US3014024A - Collagen film - Google Patents

Collagen film Download PDF

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Publication number
US3014024A
US3014024A US72237058A US3014024A US 3014024 A US3014024 A US 3014024A US 72237058 A US72237058 A US 72237058A US 3014024 A US3014024 A US 3014024A
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Prior art keywords
collagen
film
dispersion
centrifuge
fibers
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Emanuel R Lieberman
Irving B Oneson
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Johnson and Johnson
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Johnson and Johnson
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08HDERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00Macromolecular products derived from proteins
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; THEIR TREATMENT, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A23B - A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L13/00Meat products; Meat meal; Preparation or treatment thereof
    • A23L13/60Comminuted or emulsified meat products, e.g. sausages; Reformed meat from comminuted meat product
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08HDERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00Macromolecular products derived from proteins
    • C08H1/06Macromolecular products derived from proteins derived from horn, hoofs, hair, skin or leather
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00Compositions of proteins; Compositions of derivatives thereof
    • C08L89/04Products derived from waste materials, e.g. horn, hoof or hair
    • C08L89/06Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin, e.g. gelatin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2389/00Characterised by the use of proteins; Derivatives thereof
    • C08J2389/04Products derived from waste materials, e.g. horn, hoof or hair
    • C08J2389/06Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S530/00Chemistry: natural resins or derivatives; peptides or proteins; lignins or reaction products thereof
    • Y10S530/827Proteins from mammals or birds
    • Y10S530/84Bones; tendons; teeth; cartilage

Description

United rates Patent @ffice Patented Dec. 19, 1961 3,014,024 COLLAGEN FILM Emanuel R. Lieberman and lrving B. Oneson, Somerville, N.J., assignors to Johnson & Johnson, a corporation of New Jersey No Drawing. Filed Mar. 19, 1958, Ser. No. 722,376 2 Claims. (Cl. 260-117) The present invention relates to a highly oriented collagen film of uniform thickness, characterized by an eX- ceptional tensile strength in the direction of orientation and to a method of preparing the collagen film.

Films of collagen are customarily prepared by casting (pouring) a fluid dispersion of collagen fibers on a fiat or screened surface and permitting the dispersing media to evaporate. In general, one or two days are required to completely evaporate the dispersing media at room temperature, the residual film being uneven and varying widely in cross-section. The prior art collagen films have not been uniform in thickness because of the viscous nature of the collagen dispersions and the non-uniform manner of drying. Moreover, since the collagen dispersion is laid down in a fiat surface without the application of any external force, the individual collagen fibers in the dried film are in a random and disoriented state.

Attempts to speed up the process described above by elevating the temperature results in denaturation and degradation of the collagen fibers to such a degree that gelatin films are obtained in place of the desired collagen films. Removal of the liquid phase in a vacuum is also impractical as the viscous dispersion foams and the resulting film has a rough and uneven surface. Blowing air over the collagen dries the surface rapidly, but the dried surface film then interferes with evaporation of the solvent trapped beneath this surface layer.

It is an object, therefore, of the present invention to substantially reduce the time required in the manufacture of collagen films.

It is a further object of the present invention to produce a clear collagen film that is extremely uniform in thickness.

, -t is also an object of the present invention to pro-- duce a dry uniform collagen film at least 5 mills in thickness.

Still another object of the present invention is to manufacture a collagen film characterized by a substantial orientation of the collagen fibers in a single direction and an improved tensile strength in the direction of orientation.

Another object of the present invention is to provide a process that will enable the operator to add plasticizers and/or tanning agents to the collagen film after it has been formed.

It has now been discovered that superior collagen films may be obtained by centrifuging a uniform collagen dispersion of comparatively low viscosity. A basket centrifuge is particularly well adapted to the present process, and for ready removal of the dried collagen film, a filter cloth is placed into the basket centrifuge prior to addition of the collagen dispersion.

The collagen dispersion that is suitable for the present invention should contain collagen fibers in a pure and undenatured state. Such a dispersion may be obtained by swelling collagen in aqueous acid solutions and removing the associated impurities that do not swell by filtration. The preparation of a collagen dispersion that is satisfactory for the practice of the present invention has been described in the Salo Patent No. 2,598,608. The concentration of the collagen fibers in the dispersion should preferably be maintained below about 1% as higher concentrations in the neighborhood of 2% 01' above are too viscous to give satisfactory films unless a special type of centrifuge is employed that has an interior blade to distribute the dispersion. Excellent results have been obtained with a dispersion containing 0.5% by weight collagen fibers.

The following examples illustrate procedures suitable for the production of collagen films from collagen fiber dispersions, but are not intended to limit the scope of this invention.

Example I Beef tendon from freshly killed steers is trimmed free of fat and other extraneous tissues. The cleaned tendon is sliced and the slices are added to about 20 volumes of 2.55.0% acetic acid. The mixture is stirred for approximately four hours, during which time the collagen is swollen. The mixture is then diluted with an addition- 211 volumes of Water to facilitate removal of unswollen particles by filtration. The diluted dispersion is filtered under pressure through a ZO-mesh stainless steel screen. The filtered liquid at this stage contains approximately ().1% collagen and small unswollen particles that are not removed by the first filtration step. These impurities may be removed by additional filtration through successively finer screens or by centrifuga'- tion.

The dilute dispersions of pure collagen fibers is next treated with Normal ammonium hydroxide to neutralize all of the acetic acid (pH 7.0). The collagen fibers that are precipitated by the ammonium hydroxide are thoroughly washed in distilled water to remove all traces of salts and the washed fibers are redispersed in an aqueous acid solution containing 6 grams of malonic acid per liter. The dispersion so obtained contains 0.5% by weight collagen fibers.

Example 11 A canvas filter cloth is wetted down with concentrated ammonia and placed into a basket centrifuge 4 /2 inches in diameter. Two hundred and fifty cubic centimeters of the 0.5% aqueous collagen dispersion described in Example I above is added to the centrifuge, which is rotated at just sufficient speed to bring the dispersion evenly up the sides of the basket onto the canvas cloth. The film so formed is then sprayed with about 20 cc.

of ammonia to precipitate the collagen fibers and the The tensile strength of this film is measured perpen dicular to and parallel with the direction of fiber orientation.

Strips of the film exactly one-half inch in I width are tested on an Instron tester and compared with a control film of the same width obtained by casting the dispersion of Example I on a fine wire mesh base. The results indicate a distinct orientation of collagen fibers as a result of the centrifugal force on the collagen dispersion and the subsequently precipitated fibers.

Example III The procedure of Example II is repeated using an 0.5% aqueous dispersion prepared from the sheath tendon of cattle swollen in an 0.1% malonic acid solution. The dispersion is added to the centrifuge basket and the speed immediately brought to 1750 r.p.m. After two minutes, concentrated ammonia is sprayed on the dispersion and the film is sprayed again after ten minutes. The speed is maintained at 1750 r.p.m. for 35 minutes, raised to 2600 r.p.m. for 40 minutes and finally to 3500 r.p.m. for 25 minutes. The speed is reduced to 2600 r.p.m. for 20 minutes, during which time the film is dried by means of a draft of Warm air. This film has a thickness of 2.5 mills with a perpendicular tensile strength of 9.5 pounds and a parallel tensile strength of 19.9 pounds.

Example IV The perforated basket of a large centrifuge 20 inches in diameter is lined with an Orlon filter cloth saturated with concentrated ammonium hydroxide. This centrifuge is rotated at 800 r.p.m. while 4 liters of an 0.47% collagen dispersion prepared as described in Example I above, is added slowly to the centrifuge over a period of ten seconds. The surface of the dispersion layer is then sprayed immediately with concentrated ammonia, and is sprayed two more times at one-hour intervals. The speed of the centrifuge is then increased to 1500 r.p.m. and the centrifuge is allowed to spin at this speed for an additional three hours. Finally, a current of air at 35 C., is passed into the centrifuge for half an hour. A very thin film is obtained, approximately 1.0 mil in thickness. The tensile strength of this film is indicated on the Instron tensile tester is 5.5 pounds in a direction perpendicular to the fiber orientation and 11.0 pounds in a direction parallel to the fiber orientation.

Example V The procedure of Example II is repeated and the film, after spraying with 20 cc. of ammonia and spinning for 1 hours at 2500 r.p.m., is sprayed with 20 cc. of a 2% formaldehyde solution. The basket is allowed to spin at a speed of 2500 r.p.m. for half an hour and then sprayed again with an additional 25 cc. of 2% f0rmal dehyde solution. One-half hour after the second addition of formaldehyde, the speed of the centrifuge is increased to 3500 r.p.m. and a draft of warm air is directed into the basket until the collagen film is completely dry. The dried film is easily removed from the canvas cloth and has properties similar to those obtained when the film is tanned in a formaldehyde tanning bath. In a similar manner, aqueous solutions of known plasticizers such as glycerol or sorbitol can be sprayed directly into the centrifuge to produce a plasticized collagen film.

Strips of collagen film prepared by the procedure described above may be sterilized and used as a surgical suture or ligature for the purposes described in United States Patent No. 2,039,145. Such films may be used in surgery for hernia repair and may be formed into tubes for arterial graphs.

The collagen films of the present invention are also useful in wrapping meat products such as ground sausage.

While the invention has been described with particular reference to specific embodiments, it is to be under stood that it is not to be limited thereto, but it is to be construed broadly and restricted solely by the scope of the appended claims.

What is claimed is:

1. A collagen film of uniform thickness characterized by a substantial orientation of collagen fibers in a single direction and a tensile strength in the direction of orientation at least about 1.6 times the tensile strength in a direction perpendicular to the direction of orientation; produced by centrifuging an acid dispersion of collagen fibers to form a film, spraying the film with an alkaline reagent to neutralize the acid and continuing to centrifuge until the dispersing liquid has been substantially removed from the film and removing the film so obtained from the centrifuge.

2. A collagen film as described in claim 1, the thickness of which is at least 5 mils.

References Cited in the file of this patent UNITED STATES PATENTS 669,119 Krank Mar. 5, 1901 925,328 Goldsmith June 15, 1909 2,039,262 Schulte Apr. 28, 1936 2,058,835 Schulte Oct. 27, 1936 2,114,220 Freudenberg et al. Apr. 12, 1938 2,280,636 Kraft Apr. 21, 1942 2,518,504 Stott Aug. 15, 1950 2,598,608 Salo et al. May 27, 1952 2,747,228 Braun et al. May 29, 1956 2,842,799 Politzer July 15, 1958 FOREIGN PATENTS 133,428 Sweden Oct. 30, 1951

Claims (1)

1. A COLLAGEN FILM OF UNIFORM THICKNESS CHARACTERIZED BY A SUBSTANTIAL ORIENTATION OF COLLAGEN FIBERS IN A SINGLE DIRECTION AND A TENSILE STRENGTH IN THE DIRECTION OF ORIENTATION AT LEAST ABOUT 1.6 TIMES THE TENSILE STRENGTH IN A DIRECTION PERPENDICULAR TO THE DIRECTION OF ORIENTATION, PRODUCED BY CENTRIFUGING AN ACID DISPERSION OF COLLAGEN FIBERS TO FORM A FILM, SPRAYING THE FILM WITH AN ALKALINE REAGENT TO NEUTRALIZE THE ACID AND CONTINUING TO CENTRIFUGE UNTIL THE DISPERSING LIQUID HAS BEEN SUBSTANTIALLY REMOVED FROM THE FILM AND REMOVING THE FILM SO OBTAINED FROM THE CENTRIFUGE.
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Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3152203A (en) * 1961-05-31 1964-10-06 Dow Chemical Co Preparation of collagen films
US3272204A (en) * 1965-09-22 1966-09-13 Ethicon Inc Absorbable collagen prosthetic implant with non-absorbable reinforcing strands
US3285903A (en) * 1962-05-24 1966-11-15 American Cyanamid Co Collagen film
US3723244A (en) * 1971-01-18 1973-03-27 Atomic Energy Commission Fibrous fibrin sheet and method for producing same
US4621482A (en) * 1985-04-18 1986-11-11 Naturin-Werk Becker & Co. Method and apparatus for forming netted meat products wrapped in an edible collagen film
US4670014A (en) * 1984-02-21 1987-06-02 Bioetica S.A. Implantable, biocompatible reservoirs permitting conservation, cellular culturing, or controlled liberation of an active principle
US4716713A (en) * 1985-04-18 1988-01-05 Naturin-Werk Becker & Co. Method and apparatus for forming netted meat products wrapped in an edible collagen film
US4719116A (en) * 1986-08-27 1988-01-12 Naturin-Werk Becker & Co. Smoked meat product and method and apparatus for making the same
US4910034A (en) * 1984-08-28 1990-03-20 Naturin-Werk Becker And Co. Process for the production of meat products
US5138030A (en) * 1989-10-10 1992-08-11 Pachence James M Process for extracting type I collagen form an avian source, and applications therefor
US5256418A (en) * 1990-04-06 1993-10-26 Organogenesis, Inc. Collagen constructs
US5714582A (en) * 1995-03-17 1998-02-03 Bioscience Consultants Invertebrate type V telopeptide collagen, methods of making, and use thereof
US5731417A (en) * 1994-04-25 1998-03-24 Becton, Dickinson And Company Cell culture substrates and method of making
US6337389B1 (en) 1995-03-17 2002-01-08 Bioscience Consultants, L.L.C. Method and process for the production of collagen preparations from invertebrate marine animals and compositions thereof
US6482240B1 (en) 1999-12-07 2002-11-19 Ed. Geistlich Soehne Ag Fur Chemische Industrie Method of making a collagen membrane from porcine skin
DE4343670C2 (en) * 1993-12-21 2003-05-28 Becker & Co Naturinwerk Edible food casing
US20040161500A1 (en) * 2001-08-21 2004-08-19 Franz Maser Multi-perforated collagen film
US20050087075A1 (en) * 2003-10-28 2005-04-28 Thomas Mysker Apparatus and method to net food products in shirred tubular casing
US20050113910A1 (en) * 2002-01-04 2005-05-26 David Paniagua Percutaneously implantable replacement heart valve device and method of making same
US20060002980A1 (en) * 2003-06-20 2006-01-05 Ringeisen Timothy A High density fibrous polymers suitable for implant
CN102580166A (en) * 2012-02-27 2012-07-18 浙江大学 Medical bionic transparent film implanting material, and preparation method and application of material
US8361144B2 (en) 2010-03-01 2013-01-29 Colibri Heart Valve Llc Percutaneously deliverable heart valve and methods associated therewith
US20130040885A1 (en) * 2009-08-28 2013-02-14 Tissue Science Laboratories Plc Collagen pad
US9119738B2 (en) 2010-06-28 2015-09-01 Colibri Heart Valve Llc Method and apparatus for the endoluminal delivery of intravascular devices
US9737400B2 (en) 2010-12-14 2017-08-22 Colibri Heart Valve Llc Percutaneously deliverable heart valve including folded membrane cusps with integral leaflets

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* Cited by examiner, † Cited by third party
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CN105348819A (en) * 2015-11-25 2016-02-24 荣成广润水产食品有限公司 Preparation method for tilapia skin collagen edible film

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US669119A (en) * 1900-10-12 1901-03-05 Albert Krank Process of producing bodies with parabolic surfaces.
US925328A (en) * 1907-10-07 1909-06-15 Byron B Goldsmith Gelatoid thermoplastic compound.
US2039262A (en) * 1933-02-11 1936-04-28 Koninklijke Pharma Fab Nv Process for the manufacture of threads, strings, bands, films, and the like
US2114220A (en) * 1932-11-28 1938-04-12 Freudenberg Hans Manufacture of artificial sausage skins or casings
US2280636A (en) * 1940-04-17 1942-04-21 Gen Tire & Rubber Co Latex rubber casting
US2518504A (en) * 1947-06-17 1950-08-15 Polymer Corp Method for fabricating nylon bushings
US2598608A (en) * 1946-06-11 1952-05-27 Research Corp Preparation of collagenous materials
US2747228A (en) * 1955-01-19 1956-05-29 Braun Fa B Production of collagen strands
US2842799A (en) * 1955-03-03 1958-07-15 Politzer Alfred Method of producing artificial sponges

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US669119A (en) * 1900-10-12 1901-03-05 Albert Krank Process of producing bodies with parabolic surfaces.
US925328A (en) * 1907-10-07 1909-06-15 Byron B Goldsmith Gelatoid thermoplastic compound.
US2114220A (en) * 1932-11-28 1938-04-12 Freudenberg Hans Manufacture of artificial sausage skins or casings
US2039262A (en) * 1933-02-11 1936-04-28 Koninklijke Pharma Fab Nv Process for the manufacture of threads, strings, bands, films, and the like
US2058835A (en) * 1933-02-11 1936-10-27 Koninklijke Pharma Fab Nv Process for the manufacture of threads, strings, bands, films, and the like
US2280636A (en) * 1940-04-17 1942-04-21 Gen Tire & Rubber Co Latex rubber casting
US2598608A (en) * 1946-06-11 1952-05-27 Research Corp Preparation of collagenous materials
US2518504A (en) * 1947-06-17 1950-08-15 Polymer Corp Method for fabricating nylon bushings
US2747228A (en) * 1955-01-19 1956-05-29 Braun Fa B Production of collagen strands
US2842799A (en) * 1955-03-03 1958-07-15 Politzer Alfred Method of producing artificial sponges

Cited By (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3152203A (en) * 1961-05-31 1964-10-06 Dow Chemical Co Preparation of collagen films
US3285903A (en) * 1962-05-24 1966-11-15 American Cyanamid Co Collagen film
US3272204A (en) * 1965-09-22 1966-09-13 Ethicon Inc Absorbable collagen prosthetic implant with non-absorbable reinforcing strands
US3723244A (en) * 1971-01-18 1973-03-27 Atomic Energy Commission Fibrous fibrin sheet and method for producing same
US4670014A (en) * 1984-02-21 1987-06-02 Bioetica S.A. Implantable, biocompatible reservoirs permitting conservation, cellular culturing, or controlled liberation of an active principle
US4910034A (en) * 1984-08-28 1990-03-20 Naturin-Werk Becker And Co. Process for the production of meat products
US4621482A (en) * 1985-04-18 1986-11-11 Naturin-Werk Becker & Co. Method and apparatus for forming netted meat products wrapped in an edible collagen film
US4716713A (en) * 1985-04-18 1988-01-05 Naturin-Werk Becker & Co. Method and apparatus for forming netted meat products wrapped in an edible collagen film
US4719116A (en) * 1986-08-27 1988-01-12 Naturin-Werk Becker & Co. Smoked meat product and method and apparatus for making the same
US5138030A (en) * 1989-10-10 1992-08-11 Pachence James M Process for extracting type I collagen form an avian source, and applications therefor
US5256418A (en) * 1990-04-06 1993-10-26 Organogenesis, Inc. Collagen constructs
DE4343670C2 (en) * 1993-12-21 2003-05-28 Becker & Co Naturinwerk Edible food casing
US5731417A (en) * 1994-04-25 1998-03-24 Becton, Dickinson And Company Cell culture substrates and method of making
US5714582A (en) * 1995-03-17 1998-02-03 Bioscience Consultants Invertebrate type V telopeptide collagen, methods of making, and use thereof
US6337389B1 (en) 1995-03-17 2002-01-08 Bioscience Consultants, L.L.C. Method and process for the production of collagen preparations from invertebrate marine animals and compositions thereof
US20020147154A1 (en) * 1995-03-17 2002-10-10 Lloyd Wolfinbarger Method and process for the production of collagen preparations from invertebrate marine animals and compositions thereof
US6916910B2 (en) 1995-03-17 2005-07-12 Bioscience Consultants Method and process for the production of collagen preparations from invertebrate marine animals and compositions thereof
US6482240B1 (en) 1999-12-07 2002-11-19 Ed. Geistlich Soehne Ag Fur Chemische Industrie Method of making a collagen membrane from porcine skin
US20030115677A1 (en) * 1999-12-07 2003-06-26 Zdenek Eckmayer Method of making a collagen membrane from porcine skin
US7022358B2 (en) 1999-12-07 2006-04-04 Ed. Geistlich Sohne Ag Fur Chemische Industrie Collagen membrane made from porcine skin
US7429349B2 (en) 2001-08-21 2008-09-30 Naturin Gmbh And Co. Method of perforating a flat film based on collagen
US20040161500A1 (en) * 2001-08-21 2004-08-19 Franz Maser Multi-perforated collagen film
US8109995B2 (en) 2002-01-04 2012-02-07 Colibri Heart Valve Llc Percutaneously implantable replacement heart valve device and method of making same
US9186248B2 (en) 2002-01-04 2015-11-17 Colibri Heart Valve Llc Percutaneously implantable replacement heart valve device and method of making same
US9125739B2 (en) 2002-01-04 2015-09-08 Colibri Heart Valve Llc Percutaneous replacement heart valve and a delivery and implantation system
US8900294B2 (en) 2002-01-04 2014-12-02 Colibri Heart Valve Llc Method of controlled release of a percutaneous replacement heart valve
US8790398B2 (en) 2002-01-04 2014-07-29 Colibri Heart Valve Llc Percutaneously implantable replacement heart valve device and method of making same
US8308797B2 (en) 2002-01-04 2012-11-13 Colibri Heart Valve, LLC Percutaneously implantable replacement heart valve device and method of making same
US20050113910A1 (en) * 2002-01-04 2005-05-26 David Paniagua Percutaneously implantable replacement heart valve device and method of making same
US9610158B2 (en) 2002-01-04 2017-04-04 Colibri Heart Valve Llc Percutaneously implantable replacement heart valve device and method of making same
US20090030511A1 (en) * 2002-01-04 2009-01-29 David Paniagua Percutaneously implantable replacement heart valve device and method of making same
US9554898B2 (en) 2002-01-04 2017-01-31 Colibri Heart Valve Llc Percutaneous prosthetic heart valve
US8633299B2 (en) 2003-06-20 2014-01-21 Kensey Nash Bvf Technology Llc High density fibrous polymers suitable for implant
US7910690B2 (en) 2003-06-20 2011-03-22 Kensey Nash Bvf Technology, Llc High density fibrous polymers suitable for implant
US20060002980A1 (en) * 2003-06-20 2006-01-05 Ringeisen Timothy A High density fibrous polymers suitable for implant
US7214765B2 (en) * 2003-06-20 2007-05-08 Kensey Nash Corporation High density fibrous polymers suitable for implant
US20070202148A1 (en) * 2003-06-20 2007-08-30 Ringeisen Timothy A High density fibrous polymers suitable for implant
US20110133368A1 (en) * 2003-06-20 2011-06-09 Ringeisen Timothy A High density fibrous polymers suitable for implant
US8188229B2 (en) * 2003-06-20 2012-05-29 Kensey Nash Bvf Technology, Llc High density fibrous polymers suitable for implant
US20050087075A1 (en) * 2003-10-28 2005-04-28 Thomas Mysker Apparatus and method to net food products in shirred tubular casing
US7404758B2 (en) 2003-10-28 2008-07-29 Poly-Clip System Corp. Apparatus and method to net food products in shirred tubular casing
US7063610B2 (en) 2003-10-28 2006-06-20 Poly-Clip System Corp. Apparatus and method to net food products in shirred tubular casing
US20050101240A1 (en) * 2003-10-28 2005-05-12 Thomas Mysker Apparatus and method to net food products in shirred tubular casing
US20130040885A1 (en) * 2009-08-28 2013-02-14 Tissue Science Laboratories Plc Collagen pad
US8361144B2 (en) 2010-03-01 2013-01-29 Colibri Heart Valve Llc Percutaneously deliverable heart valve and methods associated therewith
US9119738B2 (en) 2010-06-28 2015-09-01 Colibri Heart Valve Llc Method and apparatus for the endoluminal delivery of intravascular devices
US9737400B2 (en) 2010-12-14 2017-08-22 Colibri Heart Valve Llc Percutaneously deliverable heart valve including folded membrane cusps with integral leaflets
CN102580166A (en) * 2012-02-27 2012-07-18 浙江大学 Medical bionic transparent film implanting material, and preparation method and application of material

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GB866628A (en) 1961-04-26 application

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