EP1763552A1 - Lyophilisierter klebstoff auf kollagenbasis und dessen verwendung zur herstellung einer haftprothese - Google Patents
Lyophilisierter klebstoff auf kollagenbasis und dessen verwendung zur herstellung einer haftprotheseInfo
- Publication number
- EP1763552A1 EP1763552A1 EP05789856A EP05789856A EP1763552A1 EP 1763552 A1 EP1763552 A1 EP 1763552A1 EP 05789856 A EP05789856 A EP 05789856A EP 05789856 A EP05789856 A EP 05789856A EP 1763552 A1 EP1763552 A1 EP 1763552A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- collagen
- modified
- prosthesis
- glue
- aldehyde
- 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.)
- Withdrawn
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/10—Polypeptides; Proteins
- A61L24/102—Collagen
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/043—Mixtures of macromolecular materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/04—Starch derivatives
- C09J103/10—Oxidised starch
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
- C09J189/04—Products derived from waste materials, e.g. horn, hoof or hair
- C09J189/06—Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/26—Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
- C08L3/10—Oxidised starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
-
- 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
Definitions
- the present invention is in the field of adhesives for surgical or therapeutic use.
- the present invention relates to a glue comprising a mixture of collagen and an aldehyde crosslinking agent or aldehyde-modified modified collagen in freeze-dried form. It also relates to a method of preparing such a glue, its applications, the association of this glue to a prosthetic material to obtain sticky prostheses and the method of preparation of said prostheses.
- This glue is particularly suitable for gluing two biological tissues together or for gluing a prosthesis onto a biological tissue. It can also be applied directly to a biological tissue. In the latter case, it can in particular be used as a local hemostatic agent or as a carrier for active agents with controlled release.
- Biological glues on the market are essentially of two types: fibrin-based glues and collagen-based glues.
- Fibrin-based adhesives such as Tissucol, have been used since the 1970s. These glues contain fibrinogen whose polymerization is induced by a thrombin solution in the presence of factor XIII and fibronectin. This polymerization leads to the formation of a fibrin clot which makes the bonding. In fact, it is a matter of recreating a coagulation phenomenon in situ. The problem with these glues is the use of products derived from human plasma, with the risk of contamination by viruses or associated unconventional transmissible agents.
- Collagen is particularly well suited for use in a glue since this biomaterial, capable of solidifying and then resorbing, is biocompatible. However, collagen as such has a low tackiness.
- GRF glue or French glue.
- Resorcinol combined with formaldehyde allows the crosslinking of collagen and the formation of a solid polymer network. Toxicity problems essentially related to the addition of formaldehyde have been observed (Braunwald et al., Surgery, 59: 1024-1030 (1966), Bachet et al., J. Thorac, Cardiovasc., Surg., 83: 212-217 ( 1982)).
- the document EP 0 862 468 describes, for its part, the use of a macromolecular polyaldehyde, such as oxidized starch, for the crosslinking of a collagenic component in the context of biodegradable biological adhesives. Indeed, it is shown that the mixture of such an aldehyde and a collagenic component, both in aqueous solution or rehydrated after lyophilization, are able to form an adherent crosslinked material, without diffusion phenomenon of the aldehyde.
- a macromolecular polyaldehyde such as oxidized starch
- the required device is complex and delicate handling for the user. It requires: storage means and provision of two separate compositions, - the supply of these compositions in heating syringes, their extemporaneous mixing by means of a specific device, - the application of the mixture, in the best delays, at the level of the wound to be treated.
- EP 0 913 162 contemplates the application of a reinforcement associated with collagen, for example bovine collagen cross-linked by glutaraldehyde, for the treatment of hernias.
- the bonding is obtained by applying an energy and a pressure, the energy having the effect of creating free ends at the level of the collagen fibers and the pressure or force creating new bonds between these ends and the polymeric chains of other surfaces involved.
- the product is directly ready for use and storage is facilitated.
- obtaining the sticky effect depends on the contribution by the practitioner of a source of energy. This step requires the presence of a specific material and greatly complicates the surgical technique. It does not present much interest in terms of cost and time compared to the usual fastening means (staples and sutures).
- the Applicant has developed a product, obtained by lyophilization of a mixture of collagen and an aldehyde, or collagen having aldehyde functions, and which has very interesting sticky properties.
- the glue thus obtained consists solely of collagen and the crosslinking agent comprising at least one aldehyde function or collagen modified so as to have at least one aldehyde function.
- additives increasing the wetting power of the adhesive may, for example, be sugar polymers (dextrin and starch).
- the adhesive according to the invention also contains elements capable of polymerizing with the aldehyde to increase the crosslinking, such as, for example, phenols, and more particularly resorcinol.
- collagen collagen native, partially denatured, or completely denatured (gelatin). This includes in particular type I and / or III collagen, of animal (for example bovine), fibrous or pepsin origin. The collagen is then in the form of a suspension or solution (also called gel), respectively, depending on the solubility of said collagen.
- the crosslinking can be carried out using any molecule carrying at least one aldehyde function capable of reacting with collagen.
- small molecules such as glutaraldehyde, act as a crosslinking agent and are thereby mixed with the collagen.
- the crosslinking agent may be advantageous for the crosslinking agent to have a molecular weight sufficient to prevent diffusion phenomena after its release from the complex with the collagen that inevitably takes place in vivo.
- the crosslinking agent is a biodegradable macromolecular polyaldehyde oxidized polysaccharide or mucopolysaccharide of natural origin, such as starch, dextran, agarose, cellulose, chitosan, alginic acid, glycosaminoglycans, hyaluronic acid, chondroitin sulfate or their derivatives. derivatives.
- a biodegradable macro molecular polyaldehyde of natural origin such as oxidized starch is advantageously used.
- the aldehyde functions are provided by the collagen itself.
- collagen is modified to create aldehyde functions.
- the aldehyde functions are introduced on the collagen either by grafting said functions or by enzymatic reaction. In these two cases, only lysine residues of collagen are modified for the creation of aldehyde functions.
- the collagen is modified by oxidative cleavage, as described in document FR 2 715 309, which results in the creation of aldehyde functions at the level of lysine residues at the same time. and sugars of collagen.
- an acid solution of collagen is incubated at ambient temperature, in the presence of a periodic acid solution, or a salt thereof, at a concentration of between 1 and 10 -5 M.
- the preparation of such an adhesive is carried out by mixing solutions (or suspensions) of collagen on the one hand, and aldehyde on the other hand.
- the mixture is produced at acidic pH, in particular at a pH of between 3 and 5.5 so that the crosslinking does not take place or the latter is incomplete.
- 5 to 2000 ⁇ mol of aldehyde function per gram of collagen is brought into contact.
- the collagen itself serves as a source of aldehyde functions, it is modified so as to create 5 to 2000 ⁇ mol of aldehyde functions per gram of collagen and is maintained at a pH of between 3 and 5.5.
- lyophilization is characterized by vacuum drying of the frozen mixture.
- lyophilization has many advantages. In particular, it makes it possible to stop the uncompleted crosslinking reaction and thus to stabilize the product before use. This stability in dry form at room temperature is a notable improvement over biological adhesives which conventionally must be stored at 40 ° C.
- the product obtained is rich in collagen, compared to products in solution which are limited by their excessive viscosity.
- the product in lyophilized form has the advantage of being easily manipulated by the practitioner, compared to liquid formulations. Thus it is possible to use the lyophilized glue by laparoscopy.
- Sterilization represents the final step in the preparation of the glue or prostheses according to the invention. It can be performed using physical agents, such as rays ⁇ ) ethylene or hydrogen peroxide.
- an adhesive is in the form of a lyophilizate, which is solid and easy to handle. Such an adhesive can then be packaged in the form of a sponge or a powder. Its sticky effect develops fully once the glue is introduced into the human body, the physiological conditions reinforcing the collagen crosslinking by solubilization and pH increase.
- this preparation has the advantage of combining tackiness and haemostatic power. Indeed, unlike gelatin-based glues, collagen, while maintaining its structure, promotes coagulation. This glue is therefore perfectly suitable for bonding biological tissues to one another.
- an adhesive according to the invention may be associated with a prosthetic material to ensure its bonding at a biological tissue.
- the prosthetic materials generally have a role of reinforcement and are for example constituted of woven network (for example polyester fibers), nonwoven, knitted or polypropylene.
- the prosthetic material is a polyester, polypropylene or cellulose lattice.
- the invention also relates to a preferred method of preparation of such a sticky lyophilized prosthesis.
- the prosthetic material is immersed in the solution (or suspension) obtained by mixing the collagen with the crosslinking agent and / or containing the collagen bearing aldehyde functions. In other words, pouring said preparation on the prosthetic material.
- the preferred embodiments relating to the mixture of collagen with the crosslinking agent and / or the modified collagen bearing aldehyde functions are the same as those described above in relation to the lyophilized adhesive, in particular as regards the crosslinking agents. collagen modification protocols or the presence of additives.
- the whole is then subjected to lyophilization. This gives rise to an intimate association between the material and the glue. Again, in the therapeutic or surgical context, it is necessary to sterilize the prosthesis, according to the protocols described above.
- This glue can be used, for example, during interventions in visceral and parietal surgery where it is necessary to fix the prosthesis to a tissue. Subsequently, the prosthetic reinforcement is subjected to cell recolonization and tissue integration, to treat, for example, evenings or hernias.
- an anti-adhering effect can be created on one of the faces of the prosthesis thus obtained, by casting before sterilization of a functionalized hyaluronic acid gel (with nitrogen, amide, dihydrazide, etc. functions). and crosslinked (for example by means of oxidized starch). After coating and drying, and before sterilization, the product obtained may optionally be subjected to freeze-drying and / or steaming again, in order to further structure the film. Finally, a prosthesis of which one of the faces is coated with functionalized and cross-linked hyaluronic acid is obtained.
- Figures 1 and 2 Bonding strength (N strength) at 2 hours and 20 hours of different glues: - Sample 1 (collagen);
- sample 2 according to the invention (collagen + glutaraldehyde); sample 3 according to the invention (collagen + oxidized starch);
- sample 4 according to the invention (collagen modified by grafting); sample 5 according to the invention (collagen modified by grafting + resorcinol); sample 6 according to the invention (collagen modified by oxidation + resorcinol); cyanoacrylate glue;
- glue consisting of a solution of collagen and oxidized starch; glue based on fibrin.
- Sample No. 1 freeze-dried collagen without further treatment is irradiated with ⁇ -rays at a dose of 20 kGy.
- Sample No. 2 To the collagen in the form of a suspension is added with mechanical stirring a solution of glutaraldehyde at 20 mmol / L so as to finally obtain 3500 ppm of aldehyde functions relative to collagen. The mixture obtained is poured into cells and freeze-dried for 48 hours at a final vacuum of less than 0.5 mbar. The product is finally irradiated with ⁇ -rays at a dose of 20 kGy.
- sample No. 3 to the collagen in the form of a suspension is added with mechanical stirring a solution of oxidized starch 3% (containing about 300 ⁇ mol of aldehyde functions / g of solution) according to the volume ratio collagen / starch 20: 1 .
- the mixture obtained is poured into cells and freeze-dried for 48 hours at a final vacuum of less than 0.5 mbar.
- the product is finally irradiated with ⁇ -rays at a dose of 20 kGy.
- sample No. 5 similar to test 4, with addition of 0.07% of resorcinol in final concentration, in the solution before lyophilization.
- the product is irradiated with gamma rays at a dose of 25 kGy.
- sample No. 6 the collagen at 2% is oxidized by means of a solution of periodic acid at 5 mM for 3 hours at 22 ° C. Thereafter the collagen precipitated in saline medium is washed to remove residual periodic acid then partially dried with acetone. The resulting fibers are taken up so as to form a 0.7% gel to which 0.07% of resorcinol is finally added. The mixture thus obtained is cast in cavities and lyophilized for 48 hours at a final vacuum of less than 0.5 mbar. The product is finally irradiated with gamma rays at a dose of 25 kGy. During these various tests, the glue is associated, during the freeze-drying stage, with a polyester prosthesis used as a wall reinforcement. It should be noted that the sterilization of samples containing partially crosslinked collagen (samples 2 and 3), carried out at 20 kGy or 25 kGy, by ⁇ or ⁇ radiation, has no impact on the bonding levels obtained.
- the products are subjected to a bonding test.
- This test consists of placing the prosthesis coated with the glue between two muscle pieces soaked in buffer pH 7. The latter are incubated at 37 ° C. in a humid medium to recreate the conditions of the device implanted internally.
- Test 6 has the greatest adhesive strength, even superior to cyanoacrylate glue.
- freeze-dried form is advantageous if the adhesive strength of the test 3 is compared with a similar liquid formulation (collagen / starch control). It also strengthens the muscle adhesion force in the early stages. Thus, the freeze-dried tests show a superior bonding strength to the controls in liquid form, after 2 hours.
- resorcinol allows on the one hand to increase the bonding force, as shown by the comparison of tests 4 and 5. It allows above all to stabilize the bonding strength over time. Thus, contrary to tests 2 to 4, the forces obtained at 2Oh for the resorcinol tests (tests 5 and 6) are greater than or equal to those obtained at 2h.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0407646A FR2872822B1 (fr) | 2004-07-08 | 2004-07-08 | Colle lyophilisee a base de collagene et son utilisation pour la fabrication de protheses collantes |
FR0407644A FR2872821B1 (fr) | 2004-07-08 | 2004-07-08 | Colle lyophilisee a base de collagene et son utilisation pour la fabrication de protheses collantes |
PCT/FR2005/050550 WO2006005890A1 (fr) | 2004-07-08 | 2005-07-07 | Colle lyophilisee a base de collagene et son utilisation pour la fabrication de protheses collantes |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1763552A1 true EP1763552A1 (de) | 2007-03-21 |
Family
ID=35276341
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05789856A Withdrawn EP1763552A1 (de) | 2004-07-08 | 2005-07-07 | Lyophilisierter klebstoff auf kollagenbasis und dessen verwendung zur herstellung einer haftprothese |
Country Status (3)
Country | Link |
---|---|
US (1) | US8137450B2 (de) |
EP (1) | EP1763552A1 (de) |
WO (1) | WO2006005890A1 (de) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8673354B2 (en) * | 2007-11-05 | 2014-03-18 | Technion Research And Development Foundation Ltd. | Adhesives and methods of applying the same |
CN102149765A (zh) * | 2008-07-03 | 2011-08-10 | 嘉吉公司 | 蛋白质和淀粉组合物、及其制备方法和用途 |
PL2437797T3 (pl) | 2009-06-01 | 2014-01-31 | Technion Res & Dev Foundation | Wieloskładnikowe kleje, ich wytwarzanie i ich zastosowanie |
GB201003656D0 (en) | 2010-03-05 | 2010-04-21 | Tigenix Ltd | Fabrication process |
FR2962883B1 (fr) * | 2010-07-26 | 2014-10-10 | Sec Snc | Procede de fractionnement de sous-produit animal issu des procedes utilises dans la filiere de la charcuterie industrielle |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4280954A (en) * | 1975-07-15 | 1981-07-28 | Massachusetts Institute Of Technology | Crosslinked collagen-mucopolysaccharide composite materials |
AT359652B (de) * | 1979-02-15 | 1980-11-25 | Immuno Ag | Verfahren zur herstellung eines gewebekleb- stoffes |
DE3203775A1 (de) | 1982-02-04 | 1983-08-11 | Behringwerke Ag, 3550 Marburg | Fibrinogenzubereitung, verfahen zu ihrer herstellungund ihre verwendung |
EP0164483B1 (de) * | 1984-06-12 | 1989-08-16 | Oscobal Ag | Verfahren zur Herstellung von Knochenersatzmaterial |
US5171273A (en) * | 1989-01-13 | 1992-12-15 | University Of Medicine And Dentistry Of New Jersey | Synthetic collagen orthopaedic structures such as grafts, tendons and other structures |
US5385606A (en) * | 1992-07-06 | 1995-01-31 | Kowanko; Nicholas | Adhesive composition and method |
US5876444A (en) * | 1996-04-01 | 1999-03-02 | Lai; Wen-Fu | Reconstituted collagen template and the process to prepare the same |
FR2754268B1 (fr) * | 1996-10-07 | 1998-12-24 | Dev Des Utilisations Du Collag | Composition adhesive a base de polyaldehyde macromoleculaire et procede de reticulation de collagene ou de gelatine |
US6309670B1 (en) * | 1997-01-15 | 2001-10-30 | Orquest, Inc. | Collagen-polysaccharide matrix for treatment of bone tumors |
US5866165A (en) * | 1997-01-15 | 1999-02-02 | Orquest, Inc. | Collagen-polysaccharide matrix for bone and cartilage repair |
WO1998031403A1 (en) * | 1997-01-16 | 1998-07-23 | Cohesion Corporation | Lyophilized collagen-based biomaterials, process of preparation and uses thereof |
US6004333A (en) | 1997-10-31 | 1999-12-21 | Ethicon Endo-Surgery, Inc. | Prosthetic with collagen for tissue repair |
US6630457B1 (en) * | 1998-09-18 | 2003-10-07 | Orthogene Llc | Functionalized derivatives of hyaluronic acid, formation of hydrogels in situ using same, and methods for making and using same |
FR2786400B1 (fr) * | 1998-11-30 | 2002-05-10 | Imedex Biomateriaux | Procede de preparation d'un materiau collagenique a vitesse de biodegradation in vivo controlee et materiaux obtenus |
ES2242631T3 (es) | 1999-07-21 | 2005-11-16 | Imedex Biomateriaux | Espuma de una proteina adhesiva para usos quirurgicos y/o terapeuticos. |
JP2004512145A (ja) * | 2000-10-31 | 2004-04-22 | デピュイ・アクロメッド・インコーポレイテッド | 骨および軟骨の修復用の鉱物質化したコラーゲン−多糖類型基質 |
RU2264294C2 (ru) * | 2001-08-24 | 2005-11-20 | Мэттью Р. КУУК | Держатель контейнера для напитков |
JP2005008574A (ja) * | 2003-06-19 | 2005-01-13 | Takasago Internatl Corp | コラーゲン産生促進剤 |
-
2005
- 2005-07-07 WO PCT/FR2005/050550 patent/WO2006005890A1/fr not_active Application Discontinuation
- 2005-07-07 EP EP05789856A patent/EP1763552A1/de not_active Withdrawn
- 2005-07-07 US US11/570,979 patent/US8137450B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
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See references of WO2006005890A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2006005890A1 (fr) | 2006-01-19 |
US20080295735A1 (en) | 2008-12-04 |
US8137450B2 (en) | 2012-03-20 |
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