CN111388764B - Degradable metal anastomosis nail and preparation method thereof - Google Patents
Degradable metal anastomosis nail and preparation method thereof Download PDFInfo
- Publication number
- CN111388764B CN111388764B CN202010262841.5A CN202010262841A CN111388764B CN 111388764 B CN111388764 B CN 111388764B CN 202010262841 A CN202010262841 A CN 202010262841A CN 111388764 B CN111388764 B CN 111388764B
- Authority
- CN
- China
- Prior art keywords
- degradable
- staple
- round wire
- zinc alloy
- zinc
- 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.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 230000003872 anastomosis Effects 0.000 title abstract description 13
- 229910052751 metal Inorganic materials 0.000 title abstract description 13
- 239000002184 metal Substances 0.000 title abstract description 13
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 42
- 239000002344 surface layer Substances 0.000 claims abstract description 10
- 229920000620 organic polymer Polymers 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 27
- 229910045601 alloy Inorganic materials 0.000 claims description 23
- 239000000956 alloy Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 10
- 238000005260 corrosion Methods 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229920006237 degradable polymer Polymers 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000002861 polymer material Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000004323 axial length Effects 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 238000003723 Smelting Methods 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 238000005452 bending Methods 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 230000007721 medicinal effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical class [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 17
- 229910000861 Mg alloy Inorganic materials 0.000 description 14
- 239000007943 implant Substances 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 210000001519 tissue Anatomy 0.000 description 8
- 230000000968 intestinal effect Effects 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 238000001727 in vivo Methods 0.000 description 6
- 238000001356 surgical procedure Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 210000000988 bone and bone Anatomy 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 210000001035 gastrointestinal tract Anatomy 0.000 description 3
- 230000035876 healing Effects 0.000 description 3
- 238000001192 hot extrusion Methods 0.000 description 3
- 238000005098 hot rolling Methods 0.000 description 3
- 239000002504 physiological saline solution Substances 0.000 description 3
- 210000004509 vascular smooth muscle cell Anatomy 0.000 description 3
- 206010018910 Haemolysis Diseases 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910017706 MgZn Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 229910009369 Zn Mg Inorganic materials 0.000 description 2
- 229910007573 Zn-Mg Inorganic materials 0.000 description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical class [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 2
- 230000001174 ascending effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 210000004204 blood vessel Anatomy 0.000 description 2
- 230000004663 cell proliferation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 231100000135 cytotoxicity Toxicity 0.000 description 2
- 230000003013 cytotoxicity Effects 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 210000003238 esophagus Anatomy 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000011902 gastrointestinal surgery Methods 0.000 description 2
- 230000008588 hemolysis Effects 0.000 description 2
- 208000014617 hemorrhoid Diseases 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000011164 ossification Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010068797 Anastomotic fistula Diseases 0.000 description 1
- 206010056346 Anastomotic haemorrhage Diseases 0.000 description 1
- 206010051268 Anastomotic stenosis Diseases 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- 208000037408 Device failure Diseases 0.000 description 1
- 206010019909 Hernia Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229910019805 Mg2Zn11 Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 208000031481 Pathologic Constriction Diseases 0.000 description 1
- 208000026137 Soft tissue injury Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- VCQAIUIHXQEIHD-UHFFFAOYSA-N [Zn].[Sr] Chemical class [Zn].[Sr] VCQAIUIHXQEIHD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 208000038016 acute inflammation Diseases 0.000 description 1
- 230000006022 acute inflammation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010171 animal model Methods 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 239000002473 artificial blood Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000003833 cell viability Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 208000037976 chronic inflammation Diseases 0.000 description 1
- 230000006020 chronic inflammation Effects 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical class [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000002674 endoscopic surgery Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003102 growth factor Substances 0.000 description 1
- 206010020718 hyperplasia Diseases 0.000 description 1
- 238000011532 immunohistochemical staining Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical class [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 238000004372 laser cladding Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- KUJOABUXCGVGIY-UHFFFAOYSA-N lithium zinc Chemical class [Li].[Zn] KUJOABUXCGVGIY-UHFFFAOYSA-N 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical class [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- 210000004877 mucosa Anatomy 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 201000008968 osteosarcoma Diseases 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000002980 postoperative effect Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 210000001243 pseudopodia Anatomy 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 210000000664 rectum Anatomy 0.000 description 1
- 238000002271 resection Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical class [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000036262 stenosis Effects 0.000 description 1
- 208000037804 stenosis Diseases 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Abstract
A degradable metal anastomosis nail and a preparation method thereof belong to the technical field of medical appliances. Consists of a suture nail body processed by medical degradable zinc alloy wires and a degradable organic polymer surface layer attached to the surface of the zinc alloy suture nail body. The staple body is staple-like. The degradable anastomat can be naturally degraded in organisms, and can be degraded from the bodies within a certain time after the medical effect is achieved.
Description
Technical Field
The invention relates to the technical field of medical instrument design and production, in particular to a surgical repair and reconstruction anastomosis nail with excellent biocompatibility, proper biomechanical property and biodegradability for clinical use and a preparation method thereof.
Background
The invention and the application of the suture-free surgical technique are great progress and development in the surgical field, and the suture-free surgical technique is simple and rapid to operate, shortens the operation time, and is easy to complete suturing and anastomosis with narrow operation field, deep position and difficult manual operation, the operation range is enlarged, the operation complications are reduced, and the hospitalization time is shortened. Thus, as one of the most successful surgical techniques at present, the use of seamless anastomosis has become increasingly widespread. The anastomat is a tool for a doctor to suture tissues or organs to be anastomosed by adopting a suture nail instead of the traditional manual suture method, and has the advantages of quick suture, simple and convenient operation, few side effects and operation complications and the like. In 1908, hungarian manufactured the first stapler in the world, and then improved and gradually popularized clinically, especially in the last decade, anastomat has become a conventional tool for gastrointestinal surgery in the european and american countries, and also in the country, has become an indispensable tool for gastrointestinal surgery. According to market research aiming at the sales condition of the medical anastomat, the dosage of the anastomotic staples per year is over 500 ten thousand sets nationwide. The anastomat is a device used in medicine to replace manual suturing, and the main working principle is to utilize titanium nails to anastomose tissues, which is similar to a stapler. According to the application scope, the surgical stapler can be mainly divided into a skin stapler, a digestive tract (esophagus, stomach intestine and the like) circular stapler, a rectum stapler, a circular hemorrhoid stapler, a circumcision stapler, a blood vessel stapler, a hernia stapler, a lung cutting stapler and the like, but the current traditional stapler staples are all made of titanium alloy or tantalum metal with excellent chemical stability, the surgical staples exist in a patient for a long time after the surgery, so that part of the patient has foreign body sensation for a long time, and in the future medical examination of nuclear magnetic resonance and the like, artifacts and local soft tissue injury (nuclear magnetism can cause metal heating) can be generated at the positions of the staples in the body, the examination effect and accuracy can be influenced, and especially the tissue hyperplasia at the sewed positions can be caused, and the problems of post-surgery cavity stenosis and the like can be caused. The degradable metal nail is suitable for a tubular anastomat and an anorectal anastomat, is mainly used for anastomosis of various cavity tracts and is disposable, and the working principle is that two layers of cavity tract tissues can be sutured together by two rows of annular and crossed staples which are punched into the cavity tract tissues, and redundant cavity tract tissues are simultaneously resected by an internally arranged annular knife, so that a circular anastomosis opening is formed, and the cavity tract anastomosis is completed. Clinically, the anastomotic device is mainly used for operations such as alimentary canal reconstruction under endoscopic surgery, mucosa circular cutting on hemorrhoids and the like, has anastomosis and artificial blood vessel implantation of large arteries by using a tubular anastomat, and has typical advantages: the wound is small, the time consumption is low, and the incidence rate of postoperative anastomotic fistula, anastomotic hemorrhage, anastomotic stenosis and the like is low.
The materials selected therefore not only require simple surgical procedures and reduced complications, but also allow for repeated shaping, provide suture stability, and be absorbed by the body after completion of the procedure. So far, no ideal repairing material has excellent mechanical property and biological compatibility, can guide soft tissue healing, and can be completely degraded or absorbed by the repairing material, so that physiological healing is realized. The staple materials currently used mainly comprise two types of non-degradable metals and degradable high molecular polymers. The common metals are tantalum, titanium alloy plates or stainless steel, which are convenient to mold, but as permanent implants, the permanent implants are subjected to long-term physical stimulation, complications are caused by long-term foreign body stimulation, and local chronic inflammatory reactions are caused. While these metallic staples are now temporarily able to meet clinical needs, in the long run, the development of biodegradable, more biocompatible staples has become a trend. Although the degradable high polymer material can be used for repairing the degradable anastomat, the mechanical property of the degradable high polymer material is relatively poor, and the acidic degradation product is easy to cause acute or chronic inflammation and the like. The development of biodegradable metal staples is therefore one of the important directions for current staple research. In addition, the degradable metal nail can be formed into a coating by an ion beam auxiliary deposition method, an electrodeposition method, a chemical vapor deposition method, an arc deposition method, an ion implantation method and a thermal spraying method through a laser cladding method, has a compact structure, is firmly combined with a metal implant, controls the degradation rate of the degradable metal on the one hand, and enables the implant to have excellent bioactivity and biocompatibility on the other hand. The invention provides a degradable anastomat which is convenient to use, safe and effective.
Disclosure of Invention
In order to overcome the defects in the prior art, the technical scheme adopted by the invention is a degradable metal anastomat and a preparation method.
The degradable anastomat is characterized by comprising a suture nail body (1) formed by processing medical degradable zinc alloy wires and a degradable organic polymer surface layer (2) attached to the surface of the zinc alloy suture nail body. The staple body is similar to a staple shape, and the staple body structure is as follows: the two ends of the middle long round wire A (3) are respectively provided with a short round wire B (4) perpendicular to the long round wire A, the short round wire B and the long round wire A are of an integrated structure, namely the same zinc alloy round wire is adopted, the two short round wires B are positioned on the same side of the long round wire A and are coplanar with the long round wire A, and the plane is called C; the end of the short-section round wire B, namely the end which is not connected with the long-section round wire, is provided with a wedge-shaped structure, wherein the wedge-shaped structure is formed by cutting the short-section round wire B from the outer side by adopting a plane D vertical to a plane C, and the included angle between the plane D and the short-section round wire B is preferably an acute angle, and is preferably 45-60 degrees; the axial length of the long round wire A is the length of the staple body, and the axial length of the short round wire B is the height of the staple body; the diameters of the long round wire A and the short round wire B can be designed according to the needs. The thickness of the degradable polymer surface layer is 5-30 micrometers. The length of the stitching nail is 63-103mm, and the allowable error is +/-2 mm; the staple height is 3.8-4.5mm, and the tolerance is + -0.2 mm.
The content of the alloy elements in the degradable zinc alloy can meet the biomedical requirement range, so that the degradation products can not cause tissue toxic reaction, and the binary or ternary zinc alloy is selected from pure zinc series or zinc-magnesium series, zinc-calcium series, zinc-lithium series, zinc-strontium series, zinc-manganese series, zinc-iron series, zinc-copper series and zinc-silver series. Degradable zinc alloy components: the zinc content is more than or equal to 95%, and one or more of Mg, sr, li, mn, fe, ca, cu and Ag elements can be contained, wherein the total weight content of calcium, copper and silver elements is less than or equal to 3%, the total weight content of Mg, ca, sr, li, mn, fe is less than or equal to 1%, and other impurities or other elements which are 0 or indispensable are contained.
The degradable high polymer material is selected from chitosan and polylactic acid; chitosan is a natural high molecular polymer with viscosity, good biocompatibility, biodegradability, film forming property and drug carrying property, and is often used as a growth factor carrier and a bracket material to be applied to bone tissue engineering.
The preparation of the degradable anastomat by using the anastomat comprises the following steps:
(1) The staple body is prepared by smelting and casting an as-cast alloy, wherein the raw materials comprise high-purity zinc (99.9 wt%) and an intermediate alloy in a resistance furnace with protective gas; preparing raw materials according to the proportion of the designed components; after the raw materials are completely melted, stirring and standing are carried out, and the melted materials are cast on a die, wherein protective gas is required to be introduced in the process.
(2) Obtaining zinc alloy wire
Carrying out heat treatment on the zinc alloy ingot casting material obtained in the step (1), and drawing the zinc alloy ingot casting material into a required wire; in the initial stage of the successive drawing process, annealing treatment is carried out on the profile at 500 ℃, so that the corrosion resistance of the zinc alloy is improved from the inside; bending the wire material according to the designed size to prepare a staple;
(3) Alkaline heat treatment of the surface of the formed zinc alloy staples:
Corroding the staples obtained in the step (2) by adopting acid (1 wt% nitric acid solution), cleaning, and increasing the surface roughness; preparing a 1M NaOH alkali solution in advance, putting the sample subjected to acid etching in a small reaction kettle, adding the prepared alkali solution, and completely immersing the sample; sealing the reaction kettle, horizontally putting the reaction kettle into an oven, and heating the reaction kettle for 5 to 8 hours at the temperature of 120 to 150 ℃; slowly cooling along with a furnace, taking out a sample, ultrasonically cleaning with deionized water, and drying in an oven to obtain a treated zinc alloy staple;
(4) Forming degradable polymer coating
Preparing a degradable high polymer material into a solution, sucking the solution at room temperature by using a syringe, injecting the solution into a groove die with the same structure as the staples, lightly placing the staples in the step (3) at the center of the die, slowly filling the solution into the die, rapidly transferring the die into a refrigerator, pre-freezing, placing the die into a freeze dryer, drying and forming the material, and taking out the material; or directly coating degradable polymer material solution on the suture, and then drying.
Further preferred is the heat treatment described in step (2): in order to improve the mechanical properties, the zinc alloy ingot requires a heat treatment process of further hot rolling and hot extrusion. Hot rolling, cutting an as-cast zinc alloy ingot into thick plates, preheating to 250 ℃, and rolling thinner plates after 3 hours; the reduction of the thickness of the steel plate is that the steel plate is heated for 0.2 mm for one time, and the steel plate is reheated to 250 ℃ and kept for 10 minutes between each pass; hot extrusion, first cutting into cylinders with larger diameters, preheating to 210 ℃ for 3 hours, and then extruding into cylinders with relatively smaller diameters.
The anastomat is made of degradable staples, the entity is made of degradable zinc alloy wires, and the surface layer is made of degradable polymer surface layers. The solid and surface materials can also be degraded in vivo and have excellent biocompatibility. Compared with the prior art, the invention has the beneficial effects that:
(1) The degradable anastomat can be naturally degraded in organisms, and can be degraded in vivo within a certain time after the medical effect is achieved, so that physiological and mental burden of patients caused by foreign matters in vivo is avoided.
(2) The degradable anastomat in the organism avoids using Al and rare earth metal in component design, and ensures the biosafety of the material in terms of material selection.
(3) The degradable anastomat in the organism has high corrosion resistance, good plastic deformation capability and good biocompatibility, meets the requirement of the implanted material on the corrosion rate, has no obvious cytotoxicity and good tissue compatibility, and can meet the requirement of the implanted material on the biocompatibility.
(4) The degradable anastomat in the organism adopts polylactic acid high polymer, on one hand, the mechanical property of the anastomat can be adjusted, so that the mechanical property can meet the function of anastomosis maintenance as much as possible, and on the other hand, the corrosion resistance of the magnesium alloy bracket can be improved to a certain extent.
(5) In the production process of the degradable anastomat in the organism, in the heat treatment process, after the profile is extruded and molded, the profile is annealed at 500 ℃, so that the corrosion resistance of the zinc alloy is improved from the inside; subsequent alkaline heat treatment improves the corrosion resistance of the zinc alloy from the outside.
Drawings
FIG. 1 is a 3D modeling of a stapler nail;
FIG. 2 is a finished stapler nail;
FIG. 3 is a metallographic photograph;
FIG. 4XRD diffraction pattern;
FIG. 5 is a graph showing the mass loss rate of zinc-magnesium alloy in physiological saline;
FIG. 6 shows a normal saline pH line graph of zinc magnesium alloy.
Detailed Description
The invention will now be further illustrated by the following examples, which are given by way of illustration only and not by way of limitation, and are not intended to limit the scope of the invention.
Example 1
The anastomat comprises a suture nail body processed by medical degradable zinc alloy wires and a degradable polymer surface layer attached to the surfaces of the zinc alloy wires and used for hole sealing treatment. The entity is characterized by being staple-like. The basic size of the stapling length of the anastomat used degradable staples is 63-103mm, and the allowable error is +/-2 mm. The basic size of the height of the degradable anastomat used by the anastomat is 3.8-4.5mm, and the allowable error is +/-0.2 mm. As shown in fig. 2.
The anastomat is prepared from degradable zinc alloy wires by using degradable anastomotic nail entities, and the surface layer is prepared from a degradable polymer surface layer. So that it can be degraded in vivo and has excellent biocompatibility. Is suitable for anastomosis suturing of gastrointestinal tract and esophagus in human digestive tract operation.
The preparation method specifically comprises the following steps:
(1) Preparing zinc-calcium alloy:
The experiments used as-cast alloy feedstock comprised high purity zinc (99.9 wt%) and magnesium or/and magnesium oxide master alloys. Smelting and casting in a resistance furnace with mixed shielding gas; preparing raw materials according to the component proportion of Zn-1% Mg (or adopting calcium oxide intermediate alloy to correspond to Zn-1% Ca); after the raw materials are completely melted, stirring and standing are carried out fully. The melted material is cast onto a mold (this process requires the passage of a shielding gas).
(2) Obtaining zinc alloy wire
The zinc alloy ingot material was subjected to heat treatment (a heat treatment process requiring further hot rolling and hot extrusion of the zinc alloy ingot in order to improve mechanical properties. For a rolled sample, the as-cast zinc alloy ingot was cut into thick plates, preheated to 250 ℃ for 3 hours, and then a thinner plate was rolled. The reduction in thickness of the steel plate was a single pass of heating by 0.2 mm, and the steel plate was reheated to 250 ℃ between each pass for 10 minutes. In the initial stage of the successive drawing process, the profile is subjected to a finish annealing treatment at 500 ℃. The stapler uses degradable staples with a staple length of a basic size of 63mm and a height of a basic size of 3.8mm. And bending the wire into a staple shape according to the designed size.
(3) Surface alkali heat treatment of the formed zinc alloy anastomat:
Preparing a low-concentration 1M NaOH alkali solution in advance, putting a sample (1 wt% nitric acid solution) subjected to acid etching in advance into a 25ml small-sized reaction kettle, and adding the alkali solution prepared in advance to completely submerge the sample. The reaction vessel was sealed horizontally and placed in an oven and heated at 140 degrees celsius for 6 hours. And slowly cooling along with a furnace, taking out a sample, ultrasonically cleaning the sample with deionized water for three times, and drying the sample in a drying oven at 37 ℃ for 15min to obtain the treated zinc alloy anastomat.
(4) Forming degradable polymer coating
Preparing chitosan into a solution, sucking the solution at room temperature by using a syringe, injecting the solution into a mold, lightly placing a zinc alloy wire at the center of the mold, slowly filling the solution into the mold, rapidly transferring the mold into a refrigerator at the temperature of minus 20 ℃, pre-freezing for 12 hours, placing the mold in a freeze dryer for 24 hours, and taking out the material after drying and forming. Forming the degradable high polymer coating with the thickness of about 10 micrometers.
(5) Use of intestinal anastomat:
The proximal intestinal canal of the anastomat is sutured by a purse string, the nail seat is placed and tightened, the anastomat is inserted into the distal intestinal cavity, the central puncture outfit of the anastomat is penetrated out and is connected with the central rod of the nail seat of the proximal anastomat, the distal intestinal canal and the proximal intestinal canal are gradually closed by rotating the knob, and the distance between the nail seat and the base of the anastomat is adjusted according to the intestinal canal thickness, or the rotation of hands is limited. Opening the insurance; the matched wrench is tightly pinched, and the 'clicking' sound is heard to indicate that the cutting and the matching are completed. The stapler was unscrewed and gently pulled out of the distal end to check if the distal and proximal intestinal resection rings were complete.
The following is a metallographic photograph of the zinc-magnesium alloy, hardness values, XRD results, and experimental data of in vitro simulated environmental degradation:
(1) Metallographic photograph
From the structural appearance of the obtained zinc-magnesium binary alloy, it can be seen from fig. 3 that the structure of the zinc alloy is refined with the addition of magnesium, and the brighter part is alpha-Zn.
(2) Hardness of
The hardness of the Zn-Mg alloy obtained in Table 1 (sample test in cylindrical form, sample axial length 25mm, diameter 30mm, L1 and L2 being the distance from both end faces in the axial direction, D1 and D2 being the distance from the periphery in the diametric direction, hardness being average hardness)
It is known from the metallographic results that the grain refinement of zinc-magnesium alloy is performed by adding magnesium, the grain boundary area of the alloy is increased, and the resistance to dislocation slip is increased, which is shown as an increase in hardness of the alloy from a macroscopic point of view. The Vickers hardness of magnesium is between 40 and 60HV, the Vickers hardness of iron is about 315HV, and according to experiments, the zinc-magnesium alloy hardness is about 315HV, and before magnesium and iron, the alloy has good plastic toughness, and in addition, many scholars research show that the hardness and plasticity of the as-cast zinc-magnesium alloy can not achieve the effect of the degradable biological material on human body support, and a certain processing means such as work hardening is generally adopted to change the mechanical property of the zinc-magnesium alloy, so that the zinc-magnesium alloy achieves the effect of supporting the zinc-magnesium alloy on human body.
(3) XRD diffraction pattern
Fig. 4 shows the results of the X-ray diffraction test of the obtained zinc-magnesium binary alloy, wherein pure zinc is contained in the alloy, and magnesium element exists in a compound state in the alloy, and according to the conclusion, the compound in the alloy exists in MgZn 2 and MgZn 11. According to a binary phase diagram of the zinc-magnesium alloy, the zinc-magnesium alloy firstly separates out an alpha-Zn phase during equilibrium crystallization, and then separates out a zinc-magnesium eutectic structure along a grain boundary, wherein the eutectic structure is alpha-Zn and Mg2Zn11.
(4) Simulation of corrosion rate in human environment
Analysis of mass loss rate diagram of the obtained zinc-magnesium alloy in physiological saline solution.
The zinc-magnesium alloy shown in FIG. 5 has a mass of about 0.11g before degradation in physiological saline. The mass loss rate of the implant is observed to have an ascending trend, the degradation rate is basically kept in a uniform degradation mode through the height difference of adjacent reduced mass average values, and the image is basically in a proportional function, so that a plurality of problems can be deduced if the implant is implanted into a human body, wherein the problems are not caused by the unstable degradation rate.
The Zn-Mg alloy is prepared by averaging the PH values of samples at 1,3,5 and 7 days in normal saline, respectively to 7.19,8.28,8.62,9.39, and then drawing a broken line statistical chart, as shown in the normal saline PH value line chart of FIG. 6, the PH changes with time to show an ascending trend, and the PH value in normal saline is slowly increased, wherein the PH of the initial solution changes the most than the PH value in the seventh day. Wherein, the basicity of the solution indicates that the solution becomes basic due to the hydrogen-rich radical, and the generation of gas on the surface of the stone can be observed in the beginning of the experiment, thus the generation of hydrogen can be deduced.
And after the surface is made of degradable high polymer materials, on one hand, the degradation rate of the degradable metal is controlled, and on the other hand, the implant has excellent bioactivity and biocompatibility.
(5) Other research experiments on biocompatibility include blood compatibility, cytotoxicity, in vivo experimental biocompatibility, and the like.
The results show that the hemolysis rates of Zn-1Mg, zn-1Ca and Zn-1Sr (i.e., zn-1Sr alloys can also be used) alloys are all very low (< 0.2%) and far below the hemolysis safety value of 5%. Scanning electron microscope observation of platelets adhered to the surface of the material shows that all platelets are spherical and have no pseudopodia spreading, so that the materials have good blood compatibility.
Cell viability was higher in all zinc alloy leachates than in the pure Zn control. For Vascular Smooth Muscle Cells (VSMC), the addition of Mg, ca and Sr did not function to promote VSMC cell proliferation compared to the negative control. Whereas for human osteogenic sarcoma cells (MG 63), the addition of alloying elements promotes cell proliferation.
The biological safety and degradation behavior of different binary rolled Zn-1Mg, zn-1Ca and Zn-1Sr alloys in vivo are evaluated by adopting a mouse as an animal model. The rolled Zn-1Mg, zn-1Ca and Zn-1Sr alloy still keeps the shape intact after being implanted into the mouse body for 8 weeks, which proves that the rolled binary Zn-1Mg, zn-1Ca and Zn-1Sr alloy can still provide enough mechanical support after being implanted into the body for a certain time, and the implant disassembly caused by the too fast corrosion rate can not be generated. Thus effectively avoiding the problem of implant failure caused by premature loss of implant strength. At the same time, the thickness of new bone formation around the implant was observed to be greater than that of the control group, indicating that the binary zinc alloy was able to promote bone healing and new bone formation, thereby shortening the fracture repair cycle. The result of immunohistochemical staining also shows that the rolled Zn-1Mg, zn-1Ca and Zn-1Sr alloy intramedullary pin implant can obviously promote the formation of new bones, the thickness of the new bones is far greater than that of a control group, and the formation capacity of the new bones of the Zn-1Sr alloy is highest.
Claims (3)
1. The degradable anastomat is characterized by comprising a suture nail body (1) formed by processing medical degradable zinc alloy wires and a degradable organic polymer surface layer (2) attached to the surface of the zinc alloy suture nail body;
Degradable zinc alloy components: the zinc content is more than or equal to 95%, and one or more of Mg, sr, li, mn, fe, ca, cu and Ag elements can be contained, wherein the total weight content of calcium, copper and silver elements is less than or equal to 3%, the total weight content of Mg, ca, sr, li, mn, fe is less than or equal to 1%, and other impurities or other elements which are 0 or indispensable are contained;
the degradable high polymer material is selected from chitosan and polylactic acid, and the thickness of the surface layer of the degradable high polymer is 5-30 microns;
The preparation method comprises the following steps:
(1) The staple body is prepared by smelting and casting an as-cast alloy, wherein the raw materials comprise 99.9wt% of high-purity zinc and intermediate alloy in a resistance furnace with protective gas; preparing raw materials according to the proportion of the designed components; after all the raw materials are melted, stirring fully, standing, casting the melted materials onto a die, and introducing protective gas in the process;
(2) Obtaining zinc alloy wire
Carrying out heat treatment on the zinc alloy ingot casting material obtained in the step (1), and drawing the zinc alloy ingot casting material into a required wire; in the initial stage of the successive drawing process, annealing treatment is carried out on the profile at 500 ℃, so that the corrosion resistance of the zinc alloy is improved from the inside; bending the wire material according to the designed size to prepare a staple;
(3) Alkaline heat treatment of the surface of the formed zinc alloy staples:
Acid corrosion is adopted for the stitching nails obtained in the step (2), and the stitching nails are cleaned, so that the surface unevenness is increased; preparing a 1M NaOH alkali solution in advance, putting the sample subjected to acid etching in a small reaction kettle, adding the prepared alkali solution, and completely immersing the sample; sealing the reaction kettle, horizontally putting the reaction kettle into an oven, and heating the reaction kettle for 5 to 8 hours at the temperature of 120 to 150 ℃; slowly cooling along with a furnace, taking out a sample, ultrasonically cleaning with deionized water, and drying in an oven to obtain a treated zinc alloy staple;
(4) Forming degradable polymer coating
Preparing a degradable high polymer material into a solution, sucking the solution at room temperature by using a syringe, injecting the solution into a groove die with the same structure as the staples, lightly placing the staples in the step (3) at the center of the die, slowly filling the solution into the die, rapidly transferring the die into a refrigerator, pre-freezing, placing the die into a freeze dryer, drying and forming the material, and taking out the material; or directly coating degradable polymer material solution on the suture, and then drying.
2. A degradable staple for use with a stapler according to claim 1, wherein the staple body is staple-like and the staple body structure is: the two ends of the middle long round wire A (3) are respectively provided with a short round wire B (4) perpendicular to the long round wire A, the short round wire B and the long round wire A are of an integrated structure, namely the same zinc alloy round wire is adopted, the two short round wires B are positioned on the same side of the long round wire A and are coplanar with the long round wire A, and the plane is called C; the end of the short-section round wire B, namely the end which is not connected with the long-section round wire, is provided with a wedge-shaped structure, wherein the wedge-shaped structure is formed by cutting the short-section round wire B from the outer side by adopting a plane D vertical to a plane C, and the included angle between the plane D and the short-section round wire B is 45-60 degrees; the axial length of the long round wire A is the length of the staple body, and the axial length of the short round wire B is the height of the staple body.
3. A degradable staple for use with a stapler according to claim 1, wherein the staple length is 63-103mm, the tolerance is ± 2mm; the staple height is 3.8-4.5mm, and the tolerance is + -0.2 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010262841.5A CN111388764B (en) | 2020-04-03 | Degradable metal anastomosis nail and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010262841.5A CN111388764B (en) | 2020-04-03 | Degradable metal anastomosis nail and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111388764A CN111388764A (en) | 2020-07-10 |
| CN111388764B true CN111388764B (en) | 2024-06-04 |
Family
ID=
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140065009A1 (en) * | 2012-08-31 | 2014-03-06 | Thomas Imwinkelried | Ultrapure magnesium alloy with adjustable degradation rate |
| CN205041835U (en) * | 2015-06-18 | 2016-02-24 | 赵宇 | Nail is sewed up to degradable for anastomat |
| CN106086562A (en) * | 2016-07-26 | 2016-11-09 | 常州华森医疗器械有限公司 | Biological degradable in vivo anastomosis staple and production technology thereof |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140065009A1 (en) * | 2012-08-31 | 2014-03-06 | Thomas Imwinkelried | Ultrapure magnesium alloy with adjustable degradation rate |
| CN205041835U (en) * | 2015-06-18 | 2016-02-24 | 赵宇 | Nail is sewed up to degradable for anastomat |
| CN106086562A (en) * | 2016-07-26 | 2016-11-09 | 常州华森医疗器械有限公司 | Biological degradable in vivo anastomosis staple and production technology thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN213076762U (en) | Degradable metal anastomosis nail | |
| Auricchio et al. | SMA biomedical applications | |
| WO2017152878A1 (en) | Degradable zinc base alloy implant material and preparation method and use thereof | |
| Song | History and current situation of shape memory alloys devices for minimally invasive surgery | |
| CN106319287A (en) | Biodegradable medical Zn-Li-X series alloy material and preparation method and application | |
| ES2429939T3 (en) | Medical devices that have alloy compositions | |
| EP2769742A1 (en) | MRI visible medical device. | |
| CN108315583B (en) | Zn-Li-Mn zinc alloy and preparation method and application thereof | |
| CN109602960B (en) | Preparation method of medical zinc alloy bar with superplasticity | |
| Gierek et al. | Absorbable sutures in general surgery–review, available materials, and optimum choices | |
| EP3229852A1 (en) | ULTRAHIGH DUCTILITY, NOVEL Mg-Li BASED ALLOYS FOR BIOMEDICAL APPLICATIONS | |
| CN106282664A (en) | Biodegradable medical zinc lithium binary alloy material and preparation method and application | |
| CN109266909B (en) | Medical degradable zinc-bismuth alloy | |
| CN109811265B (en) | Fe-Mn-Cu-C alloy and medical application thereof | |
| CN111803721A (en) | Degradable zinc alloy anastomosis instrument and preparation method thereof | |
| CN111388764B (en) | Degradable metal anastomosis nail and preparation method thereof | |
| CN111676390B (en) | Zn-Ga alloy, preparation method and application thereof | |
| CN108853608B (en) | Biodegradable medical magnesium alloy patch and preparation method and application thereof | |
| CN105624495A (en) | Medical suture material and preparation method | |
| JP6823321B2 (en) | Bioabsorbable staple | |
| WO2017107858A1 (en) | Alloy material and application thereof | |
| CN111388764A (en) | Degradable metal anastomosis nail and preparation method thereof | |
| CN108853603B (en) | Biodegradable medical zinc alloy patch and preparation method and application thereof | |
| CN108785755A (en) | Application of the magnesium alloy in preparing degradable biliary tract rack | |
| TWI513480B (en) | Magnesium alloy suitable for medical implants and method for manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |