CN102908675A - Absorbable suture nail for anastomat - Google Patents
Absorbable suture nail for anastomat Download PDFInfo
- Publication number
- CN102908675A CN102908675A CN2012104241027A CN201210424102A CN102908675A CN 102908675 A CN102908675 A CN 102908675A CN 2012104241027 A CN2012104241027 A CN 2012104241027A CN 201210424102 A CN201210424102 A CN 201210424102A CN 102908675 A CN102908675 A CN 102908675A
- Authority
- CN
- China
- Prior art keywords
- magnesium alloy
- silk material
- staple
- magnesium
- degradable
- 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.)
- Pending
Links
- 229910000861 Mg alloy Inorganic materials 0.000 claims abstract description 113
- 239000000463 material Substances 0.000 claims abstract description 96
- 239000002344 surface layer Substances 0.000 claims abstract description 37
- 239000000919 ceramic Substances 0.000 claims abstract description 28
- 229920002521 macromolecule Polymers 0.000 claims abstract description 23
- 238000007789 sealing Methods 0.000 claims abstract description 16
- 239000010409 thin film Substances 0.000 claims abstract description 16
- 238000005524 ceramic coating Methods 0.000 claims abstract description 14
- 239000011247 coating layer Substances 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 15
- 239000003462 bioceramic Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000000395 magnesium oxide Substances 0.000 claims description 14
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 13
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004310 lactic acid Substances 0.000 claims description 10
- 230000001954 sterilising effect Effects 0.000 claims description 10
- 238000004659 sterilization and disinfection Methods 0.000 claims description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- 230000001680 brushing effect Effects 0.000 claims description 8
- 238000003618 dip coating Methods 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 5
- 229910000733 Li alloy Inorganic materials 0.000 claims description 4
- 229910001051 Magnalium Inorganic materials 0.000 claims description 4
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 claims description 4
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 4
- 239000001506 calcium phosphate Substances 0.000 claims description 4
- 238000004070 electrodeposition Methods 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims description 4
- KBMLJKBBKGNETC-UHFFFAOYSA-N magnesium manganese Chemical compound [Mg].[Mn] KBMLJKBBKGNETC-UHFFFAOYSA-N 0.000 claims description 4
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 4
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 4
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 4
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 4
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 3
- 229910000882 Ca alloy Inorganic materials 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000914 Mn alloy Inorganic materials 0.000 claims description 3
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 3
- 238000002306 biochemical method Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 238000005468 ion implantation Methods 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 238000007750 plasma spraying Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 abstract description 23
- 238000005260 corrosion Methods 0.000 abstract description 23
- 238000001727 in vivo Methods 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 239000010410 layer Substances 0.000 abstract description 4
- 210000002784 stomach Anatomy 0.000 abstract description 3
- 230000003872 anastomosis Effects 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229920000747 poly(lactic acid) Polymers 0.000 description 9
- 239000004626 polylactic acid Substances 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000001356 surgical procedure Methods 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000009958 sewing Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010407 anodic oxide Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000002496 gastric effect Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000002980 postoperative effect Effects 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920006237 degradable polymer Polymers 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000035876 healing Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 230000000968 intestinal effect Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000035807 sensation Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- 229910018131 Al-Mn Inorganic materials 0.000 description 1
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018461 Al—Mn Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- -1 Magnesium rare earth metal Chemical class 0.000 description 1
- 206010058046 Post procedural complication Diseases 0.000 description 1
- 208000035965 Postoperative Complications Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000037182 bone density Effects 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 210000004051 gastric juice Anatomy 0.000 description 1
- 238000011902 gastrointestinal surgery Methods 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- QRNPTSGPQSOPQK-UHFFFAOYSA-N magnesium zirconium Chemical class [Mg].[Zr] QRNPTSGPQSOPQK-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/11—Surgical instruments, devices or methods, e.g. tourniquets for performing anastomosis; Buttons for anastomosis
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/11—Surgical instruments, devices or methods, e.g. tourniquets for performing anastomosis; Buttons for anastomosis
- A61B17/1114—Surgical instruments, devices or methods, e.g. tourniquets for performing anastomosis; Buttons for anastomosis of the digestive tract, e.g. bowels or oesophagus
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/02—Inorganic materials
- A61L31/022—Metals or alloys
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/082—Inorganic materials
- A61L31/088—Other specific inorganic materials not covered by A61L31/084 or A61L31/086
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/10—Macromolecular materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B2017/00004—(bio)absorbable, (bio)resorbable or resorptive
Landscapes
- Health & Medical Sciences (AREA)
- Surgery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Heart & Thoracic Surgery (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Vascular Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Medical Informatics (AREA)
- Molecular Biology (AREA)
- Physiology (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention relates to an absorbable suture nail for an anastomat. The absorbable suture nail comprises a suture nail body, a degradable biological ceramic thin film bottom layer and a degradable macromolecule surface layer, wherein the suture nail body is made of medical degradable magnesium alloy wire materials, the degradable biological ceramic thin film bottom layer is attached on the surface of the magnesium alloy wire materials, and the degradable macromolecule surface layer is used for sealing holes. By the aid of surface double-layer protection formed by the degradable ceramic coating layer and the macromolecule thin film and hole sealing effect of an organic coating layer to the surface of an inorganic ceramic coating layer, the absorbable suture nail for the anastomat can be improved effectively, degrading speed of the suture nail is controlled, and the suture nail can be degraded and absorbed completely in in-vivo environment. Meanwhile, at early stage of postoperation, the suture nail has indispensable acid-resisting or alkali-resisting corrosive performance so as to resist early corrosion damage in the strong acid environment of the stomach and is applicable to anastomosis and suture after various operations in vivo, particularly alimentary canal operation.
Description
Technical field
A kind of anastomat of the present invention is with absorbing staple, the staple body that is processed by medical degradable magnesium alloy silk material, be attached to the degradable biological ceramic membrane bottom on magnesium alloy silk material surface, be used for the degradable macromolecule surface layer composition that sealing of hole is processed, in vivo can be by degradable absorption under the environment, simultaneously, commitment after surgery has again essential acidproof or alkali corrosion resistance performance, can resist the early stage corrosion failure of gastric strong acid environment, be applicable to the especially identical usefulness of sewing up of wound of early enteron feeding of the interior various operations of human body, belong to surgical stapling suture instruments technical field.
Background technology
It is the doctor in order to replace the traditional-handwork sewing method that kiss (seam) closes device, and the tissue that adopts staple to sew up to have cut or the instrument of organ have and sew up quick, easy and simple to handle reaching the advantages such as side effect and postoperative complication are seldom arranged.1908, the Hungarian has made in the world first stiching instrument, update subsequently, and gradually at clinical expansion, especially in nearly ten years, anastomat has become the conventional instrument of operation on digestive tract in American-European countries, also popularizes gradually at home, has become the requisite instrument of gastrointestinal surgery.According to the market survey for the Medical stapler sales situation, the consumption of the annual staple of coincideing in the whole nation is more than 5,000,000 covers.
But present traditional anastomat staple all adopts the fabulous titanium alloy of chemical stability or tantalum metal to make, staple long-term existence in patient after the operation, cause the patient that foreign body sensation is arranged for a long time, in the time of also can causing accepting future the medical examination such as nuclear magnetic resonance, NMR in vivo the staple position produce shadow, impact checks effect and accuracy, particularly may cause the hamartoplasia of suture site, cause the problems such as the postoperative tract is narrow.
In recent years, degradable magnesium alloy can absorb application prospect aspect the implantation instrument and be subject to the extensive concern of whole world researcher.Used for magnesium alloy has a lot of performance advantages in implantation instrument, and for example elastic modelling quantity is low, is about 41 ~ 45GPa, than titanium closer to people's bone; Its density is at 1.7 ~ 1.9g/cm
3About, close with people's compact bone bone density; Its specific strength, specific stiffness are higher, hot strength usually at 200MPa between the 300MPa; Have good biocompatibility, magnesium is one of several main metallic elements in the human body, for the growth of regulating cell with keep membrane structure and play an important role; The excessive magnesium that degraded is separated out can excrete by urine, has good safety.
Therefore, adopt the anastomat of magnesium alloy development with having the biological absorbable function, the bio-safety hidden danger of avoiding long-term existence in body, to bring, simultaneously, can effectively avoid foreign body in vivo sense and the psychological shade of postoperative, solve simultaneously the patient will be difficult to carry out the medical examinations such as nuclear magnetic resonance, NMR in future difficulty.But corrosion resistance of magnesium alloy can be relatively poor, and biodegradation rate is too fast in human body, easily cause the magnesium alloy staple before the healing of operation stitching mouth with regard to corrosion fracture, the leakage of generation anastomotic stoma.
Published utility model " absorbable magnesium alloy staple used for anastomat (publication number: CN 201617885U) " in, a kind of technical solution scheme has been proposed, namely adopt magnesium alloy silk material to make staple U-shaped body, be coated with biocompatibility on the magnesium alloy silk material surface good and have the face coat of corrosion resistance, and particularly pointing out this face coat is the coating of bio-ceramic coating, simple metal or alloy or the anodic oxide coating of magnesium alloy.
There is greatest differences in a large amount of stomach, the intestinal environment that use of different physiological environments, especially operation anastomat staple aspect Acidity of Aikalinity in the human body, for example the pH value of stomach gastric juice about 1.5, and the aobvious alkalescence of intestinal juice.Obviously, under the prerequisite that desirable absorbed staple coating for surface protection must be absorbed by Wholly-degradable under the environment in vivo, also must can provide essential acidproof or alkali corrosion resistance performance for staple inside body magnesium alloy silk material by commitment after surgery.
Usually, bioceramic that be used for to make coating comprises degradable hydroxyapatite, tricalcium phosphate, magnesium oxide etc. and nondegradable aluminium oxide, zirconium oxide, titanium oxide etc., and the former can be degraded and absorbed in vivo, but acid corrosion-resistant not; Latter's acid corrosion-resistant, but can not be degraded and absorbed, all not desirable staple protective finish.In simple metal or the alloy; only have magnesium and alloy thereof to have good degraded and absorbed performance; other parts zinc, ferroalloy also have degradation property; but equal acid corrosion-resistant not; simultaneously; the metal of a lot of acid corrosion-resistants enters titanium, tantalum etc. and can not be degraded and absorbed again, so the staple protective finish that simple metal or alloy neither be desirable.The anodic oxide coating of magnesium alloy is the magnesium oxide layer that loosens, obviously, and can not acid corrosion-resistant.
At present, the anastomat staple of clinical use all adopts the titanium alloy of excellent stability or tantalum metal to make, staple long-term existence in patient after the operation, cause the patient that foreign body sensation is arranged for a long time, in the time of also can causing accepting future the medical examination such as nuclear magnetic resonance, NMR in vivo the staple position produce shadow, impact checks effect and accuracy, particularly may cause the hamartoplasia of suture site, causes the problems such as the postoperative tract is narrow.
Utility model CN 201617885U is disclosed, adopt magnesium alloy silk material to make staple U-shaped body, be coated with biocompatibility on the magnesium alloy silk material surface good and have the face coat of corrosion resistance, and this face coat is the coating of bio-ceramic coating, simple metal or alloy or the anodic oxide coating of magnesium alloy.Although this physical ability of magnesium alloy silk material U-shaped is by degradable absorption, its face coat technical scheme can not guarantee to absorb staple have simultaneously under the environment in vivo the performance that is degraded and absorbed fully and after surgery commitment have again essential acidproof or alkali corrosion resistance performance.
Summary of the invention
Technical problem: the purpose of this invention is to provide a kind of anastomat with absorbing staple and preparation method thereof, provide a kind of whole technical scheme that solves to above-mentioned technical problem.
Technical scheme: for the problems referred to above, the technical solution that the present invention proposes is a kind of anastomat with can absorbing staple, the staple body that this anastomat is processed by medical degradable magnesium alloy silk material with staple, the degradable biological ceramic membrane bottom that is attached to the magnesium alloy silk material surface, forms for the degradable macromolecule surface layer of sealing of hole processing.Surface high molecular form surface layer is by poly (l-lactic acid); perhaps gather (D; L)-lactic acid or both copolymers or mixture; perhaps be that lactic acid is with the copolymer of glycolic; have than the better decay resistance of other degradable polymers; simultaneously; the surface texture that degradable biological ceramic membrane bottom has rough porous usually; acid in the body; the alkaline corrosion medium easily infiltrates corrosion magnesium alloy body; and the polylactic acid high molecular form surface layer of surface corrosion-resistant erosion can also carry out effective sealing of hole processing to the pore structure of bioceramic thin film bottom surface in coating procedure; therefore; double shielding and organic coating that surface degradable ceramic coating and macromolecule membrane form can effectively improve anastomat with absorbing the staple decay resistance to the sealing of hole effect on inorganic ceramic coating surface; the control anastomat degradation speed that can absorb staple; a kind of anastomat of the present invention in vivo can be by degradable absorption under the environment with absorbing staple; simultaneously; commitment after surgery has again essential acidproof or alkali corrosion resistance performance; can resist the early stage corrosion failure of gastric strong acid environment, be applicable to the especially identical usefulness of sewing up of early enteron feeding of the interior various operations of human body.
Anastomat of the present invention is with absorbing staple, the staple body that is processed by medical degradable magnesium alloy silk material, the degradable biological ceramic membrane bottom that is attached to the magnesium alloy silk material surface, be used for the degradable macromolecule surface layer that sealing of hole processes and form, the diameter of magnesium alloy silk material is 0.1mm ~ 0.6mm, the thickness of degradable biological ceramic membrane bottom is 0.1 μ m ~ 50 μ m, and the thickness of degradable macromolecule surface layer is 0.1 μ m ~ 100 μ m.
The polynary system magnesium alloy that the magnesium alloy silk material of addressing forms by a kind of of magnalium, magnesium-manganese alloy, magnesium-zinc alloy, Mg-Zr alloys, magnesium-rare earth alloy, magnesium lithium alloy, magnesium calcium alloy or magnesium silver alloy or by these system combinations through drawing, process.
The magnesium alloy silk material surface biological ceramic membrane bottom of addressing is by differential arc oxidation, anodic oxidation, electro-deposition, plasma spraying, chemical conversion, ion implantation, sputter, vapour deposition or biochemical method preparation, be hydroxyapatite coating layer, tricalcium phosphate coating, magnesium oxide coating or fluorine-containing overcoat, with the degradation speed of control magnesium alloy silk material and the dissolution rate of magnesium ion.
The degradable macromolecule surface layer material of addressing is poly (l-lactic acid), perhaps poly-(D, L)-lactic acid or both copolymers or mixture, perhaps be lactic acid with the copolymer of glycolic, polymer molecular weight is 10,000 ~ 1,500,000.
Anastomat of the present invention with the preparation method that can absorb staple is:
1) magnesium alloy that at first will choose composition is processed into magnesium alloy silk material;
2) select the ceramic coating technology, prepare required bioceramic thin film bottom on the magnesium alloy silk material surface;
3) adopt dip-coating, brushing or spraying method, have the magnesium alloy silk material surface of bioceramic thin film bottom further to prepare the degradable macromolecule surface layer on the surface;
4) the magnesium alloy silk material processing and forming that obtains with step 3) goes out staple;
5) finally by dry, check, sterilization, obtain anastomat with absorbing staple.
Or:
1) at first will choose composition the magnesium alloy drawing, be processed into magnesium alloy silk material;
2) select the ceramic coating technology that magnesium alloy silk material is carried out surface treatment, prepare required degradable biological ceramic membrane bottom on the magnesium alloy silk material surface;
3) with step 2) the magnesium alloy silk material processing and forming that obtains goes out staple;
4) adopt dip-coating, brushing or spraying method, further prepare the degradable macromolecule surface layer on the staple surface that obtains with step 3);
5) finally by dry, check, sterilization, obtain anastomat with absorbing staple.
Beneficial effect: the present invention is a kind of anastomat with can absorbing staple, staple body, the degradable biological ceramic membrane bottom that is attached to the magnesium alloy silk material surface that is processed by medical degradable magnesium alloy silk material, is used for the degradable macromolecule surface layer that sealing of hole processes and forms.Magnesium alloy silk material is to inorganic ceramic thin film bottom to the high molecular form surface layer internally, and the material that adopts is biodegradable, and therefore, the present invention can be sponged by degradable after performing the operation in vivo and healing, without remaining.
Simultaneously; surface high molecular form surface layer is by poly (l-lactic acid); perhaps gather (D; L)-lactic acid or both copolymers or mixture; perhaps be that lactic acid is with the copolymer of glycolic; it is operation stitching wire material commonly used; have than other degradable polymers better decay resistance of gelatin for example; simultaneously; the surface texture that degradable biological ceramic membrane bottom has rough porous usually; acid in the body; the alkaline corrosion medium easily infiltrates corrosion magnesium alloy body; and the polylactic acid high molecular form surface layer of surface corrosion-resistant erosion can also carry out effective sealing of hole processing to the pore structure of bioceramic thin film bottom surface in coating procedure; therefore; double shielding and organic coating that surface degradable ceramic coating and macromolecule membrane form can effectively improve anastomat with absorbing the staple decay resistance to the sealing of hole effect on inorganic ceramic coating surface; commitment after surgery has essential acidproof or alkali corrosion resistance performance; can resist the early stage corrosion failure of gastric strong acid environment; control anastomat with the degradation speed that can absorb staple, be applicable to the especially identical usefulness of sewing up of early enteron feeding of the interior various operations of human body.
The instantiation mode
The present invention is realized by the following technical programs:
The staple body that this anastomat is processed by medical degradable magnesium alloy silk material with staple, the degradable biological ceramic membrane bottom that is attached to the magnesium alloy silk material surface, be used for the degradable macromolecule surface layer that sealing of hole processes and form, the diameter of magnesium alloy silk material is 0.1mm ~ 0.6mm, the thickness of degradable biological ceramic membrane bottom is 0.1 μ m ~ 50 μ m, and the thickness of degradable macromolecule surface layer is 0.1 μ m ~ 100 μ m.
The ternary that the magnesium alloy silk material of addressing forms by a kind of of magnalium, magnesium-manganese alloy, magnesium-zinc alloy, Mg-Zr alloys, magnesium-rare earth alloy, magnesium lithium alloy, magnesium calcium alloy or magnesium silver alloy or by these system combinations or polynary system magnesium alloy through drawing, process.
Related magnesium alloy silk material material mainly comprises: magnalium series (mainly comprises Mg-Al-Zn except binary system, Mg-Al-Mn, Mg-Al-Si, four ternary systems of Mg-Al-RE and multicomponent system, alloy representative such as AZ31, AZ61, AZ91, AM60, AE21, AS21 etc. wherein contain the aluminum quality and are lower than 10%, Zn, Mn, Si, RE quality less than 5%); Magnesium manganese series (mainly be binary Mg-0.1～2.5%Mn and add elementary composition ternary system or the polynary systems such as a small amount of rare earth, calcium, zinc, represent alloy such as domestic trade mark MB1 and MB8); Magnesium zinc series (except binary system, mainly comprising Mg-Zn-Zr and Mg-Zn-Cu series, alloy representative ZK21, ZK60, ZC62 etc.); Magnesium zirconium series (mainly be binary Mg-0.1～2%Zr and add elementary composition ternary system or the polynary systems such as a small amount of rare earth, zinc, represent alloy such as K1A etc.); Magnesium rare earth metal (mainly be binary Mg-0.1 ~ 5%RE) and add elementary composition ternary system or the polynary systems such as a small amount of aluminum, zirconium, calcium, zinc); Magnesium lithium alloy (mainly be binary Mg-1 ~ 15%Li and add elementary composition ternary system or the polynary systems such as a small amount of aluminum, rare earth, zinc and silicon, represent alloy such as LA91, LAZ933 etc.); Magnesium calcium series (mainly be binary Mg-0.1 ~ 10%Ca and add elementary composition ternary system or the polynary systems such as a small amount of rare earth, zirconium, zinc); The alloy system that magnesium silver series (mainly be binary Mg-0.1 ~ 12%Ag and add elementary composition ternary system or the polynary systems such as a small amount of rare earth, zirconium, zinc, represent alloy such as QE22 etc.) etc. are different a kind of or by ternary system and the polynary system magnesium alloy of these composing systems.
The magnesium alloy silk material surface biological ceramic membrane bottom of addressing is by differential arc oxidation, anodic oxidation, electro-deposition, plasma spraying, chemical conversion, ion implantation, sputter, vapour deposition or biochemical method preparation, be hydroxyapatite coating layer, tricalcium phosphate coating, magnesium oxide coating or fluorine-containing overcoat, with the degradation speed of control magnesium alloy silk material and the dissolution rate of magnesium ion.
The degradable macromolecule surface layer material of addressing is poly (l-lactic acid), perhaps poly-(D, L)-lactic acid or both copolymers or mixture, perhaps be lactic acid with the copolymer of glycolic, polymer molecular weight is 10,000 ~ 1,500,000.
Described anastomat is with absorbing staple, and its preparation method can be: the magnesium alloy that will choose composition is processed into magnesium alloy silk material; Select suitable ceramic coating technology, prepare required bioceramic thin film bottom on the magnesium alloy silk material surface; Adopt dip-coating, brushing or spraying method, have the magnesium alloy silk material surface of bioceramic thin film bottom further to prepare the degradable macromolecule surface layer on the surface; Magnesium alloy silk material processing and forming with aforementioned acquisition goes out staple; Finally by dry, check, sterilization, obtain the present invention.
Described anastomat is with absorbing staple, and its preparation method also can be: will choose composition the magnesium alloy drawing, be processed into magnesium alloy silk material; Select suitable ceramic coating technology that magnesium alloy silk material is carried out surface treatment, prepare required degradable biological ceramic membrane bottom on the magnesium alloy silk material surface; Magnesium alloy silk material processing and forming with aforementioned acquisition goes out staple; Adopt dip-coating, brushing or spraying method, further prepare the degradable macromolecule surface layer on the staple surface of aforementioned acquisition; Finally by dry, check, sterilization, obtain the present invention.
Embodiment 1
A kind of anastomat is with absorbing staple, the U-shaped structure staple body that is processed by medical degradable AZ31B magnesium alloy silk material, the degradable magnesia ceramics thin film bottom that is attached to the magnesium alloy silk material surface, be used for the degradable poly lactic acid surface layer that sealing of hole processes and form, the diameter of magnesium alloy silk material is φ 0.30mm, magnesia ceramics thin film underlayer thickness is about 10 μ m, and the thickness of degradable poly lactic acid surface layer is about 10 μ m.
Described anastomat is as follows with the preparation process that can absorb staple:
1) at first with the drawing of AZ31B magnesium alloy, be processed into the magnesium alloy silk material that diameter is φ 0.30mm;
2) use 10g/L sodium silicate and 2g/L NaOH as the differential arc oxidation electrolyte system, magnesium alloy silk material is dipped in wherein, apply 400V voltage, the differential arc oxidation that carried out 10 minutes is processed, and makes its surface in situ generate magnesium oxide bioceramic bottom;
3) 10 gram degradable poly lactic acid are dissolved in the chloroform of 50ml, with step 2) magnesium alloy silk material processed is immersed in this solution, soak time is 1.0 minutes, can repeatedly soak, take out magnesium alloy silk material between per twice immersion, and in air, vaporing away solvent, the THICKNESS CONTROL of degradable surface layer is about 10 μ m;
4) step 3) was processed with the magnesium alloy silk material processing and forming and gone out U-shaped structure staple;
5) finally by dry, check, sterilization, obtain the present invention.
Embodiment 2
A kind of anastomat is with absorbing staple, U-shaped structure staple body, the degradable magnesium oxide that is attached to the magnesium alloy silk material surface and the hydroxyapatite ceramic thin sheet bottom that is processed by medical degradable AZ91 magnesium alloy silk material, be used for the degradable poly lactic acid surface layer that sealing of hole processes and form, the diameter of magnesium alloy silk material is φ 0.20mm, magnesium oxide and hydroxyapatite ceramic thin sheet underlayer thickness are about 5 μ m, and the thickness of degradable poly lactic acid surface layer is about 5 μ m.
Described anastomat is as follows with the preparation process that can absorb staple:
1) at first with the drawing of AZ91 magnesium alloy, be processed into the magnesium alloy silk material that diameter is φ 0.20mm;
2) use 10g/L sodium silicate, 3g/L hydroxyapatite nano-powder, 2g/L NaOH as the differential arc oxidation electrolyte system, magnesium alloy silk material is dipped in wherein, apply 400V voltage, the differential arc oxidation that carried out 5 minutes is processed, and makes its surface in situ generate one deck magnesium oxide and hydroxyapatite composite ceramics bottom;
3) 10 gram degradable poly lactic acid macromolecular materials are carried out high temperature melting, with this brushing of molten state polylactic acid or dip-coating step 2) magnesium alloy silk material processed, through solidifying curing, the THICKNESS CONTROL of degradable surface layer is about 5 μ m;
4) step 3) was processed with the magnesium alloy silk material processing and forming and gone out U-shaped structure staple;
5) finally by dry, check, sterilization, obtain the present invention.
Embodiment 3
A kind of anastomat is with absorbing staple, the U-shaped structure staple body that is processed by medical degradable AZ31B magnesium alloy silk material, the degradable hydroxyapatite bioceramic thin film bottom that is attached to the magnesium alloy silk material surface, be used for the degradable PLGA surface layer that sealing of hole processes and form, the diameter of magnesium alloy silk material is φ 0.25mm, hydroxyl apatite bioceramic thin film underlayer thickness is about 10 μ m, and the thickness of degradable PLGA surface layer is about 20 μ m.
Described anastomat is as follows with the preparation process that can absorb staple:
1) at first with the drawing of AZ31B magnesium alloy, be processed into the magnesium alloy silk material that diameter is φ 0.25mm;
2) at the electrolyte system that contains the 6g/L hydroxyapatite nano-powder, use electro-deposition techniques at magnesium alloy silk material surface electrical deposited hydroxyl apatite bioceramic bottom;
3) 10 gram degradable PLGA are dissolved in the chloroform of 50ml, with step 2) magnesium alloy silk material processed is immersed in this solution, soak time is 1.5 minutes, can repeatedly soak, take out magnesium alloy silk material between per twice immersion, and in air, vaporing away solvent, the THICKNESS CONTROL of degradable surface layer is about 20 μ m;
4) step 3) was processed with the magnesium alloy silk material processing and forming and gone out U-shaped structure staple;
5) finally by dry, check, sterilization, obtain the present invention.
Embodiment 4
A kind of anastomat is with absorbing staple, U-shaped structure staple body, the degradable magnesium oxide that is attached to the magnesium alloy silk material surface and the hydroxyapatite ceramic thin sheet bottom that is processed by medical degradable AZ91 magnesium alloy silk material, be used for the degradable PLGA surface layer that sealing of hole processes and form, the diameter of magnesium alloy silk material is φ 0.28mm, magnesium oxide and hydroxyapatite ceramic thin sheet underlayer thickness are about 10 μ m, and the thickness of degradable PLGA surface layer is about 10 μ m.
Described anastomat is as follows with the preparation process that can absorb staple:
1) at first with the drawing of AZ91 magnesium alloy, be processed into the magnesium alloy silk material that diameter is φ 0.28mm;
2) use 10g/L sodium silicate, 3g/L hydroxyapatite nano-powder, 2g/L NaOH as the differential arc oxidation electrolyte system, magnesium alloy silk material is dipped in wherein, apply 400V voltage, the differential arc oxidation that carried out 10 minutes is processed, and makes its surface in situ generate one deck magnesium oxide and hydroxyapatite composite ceramics bottom;
3) 10 gram degradable PLGA macromolecular materials are carried out high temperature melting, with this molten state PLGA brushing or dip-coating step 2) magnesium alloy silk material processed, through solidifying curing, the THICKNESS CONTROL of degradable surface layer is about 10 μ m;
4) step 3) was processed with the magnesium alloy silk material processing and forming and gone out U-shaped structure staple;
5) finally by dry, check, sterilization, obtain the present invention.
Obviously, the above embodiment of the present invention only is in order to clearly demonstrate example of the present invention, and is not to be restriction to embodiments of the present invention.For those of ordinary skill in the field; also can make other changes in different forms on the basis of the above description; here need not also can't give all embodiments exhaustive, and these belong to apparent variation or the change that spirit of the present invention amplified out and still are in protection scope of the present invention.
Claims (6)
1. an anastomat is with absorbing staple, it is characterized in that, the staple body that this anastomat is processed by medical degradable magnesium alloy silk material with staple, the degradable biological ceramic membrane bottom that is attached to the magnesium alloy silk material surface, be used for the degradable macromolecule surface layer that sealing of hole processes and form, the diameter of magnesium alloy silk material is 0.1mm ~ 0.6mm, the thickness of degradable biological ceramic membrane bottom is 0.1 μ m ~ 50 μ m, and the thickness of degradable macromolecule surface layer is 0.1 μ m ~ 100 μ m.
2. anastomat as claimed in claim 1 is with absorbing staple, it is characterized in that, the polynary system magnesium alloy that the magnesium alloy silk material of addressing forms by a kind of of magnalium, magnesium-manganese alloy, magnesium-zinc alloy, Mg-Zr alloys, magnesium-rare earth alloy, magnesium lithium alloy, magnesium calcium alloy or magnesium silver alloy or by these system combinations through drawing, process.
3. anastomat as claimed in claim 1 is with absorbing staple, it is characterized in that, the magnesium alloy silk material surface biological ceramic membrane bottom of addressing is by differential arc oxidation, anodic oxidation, electro-deposition, plasma spraying, chemical conversion, ion implantation, sputter, vapour deposition or biochemical method preparation, be hydroxyapatite coating layer, tricalcium phosphate coating, magnesium oxide coating or fluorine-containing overcoat, with the degradation speed of control magnesium alloy silk material and the dissolution rate of magnesium ion.
4. anastomat as claimed in claim 1 is with absorbing staple, it is characterized in that, the degradable macromolecule surface layer material of addressing is poly (l-lactic acid), perhaps gather (D, L)-lactic acid or both copolymers or mixture, perhaps be lactic acid with the copolymer of glycolic, polymer molecular weight is 10,000 ~ 1,500,000.
5. an anastomat as claimed in claim 1 is characterized in that the step of its preparation is with the preparation method that can absorb staple:
1) magnesium alloy that at first will choose composition is processed into magnesium alloy silk material;
2) select the ceramic coating technology, prepare required bioceramic thin film bottom on the magnesium alloy silk material surface;
3) adopt dip-coating, brushing or spraying method, have the magnesium alloy silk material surface of bioceramic thin film bottom further to prepare the degradable macromolecule surface layer on the surface;
4) the magnesium alloy silk material processing and forming that obtains with step 3) goes out staple;
5) finally by dry, check, sterilization, obtain anastomat with absorbing staple.
6. an anastomat as claimed in claim 1 is characterized in that the step of its preparation is with the preparation method that can absorb staple:
1) at first will choose composition the magnesium alloy drawing, be processed into magnesium alloy silk material;
2) select the ceramic coating technology that magnesium alloy silk material is carried out surface treatment, prepare required degradable biological ceramic membrane bottom on the magnesium alloy silk material surface;
3) with step 2) the magnesium alloy silk material processing and forming that obtains goes out staple;
4) adopt dip-coating, brushing or spraying method, further prepare the degradable macromolecule surface layer on the staple surface that obtains with step 3);
5) finally by dry, check, sterilization, obtain anastomat with absorbing staple.
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| CN2012104241027A CN102908675A (en) | 2012-10-29 | 2012-10-29 | Absorbable suture nail for anastomat |
| PCT/CN2012/085453 WO2014067201A1 (en) | 2012-10-29 | 2012-11-28 | Anastomat-use absorbable suturing staple |
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| CN2012104241027A CN102908675A (en) | 2012-10-29 | 2012-10-29 | Absorbable suture nail for anastomat |
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| CN102908675A true CN102908675A (en) | 2013-02-06 |
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