WO2004040270A1 - Optical sensor - Google Patents
Optical sensor Download PDFInfo
- Publication number
- WO2004040270A1 WO2004040270A1 PCT/DE2002/004009 DE0204009W WO2004040270A1 WO 2004040270 A1 WO2004040270 A1 WO 2004040270A1 DE 0204009 W DE0204009 W DE 0204009W WO 2004040270 A1 WO2004040270 A1 WO 2004040270A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- optical sensor
- sensor according
- light
- optical
- cuvette
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/645—Specially adapted constructive features of fluorimeters
- G01N21/648—Specially adapted constructive features of fluorimeters using evanescent coupling or surface plasmon coupling for the excitation of fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6408—Fluorescence; Phosphorescence with measurement of decay time, time resolved fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/7703—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides
Definitions
- the invention relates to an optical sensor according to the preamble of claim 1.
- An optical sensor according to the invention can advantageously be used for determining concentrations or partial pressures of certain substances, such as chemical elements or compounds, but also for determining phers in gases or liquids become.
- concentration or partial pressure of oxygen contained in a gas mixture or a liquid can be determined very quickly and with high resolution and accuracy.
- the carbon dioxide concentration or the partial pressure for example in the breathing air, can also be determined simultaneously in medical applications.
- the phenomenon of surface plasmon resonance can also be used for substances.
- Other areas of application are the determination of nitrate concentrations and applications in chemical sensors or with biological fluorescence labels.
- the known phenomenon of the fluorescence quenching of a fluorescent substance which occurs more or less strongly depending on such a substance concentration, can also be used in the optical sensor.
- Such fluorescent substances e.g. the ruthenium complexes known per se can be embedded in a matrix and thus form a sensitive layer together with this matrix.
- fluorescence When this layer is irradiated with light of a selected, known wavelength, fluorescence can be excited.
- the fluorescence is preferably excited with a known, as constant as possible intensity of the excitation light, and the fluorescence light is then measured with optical detectors, so that a reduction or increase in the concentration of the substance to be detected or its partial pressure at any given time Fluorescence intensity can be measured and assigned to the concentration or the partial pressure.
- the light is guided for the excitation of the fluorescence and for the detection of the fluorescent light via optical waveguides, for example optical fibers.
- optical waveguides for example optical fibers.
- intensity losses that occur due to the coupling and decoupling of the respective light into such an optical waveguide must be accepted.
- miniaturization is also a result Set limits so that they are not suitable for certain applications.
- the measurement accuracy can be reduced by the condensation of water on such a sensitive layer if the temperature falls below the dew point, which can only be compensated for with considerable effort in the known solutions.
- the sensor according to the invention uses a sensitive sensor to determine the concentration and / or the partial pressure of substances contained in gas mixtures or liquids or to determine the pH value
- a fluorescent substance for example a ruthenium complex known per se, which is embedded in a matrix which consists at least partially of a polymeric material.
- the sensitive layer is in contact with the liquid or gas mixture to be detected and during the measurement, light of at least two light sources, for example laser diodes, which emit light with a wavelength, is excited during the fluorescence of the fluorescent substance is directed onto and into the layer.
- the fluorescence is quenched, so that the fluorescence intensity changes accordingly. This reduction in the fluorescence intensity can then be detected with at least one optical detector, with which the fluorescent light in the fluorescent layer can be measured, and a corresponding measured value is delivered.
- the temporal decay behavior after the end of a fluorescence excitation or a possibly occurring phase shift of the fluorescence light can also be used as measurement signals.
- the layer preferably a noble metal
- a transparent body e.g. a plate-shaped element and surface plasmon resonance are excited on the surface.
- a preferred form of such a carrier is described in WO 96/02822 AI, the disclosure content of which should be used in full.
- At least one intermediate layer can be formed between the body and the layer.
- the at least one, preferably two or more light sources and at least one optical detector for fluorescence excitation are in a preferably metallic housing, which is a conventional one
- Transistor housing or a housing in a similar shape can be added, openings being provided in this metallic housing for the entry and exit of the light from the light source (s).
- Several light sources are preferably arranged such that the light impinging on the layer and entering the layer Incoming light for fluorescence excitation, which is directed by the light sources onto the layer, does not overlap, but at least only partially, and each has different, locally separate areas or correspondingly separate areas
- Layers are irradiated with light and fluorescence is excited there unaffected by one another.
- Additional optical and electronic elements can be arranged in the metallic housing and connections lead to the outside.
- the light from the light source, fluorescent light or reflected light can be directed onto the at least one sensitive layer or optical detectors by optical elements arranged in or on the housing.
- optical lenses, optical windows can be arranged in or below the openings for the light exit in the housing, with which e.g. the fluorescence excitation light can be directed in a defined form onto the at least one sensitive layer.
- Such an arrangement of the lenses is particularly useful when the sensitive layer is arranged directly at or in the immediate vicinity of the light exit openings.
- Other suitable optical elements are also beam splitters, prisms or optical filters.
- Optical filters or windows can thus act as a kind of cover window for light inlets and outlets. At these openings, however, optical lenses for influencing the image or prisms or beam splitters for specifically influencing the respective excitation light, fluorescent light or reflected light can also be arranged or fixed there.
- the at least one sensitive Layer at a greater distance from the light exit openings other lens shapes should be used optical fibers on the metallic housing.
- Rod lenses are particularly suitable for this purpose, through which the light can be directed accordingly to a sensitive layer arranged at a greater distance.
- optical filters in the beam path of the light sources which are transparent in the desired wavelength range of the fluorescent excitation light and absorb other wavelength ranges.
- the metallic housing should be heatable or temperature-controllable.
- a temperature sensor can be present in or on the housing, which can be connected to an electronic control circuit in order to influence the temperature of the metallic housing in a suitable form, which will usually be a heater.
- the optical detector with which the fluorescent light can be measured can also be arranged inside the metallic housing, in which case there is an additional opening for the entry of fluorescent light into the housing to the optical detector.
- Such an embodiment of the optical sensor according to the invention is particularly favorable in the case when the sensitive layer is arranged in front of the light inlet and outlet openings or at a short distance from the metallic housing.
- the at least one optical detector on the side of the sensitive layer which lies opposite the side of the layer from which the irradiation with excitation light takes place.
- the metallic housing to be used according to the invention has the advantage that, due to the good thermal conductivity, adaptation to different temperatures can take place very quickly, which is particularly advantageous for any heating that may be required.
- Such housings are also available inexpensively.
- the fluorescent substances used can only provide measured values with sufficient amplitude within a limited period of use and are subject to so-called aging, it is necessary to replace the fluorescent layers with new ones at greater or lesser intervals. For this purpose, it is expedient to form the sensitive layers on a support which is easy to use and can be removed again later.
- Such a carrier can be designed, for example, in the form of a cap, which can be plugged onto the metallic housing, so that the openings for the light exit and possibly also light entry are assigned to the sensitive layer.
- Such a cap can be designed, for example, as described in PCT / DE 00/02447, which has not been previously published and whose disclosure content is to be used in full.
- the sensitive layer can be formed on a plate-shaped element that can be inserted in such a cap by clamping with a pre-tension. Such a plate-shaped element can also be glued or welded into the cap. An opening is formed in the cap through which the gas mixture or the liquid can come into contact with the sensitive layer.
- the metallic housing can also be permanently or temporarily connected to a cuvette through which the gas mixture or the liquid can be passed for measurement.
- an opening can be formed in such a cuvette, into which the metallic housing with the light exit or entrance openings pointing in the direction of the interior of the cuvette can be inserted and held as clamped as possible.
- the at least one sensitive layer can be arranged directly on the metallic housing or fastened thereon, but can also be arranged in the interior of the cuvette before the metallic housing is inserted.
- a cap-shaped carrier as has already been described, can be guided into such an opening in the cuvette and the metallic housing with the optical elements beforehand.
- the at least one sensitive layer is formed on a transparent and possibly also at least partially planar support which can be positively attached in the cuvette at a location suitable for the measurement.
- Profiles can be formed on the outer edges of the carrier, which are advantageously arranged opposite one another, which can be inserted into appropriately dimensioned and shaped contours on the cuvette and can also be brought out again if necessary.
- Suitable shapes for such profiles and contours are, for example, the so-called dovetail shapes.
- simple groove shapes and appropriately designed webs on the edge can also be used.
- Such a carrier can be replaced easily and inexpensively by a new corresponding element in the fluorescent layer if aging has occurred accordingly, it being possible advantageously to form a projection or protrusion on such a carrier which is easy to handle for insertion or removal can guarantee.
- an additional light source and an additional optical detector can be used on an optical sensor according to the invention with a cuvette.
- Light in the long range of infrared light is used and depending on it
- the light source used and the optical detector used for this purpose should be oriented as orthogonally as possible to the direction of flow of the gas mixture or the liquid which are guided through the cuvette.
- the cuvette should be designed to be as completely opaque as possible, but there are openings or windows for the different types of light.
- An arrangement of the light source and optical detector outside the cuvette is particularly suitable for infrared light, and correspondingly arranged windows are then present on the cuvette.
- the oxygen and the CO 2 concentration or the respective partial pressure can be measured simultaneously in a gas mixture, such as for example the breathing air, which is of particular interest in human medical application.
- the at least two locally separated areas of the one sensitive or also several separate layers, each of which is irradiated with light from a light source for fluorescence excitation, can be used to determine the actual measured value and the other area or the other layer to obtain one Reference signals are used.
- the fluorescence can be excited in these areas or in the separate layers in the same form, ie in the same intensity and / or the same excitation energy.
- the at least one sensitive layer can also be provided with a coating which is permeable to the substance to be detected, said coating advantageously reflecting light and very particularly advantageously from a noble metal (silver, palladium), can consist of a metal mixture or a reflective plastic.
- a noble metal silver, palladium
- Such a coating can at least considerably reduce possible external and scattered light influences.
- a silver coating is particularly suitable for measuring the oxygen concentration.
- Connection lines with at least one additional connection and valves can be present at the supply and discharge for the respective gas mixture or the liquid through the cuvette, in which the actual measurement can be carried out. With valves, the volume flow through the cuvette can be interrupted at least temporarily.
- An element can be connected to an additional connection with which a pressure difference or at least a predeterminable pressure in the cuvette can be generated or set.
- Such an element can be, for example, a pump with which the internal pressure in the cuvette can either be increased or reduced in the case of a gas mixture. For example, if oxygen and / or carbon dioxide in air is to be detected, can simple ambient air can be used to perform a calibration without additional standard gases.
- the ambient air in the cuvette is either compressed so that the internal pressure increases or the pressure is reduced accordingly by a vacuum pump. If the internal pressure inside the cuvette is known, a simple and quick calibration can be carried out by changing the partial pressure and measuring for at least oxygen.
- the supply and discharge lines for a gas mixture in or from the cuvette can be closed with valves during the time the pressure is increased or decreased.
- a check valve can be arranged, which allows a flow through the cuvette only in one direction.
- connections to cuvettes are often flexible, made of elastic materials such as Hoses are formed, so-called pinch valves, with which such a hose can only be compressed, can also be used as suitable valves.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2002342546A AU2002342546A1 (en) | 2002-10-23 | 2002-10-23 | Optical sensor |
EP02779175A EP1590655A1 (en) | 2002-10-23 | 2002-10-23 | Optical sensor |
PCT/DE2002/004009 WO2004040270A1 (en) | 2002-10-23 | 2002-10-23 | Optical sensor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/DE2002/004009 WO2004040270A1 (en) | 2002-10-23 | 2002-10-23 | Optical sensor |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2004040270A1 true WO2004040270A1 (en) | 2004-05-13 |
WO2004040270A8 WO2004040270A8 (en) | 2005-03-17 |
Family
ID=32235218
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE2002/004009 WO2004040270A1 (en) | 2002-10-23 | 2002-10-23 | Optical sensor |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1590655A1 (en) |
AU (1) | AU2002342546A1 (en) |
WO (1) | WO2004040270A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2510014C1 (en) * | 2012-09-14 | 2014-03-20 | Федеральное государственное бюджетное учреждение науки Физический институт им. П.Н. Лебедева Российской академии наук (ФИАН) | Method of determining low concentrations of molecules of volatile substances in gaseous medium |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4518259A (en) * | 1982-07-26 | 1985-05-21 | Eastman Kodak Company | Light guide reflectometer |
US5039491A (en) * | 1989-01-27 | 1991-08-13 | Metricor, Inc. | Optical oxygen sensor |
EP0720014A1 (en) * | 1994-12-28 | 1996-07-03 | Hoechst Aktiengesellschaft | Optical sensor apparatus for detecting vapor of organic solvent |
JPH09329553A (en) * | 1996-06-07 | 1997-12-22 | Hoechst Ind Kk | Optical sensor for detection chemical substance dissolved or dispersed in water |
EP0834848A2 (en) * | 1996-10-02 | 1998-04-08 | Texas Instruments Incorporated | Fixed optic sensor system and distributed sensor network |
US5917607A (en) * | 1996-04-25 | 1999-06-29 | Fuji Photo Film Co., Ltd. | Surface plasmon sensor for multiple channel analysis |
JPH11183372A (en) * | 1997-12-19 | 1999-07-09 | Toto Ltd | Spr sensor device, analysis system and detecting method using it |
WO1999049302A1 (en) * | 1998-03-20 | 1999-09-30 | Aventis Research & Technologies Gmbh & Co. Kg | Optical sensor |
EP0973023A1 (en) * | 1998-07-14 | 2000-01-19 | Texas Instruments Incorporated | High throughput surface plasmon resonance analysis system |
JP2000065731A (en) * | 1998-08-24 | 2000-03-03 | Nippon Laser Denshi Kk | Surface plasmon resonance angle detection device and sample supply collection method |
JP2000180354A (en) * | 1998-12-18 | 2000-06-30 | Mitsubishi Heavy Ind Ltd | Measuring method for harmful halogen compound by using surface plasmon resonance |
EP1079225A1 (en) * | 1999-08-26 | 2001-02-28 | Fuji Photo Film Co., Ltd. | Surface plasmon sensor for analyzing liquid sample or humid atmosphere |
JP2002122600A (en) * | 2000-10-12 | 2002-04-26 | Nippon Laser & Electronics Lab | Sensor chip for biosensor |
-
2002
- 2002-10-23 WO PCT/DE2002/004009 patent/WO2004040270A1/en not_active Application Discontinuation
- 2002-10-23 EP EP02779175A patent/EP1590655A1/en not_active Withdrawn
- 2002-10-23 AU AU2002342546A patent/AU2002342546A1/en not_active Abandoned
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4518259A (en) * | 1982-07-26 | 1985-05-21 | Eastman Kodak Company | Light guide reflectometer |
US5039491A (en) * | 1989-01-27 | 1991-08-13 | Metricor, Inc. | Optical oxygen sensor |
EP0720014A1 (en) * | 1994-12-28 | 1996-07-03 | Hoechst Aktiengesellschaft | Optical sensor apparatus for detecting vapor of organic solvent |
US5917607A (en) * | 1996-04-25 | 1999-06-29 | Fuji Photo Film Co., Ltd. | Surface plasmon sensor for multiple channel analysis |
JPH09329553A (en) * | 1996-06-07 | 1997-12-22 | Hoechst Ind Kk | Optical sensor for detection chemical substance dissolved or dispersed in water |
EP0834848A2 (en) * | 1996-10-02 | 1998-04-08 | Texas Instruments Incorporated | Fixed optic sensor system and distributed sensor network |
JPH11183372A (en) * | 1997-12-19 | 1999-07-09 | Toto Ltd | Spr sensor device, analysis system and detecting method using it |
WO1999049302A1 (en) * | 1998-03-20 | 1999-09-30 | Aventis Research & Technologies Gmbh & Co. Kg | Optical sensor |
EP0973023A1 (en) * | 1998-07-14 | 2000-01-19 | Texas Instruments Incorporated | High throughput surface plasmon resonance analysis system |
JP2000065731A (en) * | 1998-08-24 | 2000-03-03 | Nippon Laser Denshi Kk | Surface plasmon resonance angle detection device and sample supply collection method |
JP2000180354A (en) * | 1998-12-18 | 2000-06-30 | Mitsubishi Heavy Ind Ltd | Measuring method for harmful halogen compound by using surface plasmon resonance |
EP1079225A1 (en) * | 1999-08-26 | 2001-02-28 | Fuji Photo Film Co., Ltd. | Surface plasmon sensor for analyzing liquid sample or humid atmosphere |
JP2002122600A (en) * | 2000-10-12 | 2002-04-26 | Nippon Laser & Electronics Lab | Sensor chip for biosensor |
Non-Patent Citations (6)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 04 31 March 1998 (1998-03-31) * |
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 12 29 October 1999 (1999-10-29) * |
PATENT ABSTRACTS OF JAPAN vol. 2000, no. 06 22 September 2000 (2000-09-22) * |
PATENT ABSTRACTS OF JAPAN vol. 2000, no. 09 13 October 2000 (2000-10-13) * |
PATENT ABSTRACTS OF JAPAN vol. 2002, no. 08 5 August 2002 (2002-08-05) * |
RICHARDS J D ET AL: "SURFACE-PLASMON EXCITATION USING A POLARIZATION-PRESERVING OPTICAL FIBER AND AN INDEX-MATCHING FLUID OPTICAL CELL", APPLIED OPTICS, OPTICAL SOCIETY OF AMERICA,WASHINGTON, US, vol. 32, no. 16, 1 June 1993 (1993-06-01), pages 2901 - 2906, XP000345889, ISSN: 0003-6935 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2510014C1 (en) * | 2012-09-14 | 2014-03-20 | Федеральное государственное бюджетное учреждение науки Физический институт им. П.Н. Лебедева Российской академии наук (ФИАН) | Method of determining low concentrations of molecules of volatile substances in gaseous medium |
Also Published As
Publication number | Publication date |
---|---|
AU2002342546A1 (en) | 2004-05-25 |
EP1590655A1 (en) | 2005-11-02 |
WO2004040270A8 (en) | 2005-03-17 |
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