GB2461125A - A silk membrane for bone graft material - Google Patents

A silk membrane for bone graft material Download PDF

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Publication number
GB2461125A
GB2461125A GB0811628A GB0811628A GB2461125A GB 2461125 A GB2461125 A GB 2461125A GB 0811628 A GB0811628 A GB 0811628A GB 0811628 A GB0811628 A GB 0811628A GB 2461125 A GB2461125 A GB 2461125A
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GB
United Kingdom
Prior art keywords
membrane
silk
bone
graft material
bone graft
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Withdrawn
Application number
GB0811628A
Other versions
GB0811628D0 (en
Inventor
Michael Rheinnecker
Rolf Zimmat
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SPINTEC ENGINEERING GmbH
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SPINTEC ENGINEERING GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by SPINTEC ENGINEERING GmbH filed Critical SPINTEC ENGINEERING GmbH
Priority to GB0811628A priority Critical patent/GB2461125A/en
Publication of GB0811628D0 publication Critical patent/GB0811628D0/en
Priority to PCT/EP2009/055866 priority patent/WO2009156226A2/en
Publication of GB2461125A publication Critical patent/GB2461125A/en
Withdrawn legal-status Critical Current

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/36Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix
    • A61L27/3641Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix characterised by the site of application in the body
    • A61L27/3645Connective tissue
    • A61L27/365Bones
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/28Bones
    • A61F2/2846Support means for bone substitute or for bone graft implants, e.g. membranes or plates for covering bone defects
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/30Inorganic materials
    • A61L27/32Phosphorus-containing materials, e.g. apatite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/36Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix
    • A61L27/3604Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix characterised by the human or animal origin of the biological material, e.g. hair, fascia, fish scales, silk, shellac, pericardium, pleura, renal tissue, amniotic membrane, parenchymal tissue, fetal tissue, muscle tissue, fat tissue, enamel
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Transplantation (AREA)
  • Engineering & Computer Science (AREA)
  • Biomedical Technology (AREA)
  • Veterinary Medicine (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Medicinal Chemistry (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Orthopedic Medicine & Surgery (AREA)
  • Vascular Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Botany (AREA)
  • Cardiology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Inorganic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Zoology (AREA)
  • Urology & Nephrology (AREA)
  • Materials For Medical Uses (AREA)

Abstract

A silk membrane (60, 90) having two sides and coated selectively on one of the two sides with a bone graft material. The bone graft material is preferably either hydroxyapatite or B-tricalcium phosphate or a combination of these. The membrane can be made by applying synthetic bone material to a solid support, drying it then coating the synthetic bone material with a silk protein solution. When dry the membrane can be removed from the solid support. Alternatively, the silk protein solution can be applied to the solid support first then the synthetic bone material applied. The silk membrane has applications in the regeneration of bone (400), particularly in the mouth.

Description

Description
Field of the Invention
The present invention relates to a silk membrane for guided bone regeneration and a method for manufacture thereof.
Background of the invention
Guided bone regeneration (GBR) is a treatment that promotes the healing of bone defects by the exclusion of competing non-osteogenic soft tissue cells with the help of a barrier membrane. The banier membranes are refened to as GBR membranes. For example, in periodontal therapy of single or molar defects, the GBR membranes have been used by periodontal surgeons for over 20 years as barrier membranes. The GBR membrane is also relevant for oral and maxillofacial bone augmentation procedures such as sinus floor or large ridge augmentations which are frequently used to augment a patients bone mass before implanting dental implants.
T�itially the manufacture of the GBR membranes was by the use of a non-resorbable material such PTFE. Today, however, the non-resorbable GBR membranes have been substituted by bio-resorbable GBR membranes. The advantage of using bio-resorbable GBR membranes is that their use eliminates the need for a second operation for removal of the bio-resorbable GBR membrane after GBR therapy.
An example for the manufacture such a bio-resorbable GBR membranes from collagen has been described in European Patent No. EP 1023091 Bi by Ed Geistlich S�hne AG.
The use of synthetic bone graft materials, such as hydroxyapatite (HA) which can bond directly to bone, is also known in the art. Many organic materials, including silk and even spider drag line silk (Cao and Chuanbin, Langmuir 23, 10701-10705, 2007) have been used as templates to grow HA to form a mineralized structure. The mineralised structure can be used as a building block for bone implant fabrication.
Silk fibroin is a well established biornaterial which has been used extensively in the field of tissue engineering research (Altrnann et al., Biomaterials 24, 401-416, 2003). Recently, nano-fibre GBR membranes manufactured from silk fibroin without further functionalisation have been reported by Kim et al. (Journal of Biotechnology 120, 327-339, 2005). However, most research activity has been focused on the functionalisation of silk fibroin with synthetic bone graft materials; this is in order to improve the bone regeneration potential. The state of the art today is the deposition of HA through a soaking method or a co-dispersion method in phosphate and calcium solutions. For example, Wang et al. (J. Mater. Sci. Mater. Med., 15, 26 1-265, 2004) deposited HA on silk fibroin microspheres through the co-dispersion of H3P04 and Ca(HO)2. Furuzono et al. (J Biomed Mater Res, 50, 344-352, 2000 and US Patent 6395037) have reported growth of HA crystals on silk fabrics through alternate soaking in a calcium chloride solution buffered with tris-(hydroxyrnethyl) aminomethane, HC1 (hydrochloric acid) and phosphate. Recently Kino et al. reported the preparation of multilayered HA/silk fibroin membranes through alternating lamination of silk fibroin and HA/silk fibroin membranes which were prepared by growing HA crystals in solution on silk fibroin membranes (Journal of Bioscience and Bioengineering 103, 514-520, 2007). Another soaking method of using silk scaffolds as template for growing HA crystals in mineralization solutions has been described in US Patent Application 2006/0 159837 by David Kaplan.
A disadvantage of the HA coating methods is the lack of directionality during the coating method which leads to indiscriminate coating of all silk fibroin surfaces in contact with the soaking solutions. The HA functionalised silk fibroin GBR membranes prepared through the soaking method lead to the presence of HA not only on the membrane surface that is in contact with the bone defect side, but also on the membrane surface of the opposite side which is supposed to serve as an efficient banier for soft gum tissue cells.
A further disadvantage of the soaking method described in the prior art is the limited control of the quality of the HA crystals grown on the silk fibroin surface. As demonstrated, for example by Furuzono et al. in J Biomed Mater Res, 50, 344-352, 2000. There is observed a great variation in shape and diameters of the HA crystals grown on silk fibroin material through the soaking method. This variation in shape and diameter of the HA crystals could be solved by inclusion of ready made, precisely manufactured nano-sized crystalline hydroxyapatite particles, for example prepared according to the technique described in US 7,169,372 B. Such hydroxyapatite particles are claimed to offer improved biocompatibility and resorption due to the uniform nano-scale dimensions and homogeneity. However, thus far, the inclusion and even distribution of nano-sized hydroxyapatite particles in silk materials has been a technical challenge as the nano-sized hydroxyapatite particles tend to form aggregates. For example, Li et al. (Biomaterials 2006, 27: 3115-3124), reported uneven distribution and formation of aggregated hydroxyapatite clusters on the silk fibroin materials prepared by electrospinning. For medical applications, an even distribution and precise control of hydroxyapatite particles is necessary for achieving optimal bone regeneration results.
There is therefore a need to be able to manufacture a directionally coated HA silk fibroin GBR membrane. There is also a need for a silk fibroin material which presents on its surface uniform and evenly distributed, nano-scale HA crystals with precisely controlled size and shape for bone regeneration.
Summary of the invention
The object of the invention is to improve the membranes used for guided bone regeneration.
A further object of the invention is to improve the growth of bone in a dental environment.
These and other objects of the invention are solved by providing a silk membrane with one side selectively coated with a ready made, synthetic, bone graft material.
These and other objects of the invention are also solved by a method comprising: providing a first layer of ready made, synthetic bone graft particles on a surface of a casting device, drying the first layer, adding a second layer of silk fibroin solution over the first layer, drying the second layer.
In an alternative aspect of the invention, these and other objects of the invention can also be solved by a method comprising: providing a first layer of silk fibroin solution on a surface of a casting device, adding a second layer of ready made, synthetic bone graft particles over the first layer whilst the first layer is wet followed by drying.
Any synthetic bone graft material in combination with any natural or artificial silk protein or silk derived peptide feedstock may be used for manufacturing of the described silk membrane.
Description of Figures
Figure 1 shows a first method for selectively coating a silk membrane with ready made synthetic bone graft materials.
Figure 2 shows a second method for selectively coating a silk membrane with ready made synthetic bone graft materials.
Figure 3 shows an example of the silk membrane made according to the first method and/or the second method.
Figure 4 shows an example of periodontal surgery canied out using the silk membrane of the invention.
Detailed Description of the Invention
For a complete understanding of the present invention and the advantages thereof, reference is now made to the following detailed description taken in conjunction with the Figures.
It should be appreciated that the various aspects of the invention discussed herein are merely illustrative of the specific ways to make and use the invention and do not therefore limit the scope of invention when taken into consideration with the claims and the following detailed description. It will also be appreciated that features from one aspects of the invention may be combined with features from another aspect of the invention.
The teachings of the cited documents should be incorporated by reference into the description.
In particular the teachings of the Applicant's International Patent Application PCT/EP2007/OO 1775 are incorporated by reference.
A first method for the production of a silk membrane is shown in overview in Figure 1. In a first step 100, a ready made, synthetic bone graft material 10 is applied as a thin coat to a solid support 20. The solid support 20 can be made out of glass or PTFE or other materials suitable for use with proteins.
In the next step 110, the ready made, synthetic bone graft material 10 is dried on the solid support 20 to form a first layer 30. Examples of the synthetic bone graft material 10 include, but are not limited to, hydroxyapatite and B-tricalcium phosphate.
In the next step 120, a silk protein solution 40 is prepared with a silk protein content of between 0.3 % and 30 % (w/w), (as described in the applicants' international application PCT/EP2007/001775). The silk protein solution 40 is then transferred on top of the first layer 30.
lii the next step 130, the silk protein solution 40 is dried on the first layer 30 to form a second layer 50.
In the final step 140, the now formed uni-directionally coated silk fibroin membrane 60 is removed from the solid support 20 and transferred into a storage container (not shown) and stored until further use.
In a further aspect of the present invention, the uni-directionally coated silk fibroin membrane may be sterilised inside the storage container through y-radiation.
A second method of production of a silk membrane according to an aspect of the present invention, is shown in overview in Figure 2.
In a first step 200, a silk protein solution 40 is prepared with a silk protein content between 0.3 % and 30 % (w/w), (as described in the applicants' International Patent Application PCT/EP2007/001775). The silk protein solution 40, is then applied to the solid support 20 to form a first layer 70.
In the next step 210, the ready made, synthetic bone graft material 10 is applied to the first layer 70 when the first layer 70 is still wet.
lii the next step 220, the synthetic bone graft material 10 is dried on the first layer 70 to form a second layer 80.
In the final step 230, the now formed uni-directionally coated silk fibroin membrane 90 is removed from the solid support 20 and transfened into a storage container (not shown) and stored until further use.
In a further aspect of the present invention, the uni-directionally coated silk fibroin membrane may be sterilised inside the storage container through y-radiation.
A uni-directionally coated silk membrane 60 or 90 produced by either one of the methods described is shown in Figure 3.
The use of a uni-directionally coated silk membrane 60 or 90 formed by either one of the methods (100, 200) in periodontal surgery is shown in Figure 4. A section of bone 400 carries a bone defect 415 which requires GBR therapy. The uni-directionally coated silk membrane 60 or 90 produced by either one of the methods described above is placed in the position 415 with one of the sides 30 or 80 coated with the bone graft material 10 in contact with the bone 400. A non-coated side 50 or 70 is placed away from and not in contact with the bone 400.
Bone growth is guided through osteoinduction stimulated by the bone graft material 10 coated on side 30 and 80 in contact with bone 400.
The following examples of specific aspects for canying out the present invention are for illustrative purposes only, and are not intended to limit the scope of the present invention in any way.
Examples:
Example 1
Nano-crystalline hydroxyapatite paste (bone graft material -10) was applied evenly as a thin layer to the bottom of a casting form (solid support 20) with dimensions 10 x 10 x 0.05 mm and left to dry at room temperature for 12 hours. The hydroxyapatite layer formed at the bottom of the casting form was then covered with silk fibroin solution (40) produced with the apparatus described in international patent application PCT/EP2007/00 1775 and left to dry for 12 hours at room temperature. The resulting hydroxyapatite/silk membranes (60) were removed from the casting form and stored at room temperature until further use.
Mechanical handling tests demonstrated that the hydroxyapatite layer was bound firmly to the silk fibroin membrane, even after incubation in water for 24 hours. The one-sided coating of the silk membrane with the hydroxyapatite was easily detectable upon visual inspection as a rough, non-light reflecting surface. The opposite surface of the silk membrane was easily detectable upon visual inspection as shiny, light reflecting surface.
Example 2
A silk fibroin solution (40) produced with the apparatus described in international patent application PCT/EP2007/001775 was applied evenly as a thin layer to the bottom of a casting form with dimensions 10 x 10 x 0.05 mm. A hydroxyapatite powder (bone graft material -10) obtained through drying of nano-crystalline hydroxyapatite paste was applied evenly as a thin layer on top of the silk fibroin solution when the silk fibroin solution was still wet and left to dry for 12 hours at room temperature. The resulting hydroxyapatite/silk membranes (90) were removed from the casting form and stored at room temperature until further use.
Mechanical handling tests demonstrated that the hydroxyapatite coating was bound firmly to the silk fibroin membrane, even after incubation in water for 24 hours. The one-sided coating of the silk membrane with the hydroxyapatite was easily detectable upon visual inspection as rough, non-light reflecting surface. The opposite surface was easily detectable upon visual inspection as shiny, light reflecting surface.
Example 3
For use in oral surgery, a bone (400) defect (415) is exposed by standard dental surgery procedures, such as mucoperiosteal flap or sinus lift operation. The silk membrane (60, 90) prepared according to Example 1 or Example 2 is adapted to the required size with adequate cutting instruments (scissors, scalpels). After cutting, the silk membrane (60, 90) is wetted in water for 30 seconds. The silk membrane (60, 90) is then applied over the bone defect (415) with the rough, non-light reflecting surface facing the bone and the shiny, light reflecting surface facing away from the bone. The rough, non-light reflecting surface is the coated surface and the shiny, light reflecting surface is the non-coated surface of the silk membrane (60, 90). If required, the silk membrane (60, 90) is fixed with standard surgical fixation methods, such as suturing or bioresorbable pins at the bone defect site. The bone (400) defect site (415) is then closed with standard dental surgery procedures.

Claims (8)

  1. Claims 1. A silk membrane (60, 90) having two sides and coated selectively on one of the two sides with a bone graft material (10).
  2. 2. The silk membrane (60, 90) according to claim 1 wherein the bone graft material (10) is hydroxyapatite.
  3. 3. The silk membrane (60, 90) according to claim 1 wherein the bone graft material (10) is B-tricalcium phosphate.
  4. 4. The silk membrane (60, 90) according to claim 1 wherein the bone graft material (10) is a combination of hydroxyapatite and B-tricalcium phosphate.
  5. 5. A method (100) for manufacturing a bone regeneration membrane (60) selectively coated with bone graft material (10), comprising: -applying (100) a bone graft material (10) to a solid support (20); -drying (110) the bone graft material (10) on the solid support (20) to form a first layer (30), -applying (120) a silk fibroin solution (40) to the first layer (30), -drying (130) the silk fibroin solution (40) on the first layer (30) to form a second layer (50) thereby forming a uni-directionally coated silk fibroin membrane (60) with the bone graft material (10).
  6. 6. A method (200) for manufacturing a bone regeneration membrane (90) selectively coated with bone graft material (10), comprising: -applying (200) a silk fibroin (40) solution to a solid support (20) to form a first layer (70), -applying (210) the bone graft material (10) to the first layer (70) when the first layer (70) is still wet, -drying (220) the bone graft material (10) on the first layer (70) to form a second layer (80) thereby forming a uni-directionally coated silk fibroin membrane (90) with the bone graft material (10).
  7. 7. The method of claim 5 or 6, further comprising storage of the bone regeneration membrane (230).
  8. 8. A method for regenerating bone (400) comprising: placement of a first side of a silk membrane (60, 90) on a regeneration site (415), wherein a coated side (30, 80) of the silk membrane (60, 90) is placed adjacent to the bone generation site (415) and is in contact with the bone (400) and wherein a non-coated side (50, 70) of the silk membrane 60, 90) is not in contact with the bone is (400).
GB0811628A 2008-06-25 2008-06-25 A silk membrane for bone graft material Withdrawn GB2461125A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
GB0811628A GB2461125A (en) 2008-06-25 2008-06-25 A silk membrane for bone graft material
PCT/EP2009/055866 WO2009156226A2 (en) 2008-06-25 2009-05-14 A silk membrane for bone graft material and a method for manufacture thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB0811628A GB2461125A (en) 2008-06-25 2008-06-25 A silk membrane for bone graft material

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GB0811628D0 GB0811628D0 (en) 2008-07-30
GB2461125A true GB2461125A (en) 2009-12-30

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Cited By (1)

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CN111298198A (en) * 2019-04-18 2020-06-19 上海交通大学医学院附属第九人民医院 A double-layer absorbable bionic barrier film and its preparation method and application

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WO2008106485A2 (en) 2007-02-27 2008-09-04 Trustees Of Tufts College Tissue-engineered silk organs
CA2688431C (en) 2007-05-29 2016-07-05 Trustees Of Tufts College Method for silk fibroin gelation using sonication
CN101970023A (en) 2008-02-07 2011-02-09 塔夫茨大学信托人 3-dimensional silk hydroxyapatite compositions
US8501172B2 (en) 2008-09-26 2013-08-06 Trustees Of Tufts College pH-induced silk gels and uses thereof
US9074302B2 (en) 2009-09-28 2015-07-07 Trustees Of Tufts College Methods of making drawn silk fibers
CA2774643A1 (en) 2009-09-29 2011-04-07 Trustees Of Tufts College Silk nanospheres and microspheres and methods of making same
WO2011109691A2 (en) 2010-03-05 2011-09-09 Trustees Of Tufts College Silk-based ionomeric compositions
EP2611473A4 (en) 2010-09-01 2014-08-13 Tufts College BIOMATERIALS BASED ON SILK FIBROIN AND POLYETHYLENE GLYCOL
CA2815285C (en) 2010-10-19 2019-12-31 Trustees Of Tufts College Silk fibroin-based microneedles and methods of making the same
WO2012145652A1 (en) 2011-04-20 2012-10-26 Trustees Of Tufts College Dynamic silk coatings for implantable devices
GB201118000D0 (en) * 2011-10-19 2011-11-30 Orthox Ltd An implantable repair device
CN102512712B (en) * 2011-12-22 2014-12-10 南京工业大学 Silk fibroin multilayer functional film with gradient structure and preparation method thereof
CN102847194A (en) * 2012-09-17 2013-01-02 浙江星月生物科技股份有限公司 Stent type silk fibroin film insoluble in water, and preparation and application of stent type silk fibroin film
CN102847198A (en) * 2012-09-17 2013-01-02 浙江星月生物科技股份有限公司 Silk fibroin film insoluble in water, and preparation and application of silk fibroin film
CN103738932B (en) * 2013-12-13 2016-04-20 苏州大学 A kind of nanometer hydroxyapatite and preparation method thereof
CN103656756B (en) * 2013-12-13 2014-12-31 苏州大学 Nano-hydroxyapatite/silk fibroin composite membrane material and preparation method thereof
KR101602797B1 (en) * 2015-10-21 2016-03-11 대한민국 Artificial biomembrane using silk matrix and Method for manufacturing thereof
CN108969802A (en) * 2018-07-19 2018-12-11 浙江大学 A kind of double induction hydroxyapatite silk fibroin composite membrane coating preparation methods with rush osteogenesis function

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EP1852470A1 (en) * 2006-05-03 2007-11-07 Technische Universität München Multilayer Silk Protein Films

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US20060257377A1 (en) * 2005-03-11 2006-11-16 Wake Forest University Health Services Production of tissue engineered digits and limbs
WO2008134541A2 (en) * 2007-04-25 2008-11-06 Musculoskeletal Transplant Foundation Reinforced biological mesh for surgical reinforcement

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111298198A (en) * 2019-04-18 2020-06-19 上海交通大学医学院附属第九人民医院 A double-layer absorbable bionic barrier film and its preparation method and application
CN111298198B (en) * 2019-04-18 2022-03-01 上海交通大学医学院附属第九人民医院 A double-layer absorbable bionic barrier film and its preparation method and application

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Publication number Publication date
GB0811628D0 (en) 2008-07-30
WO2009156226A2 (en) 2009-12-30
WO2009156226A3 (en) 2010-09-16

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