CN117065092A - Titanium implant and preparation method and application thereof - Google Patents
Titanium implant and preparation method and application thereof Download PDFInfo
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- CN117065092A CN117065092A CN202211556484.9A CN202211556484A CN117065092A CN 117065092 A CN117065092 A CN 117065092A CN 202211556484 A CN202211556484 A CN 202211556484A CN 117065092 A CN117065092 A CN 117065092A
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- fiber
- titanium
- piezoelectric
- anodic oxidation
- titanium matrix
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 119
- 239000010936 titanium Substances 0.000 title claims abstract description 119
- 239000007943 implant Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000002513 implantation Methods 0.000 title description 4
- 239000000835 fiber Substances 0.000 claims abstract description 100
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 28
- 239000002071 nanotube Substances 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims description 71
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 42
- 238000007254 oxidation reaction Methods 0.000 claims description 39
- 230000003647 oxidation Effects 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 15
- 238000010041 electrostatic spinning Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 11
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 8
- 239000004065 semiconductor Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 4
- 102000008186 Collagen Human genes 0.000 claims description 4
- 108010035532 Collagen Proteins 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 4
- -1 PVDF-TrFE Polymers 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910002113 barium titanate Inorganic materials 0.000 claims description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 229920001436 collagen Polymers 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 4
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 4
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 claims description 4
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 4
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 claims description 4
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims description 4
- DKDQMLPMKQLBHQ-UHFFFAOYSA-N strontium;barium(2+);oxido(dioxo)niobium Chemical compound [Sr+2].[Ba+2].[O-][Nb](=O)=O.[O-][Nb](=O)=O.[O-][Nb](=O)=O.[O-][Nb](=O)=O DKDQMLPMKQLBHQ-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 claims description 2
- PSVBHJWAIYBPRO-UHFFFAOYSA-N lithium;niobium(5+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[Nb+5] PSVBHJWAIYBPRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 210000002540 macrophage Anatomy 0.000 abstract description 17
- 230000003110 anti-inflammatory effect Effects 0.000 abstract description 11
- 230000001580 bacterial effect Effects 0.000 abstract description 10
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 7
- 210000000988 bone and bone Anatomy 0.000 abstract description 7
- 230000000770 proinflammatory effect Effects 0.000 abstract description 5
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- 208000027418 Wounds and injury Diseases 0.000 abstract description 2
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- 230000002188 osteogenic effect Effects 0.000 abstract description 2
- 210000000170 cell membrane Anatomy 0.000 abstract 1
- 241000894006 Bacteria Species 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
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- 230000000694 effects Effects 0.000 description 7
- 238000001523 electrospinning Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
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- 241000191967 Staphylococcus aureus Species 0.000 description 5
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- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
- D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
-
- 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
- A61L27/06—Titanium or titanium 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
-
- 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
- A61L27/56—Porous materials, e.g. foams or sponges
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- 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
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/606—Coatings
- A61L2300/608—Coatings having two or more layers
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- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Epidemiology (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Animal Behavior & Ethology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a titanium implant and a preparation method and application thereof, and relates to the technical field of medical titanium materials. The titanium implant provided by the invention damages bacterial cell membranes through positive charge traps formed on the graded titanium dioxide nanotube array layer, so that an antibacterial function is realized; macrophages can be adhered to the piezoelectric fiber layer, and the generated piezoelectric self-stimulated electric field repolarizes from the pro-inflammatory M1 type macrophages to the anti-inflammatory M2 type macrophages to realize the anti-inflammatory function; and has the protection function of reducing the osteogenic injury in the inflammatory environment, thereby creating a good bone immune microenvironment.
Description
Technical field:
the invention relates to the technical field of medical titanium materials, in particular to a titanium implant and a preparation method and application thereof.
The background technology is as follows:
in recent years, research and application of various biomedical materials are rapidly developed, and titanium alloy become implant materials widely applied to the professional fields of stomatology, orthopedics and the like at present due to excellent biocompatibility, corrosion resistance and the like. However, pure titanium implants are biologically inert and have a lack of osseointegration capability. The surface modification of the titanium implant is carried out, the surface performance of the titanium implant is optimized, the biological effect around the titanium implant is affected, and finally the bone bonding capability of the interface is improved, so that the titanium implant has been one of the research hot spots of biomedical materials in recent years.
Those skilled in the art know that planktonic bacteria easily adhere to the surface of the implant and proliferate rapidly, which greatly affects the integration of the implant with its surrounding tissues, and that large doses of antibiotics must be clinically injected to overcome this problem. However, with the development of bacterial resistance, the problem of infection and inflammation during the planting process is avoided by injecting large doses of antibiotics, and the effect is becoming worse, which directly leads to an increased risk of planting failure. Worse, the implant site of the implant is subject to unsatisfactory osseointegration due to long-term infection and unavoidable rejection, causing irreversible damage, which significantly increases clinical risks and economic losses. Therefore, it is important to develop a multifunctional titanium implant with antibacterial, anti-inflammatory and osteogenic effects.
The invention comprises the following steps:
the technical problem to be solved by the invention is to provide the titanium implant and the preparation method thereof, and the titanium implant has the multifunctional functions of antibiosis, antiphlogosis and osteogenesis and has better application prospect.
The technical problems to be solved by the invention are realized by adopting the following technical scheme:
it is an object of the present invention to provide a titanium implant comprising a titanium matrix, a hierarchical titanium dioxide nanotube array layer and a piezoelectric fiber layer.
Another object of the present invention is to provide a method for preparing the above titanium implant, comprising the steps of:
(1) In the presence of electrolyte, titanium matrix M 0 Anodic oxidation is carried out to obtain a titanium matrix M of the deposition grading titanium dioxide nanotube array layer 3 ；
(2) Dispersing piezoelectric material in organic solvent to obtain piezoelectric suspension, and dispersing the piezoelectric suspension in titanium matrix M 3 And (3) carrying out electrostatic spinning on the surface of the titanium implant.
It is a further object of the present invention to provide a titanium implant obtained according to the aforementioned preparation method.
It is a fourth object of the present invention to provide the use of the aforementioned titanium implant in a medical implant material.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the titanium implant provided by the invention, in the electrostatic spinning process, a large number of positive charge traps are formed in the graded titanium dioxide nanotube array layer along with charge injection, and the piezoelectric fiber layer has proper aperture and negative potential so as to ensure that bacteria can reach the graded titanium dioxide nanotube array layer and then destroy bacterial membranes through the positive charge traps formed on the graded titanium dioxide nanotube array layer, thereby realizing an antibacterial function.
2. The titanium implant provided by the invention has the advantages that macrophages can be adhered to the piezoelectric fiber layer, and the anti-inflammatory function is realized by repolarizing the generated piezoelectric self-stimulated electric field from the pro-inflammatory M1 type macrophages to the anti-inflammatory M2 type macrophages.
3. The titanium implant provided by the invention has the protection effect of reducing the bone injury in the inflammatory environment, and creates a good bone immune microenvironment.
Description of the drawings:
FIG. 1 is a schematic diagram of the structure of 3DMA prepared in example 1;
FIGS. 2 and 3 are the results of plate counts and quantitative analyses of PT and 3DMA surface grown Staphylococcus aureus and Escherichia coli;
FIGS. 4 and 5 are combined images of PT and 3DMA group macrophage immunofluorescence staining and quantitative analysis results, with CD206 and iNOS as markers for M2 and M1 phenotypes, respectively;
FIGS. 6 and 7 are Van Gieson stained images of Micro CT images and hard tissue sections after PT and 3DMA implants, respectively, in the femur of a rat;
fig. 8 and 9 show Van Gieson staining images and quantitative analysis results of hard tissue sections after PT and 3DMA implantation, respectively, in the femur of rats.
The specific embodiment is as follows:
the invention is further described below with reference to specific embodiments and illustrations in order to make the technical means, the creation features, the achievement of the purpose and the effect of the implementation of the invention easy to understand.
The invention provides a titanium implant, which comprises a titanium matrix, a graded titanium dioxide nanotube array layer and a piezoelectric fiber layer.
The piezoelectric fiber layer is composed of piezoelectric fibers, and the piezoelectric fibers are at least one selected from polymer piezoelectric fibers, ceramic piezoelectric fibers and semiconductor piezoelectric fibers, and preferably the polymer piezoelectric fibers.
Further preferably, the polymer piezoelectric fiber is at least one selected from PVDF fiber, PVDF-TrFE fiber, PHB fiber, PLLA fiber, PCL fiber, PLGA fiber, PHBV fiber, collagen fiber, chitosan fiber, cellulose and derivative fiber, PVP fiber, PVA fiber, PEO fiber.
Further preferably, the ceramic piezoelectric fiber is at least one selected from the group consisting of barium titanate fiber, potassium sodium niobate fiber, lithium niobate fiber, barium strontium niobate fiber, lead zirconate titanate fiber, boron nitride fiber, and hydroxyapatite fiber.
Further preferably, the semiconductor piezoelectric fiber is at least one selected from CdS fiber, cdSe fiber, znO fiber, znS fiber, cdTe fiber, znTe fiber, gaAs fiber, gaSb fiber, inAs fiber, inSb fiber, alN fiber.
The titanium implant provided by the invention is a three-dimensional multifunctional structure formed by a graded titanium dioxide nanotube array layer and a piezoelectric fiber layer on the surface of a titanium matrix, and further, charge traps and piezoelectric self-stimulation are endowed on the surface of the titanium matrix. Bacteria can be eradicated by the piezoelectric fiber layer and by positive charge traps formed on the graded titanium dioxide nanotube array layer due to suitable pore size and electrostatic interactions; in addition, macrophages will adhere to the piezoelectric fiber layer and repolarize from pro-inflammatory M1 type macrophages to anti-inflammatory M2 type macrophages by the resulting piezoelectric self-stimulating electric field; further co-culture experiments show that the titanium implant with the three-dimensional multifunctional structure provided by the invention has the protection effect of reducing the bone formation injury in an inflammatory environment, and creates a good bone immune microenvironment.
Those skilled in the art know that macrophages play an important role in immunomodulation, regulate macrophage polarization (i.e., downregulate pro-inflammatory phenotype M1 polarization and/or upregulate anti-inflammatory phenotype M2 polarization), and can effectively promote the subsidence of inflammation by secreting a range of anti-inflammatory cytokines and other mediators, inhibiting the secretion of pro-inflammatory cytokines; meanwhile, the macrophage is an electrically excited cell, and has the characteristic of transient hyperpolarization, and the electric field can regulate the polarization of the macrophage and promote the secretion of certain anti-inflammatory cytokines. The idea of the present invention is therefore to create an electrical stimulus to modulate the anti-inflammatory polarized phenotype of macrophages to achieve the anti-inflammatory effect of titanium implants and further to produce osteogenic related proteins from M2 macrophages to achieve promotion of osteogenesis and osseointegration at the implant site.
The invention also provides a preparation method of the titanium implant, which comprises the following steps:
(1) In the presence of electrolyte, titanium matrix M 0 Anodic oxidation is carried out to obtain a titanium matrix M of the deposition grading titanium dioxide nanotube array layer 3 ；
(2) Dispersing piezoelectric material in organic solvent to obtain piezoelectric suspension, and dispersing the piezoelectric suspension in titanium matrix M 3 And (3) carrying out electrostatic spinning on the surface of the titanium implant.
The electrolyte is an ethylene glycol solution of ammonium fluoride, and the concentration of the ammonium fluoride is 75-100mmol/L, and more preferably 88mmol/L.
The anodic oxidation comprises primary anodic oxidation and secondary anodic oxidation, namely, the hierarchical titanium dioxide nanotube array is formed through anodic oxidation reactions with different conditions.
The conditions of the primary anodic oxidation are as follows: and (3) connecting the titanium matrix M0 with an anode by taking graphite as a cathode, and performing primary anodic oxidation to obtain the titanium matrix M1 loaded with the titanium dioxide nanotube array layer.
Preferably, the voltage of the primary anodic oxidation is 55-65V, the temperature is 20-35 ℃ and the time is 2-3h.
The conditions of the secondary anodic oxidation are as follows: cutting off the titanium dioxide nanotubes loaded on the surface of the titanium matrix M1 to obtain a titanium matrix M2 loaded with a bowl-shaped titanium dioxide nano array layer; and then, connecting the titanium matrix M2 with an anode by taking graphite as a cathode, and performing secondary anodic oxidation to obtain the titanium matrix M3 of the load-grading titanium dioxide nanotube array layer.
Preferably, the cutting treatment is that the titanium matrix M1 is placed in an aqueous solution for ultrasonic treatment, the ultrasonic power is 200-300W, and the ultrasonic time is 10-15min.
Preferably, the voltage of the secondary anodic oxidation is 10-15V, the temperature is 20-35 ℃ and the time is 30-50min.
The piezoelectric material is at least one selected from polymer piezoelectric material, ceramic piezoelectric material and semiconductor piezoelectric material, and is preferably polymer piezoelectric material.
Further preferably, the polymer piezoelectric material is selected from at least one of PVDF, PVDF-TrFE, PHB, PLLA, PCL, PLGA, PHBV, collagen fibers, chitosan, cellulose and derivatives, PVP, PVA, PEO.
Further preferably, the ceramic piezoelectric material is selected from at least one of barium titanate, potassium sodium niobate, lithium niobate, barium strontium niobate, lead zirconate titanate, boron nitride, and hydroxyapatite.
Further preferably, the semiconductor piezoelectric material is selected from at least one of CdS, cdSe, znO, znS, cdTe, znTe, gaAs, gaSb, inAs, inSb, alN.
The mass concentration of the piezoelectric material in the piezoelectric suspension is 5-15wt%.
The organic solvent is at least one selected from dimethyl sulfoxide, dimethylformamide, dimethylacetamide, dichloromethane, acetonitrile, tetrahydrofuran, acetone, N-methylpyrrolidone, butyrolactone, phenol, m-phenol, caprolactam, sulfolane and nitrobenzene; preferably a mixture of DMF and acetone, the mass ratio of DMF to acetone being (1-2): 1.
The humidity of the electrostatic spinning is 20-30%, the temperature is 20-30 ℃, the spraying flow rate of the piezoelectric suspension is 0.5-2mL/h, the spinning distance is 10-15cm, the voltage applied to the piezoelectric suspension is 10-15KV, and the voltage applied to the titanium matrix M3 is-10 to-3 KV.
In order to prevent oil stains or dirt on the surface of a titanium matrix from affecting the formation of a hierarchical titanium dioxide nanotube array layer, the surface of the titanium matrix is preferably subjected to surface pretreatment, specifically, the surface of the titanium matrix is subjected to progressive polishing through metallographic sand paper with different fineness, and then is washed by an organic solvent and/or deionized water; the ultrasonic treatment mode can improve the cleaning effect; preferably, the invention firstly adopts 800# to 7000# metallographic sand paper to gradually polish the surface of the titanium sheet, and then respectively uses acetone, ethanol and deionized water to carry out ultrasonic treatment on the titanium sheet.
In the preparation method of the titanium implant provided by the invention, the titanium dioxide nanotube array is formed by performing anodic oxidation reaction on the surface of the titanium matrix, and different levels of titanium dioxide nanotube arrays, namely a hierarchical titanium dioxide nanotube array layer, are formed on the surface of the titanium matrix by changing the conditions of the anodic oxidation reaction; and forming a material with a piezoelectric effect on the surface of the graded titanium dioxide nanotube array layer in an electrostatic spinning mode to form a three-dimensional multifunctional structure. In particular, the piezoelectric suspension forms a piezoelectric fiber layer after electrospinning that has an appropriate pore size and negative potential to ensure that bacteria can pass through the piezoelectric fiber layer and reach the graded titanium dioxide nanotube array layer. Because a large amount of positive charges are injected into the graded titanium dioxide nanotube array layer in the electrostatic spinning process, a large amount of positive charge traps are formed, and therefore bacteria can be killed.
The invention also provides a titanium implant obtained according to the preparation method.
The invention also provides application of the titanium implant in medical implant materials.
The present invention will be described in detail by examples.
Example 1
(1) The surface of the pure titanium foil (PT, diameter 12mm, thickness 0.25mm, purity 99.99%) was gradually polished with 800# to 7000# metallographic sand paper, and then sonicated with acetone, ethanol and deionized water, respectively. For convenience of description, the pure titanium foil PT is defined as the titanium matrix M0.
(2) Primary anodic oxidation
And (3) performing primary anodic oxidation on the titanium matrix M0, taking ethylene glycol solution of ammonium fluoride with the concentration of 88mmol/L as electrolyte, taking graphite as cathode, connecting the titanium matrix M0 with an anode, controlling the voltage to be 60V, and performing primary anodic oxidation reaction at 25 ℃ for 2.5h to obtain the titanium matrix M1.
(3) Secondary anodic oxidation
Placing the titanium matrix M1 into deionized water for ultrasonic treatment, wherein the ultrasonic power is 200W, and the ultrasonic time is 15min, so as to obtain a titanium matrix M2; and then, taking an ethylene glycol solution of ammonium fluoride with the concentration of 88mmol/L as an electrolyte, taking graphite as a cathode, connecting the titanium matrix M2 with an anode, controlling the voltage to be 12V, and carrying out secondary anodic oxidation reaction at 25 ℃ for 40min to obtain the titanium matrix M3.
(4) PVDF powder (FR 904, mw=6×10 5 ) Dissolving in a mixed solution of DMF and acetone (the mass ratio of DMF to acetone is 1.5:1) to obtain PVDF solution, wherein the concentration of PVDF powder is 10wt%; and then taking the PVDF solution as a raw material, and forming a piezoelectric fiber layer on the surface of the titanium matrix M3 by adopting an electrostatic spinning method to obtain the titanium implant.
Specific conditions of electrospinning: preparing a piezoelectric fiber layer on a titanium matrix M3 by adopting an electrostatic spinning device (E05-001, laideton precision electromechanical technology Co., ltd., china), wherein the direct current voltage received by a PVDF solution is 12KV, the titanium matrix M3 is connected to a negative electrode, and the voltage is-6 KV; delivering PVDF solution from the stainless steel needle tip at a flow rate of 1mL/h, wherein the distance between the needle tip and the titanium matrix M3 is 12cm; the relative humidity during electrospinning was 25% and the temperature was 25 ℃.
Example 2
(1) The surface of the pure titanium foil (PT, diameter 12mm, thickness 0.25mm, purity 99.99%) was gradually polished with 800# to 7000# metallographic sand paper, and then sonicated with acetone, ethanol and deionized water, respectively. For convenience of description, the pure titanium foil PT is defined as the titanium matrix M0.
(2) Primary anodic oxidation
And (3) performing primary anodic oxidation on the titanium matrix M0, taking an ethylene glycol solution of ammonium fluoride with the concentration of 88mmol/L as an electrolyte, taking graphite as a cathode, connecting the titanium matrix M0 with an anode, controlling the voltage to be 65V, and performing primary anodic oxidation reaction at 35 ℃ for 2 hours to obtain the titanium matrix M1.
(3) Secondary anodic oxidation
Placing the titanium matrix M1 into deionized water for ultrasonic treatment, wherein the ultrasonic power is 300W, and the ultrasonic time is 15min, so as to obtain a titanium matrix M2; and then, taking an ethylene glycol solution of ammonium fluoride with the concentration of 88mmol/L as an electrolyte, taking graphite as a cathode, connecting the titanium matrix M2 with an anode, controlling the voltage to be 15V, and performing secondary anodic oxidation reaction at 35 ℃ for 30min to obtain the titanium matrix M3.
(4) PVP powder (K30, mw=3.79×10 4 ) Dissolving in a mixed solution of DMF and acetone (the mass ratio of DMF to acetone is 1:1) to obtain PVP solution, wherein the concentration of PVP powder is 10wt%; and then using the PVP solution as a raw material, and forming a piezoelectric fiber layer on the surface of the titanium matrix M3 by adopting an electrostatic spinning method to obtain the titanium implant.
Specific conditions of electrospinning: preparing a piezoelectric fiber layer on a titanium matrix M3 by adopting an electrostatic spinning device (E05-001, laideton precision electromechanical technology Co., ltd., china), wherein the direct current voltage received by PVP solution is 10KV, the titanium matrix M3 is connected to a negative electrode, and the voltage is-5 KV; PVP solution is conveyed from the stainless steel needle tip at a flow rate of 1mL/h, and the distance between the needle tip and the titanium matrix M3 is 15cm; the relative humidity during electrospinning was 30% and the temperature was 25 ℃.
Example 3
(1) The surface of the pure titanium foil (PT, diameter 12mm, thickness 0.25mm, purity 99.99%) was gradually polished with 800# to 7000# metallographic sand paper, and then sonicated with acetone, ethanol and deionized water, respectively. For convenience of description, the pure titanium foil PT is defined as the titanium matrix M0.
(2) Primary anodic oxidation
And (3) performing primary anodic oxidation on the titanium matrix M0, taking an ethylene glycol solution of ammonium fluoride with the concentration of 88mmol/L as an electrolyte, taking graphite as a cathode, connecting the titanium matrix M0 with an anode, controlling the voltage to be 55V, and performing primary anodic oxidation reaction at 30 ℃ for 3 hours to obtain the titanium matrix M1.
(3) Secondary anodic oxidation
Placing the titanium matrix M1 into deionized water for ultrasonic treatment, wherein the ultrasonic power is 300W, and the ultrasonic time is 15min, so as to obtain a titanium matrix M2; and then, taking an ethylene glycol solution of ammonium fluoride with the concentration of 88mmol/L as an electrolyte, taking graphite as a cathode, connecting the titanium matrix M2 with an anode, controlling the voltage to be 10V, and carrying out secondary anodic oxidation reaction at 30 ℃ for 50min to obtain the titanium matrix M3.
(4) PCL powder (2200, mw=8×10 5 ) Dissolving in a mixed solution of DMF and acetone (the mass ratio of DMF to acetone is 2:1) to obtain a PCL solution, wherein the concentration of PCL powder is 10wt%; and then taking the PCL solution as a raw material, and forming a piezoelectric fiber layer on the surface of the titanium matrix M3 by adopting an electrostatic spinning method to obtain the titanium implant.
Specific conditions of electrospinning: preparing a piezoelectric fiber layer on a titanium matrix M3 by adopting an electrostatic spinning device (E05-001, laideton precision electromechanical technology Co., ltd., china), wherein the direct current voltage received by PCL solution is 15KV, the titanium matrix M3 is connected to a negative electrode, and the voltage is-8 KV; conveying PCL solution from a stainless steel needle tip at a flow rate of 1mL/h, wherein the distance between the needle tip and the titanium matrix M3 is 10cm; the relative humidity during electrospinning was 25% and the temperature was 25 ℃.
Structural characterization and performance testing of titanium implants:
for convenience of the following description and the identification in the drawings of the specification, the pure titanium foil is represented by PT, and the prepared titanium implant with the three-dimensional multifunctional structure is represented by 3 DMA.
1. The titanium implant prepared in example 1 was evaluated for antibacterial properties using staphylococcus aureus and escherichia coli:
individual colonies were removed from Mueller-Hinton (MH) agar solid medium using sterile rings, inoculated into 10mL MH broth and placed on a shaker for 12h. Optical Density (OD) values were measured with a nucleic acid protein analyzer to confirm that the bacterial broth and liquid medium were thoroughly mixed. Bacterial suspensions were dropped onto PT or 3DMA surfaces and incubated at 37 ℃ for 2h. The samples were then washed with sterile Phosphatase Buffer (PBS) to remove loosely attached bacteria and placed into a centrifuge tube containing 5mL of PBS. Shake on vortex mixer for 5min to allow bacteria to fall from PT or 3DMA surface into PBS liquid. 20 mu L of the bacterial-containing PBS suspension in the centrifuge tube is respectively sucked and beaten on the MH agar culture medium flat plate, bacterial liquid on the flat plate is rapidly pushed away evenly, and 3 flat plates are repeatedly pushed out of each centrifuge tube. Plates were incubated at 37℃for 12h and then removed, and the number of bacterial CFU colonies on each MH agar medium plate was counted.
The calculation formula of the antibacterial rate: [ (X-Y)/X ]. Times.100%, wherein X represents the average bacterial colony count of the control group PT group plate and Y represents the average bacterial colony count of the experimental group 3DMA group plate.
As can be seen from FIG. 2, the number of bacterial colonies of Staphylococcus aureus and Escherichia coli detected on the PT surface was greater than that of the 3DMA surface prepared in example 1, and the normalized CFU colony numbers of Staphylococcus aureus and Escherichia coli viable bacteria on the 3DMA surface were 0.429 and 0.667, respectively, compared to PT (FIG. 3). Thus, the antibacterial rates of 3DMA against staphylococcus aureus and escherichia coli on PT surfaces were 57.1% and 33.3%, respectively.
Based on the above experimental data, the antibacterial activity of 3DMA was enhanced in combination with the positive charge traps of the NT layer and the size effect of the nanofiber layer.
2. Polarized phenotype evaluation of macrophage RAW264.7 was performed on the titanium implant prepared in example 1:
RAW264.7 macrophages were seeded onto PT or 3DMA, stimulated with LPS+IFN-. Gamma.for 24h, followed by fixation of cells with 4% paraformaldehyde, rupture of membranes with 0.25% Triton, blocking with 10% goat serum, and incubation with primary antibodies to iNOS and CD206 (Abcam; 1:100) and the corresponding secondary antibodies. Positive cells of iNOS and CD206 were defined as M1 and M2 macrophages, respectively.
The immunofluorescence analysis results of FIG. 4 demonstrate that expression of the M1 macrophage inflammatory marker iNOS was inhibited and expression of the M2 macrophage surface marker CD206 was slightly increased under LPS and IFN-gamma stimulated 3DMA treatment. The quantitative analysis results of fig. 5 also show that the 3DMA treatment significantly inhibited the proportion of M1 macrophages compared to PT, while increasing the proportion of M2 macrophages. Therefore, the 3DMA has ideal immune regulation effect of inhibiting M1 to promote M2 polarization.
3. The titanium implant prepared in this example 1 was subjected to in vivo implantation experiments in rats to evaluate bone-joining performance:
male rats with 10 weeks of age SD were transplanted with PT or 3DMA at the distal outer side of femur, and 4 weeks later were harvested for Micro CT detection.
The micro-CT three-dimensional reconstructed image of FIG. 6 shows that the 3DMA set forms more new bone. Figure 7 reflects two indicators of new bone formation, bone volume percent (BV/TV) and bone density (BMD) were significantly higher in the 3DMA group than in the PT group. The Van Gieson staining results of FIGS. 8 and 9 show that the bone-implant contact rate of the 3DMA group was about 1.5 times that of the PT group. This demonstrates that 3DMA improves bone integration.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A titanium implant, characterized by: comprises a titanium matrix, a graded titanium dioxide nanotube array layer and a piezoelectric fiber layer.
2. The titanium implant of claim 1, wherein: the piezoelectric fiber layer consists of piezoelectric fibers, and the piezoelectric fibers are at least one selected from polymer piezoelectric fibers, ceramic piezoelectric fibers and semiconductor piezoelectric fibers;
preferably, the polymer piezoelectric fiber is at least one selected from PVDF fiber, PVDF-TrFE fiber, PHB fiber, PLLA fiber, PCL fiber, PLGA fiber, PHBV fiber, collagen fiber, chitosan fiber, cellulose and derivative fiber, PVP fiber, PVA fiber and PEO fiber;
preferably, the ceramic piezoelectric fiber is at least one selected from barium titanate fiber, potassium sodium niobate fiber, lithium niobate fiber, barium strontium niobate fiber, lead zirconate titanate fiber, boron nitride fiber, and hydroxyapatite fiber;
preferably, the semiconductor piezoelectric fiber is at least one selected from CdS fiber, cdSe fiber, znO fiber, znS fiber, cdTe fiber, znTe fiber, gaAs fiber, gaSb fiber, inAs fiber, inSb fiber, alN fiber.
3. A method of preparing a titanium implant according to claim 1 or 2, comprising the steps of:
(1) In the presence of electrolyte, titanium matrix M 0 Anodic oxidation is carried out to obtain a titanium matrix M of the deposition grading titanium dioxide nanotube array layer 3 ；
(2) Dispersing piezoelectric material in organic solvent to obtain piezoelectric suspension, and dispersing the piezoelectric suspension in titanium matrix M 3 And (3) carrying out electrostatic spinning on the surface of the titanium implant.
4. A method of preparation as claimed in claim 3, wherein: the electrolyte is an ethylene glycol solution of ammonium fluoride, and the concentration of the ammonium fluoride is 75-100mmol/L.
5. A method of preparation as claimed in claim 3, wherein: the anodic oxidation comprises primary anodic oxidation and secondary anodic oxidation;
preferably, the conditions of the primary anodic oxidation are: connecting a titanium matrix M0 with an anode by taking graphite as a cathode, and performing primary anodic oxidation to obtain a titanium matrix M1 loaded with a titanium dioxide nanotube array layer;
preferably, the voltage of the primary anodic oxidation is 55-65V, the temperature is 20-35 ℃ and the time is 2-3h;
preferably, the conditions of the secondary anodic oxidation are: cutting off the titanium dioxide nanotubes loaded on the surface of the titanium matrix M1 to obtain a titanium matrix M2 loaded with a bowl-shaped titanium dioxide nano array layer; then, taking graphite as a cathode, connecting a titanium matrix M2 with an anode, and performing secondary anodic oxidation to obtain a titanium matrix M3 of the load-grading titanium dioxide nanotube array layer;
preferably, the cutting treatment is that the titanium matrix M1 is placed in an aqueous solution for ultrasonic treatment, the ultrasonic power is 200-300W, and the ultrasonic time is 10-15min;
preferably, the voltage of the secondary anodic oxidation is 10-15V, the temperature is 20-35 ℃ and the time is 30-50min.
6. A method of preparation as claimed in claim 3, wherein: the piezoelectric material is at least one selected from polymer piezoelectric material, ceramic piezoelectric material and semiconductor piezoelectric material;
preferably, the polymer piezoelectric material is selected from at least one of PVDF, PVDF-TrFE, PHB, PLLA, PCL, PLGA, PHBV, collagen fiber, chitosan, cellulose and derivatives, PVP, PVA, PEO;
preferably, the ceramic piezoelectric material is at least one selected from barium titanate, potassium sodium niobate, lithium niobate, barium strontium niobate, lead zirconate titanate, boron nitride, and hydroxyapatite;
preferably, the semiconductor piezoelectric material is selected from at least one of CdS, cdSe, znO, znS, cdTe, znTe, gaAs, gaSb, inAs, inSb, alN.
7. A method of preparation as claimed in claim 3, wherein: the mass concentration of the piezoelectric material in the piezoelectric suspension is 5-15wt%;
the organic solvent is at least one selected from dimethyl sulfoxide, dimethylformamide, dimethylacetamide, dichloromethane, acetonitrile, tetrahydrofuran, acetone, N-methylpyrrolidone, butyrolactone, phenol, m-phenol, caprolactam, sulfolane and nitrobenzene.
8. A method of preparation as claimed in claim 3, wherein: the humidity of the electrostatic spinning is 20-30%, the temperature is 20-30 ℃, the spraying flow rate of the piezoelectric suspension is 0.5-2mL/h, the spinning distance is 10-15cm, the voltage applied to the piezoelectric suspension is 10-15KV, and the voltage applied to the titanium matrix M3 is-10 to-3 KV.
9. A titanium implant obtainable by the method of any one of claims 3 to 8.
10. Use of the titanium implant of claim 1 or claim 9 in a medical implant material.
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