WO1993001241A1 - Utilisation de la peau non pigmentee de poisson, en particulier de poisson plat comme nouvelle source industrielle de collagene, procede d'extraction, collagene et biomateriau ainsi obtenus - Google Patents
Utilisation de la peau non pigmentee de poisson, en particulier de poisson plat comme nouvelle source industrielle de collagene, procede d'extraction, collagene et biomateriau ainsi obtenus Download PDFInfo
- Publication number
- WO1993001241A1 WO1993001241A1 PCT/FR1992/000621 FR9200621W WO9301241A1 WO 1993001241 A1 WO1993001241 A1 WO 1993001241A1 FR 9200621 W FR9200621 W FR 9200621W WO 9301241 A1 WO9301241 A1 WO 9301241A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- collagen
- skin
- fish
- unpigmented
- flat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
- C08L89/04—Products derived from waste materials, e.g. horn, hoof or hair
- C08L89/06—Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin, e.g. gelatin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- C07K14/78—Connective tissue peptides, e.g. collagen, elastin, laminin, fibronectin, vitronectin or cold insoluble globulin [CIG]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
- C08H1/06—Macromolecular products derived from proteins derived from horn, hoofs, hair, skin or leather
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S530/00—Chemistry: natural resins or derivatives; peptides or proteins; lignins or reaction products thereof
- Y10S530/855—Proteins from animals other than mammals or birds
- Y10S530/857—Fish; fish eggs; shell fish; crustacea
Definitions
- non-pigmented fish skin in particular of fish pLat as a new industrial source of collagen, extraction process, collagen and biomaterial thus obtained.
- the present invention relates essentially to the use of the unpigmented skin of fish, in particular flat fish, as a new industrial source of collagen, a process for the extraction of collagen, as well as collagen and a biomaterial thus obtained.
- Collagen a protein that supports the connective tissues of living beings, is finding increasing applications in the cosmetic and pharmaceutical fields.
- the main properties are:
- the inventors have sought to exploit new sources of collagen making it possible to complete industrial processes, to improve yields, and thereby thereby lower the costs of preparing the protein.
- the main fabric used to obtain collagen is calf skin.
- the collection of the skin is generally not carried out under perfect sanitary conditions, which entails the obligation to use the skin as soon as possible after the slaughter of the animal.
- the pigmented fish skin cannot be used because the pigment is very difficult to remove during the process for preparing collagen.
- the protein thus obtained then leads to impure pigmented biomaterials. Therefore, the inventors turned to fish whose skin is not pigmented and which is available in large quantities.
- the species falling into this category are flatfish, in particular those which are caught in an industrial way such as sole, flounder, turbot, catfish, and whose preparation of the nets involves butchering.
- the ventral skin of these fish is not pigmented, it is available flaking in significant quantities.
- the present invention relates to the use of non-pigmented fish skin as a new industrial source of collagen.
- this non-pigmented skin is a flat fish skin, in particular a ventral skin.
- This non-pigmented skin is advantageously obtained after skinning fresh fish which is frozen immediately after skinning, which guarantees a very good quality of the raw material both bacteriologically and in that of the native character of the protein.
- an unexpected advantage lies in the fact that the skin thus recovered and frozen can be used immediately for the extraction of collagen without prior tanning work. Also, it turned out that the amount of collagen extracted from this raw material is about three times greater than that obtained from calf skin.
- the present invention also relates to a process for extracting native collagen, characterized in that non-pigmented fish skin is used which is subjected to collagen extraction.
- the non-pigmented skin is a flat fish skin, in particular a ventral skin.
- this skin is a skin obtained after skinning fresh fish which is frozen immediately after skinning. This skin is also used for collagen extraction without prior tanning work.
- acid-soluble collagen is extracted in the native state by extraction in an acid solution, as is well known to those skilled in the art.
- the native collagen is then separated by precipitation from the supernatant, by addition of a precipitation agent, for example sodium chloride. If desired, a de-crosslinking of this native collagen can be carried out.
- the invention also relates to native collagen obtained from the unpigmented skin of fish, and any biomaterial produced wholly, or in part, with such collagen.
- the industrially fished ventral sole skins are delivered frozen in 20 kg blocks. These are cut into 2 kg blocks using a band saw. The recovered pieces are then crushed and thawed using a knife mill equipped with a 40 l sealed tank. 39 kg of ground material are obtained. 2. Washing of the ground material
- the ground material is washed with two successive baths of phosphate buffer (21.7 g / l NA-, HP0, and 0.78 g / L of KH-, P0.
- the concentration in ground material is 1 kg per 5 l of bath and contact time of 1 hour
- the ground material is separated from the buffer by centrifugation using a continuous decanter rotating at 4000 rpm. phate is then removed under the same conditions by two successive washes with sterile permuted water.
- This extraction operation is carried out twice.
- the supernatants are combined and the collagen which they contain is precipitated by the addition of sodium chloride at a concentration of 7%.
- the fibers obtained are dialyzed against deionized water until the salts are completely eliminated.
- the collagen obtained can be either returned to an acid solution, or lyophilized.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Gastroenterology & Hepatology (AREA)
- Genetics & Genomics (AREA)
- Toxicology (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Biophysics (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Dermatology (AREA)
- Peptides Or Proteins (AREA)
- Cosmetics (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE69221872T DE69221872T2 (de) | 1991-07-04 | 1992-07-02 | Verwendung der nichtpigmentierten fischhaut, insbesondere von plattfischen als industrielle herkunft für kollagen. verfahren zur extrahierung, kollagen und biomaterial so erhalten. |
| US08/170,353 US5420248A (en) | 1991-07-04 | 1992-07-02 | Unpigmented fish skin, particularly from flat fish, as a novel industrial source of collagen, extraction method, collagen and biomaterial thereby obtained |
| CA002112805A CA2112805C (en) | 1991-07-04 | 1992-07-02 | Use of unpigmented fish skin, particularly from flat fish, as a novel industrial source of collagen, extraction method, and collagen and biomaterial thereby obtained |
| EP92915287A EP0592586B1 (fr) | 1991-07-04 | 1992-07-02 | Utilisation de la peau non pigmentee de poisson, en particulier de poisson plat comme nouvelle source industrielle de collagene, procede d'extraction, collagene et biomateriau ainsi obtenus |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9108400A FR2678624A1 (fr) | 1991-07-04 | 1991-07-04 | Utilisation de la peau non pigmentee de poisson, en particulier de poisson plat comme nouvelle source industrielle de collagene, procede d'extraction, collagene et biomateriau ainsi obtenus. |
| FR91/08400 | 1991-07-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1993001241A1 true WO1993001241A1 (fr) | 1993-01-21 |
Family
ID=9414727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FR1992/000621 Ceased WO1993001241A1 (fr) | 1991-07-04 | 1992-07-02 | Utilisation de la peau non pigmentee de poisson, en particulier de poisson plat comme nouvelle source industrielle de collagene, procede d'extraction, collagene et biomateriau ainsi obtenus |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5420248A (https=) |
| EP (1) | EP0592586B1 (https=) |
| JP (1) | JP2722014B2 (https=) |
| AT (1) | ATE157386T1 (https=) |
| CA (1) | CA2112805C (https=) |
| DE (1) | DE69221872T2 (https=) |
| ES (1) | ES2108759T3 (https=) |
| FR (1) | FR2678624A1 (https=) |
| WO (1) | WO1993001241A1 (https=) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2783836A1 (fr) * | 1998-08-11 | 2000-03-31 | Hokkaido Government | Collagene de poisson et son procede d'extraction et de production |
| WO2016056949A1 (ru) | 2014-10-06 | 2016-04-14 | Общество с ограниченной ответственностью "Системы качества жизни" | Способ получения уксуснокислой дисперсии высокомолекулярного рыбного коллагена |
| CN107573415A (zh) * | 2017-10-16 | 2018-01-12 | 海南三元星生物科技股份有限公司 | 一种鱼胶原蛋白的提取方法及其应用 |
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|---|---|---|---|---|
| FR2714063B1 (fr) * | 1993-12-20 | 1996-03-08 | Javenech | Procédé de préparation de collagène à partir de cnidaires, et compositions obtenues utilisables en cosmétique. |
| GB9405219D0 (en) * | 1994-03-17 | 1994-04-27 | Vickers James Ltd | Collagen finings and preparation thereof |
| JP2731833B2 (ja) * | 1995-06-26 | 1998-03-25 | 大同ほくさん株式会社 | 海洋生物を原料とした代用皮膚 |
| US6271350B1 (en) * | 1998-08-11 | 2001-08-07 | Thara & Company Ltd. | Fish collagen and method of producing same |
| FR2787968B1 (fr) * | 1998-12-31 | 2001-03-23 | Skw Biosystems | Procede de preparation de gelatine de poisson |
| FR2801313A1 (fr) * | 1999-05-19 | 2001-05-25 | Coletica | Produit collagenique contenant du collagene d'origine marine a faible odeur et de preference a proprietes mecaniques ameliorees, ainsi que son utilisation sous forme de compositions ou de produits cosmetiques ou pharmaceutiques |
| NZ501386A (en) * | 1999-11-29 | 2002-10-25 | Nz Inst For Crop & Food Res | Collagen from fish skin |
| US6790454B1 (en) | 2000-05-26 | 2004-09-14 | Coletica | Processes for the preparation of novel collagen-based supports for tissue engineering, and biomaterials obtained |
| FR2809313B1 (fr) * | 2000-05-26 | 2005-11-18 | Coletica | Procedes de preparation de nouveaux supports a base de collagene pour l'ingenieurie tissulaire et biomateriaux obtenus |
| FR2809412A1 (fr) | 2000-05-26 | 2001-11-30 | Coletica | Utilisation de collagene d'origine aquatique pour la realisation de supports destines a l'ingenierie tissulaire, et supports et biomateriaux obtenus |
| WO2001091821A1 (fr) * | 2000-05-26 | 2001-12-06 | Coletica | Supports a base de collagene pour l'ingenierie tissulaire et la preparation de biomateriaux |
| FR2809314B1 (fr) * | 2000-05-26 | 2005-11-18 | Coletica | Utilisation de collagene d'origine aquatique pour la realisation de supports destines a l'ingenierie tissulaire, et supports et biomateriaux obtenus |
| US6974679B2 (en) * | 2000-05-26 | 2005-12-13 | Coletica | Support with collagen base for tissue engineering and manufacture of biomaterials |
| JP3747412B2 (ja) * | 2000-05-26 | 2006-02-22 | エンゲルハード・リヨン | 組織工学用にデザインされた担体を製造するための水生動物起源のコラーゲンの使用並びにそれにより得られる担体及び生体材料 |
| KR20020036225A (ko) * | 2000-11-09 | 2002-05-16 | 이종윤 | 피부질환 보호-치료용 생체막 |
| ES2212870B1 (es) * | 2001-08-08 | 2005-10-01 | Consejo Superior De Investigaciones Cientificas | Estabilizacion para la conservacion y almacenamiento a temperatura ambiente de pieles y tejido conectivo de peces, y posterior produccion de colageno y/o gelatina. |
| US20040078601A1 (en) * | 2002-08-02 | 2004-04-22 | Chris Tengwall | System and method for operating a wireless device network |
| PL190737B1 (pl) | 2002-10-15 | 2006-01-31 | Przybylski Jozef Edward | Sposób otrzymywania kolagenu biologicznie aktywnego ze skór ryb łososiowatych |
| JP2005087440A (ja) * | 2003-09-17 | 2005-04-07 | Matsumoto Shika Univ | 海洋生物の原料を含む組成物、及びその組成物の製造方法 |
| JP2005095331A (ja) * | 2003-09-24 | 2005-04-14 | Ihara Suisan Kk | 魚皮真皮コラーゲンを含有する発泡体シートおよびその用途 |
| US20090312524A1 (en) * | 2003-11-28 | 2009-12-17 | Alternative Sourced Collagen, Llc | Compositions and methods comprising collagen |
| US7109300B2 (en) | 2004-04-19 | 2006-09-19 | Board Of Supervisors Of Louisiana State Univeristy And Agricultural And Mechanical College | Extraction of collagen from calcified tissues |
| CA2608708C (en) * | 2005-05-16 | 2014-04-22 | Purdue Research Foundation | Engineered extracellular matrix having a specified fibril area fraction |
| WO2007106812A2 (en) * | 2006-03-13 | 2007-09-20 | University Of South Florida | Self-assembling, collagen based material for corneal replacement |
| WO2007136634A1 (en) * | 2006-05-16 | 2007-11-29 | Purdue Research Foundation | Three dimensional purified collagen matrices |
| US20070269476A1 (en) * | 2006-05-16 | 2007-11-22 | Voytik-Harbin Sherry L | Engineered extracellular matrices control stem cell behavior |
| CN101091789B (zh) * | 2006-06-19 | 2010-11-10 | 李勇 | 海洋胶原肽在制备免疫调节药物或食品中的用途 |
| CN105327393A (zh) | 2006-06-22 | 2016-02-17 | 南佛罗里达大学 | 胶原支架、具有其的医用植入物以及使用方法 |
| US8093027B2 (en) * | 2006-09-13 | 2012-01-10 | University Of South Florida | Method for producing biocomposite comprising collagen and polymer |
| CA2663722C (en) | 2006-09-21 | 2014-12-09 | Purdue Research Foundation | Collagen preparation and method of isolation |
| GB2468102B (en) * | 2007-12-10 | 2012-12-05 | Purdue Research Foundation | Collagen-based matrices with stem cells |
| JP2009280508A (ja) * | 2008-05-20 | 2009-12-03 | Hikari Ishii | 血管老化抑制剤および老化防止抑制製剤 |
| CA2708844C (en) * | 2009-07-27 | 2016-01-05 | National Cheng Kung University | Preparation of high purity collagen |
| MX2012004037A (es) * | 2009-10-07 | 2012-10-15 | Kerecis Ehf | Material de andamiaje para el cuidado de heridas y/u otras aplicaciones para cicatrizacion de tejido. |
| US9452128B2 (en) | 2012-06-06 | 2016-09-27 | Robell Research, Inc. | Lip balm |
| US20140066379A1 (en) * | 2012-08-30 | 2014-03-06 | Body Organ Biomedical Corp. | Recombinant vector, transgenic fish egg using the same and biomaterial using the same |
| US9878071B2 (en) | 2013-10-16 | 2018-01-30 | Purdue Research Foundation | Collagen compositions and methods of use |
| EP3185922B1 (en) | 2014-08-27 | 2025-04-02 | Purdue Research Foundation | Collagen-based therapeutic delivery systems |
| US11919941B2 (en) | 2015-04-21 | 2024-03-05 | Purdue Research Foundation | Cell-collagen-silica composites and methods of making and using the same |
| ES3040675T3 (en) | 2017-01-31 | 2025-11-04 | Geniphys Inc | Methods and compositions for matrix preparation |
| EP3615568A4 (en) | 2017-04-25 | 2021-01-20 | Purdue Research Foundation | TISSUE RESTORATION THREE-DIMENSIONAL (3D) ARTIFICIAL MUSCLE |
| KR102008944B1 (ko) * | 2019-06-26 | 2019-08-08 | 김경림 | 전처리 및 추출이 모두 가능한 콜라겐 추출 장치와 이를 이용한 콜라겐 추출 방법 |
| EP4096635A4 (en) | 2020-01-27 | 2024-02-21 | GeniPhys, Inc. | BIOLOGICAL FILLER FOR TISSUE RESTORATION AND REGENERATION |
| US20240343759A1 (en) * | 2023-04-14 | 2024-10-17 | Fu Yu Hsieh | Method of preparing procollagen from freshwater fish |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR582543A (fr) * | 1923-06-07 | 1924-12-20 | Nouvelle fibre textile et procédé pour son obtention | |
| FR582544A (fr) * | 1923-06-07 | 1924-12-20 | Nouvelle matière plastique et procédé pour son obtention | |
| FR647030A (fr) * | 1927-01-27 | 1928-11-19 | Procédé perfectionné permettant l'obtention de fibres textiles de haute qualité au moyen de peaux de poissons, tels que et notamment, les chondroptérygiens-sélaciens | |
| CH229190A (de) * | 1942-03-20 | 1943-10-15 | Studiengesellschaft Der Deutsc | Verfahren zur Herstellung von Kunstleder. |
| DE736769C (de) * | 1937-12-23 | 1944-03-16 | Studiengesellschaft Der Deutsc | Verfahren zur Herstellung von plastischen Massen und Presskoerpern daraus |
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|---|---|---|---|---|
| FR2516927B1 (fr) * | 1981-11-26 | 1986-05-23 | Merieux Fond | Procede de preparation industrielle de materiaux collageniques a partir de tissus placentaires humains, materiaux collageniques humains obtenus, leur application comme biomateriaux |
| DE3248188A1 (de) * | 1982-12-27 | 1984-06-28 | Behringwerke Ag, 3550 Marburg | Verfahren zur herstellung eines kollagen-vlieses |
| JPS6283849A (ja) * | 1985-10-04 | 1987-04-17 | Reiji Yoshinaka | コラ−ゲンの精製法 |
| GB8812993D0 (en) * | 1988-06-01 | 1988-07-06 | Natural Resources Mfg Ltd | Improvements in/relating to production of protein products |
| IL87344A (en) * | 1988-08-04 | 1992-03-29 | Univ Bar Ilan | Process for the production of gelatin from fish skins |
| US5106949A (en) * | 1989-09-15 | 1992-04-21 | Organogenesis, Inc. | Collagen compositions and methods for preparation thereof |
-
1991
- 1991-07-04 FR FR9108400A patent/FR2678624A1/fr active Granted
-
1992
- 1992-07-02 JP JP5502013A patent/JP2722014B2/ja not_active Expired - Lifetime
- 1992-07-02 EP EP92915287A patent/EP0592586B1/fr not_active Expired - Lifetime
- 1992-07-02 US US08/170,353 patent/US5420248A/en not_active Expired - Lifetime
- 1992-07-02 CA CA002112805A patent/CA2112805C/en not_active Expired - Lifetime
- 1992-07-02 AT AT92915287T patent/ATE157386T1/de active
- 1992-07-02 WO PCT/FR1992/000621 patent/WO1993001241A1/fr not_active Ceased
- 1992-07-02 ES ES92915287T patent/ES2108759T3/es not_active Expired - Lifetime
- 1992-07-02 DE DE69221872T patent/DE69221872T2/de not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR582543A (fr) * | 1923-06-07 | 1924-12-20 | Nouvelle fibre textile et procédé pour son obtention | |
| FR582544A (fr) * | 1923-06-07 | 1924-12-20 | Nouvelle matière plastique et procédé pour son obtention | |
| FR647030A (fr) * | 1927-01-27 | 1928-11-19 | Procédé perfectionné permettant l'obtention de fibres textiles de haute qualité au moyen de peaux de poissons, tels que et notamment, les chondroptérygiens-sélaciens | |
| DE736769C (de) * | 1937-12-23 | 1944-03-16 | Studiengesellschaft Der Deutsc | Verfahren zur Herstellung von plastischen Massen und Presskoerpern daraus |
| CH229190A (de) * | 1942-03-20 | 1943-10-15 | Studiengesellschaft Der Deutsc | Verfahren zur Herstellung von Kunstleder. |
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| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 107, no. 17, 26 Octobre 1987, Columbus, Ohio, US; abstract no. 150796f, page 382 ; * |
| INDIAN JOURNAL OF EXPERIMENTAL BIOLOGY vol. 18, no. 7, 1 Juillet 1980, NEW DELHI pages 733 - 735 S.C.GANTAYAT ET AL. 'COLLAGEN CONTENT OF SKIN OF FRESH WATER TELEOST' * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2783836A1 (fr) * | 1998-08-11 | 2000-03-31 | Hokkaido Government | Collagene de poisson et son procede d'extraction et de production |
| WO2016056949A1 (ru) | 2014-10-06 | 2016-04-14 | Общество с ограниченной ответственностью "Системы качества жизни" | Способ получения уксуснокислой дисперсии высокомолекулярного рыбного коллагена |
| CN107573415A (zh) * | 2017-10-16 | 2018-01-12 | 海南三元星生物科技股份有限公司 | 一种鱼胶原蛋白的提取方法及其应用 |
| CN107573415B (zh) * | 2017-10-16 | 2021-09-14 | 海南华研胶原科技股份有限公司 | 一种鱼胶原蛋白的提取方法及其应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2678624A1 (fr) | 1993-01-08 |
| CA2112805A1 (en) | 1993-01-21 |
| ATE157386T1 (de) | 1997-09-15 |
| DE69221872D1 (de) | 1997-10-02 |
| US5420248A (en) | 1995-05-30 |
| EP0592586B1 (fr) | 1997-08-27 |
| ES2108759T3 (es) | 1998-01-01 |
| FR2678624B1 (https=) | 1995-06-02 |
| CA2112805C (en) | 2001-04-24 |
| EP0592586A1 (fr) | 1994-04-20 |
| JP2722014B2 (ja) | 1998-03-04 |
| DE69221872T2 (de) | 1998-01-29 |
| JPH06511269A (ja) | 1994-12-15 |
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