CN111467572B - Implant material and preparation method and application thereof - Google Patents

Implant material and preparation method and application thereof Download PDF

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CN111467572B
CN111467572B CN202010274270.7A CN202010274270A CN111467572B CN 111467572 B CN111467572 B CN 111467572B CN 202010274270 A CN202010274270 A CN 202010274270A CN 111467572 B CN111467572 B CN 111467572B
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tio
implant
implant material
coating
zinc
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CN111467572A (en
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蒋欣泉
文晋
张翔凯
王笑
李金华
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Ninth Peoples Hospital Shanghai Jiaotong University School of Medicine
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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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • 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
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/32—Phosphorus-containing materials, e.g. apatite
    • 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
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • 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
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • 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
    • 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
    • A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses

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Abstract

The invention relates to the technical field of biological materials, in particular to an implant material for osteoporosis patients and a preparation method and application thereof. The implant material comprises TiO 2 Coating of said TiO 2 The coating is doped with biological trace element components, and the TiO 2 The mass percentage of the coating is 74-78%, and the mass percentage of the biological trace element component is 22-28%; the biological trace element component is selected from strontium and/or zinc. The implant material is a material capable of promoting the peripheral osseointegration and bone regeneration of an implant material, optimizes the concentration of zinc and/or strontium on the surface of the implant, promotes the osteogenesis of osteoporosis bones and the osseointegration of the implant, has a good antibacterial effect, and prevents possible osseointegration failure and peri-implant inflammation caused by the implant material implanted into osteoporosis patients, so that the implant treatment failure is avoided.

Description

Implant material and preparation method and application thereof
Technical Field
The invention relates to the technical field of biological materials, in particular to an implant material and a preparation method and application thereof.
Background
With the advent of aging society, osteoporosis has become a common chronic disease, and the population of patients has increased. The bone mass metabolism disorder of the old is mainly caused, the dynamic balance between bone absorption and formation is broken, the bone mass absorption develops, the bone density is reduced, the bone mass is damaged, and the quality of the bone tissue of the whole body of a patient is obviously reduced. To date, osteoporosis remains a contraindication for dental implant surgery.
On the other hand, people pay more attention to oral health, and people gradually increase the restoration appeal for restoring tooth loss. Oral implant technology was invented in the 60's of the 20 th century, and the implant was invented by the teaching of Branemark who discovered the phenomenon of "osseointegration" on the surface of a titanium implant. Although titanium implants are an ideal choice for the current bone implants, in the oral implantation treatment, a large number of various flora colonize in the oral cavity due to the particularity of the oral environment. Whereas the implant must be maintained in sterile conditions for implantation in alveolar bone. Therefore, in a complex microbial environment, simple titanium implant implantation is easy to cause infection, and peri-implantitis causes the failure of the implantation operation. For osteoporosis patients with poor bone formation conditions, the blood circulation reconstruction is relatively weak, and the anti-infection capability is tested.
Therefore, it is necessary to design an implant having good osteogenesis ability and antibacterial effect suitable for osteoporosis patients. It is expected to find a method which can carry out sequence modification of surface structure and chemical components on the basis of promoting osseointegration by a common titanium implant, and can specifically induce osteogenic differentiation of mesenchymal stem cells in a bone marrow cavity of an osteoporosis patient by combining the condition that the bone quality of the osteoporosis patient is poor, thereby increasing the peripheral bone combination amount of the implant of the osteoporosis patient and consolidating the firmness of the implant. Meanwhile, antibacterial components are added on the surface of the implant, so that potential infection in the oral cavity can be effectively reduced, a better bone formation time and a sterile environment are provided for relatively slow bone formation of osteoporosis, the success rate of material implantation is increased, and later-stage infection is reduced to the greatest extent.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention is directed to an implant material with osteogenic and antibacterial effects, and a method for preparing the same and an application thereof, which are used to solve the problems of the prior art.
To achieve the above and other related objects, according to one aspect of the present invention, there is provided an implant material including TiO 2 Coating of said TiO 2 The coating is doped with biological trace element components, and the TiO 2 The mass percentage of the coating is 74-78%, and the mass percentage of the biological trace element component is 22-28Percent; the biological trace element component is selected from strontium and/or zinc.
In some embodiments of the invention, the bio-trace element component further comprises calcium and/or phosphorus.
In some embodiments of the invention, in the biological microelement component, the strontium accounts for 0-6.52% by mass; the mass percentage of the zinc is 5.58-7.22%; the mass percentage of the calcium is 1.35-5.06%; the mass percentage of the phosphorus is 10.74-12.82%.
In some embodiments of the invention, in the biological microelement component, the strontium accounts for 1.76-6.52% by mass; the mass percentage of the zinc is 5.58-7.22%; the mass percentage of the calcium is 1.35-3.75%; the mass percentage of the phosphorus is 11.41-12.82%.
In another aspect, the present invention provides a method for preparing the implant material, the method comprising the steps of:
1) adding titanium rod and/or titanium sheet or electrolyte containing calcium salt and phosphate to carry out plasma oxidation treatment to prepare TiO 2 Coating;
2) and adding zinc salt and strontium salt into the electrolyte in the step 1) to prepare the implant material.
In some embodiments of the present invention, the calcium salt in step 1) is selected from one or more of calcium acetate, calcium carbonate, and calcium glycerophosphate.
In some embodiments of the invention, the phosphate in step 1) is selected from disodium glycerophosphate.
In some embodiments of the present invention, the concentration of the phosphate in the step 1) is 0.05 to 0.20 mol/L.
In some embodiments of the present invention, the strontium salt in step 2) is selected from strontium acetate.
In some embodiments of the present invention, the molar ratio of the strontium salt to the calcium salt is 0 to 3: 1 to 4.
In some embodiments of the invention, the zinc salt in step 2) is selected from zinc acetate.
In some embodiments of the present invention, the concentration of the zinc salt in the step 2) is 0.06-0.24 mol/L.
In another aspect, the invention provides the use of the implant material of the invention in the preparation of oral implants and in the regeneration of osteoporotic bone and osseointegration of implant materials.
Drawings
FIG. 1 shows the surface morphology and XRD detection results of the implant materials prepared in examples 1-5 of the present invention.
FIG. 2 shows the ion release profile and XPS test results of the implant materials prepared in examples 1 to 5 of the present invention.
FIG. 3 shows the results of the tests of the antibacterial ability of the implant materials prepared in examples 1 to 5 of the present invention.
FIG. 4 shows the results of examining the influence of the implant materials prepared in examples 1 to 5 of the present invention on the cell proliferation ability.
FIG. 5 shows the results of examining the influence of the cell osteogenic differentiation ability of the implant materials prepared in examples 1 to 5 of the present invention on the gene layer surface.
FIG. 6 shows the results of the test of the effect of the active layer of the implant material prepared in examples 1 to 5 on the osteogenic differentiation capacity of the cells.
FIG. 7 shows the results of the test of the effect of the implant material prepared in examples 1 to 5 of the present invention on the expression of OCN proteins in cells.
FIG. 8 shows the results of examining the vascularization ability of the implant materials prepared in examples 1 to 5 of the present invention.
FIG. 9 shows the results of in vivo bone formation amount three-dimensional reconstruction of implant materials prepared in examples 1 to 5 of the present invention.
FIG. 10 shows the results of picrorhizine staining, photographing and implant surface bone formation rate calculation for in vivo osteogenesis of implant materials prepared in examples 1 to 5 of the present invention.
Detailed Description
The implant material is a material capable of promoting the peripheral osseointegration and bone regeneration of the implant material, and has a good antibacterial effect, so that infection and inflammation caused after the implant material is implanted are prevented.
In one aspect, the present invention provides an implant material comprising TiO 2 Coating of said TiO 2 The coating is doped with biological trace element components.
In the implant material provided by the invention, the TiO 2 The mass percentage of the coating can be 74-78% or 75-77%, and TiO is usually used 2 The coating is formed by plasma oxidation treatment by immersing the titanium rod and/or titanium sheet in an electrolyte, which may be, for example, an electrolyte containing calcium salts and phosphates.
In the implant material provided by the invention, the biological trace element component can be 22-28%, 23-27% or 24-26% in percentage by mass.
In a specific embodiment, the TiO 2 The mass percentage of the coating is 74-78%, and the mass percentage of the biological trace element component is 22-28%.
In the implant material provided by the invention, the biological trace element component is selected from strontium and/or zinc.
The inventor has surprisingly found through a large number of experiments that the biological effects caused by the different strontium contents are quite different. Specifically, in the biological trace element component, the strontium can be 0-6.52%, 1.76-6.52%, 2-6%, 2.5-5.5%, 3-5% or 3.5-4.5% by mass. In some specific embodiments, the biological trace element-containing strontium component is in an amount of 0%, 1.57%, 3.77%, 6.3% by weight. Within the above range, strontium can promote bone differentiation well.
In the biological trace element component, the mass percentage of zinc can be 5.58-7.22%, 5-7%, 4.5-6.5%, or 5-6%. In some specific embodiments, the bio-trace element zinc-containing component has a surface mass percent of 6%.
The biological trace element component also comprises calcium and/or phosphorus.
In the biological trace element component, the mass percentage of calcium is 1.35-5.06%, 1.35-3.75%, 1.5-5%, 2-4.5%, 2.5-4%, or 3-3.5%.
In the biological trace element component, the mass percentage of phosphorus is 10.74-12.82%, 11.41-12.82%, 11-12.5% or 11.5-12%.
In a specific embodiment, in the biological trace element component, the mass percentage of strontium is 0-6.52%; the mass percentage of the zinc is 5.58-7.22%; the mass percentage of the calcium is 1.35-5.06%; the mass percentage of the phosphorus is 10.74-12.82%.
In another specific embodiment, in the biological trace element component, the mass percentage of strontium is 1.76-6.52%; the mass percentage of the zinc is 5.58-7.22%; the mass percentage of the calcium is 1.35-3.75%; the mass percentage of the phosphorus is 11.41-12.82%.
Another aspect of the present invention provides a method for preparing an implant material, the method comprising the steps of:
1) adding a titanium rod and/or a titanium sheet into electrolyte containing calcium salt and phosphate for plasma oxidation treatment to prepare TiO 2 Coating;
2) and adding zinc salt and strontium salt into the electrolyte in the step 1) to prepare the implant material.
In the preparation method of the implant material provided by the invention, the step 1) is to add the titanium rod and/or the titanium sheet into the electrolyte containing calcium salt and phosphate for plasma oxidation treatment to prepare TiO 2 And (4) coating. The titanium rod and the titanium sheet need to be pretreated, wherein the pretreatment comprises the steps of grinding and polishing 10mm multiplied by 1mm or 20mm multiplied by 1mm sheet commercial pure titanium or 2mm multiplied by 7mm column commercial pure titanium, sequentially cleaning the titanium rod and the titanium sheet in an ultrasonic oscillator by using ethanol and deionized water, transferring the cleaned titanium rod and the titanium sheet to 5% oxalic acid solution, heating the titanium rod and the titanium sheet for 2 hours at 100 ℃, and standing the titanium rod and the titanium sheet for room temperature drying to obtain the titanium sheet or the titanium rod.
The plasma oxidation method can prepare the coating with good bioactivity on the surface of titaniumLayers, have received wide acceptance in recent years. However, the simple plasma oxidation method can generate fine cracks on the surface of the coating, and in the practical application of oral clinical implantation, the implant is implanted in the bone through a high-speed drill, and the coating is easy to peel off after the coating cracks. Therefore, if the harmfulness and the possibility of generating cracks on the surface coating of the implant are reduced to the minimum, the condition and the parameters of the plasma oxidation method are required to be effectively and accurately controlled in the preparation process, so that the separation of the coating can be effectively prevented only when the average size threshold of the titanium surface morphology is lower than the average size of the microcracks, and the mechanical strength of the titanium surface morphology is effectively improved in practical application. Meanwhile, the micro cracks on the surface of the coating enable bioactive elements to be loaded and can be continuously released from the surface of the material to the surrounding environment, and a good slow release effect is achieved. In one embodiment, titanium rods and/or sheets are added to a titanium alloy containing calcium acetate monohydrate (C) 4 H 6 O 4 Ca·H 2 O) and beta-Glycerol disodium phosphate salt (C) 3 H 7 Na 2 O 6 P·5H 2 O) is carried out plasma oxidation treatment on the material in calcium-phosphorus electrolyte, a titanium sheet is taken as an anode, a constant-current plasma electrolytic oxidation power supply with the duty ratio of 10-11% and the oxidation frequency of 800-900 Hz is adopted, and the current density is 10-50A/dm 2 The oxidation time is 3-20 minutes at the temperature of 20-30 ℃, and good and uniform TiO can be prepared 2 And (4) coating.
Further, the calcium salt in step 1) is selected from one or more of calcium acetate, calcium carbonate and calcium glycerophosphate. The calcium salt is preferably selected from calcium acetate, which is calcium acetate monohydrate (C) 4 H 6 O 4 Ca·H 2 O)。
Further, the phosphate in step 1) is selected from disodium glycerophosphate, which may be, for example, beta-glycerophosphate disodium salt (C) 3 H 7 Na 2 O 6 P·5H 2 O). The concentration of the phosphate in the step 1) is 0.05-0.20 mol/L. More specifically, the concentration of phosphate may be, for example, 0.05 mol/L.
In the preparation method of the implant material provided by the invention, step 2) is to add zinc salt and strontium salt into the electrolyte in step 1) to prepare the implant material. The strontium salt in the step 2) is selected from strontium acetate. Wherein the molar ratio of the sum of the strontium salt and the calcium salt is 0-3: 1-4, 0-3: 1-3, 2-2: 2-2, or 1-3: 1 to 3. In a specific embodiment, the sum of the concentrations of the strontium salt and the calcium salt is 0.1-0.4 mol/L. More specifically, the concentration of the strontium salt is 0-0.3 mol/L, or 0.1-0.2 mol/L. The different strontium ion concentrations can cause different biological effects, namely, the low concentration Sr can inhibit the bone absorption and promote the bone formation, and the high concentration Sr can cause abnormal bone tissue metabolism and increase the non-collagen amount in the bone and the dissolution of bone minerals. Within the above-mentioned concentration range of the present invention, strontium ions can promote bone differentiation well. The concentration of the calcium salt is 0.1-0.4 mol/L, or 0.2-0.3 mol/L.
Further, the zinc salt in the step 2) is selected from zinc acetate. The concentration of the zinc salt in the step 2) is 0.06-0.24 mol/L, 0.06-0.12 mol/L, 0.06-0.18 mol/L or 0.12-0.24 mol/L. The antimicrobial capacity of zinc increases with increasing concentration, but too high a concentration can affect cell compatibility. Within the concentration range of the zinc salt, the antibacterial ability can be kept, and meanwhile, the cell compatibility is good.
In a third aspect, the invention provides the use of an implant material for the preparation of an oral implant and for the regeneration of osteoporotic bone in combination with the implant material.
The invention has the beneficial effects that:
the implant material of the invention is prepared by adding the active ingredient into TiO 2 The biological trace elements are doped on the surface of the coating, zinc and strontium are cooperatively loaded, and the concentration of strontium salt and zinc salt is controlled during preparation, so that the prepared material can promote the peripheral osseointegration and bone regeneration of the implant material, has a good antibacterial effect and prevents infection and inflammation caused after the implant is implanted. Meanwhile, the implant does not show obvious toxicity and does not generate great negative effect on tissues, and the released ions can promote the osteogenic differentiation of mesenchymal stem cells, increase the bone combination amount around the implant and consolidate the firmness of the implant, particularly the osteoporosis Under the condition of poor quality of the bone, the induction of osteogenic differentiation of cells of a patient and the secretion of the bone can increase the degree of osseointegration of the implant material and increase the success rate of the implant implantation.
The following examples are provided to further illustrate the advantageous effects of the present invention.
In order to make the objects, technical solutions and advantageous technical effects of the present invention more clear, the present invention is further described in detail below with reference to examples. However, it should be understood that the embodiments of the present invention are only for explaining the present invention and are not for limiting the present invention, and the embodiments of the present invention are not limited to the embodiments given in the specification. The examples were prepared under conventional conditions or conditions recommended by the material suppliers without specifying specific experimental conditions or operating conditions.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
In the following examples, reagents, materials and instruments used are commercially available unless otherwise specified.
Example 1
Adding beta-glycerophosphoric acid disodium salt (C) to deionized water 3 H 7 Na 2 O 6 P·5H 2 O, 50mM) and calcium acetate monohydrate (C) 4 H 6 O 4 Ca·H 2 O), preparing electrolyte containing calcium/phosphate, carrying out plasma oxidation treatment on a titanium rod in the electrolyte containing calcium/phosphate, taking a titanium sheet as an anode, adopting a constant-current plasma electrolytic oxidation power supply with the duty ratio of 10% and the frequency of 800Hz, and controlling the current density to be 30A/dm 2 Oxidizing for 10min to obtain TiO 2 And (4) coating. Zinc acetate (60mM) and strontium acetate are added into the electrolyte continuously, wherein the total concentration of the calcium acetate and the zinc acetate is constant at 100mM, and the molar ratio of Sr (Sr + Ca) is adjusted to be 1: 4. The sample prepared was named 1SrZn @ TiO 2 . XRD detection proves that the prepared TiO is shown in figure 1 2 The coating is mainly in rutile phase and anatase phase. As shown in the EDS of fig. 2a, the mass percentages of the elements are: o (43.61 + -0.64 wt%), Ti (32.37 + -0.50 wt%), P (12.45 + -0.07 wt%), Ca (3.37 + -0.38 wt%), Zn (6.63 + -0.45 wt%), Sr (1.57 + -0.19).
Example 2
Adding beta-glycerophosphoric acid disodium salt (C) to deionized water 3 H 7 Na 2 O 6 P·5H 2 O, 50mM) and calcium acetate monohydrate (C) 4 H 6 O 4 Ca·H 2 O), preparing electrolyte containing calcium/phosphate, carrying out plasma oxidation treatment on the titanium rod in the electrolyte containing calcium/phosphate, taking a titanium sheet as an anode, adopting a constant-current plasma electrolytic oxidation power supply with the duty ratio of 10% and the frequency of 800Hz, and controlling the current density to be 30A/dm 2 Oxidizing for 10min to obtain TiO 2 And (4) coating. Zinc acetate (60mM) and strontium acetate are added into the electrolyte continuously, wherein the total concentration of the calcium acetate and the zinc acetate is constant at 100mM, and the molar ratio of Sr (Sr + Ca) is adjusted to be 2: 4. The sample prepared was named 2SrZn @ TiO 2 . As shown in figure 1, XRD detection proves that the prepared TiO 2 The coating is mainly in rutile phase and anatase phase. As shown in the EDS of fig. 2a, the mass percentages of the elements are: o (43.16 + -0.33 wt%), Ti (31.16 + -0.36 wt%), P (12.69 + -0.13 wt%), Ca (2.27 + -0.13 wt%), Zn (6.95 + -0.27 wt%), Sr (3.37 + -0.01).
Example 3
Glycerol disodium phosphate salt (C) was added to deionized water 3 H 7 Na 2 O 6 P·5H 2 O, 50mM) and calcium acetate (C) 4 H 6 O 4 Ca·H 2 O), preparing electrolyte containing calcium/phosphate, carrying out plasma oxidation treatment on a titanium rod in the electrolyte containing calcium/phosphate, taking a titanium sheet as an anode, adopting a constant-current plasma electrolytic oxidation power supply with the duty ratio of 10% and the frequency of 800Hz, and controlling the current density to be 30A/dm 2 Oxidizing for 10min to obtain TiO 2 And (4) coating. Zinc acetate (60mM) and strontium acetate are added into the electrolyte continuously, wherein the total concentration of the calcium acetate and the zinc acetate is constant at 100mM, and the molar ratio of Sr (Sr + Ca) is adjusted to be 3: 4. The sample prepared was named 3SrZn @ TiO 2 . XRD detection proves that the prepared TiO is shown in figure 1 2 The coating is mainly in rutile phase and anatase phase. As shown in the EDS of fig. 2a, the mass percentages of the elements are: o (43.18. + -. 0.58 wt%), Ti (31.66. + -. 0.21 wt%), P (11.52. + -. 0.11 wt%), Ca (1.40. + -. 0.05 wt%), Zn (5.93. + -. 0.35 wt%), Sr (6.32. + -. 0.20).
Example 4
Adding beta-glycerophosphoric acid disodium salt (C) to deionized water 3 H 7 Na 2 O 6 P·5H 2 O, 50mM) and calcium acetate monohydrate (C) 4 H 6 O 4 Ca·H 2 O), preparing electrolyte containing calcium/phosphate, carrying out plasma oxidation treatment on a titanium rod in the electrolyte containing calcium/phosphate, taking a titanium sheet as an anode, adopting a constant-current plasma electrolytic oxidation power supply with the duty ratio of 10% and the frequency of 800Hz, and controlling the current density to be 30A/dm 2 Oxidizing for 10min to obtain TiO 2 And (4) coating. Zinc acetate (60mM) and strontium acetate are added into the electrolyte continuously, wherein the total concentration of the calcium acetate and the zinc acetate is constant at 100mM, and the molar ratio of Sr (Sr + Ca) is adjusted to be 0: 4. The prepared sample is named as Zn @ TiO 2 . XRD detection proves that the prepared TiO is shown in figure 1 2 The coating is mainly in rutile phase and anatase phase. As shown in the EDS of fig. 2a, the mass percentages of the elements are: o (44.76 + -0.46 wt%), Ti (32.57 + -0.80 wt%), P (11.48 + -0.74 wt%), Ca (4.66 + -0.40 wt%), Zn (6.53 + -0.21 wt%), Sr (0).
Example 5
Glycerol disodium phosphate salt (C) was added to deionized water 3 H 7 Na 2 O 6 P·5H 2 O, 50mM) and calcium acetate (C) 4 H 6 O 4 Ca·H 2 O, 100mM), preparing electrolyte containing calcium/phosphate, carrying out plasma oxidation treatment on a titanium rod in the electrolyte containing calcium/phosphate, taking a titanium sheet as an anode, adopting an electrolytic oxidation power supply with the duty ratio of 10% and the frequency of 800Hz, and having the current density of 30A/dm 2 Oxidizing for 10min to obtain TiO 2 And (4) coating. As shown in the EDS of fig. 2a, the mass percentages of the elements are: o (42.22 + -0.47 wt%), Ti (34.95 + -0.16 wt%), P (17.29 + -0.45 wt%), Ca (5.55 + -0.40 wt%) Zn (0), Sr (0).
Evaluation of Performance
1) Surface characterization of materials
The surface morphology of each group of materials was characterized using a field emission scanning electron microscope (SEM; Hitachi SU8010) and an energy dispersive X-ray spectrometer (EDS). Using an X-ray diffractometer (XRD; Rigaku Ultima IV, Cu)
Figure BDA0002444223070000081
) The crystallinity of the surface coating was measured. Phase identification is performed by comparing a standard JCPDS database. The elemental chemical state of the sample was examined by X-ray photoelectron spectroscopy (XPS; ESCALB 250Xi, Mg K α (1253.6 ev)). FIGS. 1a-1e show the surface topography of various samples after plasma oxidation treatment. As can be seen in fig. 1, uniform micropore morphology was produced on the titanium dioxide surface while similar surface structures were maintained for each set of samples, indicating that the addition of the element did not significantly alter the surface morphology of the coating. In terms of composition, FIG. 1f shows that the main component of the material is anatase TiO before the incorporation of daughter zinc ions 2 . After the zinc ion is doped, a special diffraction peak of rutile phase appears. While figure 2a shows the elemental composition of each set of samples analyzed with EDS. From the Zn2p3/2XPS spectrum in FIG. 2b, the peak at the binding energy position of 1021.8eV indicates that the doped zinc is present as zinc oxide. In FIG. 2, Zn-is Zn @ TiO 2 Group (d); 1SrZn is 1SrZn @ TiO 2 Group (d); 2 SrZn-is 2SrZn @ TiO 2 Group (d); 3 SrZn-is 3SrZn @ TiO 2 And (4) grouping.
2) Experiment of ion precipitation
All samples were soaked in 10 ml Dulbecco's modified Eagle's Medium (DMEM, Gibco, USA) at 36.5 ℃ for 1, 4, 7 and 14 consecutive days. The leachate was collected at each time point and the amount of Ca, P, Sr and Zn ions released was determined by inductively coupled plasma mass spectrometry (ICP-MS; Agilent 7800). FIGS. 2c-2f reflect the release profiles of Ca, P, Zn and Sr ions from the surface of different samples during 14 days of immersion. The release characteristics of these ions are consistent with the coating EDS analysis in figure 2 a. In FIGS. 2c-2f, Zn-is Zn @ TiO 2 Group (d); 1SrZn is 1SrZn @ TiO 2 Group (d); 2 SrZn-is 2SrZn @ TiO 2 Group (d); 3 SrZn-is 3SrZn @ TiO 2 And (4) grouping.
3) Evaluation of antibacterial Properties
In biological experiments, bacteria were inoculated onto the surfaces of the various materials prepared in examples 1 to 5, and the biological behavior of the bacteria on different surfaces was observed and analyzed.
After an equal amount of staphylococcus aureus suspension was inoculated onto the surface of the material, it was placed at 37 ℃ in 5% CO 2 Is cultured for 24 hours under the wet culture environment of (2). Fixing the obtained sample in 2.5% glutaraldehyde for 2 hours, then sequentially dehydrating the sample in 30%, 50%, 70%, 80%, 90%, 95% and 100% ethanol according to the preparation method of a scanning electron microscope sample, finally spraying gold, preparing the sample, and performing on-machine observation to find that bacteria show different proliferation capacities on the surfaces of different materials. As shown in fig. 3a to 3e, the number of bacteria is significantly increased on the surface of the titanium dioxide material, while the content of bacteria is significantly decreased on the surface of the titanium dioxide material containing zinc and strontium. As shown in FIG. 3f, quantitative analysis shows that the bacteriostatic rate of the material containing zinc and strontium reaches 90%. Wherein, in FIG. 3, Zn _ is Zn @ TiO 2 Group (iv); 1SrZn is 1SrZn @ TiO 2 Group (iv); 2 SrZn-is 2SrZn @ TiO 2 Group (d); 3 SrZn-is 3SrZn @ TiO 2 And (4) grouping.
4) Cell proliferation potency assay
The materials of different components of examples 1-5 were placed in a 24-well plate, and 1ml was addedBone marrow mesenchymal stem cells of OVX rats were seeded on the surface of the material, and the proliferation of the cells was observed on the following days 1, 4 and 7, respectively. The reagent kit of CCK-8 of Dongren corporation is adopted, 10ul of CCK-8 reagent is added into every 100ul of culture solution, the culture solution is placed in an incubator for 1 hour in a dark state, and then the detection is carried out by an enzyme-labeling instrument under the wavelength of 450 nm. As can be seen from fig. 4, the various materials had no significant effect on the proliferation of cells, demonstrating the low toxicity of the materials. In FIG. 4, Zn-is Zn @ TiO 2 Group (iv); 1SrZn is 1SrZn @ TiO 2 Group (d); 2 SrZn-is 2SrZn @ TiO 2 Group (d); 3 SrZn-is 3SrZn @ TiO 2 And (4) grouping.
5) Cell osteogenic differentiation capacity assay
The different component materials were placed in 6-well and 24-well plates and the cells were seeded as described above. The method comprises the steps of adding trizol for cracking cells inoculated in a 6-pore plate after 7 days, sequentially adding chloroform, isopropanol and absolute ethyl alcohol for extracting RNA after lysate is collected, finally performing reverse transcription on the extracted RNA into cDNA by using a Takara kit, amplifying related genes by using a Polymerase Chain Reaction (PCR) technology, and observing the change of the cells in the gene level, wherein the cells stimulated by zinc and strontium ions have the up-regulation of genes such as OPN, OCN, BMP2 and ALP in the gene level and have obvious correlation with the ion concentration compared with a control group according to a graph 5, so that the osteogenic differentiation of the cells in the gene level is proved. In FIG. 5, Zn-is Zn @ TiO 2 Group (d); 1 SrZn-is 1SrZn @ TiO 2 Group (iv); 2 SrZn-is 2SrZn @ TiO 2 Group (d); 3 SrZn-is 3SrZn @ TiO 2 And (4) grouping.
In another 6-well plate, we added 300ul of RIPA lysate per well and after lysis on ice for about 30 minutes, 160 μ l of solution was taken as 1: the pNPP solution (1mg/ml) was added at a ratio of 1, and after reaction at 37 ℃ for half an hour away from light, detection was carried out at a wavelength of 405 nm. The remaining solution was assayed for protein content per volume by BCA kit according to Thermo company. Specifically, a protein standard substance is used for reacting with a reaction solution, a protein concentration curve is drawn according to an absorbance value, then a sample is used for reacting with the reaction solution, the absorbance value is brought into the concentration curve, and the protein concentration is calculated. Dividing the value of the wavelength of 405nm by the protein content to obtain To the value of alkaline phosphatase (ALP) activity per intracellular concentration. As can be seen in fig. 6, the alkaline phosphatase activity was significantly increased in BMSCs under the stimulation of zinc and strontium ions. In FIG. 6, Zn-is Zn @ TiO 2 Group (d); 1SrZn is 1SrZn @ TiO 2 Group (d); 2 SrZn-is 2SrZn @ TiO 2 Group (d); 3 SrZn-is 3SrZn @ TiO 2 And (4) grouping.
On the other hand, the material of the 24-well plate was fixed with paraformaldehyde for 30 minutes after 4 days and washed twice with PBS; treating for 1 hour at normal temperature by using 0.1 percent Trioton-100 solution; 5% goat serum is sealed for 1 hour, and then OCN primary antibody is added for incubation at 4 ℃ overnight; and (3) incubating the red fluorescent secondary antibody marked by 549 at normal temperature for 1 hour, finally staining the nucleus for 5 minutes by using a DAPI solution at room temperature, and observing the OCN expression amount under a fluorescent microscope. Fig. 7 shows that compared with the titanium dioxide material containing pure titanium dioxide and zinc ions, the surface cells of the material containing zinc ions and strontium ions have high OCN expression, which proves that the material has good osteogenic differentiation promoting effect after the two ions are added, and the ion content and the OCN expression show positive correlation. Wherein, in FIG. 7, Zn _ is Zn @ TiO 2 Group (d); 1SrZn is 1SrZn @ TiO 2 Group (d); 2 SrZn-is 2SrZn @ TiO 2 Group (iv); 3 SrZn-is 3SrZn @ TiO 2 And (4) grouping.
6) Detection of vascularization ability of materials
Cells are inoculated on the surface of the material, total cell proteins are extracted after 7 days and 10 days respectively, Western blot experiment is carried out, expression of VEGFa proteins of the cells is detected, as shown in a figure 8 result, in qualitative and quantitative detection, along with increase of zinc ions and strontium ions, expression of VEGFa in the cells is gradually increased, and the factor is known to have better effect of promoting vascularization. Therefore, the material of the invention can better promote vascularization around the implanted material. Wherein, in FIG. 8, Zn _ is Zn @ TiO 2 Group (iv); 1SrZn is 1SrZn @ TiO 2 Group (d); 2 SrZn-is 2SrZn @ TiO 2 Group (d); 3 SrZn-is 3SrZn @ TiO 2 And (4) grouping.
7) Detection of in vivo Material osteogenesis experiment
The establishment of OVX rat model and the operation of implanting femoral implant are described in the previously published paper, Strong delivery on cosmetic titanium to enhance biological activity and osseointegration in osteoporotic rats[J]Journal of Materials Chemistry B,2015,3(24): 4790-. The implant is implanted in different rat femurs according to the principle of random control: TiO 2 2 、Zn@TiO 2 、1SrZn@TiO 2 、2SrZn@TiO 2 、3SrZn@TiO 2 And n-8. calcein was injected into the abdominal cavity of the rat at an amount of 20mg/kg 6 weeks after the operation.
Rats were euthanized 8 weeks post-surgery and specimens were implanted in fomallin fixative. After fixation, the surrounding bone tissue of the implant was observed by scanning and three-dimensional computer reconstruction (fig. 9a to 9 e). 2SrZn @ TiO can be seen from FIGS. 9 f-9 j 2 、3SrZn@TiO 2 There was a significant bone gain around the group implants. Proves that the implant material can promote the formation of bone better than a pure titanium implant in the same time. Subsequently, rat samples were dehydrated in the order of alcohol 50%, 70%, 80%, 90%, 95%, 100% twice for 8 hours, and were treated transparently by soaking in xylene overnight; the permeate (xylene mixed with the embedding solution at 1: 1 volume) was soaked at room temperature for 24 hours and finally placed in the embedding solution and hardened at 37 ℃ after vacuum operation. After the embedding fluid had completely hardened, the samples were cut and buffed using a hard tissue microtome SP1600 to make 40um thick sections (fig. 9 k). Since calcein injected in sixth week after operation has fluorescence and enters into combined bone tissue along with calcium salt deposition in osteogenesis process, 2SrZn @ TiO can be found in fig. 9i by observing the section under a confocal microscope 2 、3SrZn@TiO 2 The fluorescence quantity of the calcein in the group is obviously higher than that of other groups, which proves that the surface osteogenesis quantity of the two groups of materials is higher, and the good osteogenesis promoting effect of the two groups of materials is proved. Wherein, in FIG. 9, Zn _ is Zn @ TiO 2 Group (iv); 1SrZn is 1SrZn @ TiO 2 Group (d); 2 SrZn-is 2SrZn @ TiO 2 Group (d); 3 SrZn-is 3SrZn @ TiO 2 And (4) grouping.
Finally, hard tissue sections were stained with picloram (see fig. 10a to 10e and 10g), photographed downhole, and the implant surface bone formation rate was calculated, as shown in fig. 10 f. Wherein, in FIG. 10, Zn _ is Zn @ TiO 2 Group (d); 1SrZn is 1SrZn @ TiO 2 Group (d); 2 SrZn-is 2SrZn @ TiO 2 Group (d); 3SrZn _ is 3SrZn @TiO 2 And (4) grouping.
In conclusion, the titanium implant loaded with zinc and strontium ions has a good antibacterial effect, does not show obvious toxicity, does not generate large negative effects on tissues, and the released ions can promote osteogenic differentiation of mesenchymal stem cells and in vivo osteogenic repair of an osteoporosis animal model.
The invention can load zinc and strontium ions, and can load other ions according to different requirements in other application scenes.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (2)

1. An implant material for osteopontic integration of osteoporotic bone regeneration with implant material, said implant material comprising TiO 2 Coating of said TiO 2 The coating is doped with biological trace element components, and the TiO 2 The mass percentage of the coating is 74-78%, and the mass percentage of the biological trace element component is 22-28%; the biological trace element components comprise strontium, zinc, calcium and phosphorus; the mass percentage of the strontium is 6.32 +/-0.20%; the mass percentage of the zinc is 5.93 +/-0.35 wt%; the mass percentage of the calcium is 1.40 +/-0.05 wt%; the mass percentage of the phosphorus is 11.52 +/-0.11 wt%;
the preparation method of the implant material comprises the following steps:
adding 50 mM of disodium glycerophosphate and calcium acetate into deionized water to prepare electrolyte containing calcium/phosphate, carrying out plasma oxidation treatment on a titanium rod in the electrolyte containing calcium/phosphate, taking a titanium sheet as an anode, and carrying out electrolytic oxidation by adopting constant-current plasma with the duty ratio of 10% and the frequency of 800 HzPower supply with current density of 30A/dm 2 Oxidizing for 10min to obtain TiO 2 Coating;
and adding 60mM zinc acetate and strontium acetate into the electrolyte in the step 1), wherein the total concentration of the calcium acetate and the zinc acetate is constant at 100mM, and the molar ratio of Sr (Sr + Ca) is 3:4, and preparing the implant material.
2. Use of the implant material of claim 1 for the preparation of oral implants and for osteoporotic bone regeneration and osseointegration of the implant material.
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