WO2002022075A2 - Differentiation d'odeurs a partir de signatures spectrales - Google Patents
Differentiation d'odeurs a partir de signatures spectrales Download PDFInfo
- Publication number
- WO2002022075A2 WO2002022075A2 PCT/IL2001/000883 IL0100883W WO0222075A2 WO 2002022075 A2 WO2002022075 A2 WO 2002022075A2 IL 0100883 W IL0100883 W IL 0100883W WO 0222075 A2 WO0222075 A2 WO 0222075A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fragrance material
- odor
- fragrance
- light
- micrometers
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0001—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00 by organoleptic means
Definitions
- the present invention relates to food and cosmetics processing in general and to a method and apparatus to identify odors of fragrance materials in particular.
- Linus Pauling indicated (Pauling L., Molecular architecture and Biological Reactions, Chem. Eng. News, 24, 1375 (1946); referenced by Ohloff, G., Scent and Fragrances, Springer-Nerlag, Berlin Heidelberg, (1994)), that a specific odor quality is due to the molecular shape and size of the chemical.
- Turin in 1996 (Turin, L., A spectroscopic mechanism for primary olfactory reception. Chem. Senses, 21, 773-791 (1996)), provided a detailed and plausible mechanism for the biological transduction of molecular vibrations that, while not accepting the mechanical vibrational spectroscopy theory previously proposed, replaces it with a theory that the receptor proteins act as a "biological spectroscope”. What was proposed is a process called "inelastic electron tunneling". According to Turin, an odorous molecule is first docked to its olfactory receptor protein and then may exchange electrons with this receptor by tunneling (an electron transfer between two iso-energetic levels).
- Whether the first step happens depends on the steric properties of the molecule (molecular volume and shape), while the tunneling step depends on the relation between a vibrational energy of the odorant molecule and the energy levels of the receptor.
- a Fragrance material means material, which naturally has, or is formulated to have certain useful fragrant characteristics. In most cases fragrance compositions are formulated to have a fragrance generally considered preferably pleasing or at least inoffensive to intended users of the material. Fragrance materials are used for imparting a desired odor to perfumes, raw materials for foodstuff, beverages, tobacco, skin and/or any personal or house hold product including fabric washing powders, washing liquids, fabric softeners and other fabric care products; detergents and household cleaning, scouring and disinfection products; air fresheners, room sprays and pomanders; fine fragrances; soaps, bath and shower gels, shampoos, hair conditioners and other personal cleansing products; cosmetics such as creams, ointments, toilet waters, preshave, aftershave, skin and other lotions, talcum powders, body deodorants and antiperspirants etc., for which an agreeable odor is indispensable or desirable.
- Fragrance materials of such kind are mentioned, for example, in S. Arctander, Perfume and Flavor Chemicals (Montclair, N.J., 1969.), in S. Arctander, Perfume and Flavor Materials of Natural Origin (Elizabeth, N.J., 1960.) and in "Flavor and Fragrance Materials” (Allured Publishing Co. Wheaton, 111. USA, 1991.). Fragrance compounds are also used in products that would normally have an unattractive or offensive odor to mask this odor and produce an odor that is less unattractive or offensive. Products in this category include fuel odorants.
- the (pleasing) fragrant characteristics may be the main function of the product in which the fragrance material has been incorporated, as in the case of a fine fragrance, or may be ancillary to the main function of the product, as e.g. in the case of detergents, cleaning products and skin care products.
- odor detection and evaluation plays an important role in the field of quality inspection and authentication of fragrance materials and products, for example, when the freshness of perishable foods being shipped is to be evaluated or when an exact vendor of a perfume has to be verified.
- Gas chromatography has frequently been used in the art for the purpose of measuring individual odors separately. Accordingly, there exist a commercial "Flavors and Fragrances Library" which includes several hundred vapor phase spectra, (http;/w w.nicolet.com/labsys/products/indust_App.htm).
- the gas chromatography is defective in the following points: (1). It requires sampling arrangements for the batch and the results of measurement vary depending upon particular sampling method used; (2). The measurement has to be carried out by a person skilled to some extent; (3). The apparatus useful for such measurement is relatively costly; and (4). It takes a considerable time before the results of measurement are given. Taking the last point (4) into consideration, it can be said that gas chromatography is not suited for an in-situ measurement where it is necessary to provide a real time verification of fragrance materials.
- Bjarno uses a correlation between particular absorption bands in the IR spectrum of a fat sample to the "Boar taint" of this sample, to identify articles, which carried this taint.
- a method to compare odor character of fragrance materials comprising the steps of: (a) providing a first fragrance material and a second fragrance material, each of the fragrance materials has a characteristic odor, the characteristic odor of the first fragrance material and the characteristic odor of the second fragrance material have a degree of similarity; (b) measuring an optical absorption spectrum of the first fragrance material and an optical absorption spectrum of the second fragrance material and, (c) predicting the degree of similarity between the characteristic odor of the first fragrance material and the characteristic odor of second fragrance material according to a pre-determined criterion which is related to a difference between the optical absorption spectrum of the first fragrance material and the optical absorption spectrum of the second fragrance material.
- a method for on-line detection of a change in an odor character of fluid fragrance material comprising the steps of: (a) providing a fragrance material having a characteristic odor, the fragrance material has a reference absorption spectrum which is associated with the characteristic odor thereof; (b) monitoring on-line an absorption spectrum of the fragrance material and, (c) correlating a detectable change in the measured absorption spectrum of the fragrance material with respect to the reference absorption spectrum of the fragrance material to a change in the characteristic odor of the fragrance material.
- a method for authentication of a fragrance material according to its odor character comprising the steps of: (a) providing a fragrance material having a characteristic odor; (b) measuring an optical absorption spectrum of the fragrance material and, (c) look up of the optical absorption spectrum of the fragrance material in a data base which includes optical absorption spectra of certified fragrance materials to determine an authenticity of the fragrance material.
- an odor identifying apparatus comprising of: (a) a tube which confines a fluid fragrance material; the tube transmits light passing perpendicularly to its longitudinal axis, (b) a light source delivering a beam of light in a direction that is about perpendicular to a wall of the tube, the beam of light is transmitted through the fluid fragrance material in the tube and, (c) a device to detect light at a wavelength of the beam of light, the tube is positioned between the light source and the device to detect light.
- an odor identifying system comprising: (a) an apparatus which measures an absorption spectrum of a fragrance material at a wavelength interval; (b) a data base containing an absorption spectrum of at least one fragrance material at said wavelength interval; (c) an algorithm for comparing absorption spectra of at least two fragrance materials and, (d) a qualitative criterion to differentiate between odor characteristic of fragrance materials according to a result of said comparison.
- FIG. 1 shows absorption spectra of two samples of 2,3 Hexanedione having similar odor character.
- FIG. 2 shows absorption spectra of two samples of 2,3 Hexanedione having dissimilar odor character.
- FIG. 3 shows absorption spectra of two samples of 2,3 Pentanedione FCC 98% having similar odor character.
- FIG. 4 shows absorption spectra of two samples of 2,3 Pentanedione FCC 98% having dissimilar odor character.
- FIG. 5 shows absorption spectra of two samples of Trans-2- Hexanol having similar odor character.
- FIG. 6 shows absorption spectra of two samples of Trans-2-Hexanal having similar odor character.
- FIG. 7 shows absorption spectra of two samples of 3,4 Hexanedione having similar odor character.
- FIG. 8 shows absorption spectra of two samples of 3,4 Hexanedione having dissimilar odor character.
- FIG. 9 shows absorption spectra of another two samples of 3,4 Hexanedione having dissimilar odor character.
- FIG. 10 shows absorption spectra of two samples of L-Carveol having similar odor character.
- FIG. 11 shows a set up for an on line classification of fragrant fluids according to their odor character.
- FIG. 12 shows a second set up for an on line classification of fragrant fluids according to their odor character.
- fragrance compounds which have different odor characteristics and which are indistinguishable within the resolution of chromatographic and mass spectrometric methods can be distinguished by optical absorption measurements in the wavelength range of 0.3-2.5 ⁇ m (UV to near IR).
- Liquid samples of various fragrance materials were subjected to the analytical methods of thin layer chromatography, gas chromatography, high pressure liquid chromatography and mass spectrometry gas chromatography.
- samples were prepared in pairs in which each member of the pair represented a different lot of this compound.
- Members of a single pair with identical composition will be referred hereafter having a "similar” odor character, or a "dissimilar” odor character, as had been determined by an odor panel of 3 experienced persons.
- the samples were subjected to a spectroscopic evaluation which was based on the analysis of the absorption spectra of the samples.
- a high spectral resolution instrument of type Lambda 900 from Perkin Elmer was used to measure the absorption spectra of the liquid samples in the spectral region between 0.2-3 ⁇ m.
- the Lambda 900 is a dual beam instrument and in the sample chamber one beam was allowed to pass through an empty quartz cell and the other beam passed through a quartz cell of identical dimensions which contained the sample.
- the spectra were recorded using a computer with dedicated software. Care was taken to clean and dry the cell walls after each sample was measured.
- Feature2 d ⁇ 1 are in nanometers.
- each example consists of two samples with an identical composition of a certain compound.
- the samples have either similar or dissimilar odor character and their spectral curves are plotted in the respective figures from which also Feature 1 and Feature2 are deduced.
- Feature 1 and more specifically Feature2 are sensitive to the odor dissimilarity between the two samples of an example and their numerical value can be used to establish a quantitative criterion, which will classify the samples according to the organoleptic evaluation.
- samples of the compound 2,3 Hexanedione for which Featurel ⁇ 5 have a similar odor character E.g. samples of the compound 2,3 Hexanedione for which Featurel ⁇ 5 have a similar odor character.
- Feature 1 and Feature2 together with a different or multi wavelength range to establish other spectral criteria for odor character similarity. For example: Cross correlation coefficient, wavelet analysis, Fourier analysis and Beyesian decision rules.
- a first embodiment of the invention includes the comparison of the rigorous spectra of fragrance compounds which was measured with a spectrometer as described above.
- a variation of this measurement in the double beam mode can be done by measuring directly the difference spectrum of two materials. This is done by introducing the two samples into the sample and the reference compartment of the double beam spectrophotometer respectively.
- FIGURE 11 Another embodiment 20 of the present invention is shown in FIGURE 11. This is a dedicated setup which is based on absorption measurements for real time on-line spectral classification of liquid or gaseous samples according to their odor character.
- the setup includes a transparent quartz tube or preferably a quartz hollow body with a rectangular cross section 28, in which a fluid is either flowing or standing still.
- the tube can be opaque and equipped with two flat transparent windows 27 on opposite side of the tube, which allow the introduction and collection of a flat beam of light 22 sampling the fluid 24 which is confined within the tube.
- the beam of light originates from any suitable light source (not shown) in the spectral region of between about 0.3 to about 20 ⁇ m, e.g. a halogen lamp, a deuterium lamp, a tungsten filament lamp, a glow bar, a plurality of light emitting diodes or a tunable laser.
- a suitable light source not shown
- the transmitted light is measured by a detector array 23 which includes a plurality of detector units which are sensitive to light at the wavelengths employed.
- each detector unit of the array has its light sensitive surface covered by a narrow band-pass optical filter 24 which transmits light only at a selective wavelength.
- the measurement of the spectrum consists of the simultaneous response of all the detector units of the array, each one at the wavelength transmitted by its respective filter.
- white light of the light source can be dispersed before or after its passage through tube 28 by a prism, a grating or a like so that each detector unit of the array 23 is illuminated with a monochromatic light and no need for optical filter 24 exists.
- the number of spectral bands as well as their bandwidth is determined according to a bank of spectral signatures of samples that have their abso ⁇ tion spectra correlated to their odor.
- a bank of spectral signatures of samples that have their abso ⁇ tion spectra correlated to their odor In another embodiment 30 shown in FIGURE 12 only one detector 33 is used and the light is focused on its surface by a lens 35.
- replaceable filters 34 at a desired wavelength are introduced before the detector by, e.g. using a rotating wheel 36 which has a plurality of filters mounted on its circumference and which is driven by a step motor (not shown).
- the number of filters as well as their bandwidth is determined according to a bank of spectral signatures of samples that have their absorption spectra correlated to their odor. These signatures are collected by laboratory measurements with a high-resolution spectrophotometer.
- FIGURES 11, 12 can also be used to determine changes in the odor character of a fluid when it takes place inside the sampled volume.
- the change in the odor character may occur as part of a chemical process, e.g. oxidation and the odor character change can be detected by the change in the measured spectral signature.
- the fluid odor discrimination is noninvasive and has thus advantages over prevailing instruments and methods used to discriminate between fluid odor changes in a dynamic flow situation when these changes are associated with composition changes that could be observed by the aforesaid methods.
- a measured abso ⁇ tion spectrum of a sample of a fragrance material of an unknown origin is compared to a reference abso ⁇ tion spectrum associated with a certified lot of such a fragrance material, which is stored in a data-base, in order to determine the authenticity of the sample.
Abstract
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002526330A JP2004508570A (ja) | 2000-09-18 | 2001-09-20 | スペクトル標識に基づいたにおい識別 |
IL14972501A IL149725A0 (en) | 2000-09-18 | 2001-09-20 | Odor discrimination based on spectral signatures |
AU2001294148A AU2001294148A1 (en) | 2000-09-18 | 2001-09-20 | Odors discrimination based on spectral signatures |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US66400700A | 2000-09-18 | 2000-09-18 | |
US09/664,007 | 2000-09-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002022075A2 true WO2002022075A2 (fr) | 2002-03-21 |
WO2002022075A3 WO2002022075A3 (fr) | 2002-07-25 |
Family
ID=24664117
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IL2001/000883 WO2002022075A2 (fr) | 2000-09-18 | 2001-09-20 | Differentiation d'odeurs a partir de signatures spectrales |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP2004508570A (fr) |
AU (1) | AU2001294148A1 (fr) |
IL (1) | IL149725A0 (fr) |
WO (1) | WO2002022075A2 (fr) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1236997A2 (fr) * | 2001-03-02 | 2002-09-04 | Kao Corporation | Appareil pour collecter des ingrédients de fragrances |
WO2006111476A1 (fr) * | 2005-04-21 | 2006-10-26 | Symrise Gmbh & Co. Kg | Procede permettant la separation et l'evaluation sensorielle d'aromes |
CN102608244A (zh) * | 2012-03-02 | 2012-07-25 | 红云红河烟草(集团)有限责任公司 | 用于同时测定卷烟烟丝中几种香味物质的检测方法 |
CN102680627A (zh) * | 2012-05-15 | 2012-09-19 | 上海烟草集团有限责任公司 | 一种烟叶中关键致香物质的分析与鉴别方法 |
US9226874B2 (en) | 2002-10-31 | 2016-01-05 | Purdue Pharma L.P. | Pharmaceutical identification |
CN105445392A (zh) * | 2015-11-13 | 2016-03-30 | 中国烟草总公司郑州烟草研究院 | 直接溶剂萃取气相色谱质谱联用技术分析检测烟草中碱性香味成分的方法 |
US10710429B2 (en) | 2017-08-24 | 2020-07-14 | Ford Global Technologies, Llc | Vehicle cabin odor detection and amelioration |
CN114324191A (zh) * | 2022-01-07 | 2022-04-12 | 柳州职业技术学院 | 一种基于智能控制的气味测定系统 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101198233A (zh) * | 2006-12-08 | 2008-06-11 | 奥斯兰姆奥普托半导体有限责任公司 | 电器 |
CN109765336B (zh) * | 2018-12-26 | 2022-04-05 | 信阳师范学院 | 一种烟草薄片感官评价和化学成分相关性分析方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4268751A (en) * | 1979-04-02 | 1981-05-19 | Cmi Incorporated | Infrared breath analyzer |
US4563893A (en) * | 1983-04-22 | 1986-01-14 | Necmi Tanyolac | Methods and apparatus for detection and identification of volatile materials and odors |
US5090232A (en) * | 1989-05-19 | 1992-02-25 | Wakabayashi & Co. | Method and apparatus for detecting odors |
US5654497A (en) * | 1992-03-03 | 1997-08-05 | Lockheed Martin Energy Systems, Inc. | Motor vehicle fuel analyzer |
US5675070A (en) * | 1996-02-09 | 1997-10-07 | Ncr Corporation | Olfatory sensor identification system and method |
US6040189A (en) * | 1996-03-21 | 2000-03-21 | California Institute Of Technology | Gas sensor test chip sensing method |
-
2001
- 2001-09-20 AU AU2001294148A patent/AU2001294148A1/en not_active Abandoned
- 2001-09-20 IL IL14972501A patent/IL149725A0/xx unknown
- 2001-09-20 WO PCT/IL2001/000883 patent/WO2002022075A2/fr active Application Filing
- 2001-09-20 JP JP2002526330A patent/JP2004508570A/ja active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4268751A (en) * | 1979-04-02 | 1981-05-19 | Cmi Incorporated | Infrared breath analyzer |
US4563893A (en) * | 1983-04-22 | 1986-01-14 | Necmi Tanyolac | Methods and apparatus for detection and identification of volatile materials and odors |
US5090232A (en) * | 1989-05-19 | 1992-02-25 | Wakabayashi & Co. | Method and apparatus for detecting odors |
US5654497A (en) * | 1992-03-03 | 1997-08-05 | Lockheed Martin Energy Systems, Inc. | Motor vehicle fuel analyzer |
US5675070A (en) * | 1996-02-09 | 1997-10-07 | Ncr Corporation | Olfatory sensor identification system and method |
US6040189A (en) * | 1996-03-21 | 2000-03-21 | California Institute Of Technology | Gas sensor test chip sensing method |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1236997A2 (fr) * | 2001-03-02 | 2002-09-04 | Kao Corporation | Appareil pour collecter des ingrédients de fragrances |
EP1236997A3 (fr) * | 2001-03-02 | 2004-09-15 | Kao Corporation | Appareil pour collecter des ingrédients de fragrances |
US9226874B2 (en) | 2002-10-31 | 2016-01-05 | Purdue Pharma L.P. | Pharmaceutical identification |
US9233049B2 (en) | 2002-10-31 | 2016-01-12 | Purdue Pharma L.P. | Pharmaceutical identification |
WO2006111476A1 (fr) * | 2005-04-21 | 2006-10-26 | Symrise Gmbh & Co. Kg | Procede permettant la separation et l'evaluation sensorielle d'aromes |
US7879378B2 (en) | 2005-04-21 | 2011-02-01 | Symrise Gmbh & Co. Kg | Process for the separation and sensory evaluation of flavours using HTLC |
CN102608244A (zh) * | 2012-03-02 | 2012-07-25 | 红云红河烟草(集团)有限责任公司 | 用于同时测定卷烟烟丝中几种香味物质的检测方法 |
CN102680627A (zh) * | 2012-05-15 | 2012-09-19 | 上海烟草集团有限责任公司 | 一种烟叶中关键致香物质的分析与鉴别方法 |
CN105445392A (zh) * | 2015-11-13 | 2016-03-30 | 中国烟草总公司郑州烟草研究院 | 直接溶剂萃取气相色谱质谱联用技术分析检测烟草中碱性香味成分的方法 |
US10710429B2 (en) | 2017-08-24 | 2020-07-14 | Ford Global Technologies, Llc | Vehicle cabin odor detection and amelioration |
CN114324191A (zh) * | 2022-01-07 | 2022-04-12 | 柳州职业技术学院 | 一种基于智能控制的气味测定系统 |
Also Published As
Publication number | Publication date |
---|---|
IL149725A0 (en) | 2002-11-10 |
JP2004508570A (ja) | 2004-03-18 |
WO2002022075A3 (fr) | 2002-07-25 |
AU2001294148A1 (en) | 2002-03-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11428678B2 (en) | System and method for scent perception measurements and for construction of a scent database | |
Santos et al. | Rapid detection and quantification of milk adulteration using infrared microspectroscopy and chemometrics analysis | |
US6040906A (en) | Resonance raman spectroscopy for identifying and quantitating biomatter, organic, and inorganic analytes | |
Di Natale et al. | Outer product analysis of electronic nose and visible spectra: application to the measurement of peach fruit characteristics | |
US5675070A (en) | Olfatory sensor identification system and method | |
US7167815B2 (en) | Measuring the intensity of odors | |
Jha et al. | Molecular imprinted polyacrylic acids based QCM sensor array for recognition of organic acids in body odor | |
Cosio et al. | Electronic noses and tongues | |
JPH11500821A (ja) | 芳香、臭気物質を検出する方法及び装置並びに応用 | |
WO2002022075A2 (fr) | Differentiation d'odeurs a partir de signatures spectrales | |
Cozzolino et al. | Relationship between sensory analysis and near infrared spectroscopy in Australian Riesling and Chardonnay wines | |
JPH10170422A (ja) | 複合型匂いセンサ | |
Fenner et al. | The application of electronic nose technology to environmental monitoring of water and wastewater treatment activities | |
Mirghani et al. | A new method for determining gossypol in cottonseed oil by FTIR spectroscopy | |
US20090070045A1 (en) | Diagnosis supporting system | |
Sarig | PH—Postharvest Technology: Potential Applications of Artificial Olfactory Sensing for Quality Evaluation of Fresh Produce | |
Kuriakose et al. | Detection and quantification of adulteration in sandalwood oil through near infrared spectroscopy | |
Newman | Electronic noses | |
Benedetti et al. | Comparison of an electronic nose with the sensory evaluation of food products by “triangle test” | |
Korotcenkov | Chemical Sensors: Comprehensive Sensor Technologies Volume 6: Chemical Sensors Applications | |
Bultel et al. | Use of digital olfaction to standardize cabin odor testing in automotive interiors | |
Duffee | Appraisal of odor-measurement techniques | |
Setiowaty et al. | A rapid Fourier transform infrared spectroscopic method for the determination of 2-TBARS in palm olein | |
Mirghani et al. | Multivariate calibration of Fourier transform infrared spectra for determining thiobarbituric acid-reactive substance content in palm oil | |
Bonnefille | Electronic nose technology and applications |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PH PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
WWE | Wipo information: entry into national phase |
Ref document number: 149725 Country of ref document: IL |
|
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 2002 526330 Kind code of ref document: A Format of ref document f/p: F |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
122 | Ep: pct application non-entry in european phase |