CN111295207B - 镁或镁合金制成的可吸收植入材料 - Google Patents
镁或镁合金制成的可吸收植入材料 Download PDFInfo
- Publication number
- CN111295207B CN111295207B CN201980004412.3A CN201980004412A CN111295207B CN 111295207 B CN111295207 B CN 111295207B CN 201980004412 A CN201980004412 A CN 201980004412A CN 111295207 B CN111295207 B CN 111295207B
- Authority
- CN
- China
- Prior art keywords
- magnesium
- implant material
- nanodiamond
- fluorescent
- magnesium alloy
- 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
Images
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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/005—Fluorescence in vivo characterised by the carrier molecule carrying the fluorescent agent
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0063—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres
- A61K49/0065—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres the luminescent/fluorescent agent having itself a special physical form, e.g. gold nanoparticle
- A61K49/0067—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres the luminescent/fluorescent agent having itself a special physical form, e.g. gold nanoparticle quantum dots, fluorescent nanocrystals
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/08—Carbon ; Graphite
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
- A61L27/427—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of other specific inorganic materials not covered by A61L27/422 or A61L27/425
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
-
- 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
- A61L31/02—Inorganic materials
- A61L31/024—Carbon; Graphite
-
- 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
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L31/121—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
- A61L31/124—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of other specific inorganic materials not covered by A61L31/122 or A61L31/123
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/442—Colorants, dyes
-
- 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Heart & Thoracic Surgery (AREA)
- Vascular Medicine (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Surgery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Biomedical Technology (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Materials For Medical Uses (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明涉及由镁或镁合金制成的可吸收的植入材料及其制备方法。现有可吸收植入材料的缺点在于迄今为止其吸收作用只能经由X射线或CT检测来追踪。本发明提供了一种可吸收的植入材料,其包括在镁或镁合金的基质中均匀分布的荧光纳米金刚石。荧光纳米金刚石对生物无害,并且由于具有氮空位中心(NV中心)而在近红外范围内提供稳定的发射。这允许植入材料在患者血浆中的检测。本发明的可吸收的植入材料的制备方法包括将镁或镁合金熔化,将纳米金刚石添加到熔体中,并对具有纳米金刚石的镁或镁合金的熔体进行超声处理。
Description
技术领域
本发明涉及由镁或镁合金制成的植入材料及其制造方法。
背景技术
在兽医学和人类医学中,承重长骨骨折的治疗均采用医用钢或钛制成的医用植入物。但是,这些植入物的机械特性比骨头更坚硬,这可能导致应力屏蔽现象。由于这些以及其他原因,这种植入物通常在其功能完成之后再被移除,这样就会由于所需的麻醉和新的组织创伤而使患者虚弱。
可吸收植入物对于骨折治疗越来越受到关注。这里的目的是通过随着愈合骨骼强度的增加缓慢降低其稳定性来对植入物进行应力调节。迄今为止,尚未实现由不同聚合物制成的可吸收植入物的最佳用途,原因是它们在受力骨骼处的强度较低。相比之下,与其他金属植入材料相比,镁及其合金具有类骨的弹性模量以及良好的拉伸和挤压强度。镁及其合金比可吸收的聚合物具有更高的强度和更大的弹性模量,因此是科学研究的重点。例如,由EP 2 318 057 B1及其中引用的出版物或从DE 10 2005 060 203 A1已知用于治疗骨折的可生物吸收的植入物,特别是由镁或镁合金制成的植入物。
可吸收的植入物不仅用于骨折治疗。如今,由镁及其合金制成的植入物经常被用作治疗狭窄(血管紧缩)的支架。支架的两个纵向端部均有管状或空心圆柱形的基架。将这种内置假体的管状基架被引入待治疗的血管并用于支撑血管。由EP 2 198 898 B1及其中引用的出版物已知由镁或镁合金制成的可生物降解的支架。
然而,现有植入物的缺点在于,迄今为止,其吸收作用只能经由X射线或CT检测来追踪,而这种检测相对复杂且成本高昂。本发明的目的是提供一种由镁或镁合金制成的植入材料及其制备方法,其在患者体内的吸收可以采用简单的方式追踪,而无需进行X射线或CT检测。
发明内容
本发明的目的可通过权利要求1所述的植入材料来实现,所述植入材料包括在镁或镁合金的基质中具有氮空位中心的均匀分布的荧光纳米金刚石,其中所述荧光纳米金刚石具有氮空位中心(NV中心),其在由532nm激光束激发后,具有可检测的在波长650nm至700nm之间居中的荧光带。所述目的还可通过权利要求8所述的植入材料的制造方法来实现,其中包括熔化镁或镁合金,将具有氮空位中心的荧光纳米金刚石添加到所述熔体中,并且具有纳米金刚石的镁或镁合金熔体经过超声波处理。
具体实施方式
荧光纳米金刚石(FND)是已知的蛋白质标记,例如可见于K.Merchand和S.K.Sarkar,IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM ELECTRONICS,VOL.22,NO.3,MAY/JUNE 2016。迄今为止,这些已用于可视化生物细胞过程的研究。荧光纳米金刚石在生物学上无害,并且由于氮空位中心(NV中心)而在近红外范围内提供稳定的发射。
钻石中的NV中心由一个氮原子,其取代了钻石晶格中的碳原子,以及钻石晶格中直接相邻的空位形成。此空缺使NV中心可以具有负性(NV—中心)或中性(NV0中心)的电荷。钻石的NV中心具有非超常的光物理特性。
在生物成像的情况下,带负电的NV—中心的超常性质是可以在480nm至580nm之间进行光激发,从而发出以大约700nm为中心的宽发光带。激发态寿命为大约17ns,例如描述于J.M.Say,“Luminescent Nanodiamonds for Biomedical Applications”,Biophys.Rev.(2011)3:171-184。中性的NV0中心在637nm处发出相对较锐利的线。
具有氮空位的荧光纳米金刚石的生产描述于例如US 2014/0065424 A1或WO2017/108655 A1,其在此通过引用全部并入本文。
为了生产具有氮空位中心的荧光纳米金刚石,必须在受控条件下破坏其晶格以形成这些氮空位中心,否则将无法进行光学成像。这通常是通过在粒子加速器中用快速离子辐照纳米金刚石来实现,就如US 2014/0065424 A1所述的方法,在7MeV至15MeV的加速能量下用电子束辐照。这些加速的离子能够将碳原子从纳米金刚石的晶格中敲出,因此留下被描述为空位的孔,并且在高温下与作为杂质的晶体中存在的氮原子耦合。取缔加速器中的昂贵和昂贵的辐射,较新的方法利用核反应堆中的辐射,其反应快得多且成本更低。为此,纳米晶必须首先分散在熔融的氧化硼中,然后在核反应堆中进行中子辐射。硼核捕获中子会产生密集的氦和锂离子簇,它们在纳米晶体中的作用与加速剂中产生的离子相同:晶体缺陷的受控生成。
在本发明的一种实施方式中,荧光纳米金刚石具有大于10ppm,优选大于20ppm,更优选大于25ppm的氮空位中心浓度,取决于532nm激光束激发后的落射荧光,由532nm激光束激发后落射荧光确定纳米金刚石中氮空位中心浓度的方法可见于例如Chi-Chen Fu etal.“Characterization and application of single fluorescent nanodiamonds ascellular biomarkers”,PNAS,Vol.194,Nr.3,727-732(2007),其通过引用完全纳入本文。氮空位中心的浓度尤其是通过将测得的荧光强度与“单个缺陷”钻石的荧光强度进行比较来确定的(参见Chi-Chen Fu et al.的引用文献)。这样的数据公开于例如F.Treussart etal.(2006)Physica B Condensed Matter 376:926-929。
满足这些特征的荧光纳米金刚石也可商购于例如Sigma-Aldrich Chemie GmbH,Steinheim,Germany。
用于研究传输特性的合适光源包括能够激活NV中心的任何光源,例如氦氖激光器,其632.7nm的波长大致对应于NV光谱的ZPL,或固态激光器(JL-LD532-GTE;Jetlser),其在532nm波长操作。
图1显示了室温下纳米金刚石中NV中心的荧光光谱,由532nm激光束激发。该图显示了以约700nm波长为中心的宽荧光带。
本发明的植入材料,其由镁或镁合金制成并且包含均匀分布的荧光纳米金刚石,可以通过铸造来生产。随后可以通过诸如MIM技术的粉末冶金工艺将其挤出或加工成植入物制品。植入材料在患者体内的吸收导致荧光纳米金刚石进入血液循环,在此可以通过荧光光谱法或其他手段进行检测。荧光纳米金刚石逐渐从体内排出。这提供了等离子体中的洗入/洗出轮廓,在校准之后,可以得出有关植入材料吸收的结论。
当使用镁合金作为基质材料时,优选采用不被认为对健康有害的合金元素。优选使用镁合金,其合金元素选自锂,钙,钾,锶,钡,钪,钇,镧,镨,钕,钐,铕,钆,镝,硅,铜,锌,镓,金,银,铋,铁及其组合。更优选使用的镁合金例如可见于DE 10 2016 007 176 A1或DE10 2016 119 227 A1,其在此通过引用全部纳入本文。
根据本发明,当镁或镁合金熔化时,将纳米金刚石添加到熔体中,并且对具有纳米金刚石的镁或镁合金的熔体进行超声处理,从而形成植入材料。
这种使纳米颗粒均匀分布在镁或镁合金的熔体中的方法被描述于H.Dieringa etal.“Ul-trasound Assisted Casting of an AM60 Based Metal Matrix Nanocomposite,Its Properties,and Recyclability”in Metals 2017,7,338,其在此通过引用全部纳入本文。
在用于生产本发明的植入材料的优选方法中,优选地第一步将镁或镁合金在炉中永久性模具中及保护气体下搅拌熔融,第二步将熔体与纳米金刚石混合。在第三步,使用超声波发生器将引入到熔体中的纳米金刚石分散并解聚。进一步优选地,在移除搅拌器和超声波发生器之后,将包含熔体的永久模具浸入水浴中。这使得熔体从“底部到顶部”凝固,从而避免腔隙的形成。
如此产生的植入材料随后可以通过常规手段作进一步的处理。例如,可将植入材料重新熔化,然后倒入所需的模具中以形成植入物制品。材料也可以被挤出以由挤出物制造植入物。还可以将植入材料进一步加工成粉末,然后通过金属注射成型(MIM)进一步加工成植入物制品。
本发明的植入材料优选地包含在镁或镁合金的基质中均匀分布的荧光纳米金刚石,基于镁/镁合金的重量,其含量为0.1重量%至5重量%,优选0.5重量%至1.5重量%。纳米金刚石的粒度优选为1至20nm,尤其优选为3至8nm。
如上所述,为了根据本发明的植入材料,如H.Dieringa等人所述,优选地第一步将镁或镁合金在炉中的永久模具中并在保护气体下搅拌熔融,例如描述于H.Dieringa etal.“Ultrasound Assisted Casting of an AM60 Based Metal Matrix Nanocomposite,Its Properties,and Recyclability”in Metals 2017,7,338。熔体优选采用机械搅拌,其速度优选为150至250rpm。然后将荧光纳米金刚石添加到熔体中。在添加荧光纳米金刚石之后,熔体用超声处理。这优选地通过将超声波发生器引入熔体中来实现。超声处理优选地进行1min至10min,更优选2min至5min。
优选的是,在混合和超声处理之后,除去搅拌器和超声波发生器,并将永久铸模从熔炉中缓慢降到水浴中,在此熔体固化。
随后可以通过常规方式将如此生产的植入材料作进一步处理。例如,可将植入材料重新熔化,然后倒入所需的模具中以提供金属植入物制品。本发明的植入材料也可以被挤出并由挤出物形成植入物制品。
本发明的植入材料也可以通过MIM技术加工成金属植入物制品。通过使用MIM技术,可以将小型、复杂且形状精确的金属部件制成近终形状。MIM技术属于所谓的粉末冶金工艺,其中要生产的组件的原材料是金属细粉而不是固体金属。MIM代表金属注射成型。在MIM工艺中,通过添加热塑性粘合剂使金属粉末可流动,并将可流动的混合物引入注塑模具中。模制后,再次除去粘合剂部分,并烧结组件。镁成分可以使用MIM技术制备,其方法描述于M.Wolff et.al.“Magnesium powder injection moulding for biomedicalapplication”,Powder Metallurgy,2014(Vol.57,No.5),331-340,其在此通过引用全部纳入本文。
当使用MIM技术时,粘合剂可在初步成型/造型过程中提供临时粘合,并确保组件的稳定性,直到通过烧结最终压实金属粉末为止。通常在烧结之前已经除去一部分粘合剂,例如使用溶剂(溶剂脱粘剂)。粘合剂的其余部分在大约300℃至500℃的温度下分解,并在热脱胶过程中以气态形式逸出。
Claims (15)
1.一种植入材料,其包括在镁或镁合金的基质中具有氮空位中心的均匀分布的荧光纳米金刚石,其中所述荧光纳米金刚石具有氮空位中心(NV中心),其在被532nm激光束激发后具有中心波长在650nm至700nm的可检测的荧光带,所述材料用于骨折治疗或狭窄治疗,其中所述植入材料在人或动物体内的吸收通过血浆中荧光光谱来确定。
2.根据权利要求1所述的植入材料,其中所述荧光纳米金刚石具有大于10ppm的氮空位中心浓度,其由532nm激光束激发后的落射荧光确定。
3.根据权利要求2所述的植入材料,其中所述荧光纳米金刚石具有大于20ppm的氮空位中心浓度。
4.根据权利要求1所述的植入材料,其中均匀分布的所述荧光纳米金刚石的浓度为0.1重量%至5重量%,基于所述基质中镁/镁合金的重量。
5.根据权利要求4所述的植入材料,其中均匀分布的所述荧光纳米金刚石的浓度为0.5重量%至1.5重量%,基于所述基质中镁/镁合金的重量。
6.根据权利要求1所述的植入材料,其中所述荧光纳米金刚石的粒径为1至20nm。
7.根据权利要求6所述的植入材料,其中所述荧光纳米金刚石的粒径为3至8nm。
8.前述权利要求任一项所述植入材料的制备方法,其中将镁或镁合金熔化,将纳米金刚石添加到熔体中,并且对具有纳米金刚石的镁或镁合金的熔体进行超声处理。
9.根据权利要求8所述的方法,包括第一步将镁或镁合金在炉中的永久性模具中并在保护气体下搅拌熔融,其中熔体采用机械搅拌,然后将荧光纳米金刚石添加至熔体,并且在加入荧光纳米金刚石后对所述熔体进行超声处理。
10.根据权利要求8至9任一项所述的方法,其中所述超声处理的时间为1min至10min。
11.根据权利要求8至9任一项所述的方法,其中在所述超声处理之后,将模具转移到水浴中,在此所述熔体固化。
12.根据权利要求8至9任一项所述的方法,其中将所述植入材料重新熔化,然后倒入所需的模具中以提供金属植入物。
13.根据权利要求8至9任一项所述的方法,其中将所述植入材料挤出,并且挤出物用作制备植入物的前体。
14.根据权利要求8至9任一项所述的方法,其中使用MIM技术将所述植入材料转换成金属植入物。
15.一种检测可吸收植入材料的吸收的方法,包括利用在532nm激光束激发后人或动物体内血浆的荧光光谱,其中所述植入材料包括在镁或镁合金的基质中具有氮空位中心的均匀分布的荧光纳米金刚石,其中所述荧光纳米金刚石具有氮空位中心(NV中心),所述氮空位中心具有中心波长在650nm至700nm的可检测的荧光带。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP18170669.8A EP3563880A1 (de) | 2018-05-03 | 2018-05-03 | Resorbierbares implantatmaterial aus magnesium oder einer magnesiumlegierung |
EP18170669.8 | 2018-05-03 | ||
PCT/EP2019/060326 WO2019211121A1 (de) | 2018-05-03 | 2019-04-23 | Resorbierbares implantatmaterial aus magnesium oder einer magnesiumlegierung |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111295207A CN111295207A (zh) | 2020-06-16 |
CN111295207B true CN111295207B (zh) | 2023-04-28 |
Family
ID=62116297
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201980004412.3A Active CN111295207B (zh) | 2018-05-03 | 2019-04-23 | 镁或镁合金制成的可吸收植入材料 |
Country Status (5)
Country | Link |
---|---|
US (1) | US11969482B2 (zh) |
EP (2) | EP3563880A1 (zh) |
CN (1) | CN111295207B (zh) |
CA (1) | CA3068113A1 (zh) |
WO (1) | WO2019211121A1 (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2022230733A1 (zh) * | 2021-04-30 | 2022-11-03 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100496458B1 (ko) * | 2002-09-02 | 2005-06-23 | 재단법인서울대학교산학협력재단 | 생체 흡수형 생체 활성 결정화 유리 및 그 제조 방법 |
DE102005060203B4 (de) | 2005-12-14 | 2009-11-12 | Gkss-Forschungszentrum Geesthacht Gmbh | Biokompatibler Magnesiumwerkstoff, Verfahren zu seiner Herstellung und seiner Verwendung |
EP1990313A1 (en) | 2007-05-10 | 2008-11-12 | INSERM (Institut National de la Santé et de la Recherche Médicale) | Method to produce light-emitting nano-particles of diamond |
DE102008037200B4 (de) | 2008-08-11 | 2015-07-09 | Aap Implantate Ag | Verwendung eines Druckgussverfahrens zur Herstellung eines Implantats aus Magnesium sowie Magnesiumlegierung |
DE102008054920A1 (de) | 2008-12-18 | 2010-07-01 | Biotronik Vi Patent Ag | Implantat sowie Verfahren zur Herstellung einer Schichtstruktur |
US20100269837A1 (en) * | 2009-03-26 | 2010-10-28 | Seventh Sense Biosystems, Inc. | Monitoring of implants and other devices |
EP2606917A1 (en) * | 2011-12-20 | 2013-06-26 | Steinmüller-Nethl, Doris | Porous scaffold with carbon-based nanoparticles |
US10532134B2 (en) * | 2012-04-18 | 2020-01-14 | Drexel University | Thixotropic processing of magnesium composites with a nanoparticles-haloed grain structure for biomedical implant applications |
US9486163B2 (en) * | 2014-02-21 | 2016-11-08 | Verily Life Sciences Llc | Silicon-vacancy-doped nanodiamonds for molecular and cellular imaging |
DE102014108142B4 (de) * | 2014-03-27 | 2022-07-07 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Mit einer oder mehreren Koordinationsverbindungen der Seltenen Erden belegter Nanodiamant und dessen Verwendung als lumineszierendes Material in Schichten und Formkörpern sowie Verfahren zu dessen Herstellung |
DE102016007176A1 (de) | 2015-06-11 | 2017-01-12 | Meotec GmbH & Co. KG | Resorbierbares Implantat mit hoher Reinheit und guten mechanischen Eigenschaften |
GB201522512D0 (en) | 2015-12-21 | 2016-02-03 | Element Six Ltd | Flourescent diamond particles and methods of fabricating the same |
DE102016119227A1 (de) | 2016-10-10 | 2018-04-12 | Cortronik GmbH | Bioresorbierbare Implantate aus extrudiertem Pulver mit variierender chemischer Zusammensetzung |
EP3636289B1 (de) * | 2018-10-10 | 2021-09-29 | Helmholtz-Zentrum hereon GmbH | Resorbierbares implantatmaterial aus magnesium oder einer magnesiumlegierung mit dotierten nanodiamanten |
-
2018
- 2018-05-03 EP EP18170669.8A patent/EP3563880A1/de not_active Withdrawn
-
2019
- 2019-04-23 WO PCT/EP2019/060326 patent/WO2019211121A1/de unknown
- 2019-04-23 EP EP19718401.3A patent/EP3621664B1/de active Active
- 2019-04-23 CN CN201980004412.3A patent/CN111295207B/zh active Active
- 2019-04-23 US US16/626,619 patent/US11969482B2/en active Active
- 2019-04-23 CA CA3068113A patent/CA3068113A1/en active Pending
Also Published As
Publication number | Publication date |
---|---|
US20200129642A1 (en) | 2020-04-30 |
EP3621664A1 (de) | 2020-03-18 |
CA3068113A1 (en) | 2019-11-07 |
CN111295207A (zh) | 2020-06-16 |
WO2019211121A1 (de) | 2019-11-07 |
EP3621664B1 (de) | 2022-05-04 |
EP3563880A1 (de) | 2019-11-06 |
US11969482B2 (en) | 2024-04-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102074388B1 (ko) | 생분해성 금속 임플란트 | |
EP2422821B1 (en) | Biodegradable implant and method for manufacturing same | |
Koike et al. | Evaluation of titanium alloy fabricated using electron beam melting system for dental applications | |
Čapek et al. | Microstructural and mechanical properties of biodegradable iron foam prepared by powder metallurgy | |
RU2608152C2 (ru) | Способ изготовления медицинского имплантата из магниевого сплава | |
US10426869B2 (en) | Biodegradable magnesium alloys and composites | |
US20110054629A1 (en) | Composite implant having porous structure filled with biodegradable alloy and method of magnesium-based manufacturing the same | |
CN102978495A (zh) | 一种Mg-Sr-Zn系合金及其制备方法 | |
US10532134B2 (en) | Thixotropic processing of magnesium composites with a nanoparticles-haloed grain structure for biomedical implant applications | |
Han et al. | Effect of Mn element addition on the microstructure, mechanical properties, and corrosion properties of Mg-3Zn-0.2 Ca Alloy | |
CN111295207B (zh) | 镁或镁合金制成的可吸收植入材料 | |
KR20200056462A (ko) | 증가된 분해 속도를 갖는 fe-mn 흡수성 임플란트 합금 | |
Wang et al. | Progress in partially degradable titanium-magnesium composites used as biomedical implants | |
KR101485296B1 (ko) | 생체분해성 임플란트 및 이의 제조방법 | |
Masseli et al. | Mechanical and physical characterization of hydroxyapatite/alumina biocomposites produced by the powder metallurgy route for biomedical applications | |
CN111020324A (zh) | 由含有掺杂纳米金刚石的镁或镁合金组成的可吸收植入材料 | |
WO2017170964A1 (ja) | 医療用カルシウム系金属ガラス合金成形体及びその製造方法 | |
CN113276248A (zh) | 一种表面涂覆金属的多孔骨植入物的制备方法 | |
Setyadi et al. | Composite of Magnesium and Carbonate Apatite for Biodegradable Bone Implants: A Comparative Study on Sintering and Extrusion Techniques. | |
Annur et al. | Preparation and characterization of porous Mg-Zn-Ca alloy by space holder technique | |
Raducanu et al. | Characterization of a Biodegradable Mg-Alloy after SLM Processing | |
Saha et al. | Accelerated corrosion of zinc, erbium and cerium co-doped Mg-alloys prepared by spark plasma sintering for bioresorbable implant applications | |
Arifvianto | Synthesis and evaluation of porous titanium scaffolds prepared with the space holder method for bone tissue engineering | |
CN118109729A (zh) | 一种生物相容性镁合金骨板及其制备方法 | |
Jha | Processing and Characterization of Ball Milled Magnesium for Biomedical Implant |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
CB02 | Change of applicant information | ||
CB02 | Change of applicant information |
Address after: Geesthacht, Germany Applicant after: Hermann von Helmholtz Center Heung Co.,Ltd. Address before: Geesthacht, Germany Applicant before: HELMHOLTZ-ZENTRUM GEESTHACHT ZENTRUM FUR MATERIAL- UND KUSTENFORSCHUNG GmbH |
|
GR01 | Patent grant | ||
GR01 | Patent grant |