, which is therefore completely eliminated. In addition, the operating time of the spectrometer is extended by the fact that a larger amount of adsorber material is usually contained in the clothing than in additional cartridges. In addition to this improvement in the wearing properties, monitoring the reliability of the protective function of the protective clothing also results as a further significant advantage, since a "smearing" of the spectrum, by transition from high-resolution to low-resolution mode, eliminates the often undesired breakthrough of a chemical in the adsorber material of the protective clothing and thus directly signals the reduction in the effectiveness or the failure of the protective clothing for the wearer. According to the invention, only the internal gas circuit for the drift gas is routed through the adsorber material of the garment; the spectrometer of any design itself is connected from the outside.
Da derartige Schutzkleidung in üblicher Weise Adsorber- materialien aus Aktivkohle oder eines Molekularsiebes oder anderer Gasreinigungsmaterialien aufweisen, ist bevorzugt vorgesehen, dass das Adsorbermaterial aus diesen Materialien besteht. Eine Änderung der Schutzkleidung ist somit leicht durchzuführen, denn es ist lediglich über
Schläuche oder dergl. ein Anschluss des Adsorbermate- riales der Schutzkleidung an den Gaskreislauf des Spek- trometers erforderlich.Since protective clothing of this type has adsorber materials made of activated carbon or a molecular sieve or other gas cleaning materials in the usual way, it is preferably provided that the adsorber material consists of these materials. A change of protective clothing is therefore easy to carry out, because it is only about Hoses or the like. A connection of the adsorber material of the protective clothing to the gas circuit of the spectrometer is required.
Nach einer ersten bevorzugten Ausgestaltung ist vorgesehen, dass der Gasauslass über einen Bypass mit dem Adsorbermaterial verbunden ist. In den Reinigungskreislauf durch das Adsorbermaterial der Schutzkleidung tritt dann nur die notwendige Driftgasmenge, während überschüssiges Gas direkt in die Umgebung abgegeben wird.According to a first preferred embodiment it is provided that the gas outlet is connected to the adsorber material via a bypass. Only the necessary amount of drift gas then enters the cleaning cycle through the adsorber material of the protective clothing, while excess gas is emitted directly into the environment.
Alternativ kann auch vorgesehen sein, dass der Gasauslass in das Adsorbermaterial mündet . Da die Schutzkleidung selbst gasdurchlässig ist, kann dann nicht als Driftgas in den Driftraum rückgeführtes Gas, das aus dem Ionenbeweglichkeitsspektromter austritt, auch durch die Kleidung selbst in die Umgebung abgegeben werden.Alternatively, it can also be provided that the gas outlet opens into the adsorber material. Since the protective clothing itself is gas-permeable, gas which is returned to the drift space and emerges from the ion mobility spectrometer cannot then be released into the environment through the clothing itself.
Bei dieser Ausführungsform ist in weiterer bevorzugter Ausgestaltung vorteilhaft vorgesehen, dass der Gaseinlass am dem Ionisationsraum abgewandten Ende in das Gewebe des Kleidungsstückes außerhalb des Adsorbermateriales mündet. Der Gaseinlass steht somit nicht mehr direkt mit der Umgebung in Kontakt, das zu analysierende Gas wird dann aus dem Gewebe aufgenommen, jedoch so, dass das Adsorbermaterial nicht durchlaufen wird. Das Ionenbeweglichkeitsspek-
trometer ist dann vollständig in die Kleidung integriert, so dass die Umgebungsluft zunächst in das Gewebe der Kleidung eintritt und von dort in das Ionenbeweglich- keitsspektrometer.In this embodiment, it is advantageously provided in a further preferred embodiment that the gas inlet at the end facing away from the ionization space opens into the fabric of the garment outside the adsorber material. The gas inlet is therefore no longer in direct contact with the surroundings, the gas to be analyzed is then absorbed from the tissue, but in such a way that the adsorber material is not passed through. The ion mobility spec The trometer is then completely integrated into the clothing so that the ambient air first enters the fabric of the clothing and from there into the ion mobility spectrometer.
Die Erfindung ist nachstehend anhand der Zeichnung beispielhaft näher erläutert. Diese zeigt in:The invention is explained in more detail below with reference to the drawing. This shows in:
Fig. 1 ein Prinzipschema eines erfindungsgemäßen miniaturisierten Ionenbeweglichkeitsspektrometers in einer ersten Ausgestaltung und inFig. 1 is a schematic diagram of a miniaturized ion mobility spectrometer according to the invention in a first embodiment and in
Fig. 2 eine zweite Ausgestaltung eines Ionenbeweglich- keitsspektrometers .2 shows a second embodiment of an ion mobility spectrometer.
Ein Ionenbeweglichkeitsspektrometer ist üblicherweise röhrenförmig ausgebildet und weist zunächst einen röhrenförmigen Ionisationsraum 5 auf, in welchem eine nicht dargestellte Ionisationsquelle angeordnet ist. Der Ionisationsraum 5 ist mit einem durch einen Pfeil angedeuteten Gaseinlass 1 versehen, durch den zu analysierende Gasmoleküle aus der Umgebung in den Ionisationsraum 5 eintreten. Der Ionisationsraum 5 ist durch ein nicht dargestelltes Ionengitter oder Ionentor von einem Driftraum 6 abgetrennt, an dessen anderem Ende eine nicht dargestellte Faraday-Platte angeordnet ist.
Im an das Ionengitter angrenzenden Randbereich des Ionisationsraumes 5 ist ein Gasauslass 2 vorgesehen. Entlang des gesamten röhrenförmigen Ionisationsräumes 5 sowie Driftraumes 6 ist ein elektrisches Feld angelegt, das nicht näher dargestellt ist.An ion mobility spectrometer is usually tubular and initially has a tubular ionization chamber 5, in which an ionization source (not shown) is arranged. The ionization chamber 5 is provided with a gas inlet 1, indicated by an arrow, through which gas molecules to be analyzed enter the ionization chamber 5 from the environment. The ionization chamber 5 is separated from a drift chamber 6 by an ion grid or ion gate (not shown), at the other end of which a Faraday plate (not shown) is arranged. A gas outlet 2 is provided in the edge region of the ionization space 5 adjoining the ion grid. An electrical field is applied along the entire tubular ionization space 5 and drift space 6, which is not shown in detail.
Im Randbereich sowohl des Ionisationsraumes 5 als auch des Driftraumes 6 können in üblicher Weise beabstandet voneinander Driftringe angeordnet sein, die ebenfalls nicht dargestellt sind. Am Ende des Driftraumes 6 ist ein Driftgaseinlass 3 angeordnet.In the edge area of both the ionization space 5 and the drift space 6, drift rings can be arranged in the usual way, which are also not shown. A drift gas inlet 3 is arranged at the end of the drift space 6.
Gas, beispielsweise aus Umgebungsluft, mit Analyten, wird durch den Gaseinlass 1 in den Ionisationsraum 5 geführt und am Gasauslass 2 wieder in die Umgebungsluft abgegeben. Ein Teil des aus dem Gasauslass 2 austretenden Gases wird über einen Bypass 2a über eine Reinigungsstufe nach der Reinigung als Driftgas über den Driftgaseinlass 3 in das Ionenbeweglichkeitsspektrometer zurückgeführt. So entsteht für das Driftgas ein Reinigungsgaskreislauf über den Bypass 2a, die Reinigungsstufe 4 zum Driftgaseinlass 3 und durch den Driftraum 6 hindurch wiederum zum Bypass 2a.Gas, for example from ambient air, with analytes is led through the gas inlet 1 into the ionization chamber 5 and is released again into the ambient air at the gas outlet 2. Part of the gas emerging from the gas outlet 2 is returned via a bypass 2a through a cleaning stage after the cleaning as a drift gas via the drift gas inlet 3 into the ion mobility spectrometer. This creates a cleaning gas circuit for the drift gas via the bypass 2a, the cleaning stage 4 to the drift gas inlet 3 and through the drift chamber 6 again to the bypass 2a.
Wesentlich für das erfindungsgemäße Ionenbeweglichkeits- spektrometer ist nun, dass die Reinigungsstufe 4 von
einem in ein Kleidungsstück 7 integrierten Adsorbermaterial 8 gebildet ist, welches beispielsweise aus Aktivkohle besteht oder von einem Molekularsieb gebildet ist. Solche Kleidungsstücke sind beispielsweise als militärische Schutzkleidung bekannt, sie werden verwendet, um Schutz vor gefährlichen Substanzen, beispielsweise Giften oder chemischen Kampfstoffen, zu bieten. Dabei kann Umgebungsluft in das Gewebe des Kleidungsstückes 7 und durch das Adsorbermaterial 8 hindurch an die Haut des Trägers gelangen, wird dabei aber beim Durchtritt durch das Adsorbermaterial 8 mehr oder weniger gereinigt, je nach Sättigungsgrad des Adsorbermateriales 8. Umgekehrt kann Luft durch die Kleidung hindurch bei 9 wieder an die Umgebung abgegeben werden.It is essential for the ion mobility spectrometer according to the invention that the cleaning stage 4 of an adsorber material 8 is formed in a garment 7, which consists for example of activated carbon or is formed by a molecular sieve. Such garments are known, for example, as military protective clothing and are used to provide protection against dangerous substances, for example poisons or chemical warfare agents. Ambient air can get into the fabric of the garment 7 and through the adsorber material 8 to the skin of the wearer, but is more or less cleaned as it passes through the adsorber material 8, depending on the degree of saturation of the adsorber material 8. Conversely, air can pass through the clothing at 9 are returned to the environment.
Erkennbar ist somit der Driftgasreinigungskreislauf des Ionenbeweglichkeitsspektrometers in die Schutzkleidung integriert, so dass zusätzliche Reinigungspatronen oder dergl., die vom Träger mitgeführt werden müssen und ein nicht unerhebliches Gewicht aufweisen, völlig entfallen können. Das Ionenbeweglichkeitsspektrometer selbst ist über den Bypass 2a und den Driftgaseinlass 3 in geeigneter Weise mit dem Adsorbermaterial 8 des Kleidungsstückes zu verbinden, auf einfachste Weise beispielweise mittels Schläuchen.
Neben der Einsparung einer zusätzlichen Reinigungspatrone für das Ionenbeweglichkeitsspektrometer weist das erfindungsgemäße Ionehbeweglichkeitsspektrometer den erheblichen weiteren Vorteil auf, dass dem Benutzer automatisch auch die Reinigungswirksamkeit seiner Schutzkleidung angezeigt wird, denn wenn das Adsorbermaterial zu stark mit Fremdstoffen beladen ist, erfolgt auch keine einwandfreie Reinigung des Driftgases mehr, was unmittelbar zu einer sichtbaren "Verschmierung" des Spektrums, durch Übergang vom hochauflösenden in den niedrigauflösenden Modus sichtbar wird, so dass dem Träger der Kleidung direkt die Verringerung der Wirkung seiner Schutzkleidung signalisiert wird und er entsprechende Maßnahmen treffen kann.The drift gas cleaning circuit of the ion mobility spectrometer can thus be seen integrated in the protective clothing, so that additional cleaning cartridges or the like, which have to be carried by the wearer and have a not inconsiderable weight, can be completely dispensed with. The ion mobility spectrometer itself can be connected via the bypass 2a and the drift gas inlet 3 in a suitable manner to the adsorber material 8 of the garment, in the simplest way, for example by means of hoses. In addition to saving an additional cleaning cartridge for the ion mobility spectrometer, the ion mobility spectrometer according to the invention has the considerable further advantage that the cleaning effectiveness of his protective clothing is automatically displayed to the user, because if the adsorber material is too heavily loaded with foreign substances, the drift gas is no longer properly cleaned , which is immediately visible to a visible "smearing" of the spectrum, by switching from high-resolution to low-resolution mode, so that the wearer of the clothing is directly signaled the reduction in the effect of his protective clothing and can take appropriate measures.
Figur 2 zeigt eine zweite Ausfuhrungsform, in der, sofern gleiche Teile betroffen sind, dieselben Bezugszeichen wie in Figur 1 verwandt sind. Im Unterschied zur Ausführungs- form nach Figur 1 entfällt bei dieser Variante ein Gasauslass 2, der in die Umgebung mündet. Vielmehr mündet der nunmehr mit 2a bezeichnete Gasauslass direkt in das Adsorbermaterial 8 des Kleidungsstückes 7 bzw. dessen Gewebes und ein Teil des aus dem Ionisationsraum 5 austretenden Gases kann über das Kleidungsstück 7 bei 9 an die Umgebung abgegeben werden, während ein Teil gereinigt und durch den Driftgaseinlass 3 hindurchströmt.
Ferner ist beim Ausführungsbeispiel nach Figur 2 vorgesehen, dass der Gaseinlass 1 nicht direkt mit der Umgebung verbunden ist, sondern mit dem Gewebe des Kleidungsstückes 7, so dass das Gas mit Analyten über das Gewebe aufgenommen wird, jedoch so, dass das Adsorbermaterial 8 dabei nicht durchlaufen wird. Damit ist für diese Ausführungsform bei 10 die Einlassstelle für den Analyten und bei 9 der Auslass .FIG. 2 shows a second embodiment in which, if the same parts are affected, the same reference numerals as in FIG. 1 are used. In contrast to the embodiment according to FIG. 1, in this variant there is no gas outlet 2 which opens into the surroundings. Rather, the now designated 2a gas outlet opens directly into the adsorber material 8 of the garment 7 or its fabric and part of the gas emerging from the ionization chamber 5 can be released to the environment via the garment 7 at 9, while a part is cleaned and cleaned by the Drift gas inlet 3 flows through. Furthermore, in the exemplary embodiment according to FIG. 2, it is provided that the gas inlet 1 is not connected directly to the environment, but rather to the fabric of the garment 7, so that the gas is absorbed via the fabric with analytes, but so that the adsorber material 8 is not is going through. For this embodiment, the inlet point for the analyte is at 10 and the outlet at 9.
Bei dieser Ausfuhrungsform ist somit das Ionenbeweglich- keitsspektrometer in das Kleidungsstück 7 integriert, so dass im Gewebe an der Stelle 10 Umgebungsluft in das Ionenbeweglichkeitsspektrometer eindringt und, ohne das Adsorbermaterial 8 zu durchlaufen, in den Gaseinlass 1 gelangt, der nun keinen direkten Kontakt mit der Umgebungsluft mehr hat. Damit kann der Gasaustausch an verschiedenen Stellen des Kleidungsstückes 7 realisiert werden, vorausgesetzt, es erfolgt keine Gasleitung über das Adsorbermaterial 8.
In this embodiment, the ion mobility spectrometer is thus integrated into the garment 7, so that ambient air penetrates into the ion mobility spectrometer at the point 10 and, without passing through the adsorber material 8, reaches the gas inlet 1, which now has no direct contact with the Ambient air has more. The gas exchange can thus be implemented at different points on the garment 7, provided that there is no gas conduction via the adsorber material 8.
Claims
1. Miniaturisiertes Ionenbeweglichkeitsspektrometer mit einem Ionisationsraum mit Gaseinlass und Gasauslass, einer Ionisationsquelle und mit einem Driftraum mit Driftgaseinlass, wobei dem Driftgaseinlass eine Gasreinigungseinrichtung vorgeschaltet ist, dadurch gekennzeichnet, dass die Gasreinigungseinrichtung von wenigstens einem in ein Kleidungsstück (7) integrierten Adsorbermaterial (8) gebildet ist.1. Miniaturized ion mobility spectrometer with an ionization chamber with gas inlet and gas outlet, an ionization source and with a drift chamber with drift gas inlet, the drift gas inlet being preceded by a gas cleaning device, characterized in that the gas cleaning device is formed by at least one adsorber material (8) integrated in a piece of clothing (7) is.
2. Ionenbeweglichkeitsspektrometer nach Anspruch 1, dadurch gekennzeichnet, dass das Adsorbermaterial (8) aus Aktivkohle besteht oder aus Molekularsieb gebildet ist.2. Ion mobility spectrometer according to claim 1, characterized in that the adsorber material (8) consists of activated carbon or is formed from molecular sieve.
3. Ionenbeweglichkeitsspektrometer nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Gasauslass über einen Bypass (2a) mit dem Adsorbermaterial (8) verbunden ist.3. Ion mobility spectrometer according to claim 1 or 2, characterized in that the gas outlet is connected to the adsorber material (8) via a bypass (2a).
4. Ionenbeweglichkeitsspektrometer nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Gasauslass (2a) in das Adsorbermaterial (8) mündet . Ionenbeweglichkeitsspektrometer nach Anspruch 4, dadurch gekennzeichnet, dass der Gaseinlass (1) am dem Ionisationsraum abgewandten Ende in das Gewebe des Kleidungsstückes (7) außerhalb des Adsorber ateriales (8) mündet. 4. ion mobility spectrometer according to claim 1 or 2, characterized in that the gas outlet (2a) opens into the adsorber material (8). Ion mobility spectrometer according to claim 4, characterized in that the gas inlet (1) opens at the end facing away from the ionization space into the fabric of the garment (7) outside the adsorber ateriales (8).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003302180A AU2003302180A1 (en) | 2002-11-26 | 2003-11-22 | Miniaturized ion mobility spectrometer |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10254960A DE10254960A1 (en) | 2002-11-26 | 2002-11-26 | Miniaturized ion mobility spectrometer |
DE10254960.5 | 2002-11-26 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2004049384A2 true WO2004049384A2 (en) | 2004-06-10 |
WO2004049384A3 WO2004049384A3 (en) | 2005-09-09 |
Family
ID=32308696
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2003/013128 WO2004049384A2 (en) | 2002-11-26 | 2003-11-22 | Miniaturized ion mobility spectrometer |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU2003302180A1 (en) |
DE (1) | DE10254960A1 (en) |
WO (1) | WO2004049384A2 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005004325A1 (en) | 2005-01-31 | 2006-08-10 | Bruker Daltonik Gmbh | Ion mobility spectrometer and method of its operation |
DE102007052802B4 (en) | 2007-11-06 | 2012-06-14 | Bruker Daltonik Gmbh | Ion mobility spectrometer and method of its operation |
DE102007052801B4 (en) | 2007-11-06 | 2010-10-07 | Bruker Daltonik Gmbh | Ion mobility spectrometer with substance collector |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5465607A (en) * | 1989-06-09 | 1995-11-14 | Research Corporation Technologies, Inc. | Explosive detection screening system |
US5952652A (en) * | 1995-05-23 | 1999-09-14 | Graseby Dynamics Limited | Ion mobility spectrometers |
US6162281A (en) * | 1998-12-23 | 2000-12-19 | Drager Sicherheitstechnik Gmbh | Device and process for displaying the exhaustion of a gas filter |
JP2001307268A (en) * | 2000-04-18 | 2001-11-02 | Yokohama Rubber Co Ltd:The | System for measuring physical quantities in surrounding atmosphere |
US6349201B1 (en) * | 1998-02-25 | 2002-02-19 | Sean Ford | Bullet-proof vest with distress signaling system |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2052750B (en) * | 1979-06-21 | 1983-03-16 | Pye Ltd | Trace material detector |
DE19543159A1 (en) * | 1995-11-18 | 1997-05-22 | Spectrospin Ag | Ion mobility spectrometer (IMS) |
DE19913220C2 (en) * | 1999-03-24 | 2001-07-05 | Gsf Forschungszentrum Umwelt | Process for the detection of trace substances and / or environmental properties |
JP3689649B2 (en) * | 2000-10-24 | 2005-08-31 | ユニテックディフェンス株式会社 | Protective components, protective clothing, and protective articles |
-
2002
- 2002-11-26 DE DE10254960A patent/DE10254960A1/en not_active Withdrawn
-
2003
- 2003-11-22 WO PCT/EP2003/013128 patent/WO2004049384A2/en not_active Application Discontinuation
- 2003-11-22 AU AU2003302180A patent/AU2003302180A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5465607A (en) * | 1989-06-09 | 1995-11-14 | Research Corporation Technologies, Inc. | Explosive detection screening system |
US5952652A (en) * | 1995-05-23 | 1999-09-14 | Graseby Dynamics Limited | Ion mobility spectrometers |
US6349201B1 (en) * | 1998-02-25 | 2002-02-19 | Sean Ford | Bullet-proof vest with distress signaling system |
US6162281A (en) * | 1998-12-23 | 2000-12-19 | Drager Sicherheitstechnik Gmbh | Device and process for displaying the exhaustion of a gas filter |
JP2001307268A (en) * | 2000-04-18 | 2001-11-02 | Yokohama Rubber Co Ltd:The | System for measuring physical quantities in surrounding atmosphere |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN Bd. 2002, Nr. 03, 3. April 2002 (2002-04-03) & JP 2001 307268 A (YOKOHAMA RUBBER CO LTD:THE), 2. November 2001 (2001-11-02) * |
Also Published As
Publication number | Publication date |
---|---|
WO2004049384A3 (en) | 2005-09-09 |
AU2003302180A1 (en) | 2004-06-18 |
AU2003302180A8 (en) | 2004-06-18 |
DE10254960A1 (en) | 2004-06-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1308186B1 (en) | Protective clothing against chemical and biological substances that are detrimental to health | |
EP1738662B1 (en) | Glove with ABC protective functions | |
DE102007052801B4 (en) | Ion mobility spectrometer with substance collector | |
EP1495784A2 (en) | Two piece combination protective suit with connection section | |
DE4214239A1 (en) | RESPIRATORY MASK WITH AN INDICATOR | |
DE3404395C2 (en) | ||
EP3996818B1 (en) | Head covering, in particualr a hood or balaclava, for use as protective clothing | |
DE60302204T2 (en) | anesthesia reflector | |
DE1931804U (en) | SPECIAL VEHICLE FOR COMBINING DAMAGE IN AREAS POISONED WITH ABC SUBSTANCES. | |
DE2744488A1 (en) | DEVICE FOR PROTECTING THE HEAD AND RESPIRATORY ORGANS | |
DE10327994A1 (en) | Protective hood outer wear for atomic, biological and chemical warfare has seal between facial seam and respirator | |
DE2111241B2 (en) | BREATHING DEVICE WITH A MASK | |
WO2004049384A2 (en) | Miniaturized ion mobility spectrometer | |
DE102014106193B4 (en) | Balaclava and CBRN protective suit | |
DE202004019969U1 (en) | Hood for protecting from chemical and biological pollutants comprises an outer hood part with an outer protective layer and an outer sealing part, and an inner hood part with an inner protective layer and an inner sealing part | |
DE2233660A1 (en) | GAS DETECTOR USING TEST TUBE | |
AT525121A1 (en) | protective hood arrangement | |
DE19650897A1 (en) | Apparatus and method for increasing the safety of respiratory masks | |
AT334162B (en) | PROTECTIVE SHIELD FOR THE PERFORMANCE OF WELDING WORK | |
DE858358C (en) | Fresh air breathing apparatus | |
Weingarten | Leben (bio-ethisch) | |
DE20308642U1 (en) | Hood, for protective clothing, e.g. used for military purposes etc, e.g. NBC protective suit, has surrounding elastic edge, to create face opening to receive gas mask | |
DE202020104366U1 (en) | Coating compound with active function | |
DE3603639A1 (en) | Fully protective overall | |
DE10334667A1 (en) | Two-piece safety- or military protective clothing has surrounding connecting section on upper part for sealed connection to lower part |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AG AL AU BA BB BR BZ CA CN CO CR CU DM DZ EC GD GE HR HU ID IL IN IS JP KP KR LC LK LR LT LV MA MG MK MN MX NZ OM PH PL RO SG TN TT UA US UZ VN YU ZA |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
122 | Ep: pct application non-entry in european phase | ||
NENP | Non-entry into the national phase |
Ref country code: JP |
|
WWW | Wipo information: withdrawn in national office |
Country of ref document: JP |