CN115501392A - Zinc oxide/zinc phosphate nanorod composite antibacterial coating and preparation method and application thereof - Google Patents
Zinc oxide/zinc phosphate nanorod composite antibacterial coating and preparation method and application thereof Download PDFInfo
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- CN115501392A CN115501392A CN202211191672.6A CN202211191672A CN115501392A CN 115501392 A CN115501392 A CN 115501392A CN 202211191672 A CN202211191672 A CN 202211191672A CN 115501392 A CN115501392 A CN 115501392A
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- Prior art keywords
- zinc oxide
- phosphate
- zinc
- coating
- nanorod
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 212
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 112
- 238000000576 coating method Methods 0.000 title claims abstract description 90
- 239000011248 coating agent Substances 0.000 title claims abstract description 89
- 239000002073 nanorod Substances 0.000 title claims abstract description 73
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 title claims abstract description 54
- 229910000165 zinc phosphate Inorganic materials 0.000 title claims abstract description 54
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000012567 medical material Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000010452 phosphate Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 230000001276 controlling effect Effects 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 230000026731 phosphorylation Effects 0.000 claims description 3
- 238000006366 phosphorylation reaction Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000010923 batch production Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 17
- 210000004027 cell Anatomy 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 235000021317 phosphate Nutrition 0.000 description 8
- 210000002901 mesenchymal stem cell Anatomy 0.000 description 7
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- 230000001988 toxicity Effects 0.000 description 7
- 231100000419 toxicity Toxicity 0.000 description 7
- 230000002924 anti-infective effect Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 210000001519 tissue Anatomy 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 102000002260 Alkaline Phosphatase Human genes 0.000 description 5
- 108020004774 Alkaline Phosphatase Proteins 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 5
- 206010067268 Post procedural infection Diseases 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 239000007943 implant Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
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- 108010035532 Collagen Proteins 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
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- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000035755 proliferation Effects 0.000 description 3
- 239000003642 reactive oxygen metabolite Substances 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- 229910001069 Ti alloy Inorganic materials 0.000 description 2
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- BSIUFWMDOOFBSP-UHFFFAOYSA-N 2-azanylethanol Chemical compound NCCO.NCCO BSIUFWMDOOFBSP-UHFFFAOYSA-N 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
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Images
Classifications
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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
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
- A61L27/425—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of phosphorus containing material, 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
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
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- 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
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- 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
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- A61L2420/00—Materials or methods for coatings medical devices
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Abstract
The invention provides a zinc oxide/zinc phosphate nanorod composite antibacterial coating as well as a preparation method and application thereof. The preparation method comprises the steps of firstly preparing a zinc oxide nanorod coating on the surface of a medical material; and then converting the zinc oxide in the zinc oxide nanorod coating into zinc phosphate by a water bath treatment method in phosphate or hydrogen phosphate solution, thereby preparing the zinc oxide/zinc phosphate nanorod composite antibacterial coating with the nano-morphology. The preparation method comprises the steps of firstly preparing the zinc oxide nanorod coating on the surface of the medical material, and then carrying out water bath treatment in phosphate or hydrogen phosphate solution to convert the zinc oxide part in the zinc oxide nanorod coating into zinc phosphate with lower degradation rate. The conversion ratio of the zinc phosphate can be regulated and controlled by regulating and controlling the parameters of the water bath treatment, so that the overall degradation rate of the coating is regulated and controlled. The coating can be uniformly and efficiently prepared on the surface of a medical material with a complex shape, has simple process and low cost, and is suitable for batch and industrial production.
Description
Technical Field
The invention relates to the technical field of medical materials, in particular to a zinc oxide/zinc phosphate nanorod composite antibacterial coating and a preparation method and application thereof.
Background
With the development of the biomaterial industry, clinical medical materials have wide application in the aspect of human tissue injury repair. For example, biomedical metal materials such as titanium and titanium alloy have been widely used in the fields of artificial joints, dental implants, orthopedic prostheses, etc.; the biomedical polymer material polyetheretherketone also has wide application in repairing intervertebral fusion cage and craniofacial injury. However, in practical clinical application, medical materials still face the problem of bacterial infection which needs to be solved urgently. The occurrence of post-operative infection affects the effectiveness of the surgery to a large extent, and post-operative infection of some implants is often catastrophic. Post-operative infection of implants, such as artificial joint replacement surgery, requires secondary surgical debridement procedures, placing a serious physiological, mental, and economic burden on the patient. Post-operative infections are generally caused by bacteria adhering to and colonizing the surface of the medical material. Therefore, the antibacterial coating is prepared on the surface of the medical material, and the occurrence of postoperative infection can be greatly reduced. In addition, when the antibacterial coating is introduced to the surface of a material, the biological toxicity of the antibacterial coating needs to be considered, so that the antibacterial coating has excellent anti-infection performance and cannot delay or even block the repair process of tissues.
Therefore, the coating which is prepared on the surface of the medical material and has the anti-infection and tissue healing promoting capabilities has important significance for the field of medical materials.
Disclosure of Invention
In order to solve the technical problems, the invention provides a zinc oxide/zinc phosphate nanorod composite antibacterial coating as well as a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a preparation method of a zinc oxide/zinc phosphate nanorod composite antibacterial coating, which comprises the steps of firstly preparing a zinc oxide nanorod coating on the surface of a medical material; and then converting the zinc oxide in the zinc oxide nanorod coating into zinc phosphate by a water bath treatment method in phosphate or hydrogen phosphate solution, thereby preparing the zinc oxide/zinc phosphate nanorod composite antibacterial coating with the nano-morphology.
Preferably, the method specifically comprises the following steps: preparing a zinc oxide seed layer on the surface of a medical material, and then forming a zinc oxide nanorod coating on the zinc oxide seed layer through hydrothermal treatment to obtain the medical material loaded with the zinc oxide nanorod coating; and step two, immersing the medical material loaded with the zinc oxide nanorod coating into phosphate or hydrogen phosphate solution for phosphorylation, and controlling the conversion ratio of zinc oxide to zinc phosphate by regulating and controlling reaction conditions to obtain the zinc oxide/zinc phosphate nanorod composite antibacterial coating.
Preferably, the reaction conditions of the second step are as follows: the pH value of the reaction system is controlled to be 8.0-10.0, the temperature is controlled to be 20-100 ℃, and the reaction time is controlled to be 1-24 h.
Preferably, the reaction conditions of the second step are as follows: the pH value of the reaction system is controlled to be 8.0, the temperature is controlled to be 60 ℃, and the reaction time is 2 hours.
Preferably, the phosphate or hydrogen phosphate solution is one or more of potassium phosphate, sodium phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate or sodium dihydrogen phosphate. That is, the phosphate or hydrogen phosphate solution includes, but is not limited to, potassium salts, and may be phosphates or hydrogen phosphates of other metal elements.
Preferably, the concentration of the phosphate or hydrogen phosphate solution is 0.01mol/L to 0.5mol/L.
Preferably, the concentration of the phosphate or hydrogen phosphate solution is 0.1mol/L.
Preferably, the step one specifically comprises the following steps of preparing a mixed solution: mixing zinc acetate (Zn (CH) 3 COO) 2 ·2H 2 O) and ethanolamine (ethanolamines) are dissolved inStirring in ethanol at room temperature for 5h to form a mixed solution; wherein the concentrations of the zinc acetate, the ethanolamine and the ethanol are all 0.05mol/L; carrying out spin coating treatment: fixing a sample on a spin coater, dropwise adding 60 mu l of the mixed solution on the surface of the sample, and then placing the sample in an oven to be treated at 120 ℃ for 10min; preparing a sample for forming a zinc oxide seed layer: after repeating the spin coating process for three times, transferring the sample into a muffle furnace to be processed at 500 ℃ for 30min, thereby forming a zinc oxide seed layer on the surface of the sample; preparing a zinc oxide nanorod coating: the sample on which the zinc oxide seed layer was formed was placed in a hydrothermal reactor containing 0.025mol/L zinc nitrate (Zn (NO) 3 ) 2 ·6H 2 O) and 0.025mol/L hexamethylenetetramine (hexamethylenetetramine) in water solution at 90 ℃ for 5h to obtain the zinc oxide nanorod coating. Wherein, the sample is a medical material or a medical implant material.
The invention provides a zinc oxide/zinc phosphate nanorod composite antibacterial coating, and the zinc oxide/zinc phosphate nanorod composite antibacterial coating is prepared by the preparation method of the zinc oxide/zinc phosphate nanorod composite antibacterial coating.
The third aspect of the invention also provides the application of the zinc oxide/zinc phosphate nanorod composite antibacterial coating in the field of medical materials, and is particularly suitable for the field of medical implant materials.
Compared with the prior art, the technical scheme provided by the invention at least has the following advantages:
the invention provides a zinc oxide/zinc phosphate nanorod composite antibacterial coating as well as a preparation method and application thereof. The preparation method comprises the steps of firstly preparing the zinc oxide nanorod coating on the surface of the medical material, and then carrying out water bath treatment in phosphate or hydrogen phosphate solution to convert the zinc oxide part in the zinc oxide nanorod coating into zinc phosphate with lower degradation rate. The conversion ratio of the zinc phosphate can be regulated and controlled by regulating and controlling the parameters of the water bath treatment, so that the overall degradation rate of the coating is regulated and controlled. The coating can be uniformly and efficiently prepared on the surface of a medical material with a complex shape, has simple process and low cost, and is suitable for batch and industrial production.
The prepared zinc oxide/zinc phosphate composite coating with the nano-morphology not only has good anti-infection capacity, but also greatly reduces the biological toxicity of the original zinc oxide nano-rod coating. Wherein, by controlling the proper zinc phosphate conversion ratio, the proper amount of zinc ions released in the degradation process can be achieved, thereby achieving the purpose of promoting the healing of tissues.
The zinc oxide/zinc phosphate composite coating is applied to the medical field as an antibacterial coating, can obtain a medical material with dual functions of resisting infection and promoting healing, can reduce the occurrence of infection after implantation, and particularly can be used on the surface of an orthopedic hard tissue implantation material, such as metal-based titanium, titanium alloy, medical stainless steel and the like. Meanwhile, the coating endows the surface of the medical material with anti-infection capability, has no biological toxicity and can promote tissue repair.
Drawings
One or more embodiments are illustrated by corresponding figures in the drawings, which are not to be construed as limiting the embodiments, unless expressly stated otherwise, and the drawings are not to scale.
FIG. 1a is a scanning electron micrograph of the surface of a Ti-ZnO sample in example 1;
FIG. 1b is a SEM photograph of the surface of the Ti-ZnP0.5 sample in example 1;
FIG. 1c is a scanning electron micrograph of the surface of the Ti-ZnP1 sample of example 1;
FIG. 1d is a scanning electron micrograph of the surface of the Ti-ZnP2 sample of example 1;
FIG. 1e is a scanning electron micrograph of the surface of the Ti-ZnP3 sample of example 1;
FIG. 2 is a graph showing the results of example 2 in which a Ti-ZnO sample was treated with 0.1M dipotassium hydrogen phosphate (K) 2 HPO 4 ·3H 2 Scanning electron microscope pictures of the samples obtained after treatment in aqueous solution of O) at 60 ℃, 70 ℃ and 80 ℃ for 2 h;
FIG. 3a is a TEM photograph of the surface of the Ti-ZnO sample in example 3;
FIG. 3b is a TEM micrograph of the surface of the Ti-ZnP1 sample in example 3;
FIG. 3c is a TEM micrograph of the surface of the Ti-ZnP2 sample of example 3;
FIG. 4a is an X-ray diffraction analysis of the groups of samples from example 4;
FIG. 4b is the X-ray photoelectron spectroscopy full spectrum of each set of samples in example 4;
FIG. 4c is the atomic percentage of the surface elements of each set of treated samples in example 4;
FIG. 4d is the hydrophilicity and hydrophobicity of the surface of each set of treated samples in example 4;
FIG. 5 is a scanning electron micrograph of the surfaces of the respective groups of samples of example 5 after a scratch test;
FIG. 6 shows the release trend of zinc ions after 30 days of soaking in Hank's buffer solution for each group of samples in example 6;
FIG. 7 is a scanning electron microscope photograph of the sample surface of each group of samples in example 7 soaked in Hank's buffer solution for 30 at each time;
FIG. 8 is the proliferation of mesenchymal stem cells in example 8 after culturing on the surface of each group of samples;
FIG. 9a is the activity of alkaline phosphatase after differentiation of the mesenchymal stem cells into osteoblasts was induced on the surfaces of the respective groups of samples in example 9;
fig. 9b is collagen secretion of the mesenchymal stem cells induced into the osteoblasts on the surfaces of the respective groups of samples in example 9;
fig. 9c is a graph showing the mineralization of extracellular matrix after the differentiation of bone marrow mesenchymal stem cells into osteoblasts on the surfaces of respective groups of samples in example 9;
FIG. 10a is a photograph showing the survival of Staphylococcus aureus and Escherichia coli cultured on the surfaces of respective groups of samples measured by the plate coating method in example 10;
FIG. 10b is the antibacterial ratio against Staphylococcus aureus and Escherichia coli of the surfaces of the respective groups of samples calculated in example 10.
Detailed Description
In order to solve the problems in the prior art, the inventor finds that the zinc oxide nanorod coating has the advantages of simple preparation process, low cost, suitability for preparation on large-area complex surfaces and the like. More importantly, the zinc oxide nanorod coating has broad-spectrum antibacterial activity and is expected to be widely applied as an antibacterial coating in the field of medical materials. It is generally believed that the broad spectrum antibacterial performance of zinc oxide nanorod arrays comes from three aspects: 1) The sterilization function of zinc ions released by the degradation of the coating; 2) Destructive effect of Reactive Oxygen Species (ROS), generated by zinc oxide itself as a semiconductor material, on cell membranes, cytoplasm and genetic material of bacteria; 3) The appearance of the nano-rod has a physical puncture effect on the cell wall of bacteria. However, the zinc oxide nanorod coating has an excessively fast degradation rate under physiological conditions, releases a large amount of zinc ions during the degradation process, and generates strong toxicity to tissue cells under the combined action of the zinc oxide nanorod coating and ROS generated by zinc oxide. Therefore, in order to improve the antibacterial application prospect of the zinc oxide nanorod coating, the degradation rate of the zinc oxide nanorod coating needs to be adjusted, so that the zinc oxide nanorod coating has a good tissue repair promoting function on the premise of maintaining good antibacterial performance.
The inventor finds that the zinc oxide nanorod coating prepared on the surface of the material is subjected to phosphorylation treatment, and is partially converted into zinc phosphate, so that the degradation rate of the coating can be reduced on the premise of maintaining the nanorod morphology and excellent antibacterial performance. The zinc ions released at a proper degradation rate not only do not cause biological toxicity, but also can promote the repair function of tissue cells.
Based on the method, the invention provides a method for preparing the zinc oxide/zinc phosphate composite coating with the nanorod morphology on the surface of the medical material. The coating has good anti-infection performance, does not generate biological toxicity and can promote tissue repair.
The present invention will be described in detail with reference to the following embodiments.
The feasibility of the invention is proved by constructing a zinc oxide/zinc phosphate nanorod composite coating on the surface of the metal-based medical orthopedic implant material pure titanium serving as a substrate.
Example 1
After medical grade pure titanium sheets with the diameter of 14mm and the thickness of 2mm are polished by 2000-mesh abrasive paper, the medical grade pure titanium sheets are sequentially cleaned by acetone, alcohol and deionized water in an ultrasonic mode. The pretreated sample was labeled Ti.
Mixing zinc acetate (Zn (CH) 3 COO) 2 ·2H 2 O) and ethanolamine (ethanolamine) were dissolved in ethanol to make the concentrations thereof each 0.05M and stirred at room temperature for 5 hours. After Ti was fixed to a spin coater and 60. Mu.l or more of the solution was dropped on the Ti surface, the sample was treated in an oven at 120 ℃ for 10min. After the above process was repeated three times, the sample was transferred to a muffle furnace and treated at 500 ℃ for 30min to form a ZnO "seed layer" on the Ti surface. The sample was then placed in a hydrothermal kettle containing 0.025M zinc nitrate (Zn (NO) 3 ) 2 ·6H 2 O) and 0.025M hexamethylenetetramine (hexamethylenetetramine) at 90 ℃ for 5h to obtain a zinc oxide nanorod coating. The obtained sample was labeled as Ti-ZnO. Wherein "M" is "mol/L".
Further adding Ti-ZnO in the presence of 0.1M dipotassium hydrogen phosphate (K) 2 HPO 4 ·3H 2 O) at 60 c for several hours, the zinc oxide nanorod array was partially converted into zinc phosphate. The samples obtained are labelled Ti-ZnP0.5, ti-ZnP1, ti-ZnP2, and Ti-ZnP3, respectively, where the numbers indicate the number of hours of treatment.
The surface topography of the different samples was observed using a Scanning Electron Microscope (SEM). FIGS. 1a-e are SEM pictures of a zinc oxide nanorod coating, ti-ZnP0.5, ti-ZnP1, ti-ZnP2, and Ti-ZnP3, respectively. It can be seen from the figure that when the reaction time is 0.5h, the surface appearance is basically not changed compared with the zinc oxide nano-rod coating. The bottom of the nanorod began to transform into a block after 1h of reaction, and this change was more evident after 2h and 3 h.
Example 2
The Ti-ZnO in example 1 was dissolved in a solution containing 0.1M dipotassium hydrogenphosphate (K) 2 HPO 4 ·3H 2 O) at 60 ℃, 70 ℃ and 80 ℃ for 2h, and then the surface topography of the different samples was observed using a Scanning Electron Microscope (SEM) (fig. 2). It can be seen that the bottom of the nano rod is converted into a block with the increase of temperatureThe trend is more pronounced, indicating that an increase in temperature is more favorable for the conversion of zinc oxide to zinc phosphate.
Example 3
The surfaces of each set of samples were observed using a Transmission Electron Microscope (TEM). FIGS. 3a-c are TEM pictures of zinc oxide nanorod coating, ti-ZnP1, and Ti-ZnP2, respectively. As can be seen from FIG. 3a, the interplanar spacing of 1.92nm corresponds to zinc oxide crystals. While in the samples of reaction 1h (FIG. 3 b) and 2h (FIG. 3 c), the crystal structures of zinc oxide and zinc phosphate were observed at the same time. Indicating that some of the zinc oxide in the zinc oxide nanorod coating was converted to zinc phosphate after treatment in a hydrogen phosphate solution.
Example 4
The crystal structure of the coating was analyzed using X-ray diffraction (XRD). From FIG. 4a, it can be seen that the coating on the surface of the Ti-ZnP1 and Ti-ZnP2 samples has two crystal forms of zinc oxide and zinc phosphate.
The sample surface was subjected to wide-field X-ray photoelectron spectroscopy (XPS) scanning to obtain the XPS survey spectrum shown in fig. 4 b. Wherein the intensity of the characteristic peak represents the content of the element on the surface. Comparing the spectra of different groups of samples, the characteristic peak of phosphorus element is increased on the surfaces of Ti-ZnP1 and Ti-ZnP2 samples. FIG. 4c is an analysis of the XPS results showing the atomic percentages of the elements on the surface of the material, showing that the Ti and Ti-ZnO samples contained essentially no phosphorus on the surface, while the Ti-ZnP1 and Ti-ZnP2 samples contained greatly increased amounts of phosphorus on the surface, indicating that hydrothermal treatment in hydrogen phosphate successfully converted zinc oxide to zinc phosphate.
And testing the surface wettability of the material by using a static water contact angle tester. Figure 4d is the static water contact angle results for each set of samples. The abscissa is the sample name and the ordinate is the degree of contact angle. As can be seen from fig. 4d, the contact angle of the untreated Ti sample is around 60 °; after the zinc oxide nanorod coating is prepared on the Ti surface, the contact angle is reduced to about 22 degrees; after converting the zinc oxide portion to zinc phosphate, the contact angle further decreases.
Example 5
And detecting the bonding force between the formed coating and the substrate by adopting a scratch test. After the scratch was formed on the surface of the sample, the peeling of the coating layer from both sides of the scratch was observed by SEM. As can be seen from FIG. 5, the scratch edges of all three samples did not crack or fall off in a large area, which indicates that the coating prepared by the present invention has good bonding force with the substrate.
Example 6
The samples of each group were immersed in Hank's buffer and stored at 37 ℃ to detect the release of zinc ions under simulated physiological conditions in vivo. As can be seen from FIG. 6, the zinc ions were released continuously from each group of samples within the detection period of 30 days. The Ti-ZnO sample releases the fastest speed, the Ti-ZnP1 sample releases the second time, and the Ti-ZnP2 sample releases the slowest speed of zinc ions. It is demonstrated that the partial conversion of zinc oxide into zinc phosphate significantly reduces the release rate of zinc ions.
Example 7
Samples stored in Hank's buffer as described in example 6 for various times were removed and observed for surface topography using SEM. As shown in fig. 7, after the Ti — ZnO sample is soaked in the solution for 5 days, the nanorod structures on the surface begin to collapse; after 20 days of soaking, the rod-like structure completely disappeared and a hole-like etch pit was formed. The surface appearance of the Ti-ZnP1 and Ti-ZnP2 samples is only slightly changed in the process of 30 days of soaking. The above results are consistent with those in example 6 and show that the degradation rate of the surface coating can be greatly slowed down after the zinc oxide is partially converted into zinc phosphate.
Example 8
The human-derived bone marrow mesenchymal stem cells were inoculated and cultured on the surface of each group of samples. FIG. 8 shows the proliferation of cells obtained by using the CCK-8 assay kit after culturing the cells on the surface of the sample for 1 day, 3 days, and 5 days. Wherein the abscissa is the number of days for cell culture, and the ordinate is the absorbance of the corresponding well of the detection kit at a wavelength of 450 nm. Higher absorbance indicates faster proliferation. As can be seen from the results, the cells cultured on the Ti surface can normally proliferate with the increase of the culture time, while the cells on the Ti-ZnO surface completely lose activity after 1 day of culture due to the strong cytotoxicity of the zinc oxide. Although the Ti-ZnP1 sample reduces the toxicity of the Ti-ZnO sample, the Ti-ZnP1 sample still inhibits the cell activity to a certain extent compared with Ti. And the cells on the surface of the Ti-ZnP2 sample are basically the same as those on the surface of Ti. The above results show that as part of zinc oxide in the zinc oxide nanorod coating is converted into zinc phosphate, which degrades more slowly, the biotoxicity of the material is greatly reduced, and as the reaction time is prolonged, the conversion ratio of zinc phosphate increases and the cytotoxicity of the coating is lower.
Example 9
Bone marrow mesenchymal stem cells on the surface of each group of samples were cultured using an osteoinduction medium for 3 days, 7 days and 14 days to differentiate into osteoblasts, and then the activity of a marker enzyme alkaline phosphatase (ALP) in the early formation stage of osteoblasts (fig. 9 a), the collagen secreted from the cells (fig. 9 b), and the mineralization of extracellular matrix (fig. 9 c) were examined. The abscissa of the results is the number of days of cell induction, and the ordinate of FIG. 9a is the activity of ALP, and its activity was normalized using the total protein content in the cells; FIGS. 9b-c are graphs showing the absorbance of the detection kit at 570nm wavelength, where higher absorbance indicates higher mineralization of the extracellular matrix. The results show that the Ti-ZnO sample has stronger cytotoxicity, so that osteoblasts are difficult to grow normally on the surface of the sample and are difficult to differentiate into osteoblasts; the cells cultured on the surface of Ti-ZnP1 have a certain osteoblast differentiation tendency; the cells cultured on the surface of the Ti-ZnP2 sample have the highest ALP activity, the most collagen secretion after 21 days of induction and the highest mineralization degree of extracellular matrix. The results prove that the Ti-ZnP2 can promote the osteogenic differentiation of the bone marrow mesenchymal stem cells.
Example 10
And (3) culturing bacteria on the surfaces of all groups of samples to culture staphylococcus aureus and escherichia coli so as to detect the antibacterial performance of the surfaces of the samples. As can be seen from FIG. 10a, the Ti surface has no antibacterial effect, and the ZnO surface has the best antibacterial effect, and almost all bacteria on the surface can be killed. The antibacterial effect of the surfaces of Ti-ZnP1 and Ti-ZnP2 is slightly poor, but the calculated antibacterial rate is more than 90 percent. The above results demonstrate that the Ti-ZnP1 and Ti-ZnP2 samples have excellent anti-infective ability.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the present application, and that various changes in form and details may be made therein without departing from the spirit and scope of the present application in practice. Various changes and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the application, and it is intended that the scope of the application be limited only by the claims appended hereto.
Claims (10)
1. A preparation method of a zinc oxide/zinc phosphate nanorod composite antibacterial coating is characterized by comprising the steps of firstly preparing a zinc oxide nanorod coating on the surface of a medical material; and then converting the zinc oxide in the zinc oxide nanorod coating into zinc phosphate by a water bath treatment method in phosphate or hydrogen phosphate solution, thereby preparing the zinc oxide/zinc phosphate nanorod composite antibacterial coating with the nano-morphology.
2. The method for preparing the zinc oxide/zinc phosphate nanorod composite antibacterial coating of claim 1, wherein the method specifically comprises the following steps:
preparing a zinc oxide seed layer on the surface of a medical material, and then forming a zinc oxide nanorod coating on the zinc oxide seed layer through hydrothermal treatment to obtain the medical material loaded with the zinc oxide nanorod coating;
and secondly, immersing the medical material loaded with the zinc oxide nanorod coating into phosphate or hydrogen phosphate solution for phosphorylation, and controlling the conversion ratio of zinc oxide to zinc phosphate by regulating and controlling reaction conditions to obtain the zinc oxide/zinc phosphate nanorod composite antibacterial coating.
3. The method for preparing the zinc oxide/zinc phosphate nanorod composite antibacterial coating according to claim 2, wherein the reaction conditions of the second step are as follows: the pH value of the reaction system is controlled to be 8.0-10.0, the temperature is controlled to be 20-100 ℃, and the reaction time is 1-24 h.
4. The method for preparing the zinc oxide/zinc phosphate nanorod composite antibacterial coating according to claim 3, wherein the reaction conditions in the second step are as follows: the pH value of the reaction system is controlled to be 8.0, the temperature is controlled to be 60 ℃, and the reaction time is 2h.
5. The method of preparing a zinc oxide/zinc phosphate nanorod composite antibacterial coating according to claim 2, wherein the phosphate or hydrogen phosphate solution is one or more of potassium phosphate, sodium phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate or sodium dihydrogen phosphate.
6. The method for preparing a zinc oxide/zinc phosphate nanorod composite antibacterial coating of claim 2, wherein the concentration of the phosphate or hydrogen phosphate solution is 0.01-0.5 mol/L.
7. The method for preparing the zinc oxide/zinc phosphate nanorod composite antibacterial coating according to claim 6, wherein the concentration of the phosphate or hydrogen phosphate solution is 0.1mol/L.
8. The preparation method of the zinc oxide/zinc phosphate nanorod composite antibacterial coating according to claim 1, wherein the first step specifically comprises the following steps,
preparing a mixed solution: dissolving zinc acetate and ethanolamine in ethanol, and stirring for 5 hours at room temperature to form a mixed solution; wherein the concentrations of the zinc acetate, the ethanolamine and the ethanol are all 0.05mol/L;
carrying out spin coating treatment: fixing a sample on a spin coater, dropwise adding 60 mu l of the mixed solution on the surface of the sample, and then placing the sample in an oven to be treated at 120 ℃ for 10min;
preparing a sample for forming a zinc oxide seed layer: after repeating the spin coating process for three times, transferring the sample into a muffle furnace to be processed at 500 ℃ for 30min, thereby forming a zinc oxide seed layer on the surface of the sample;
preparing a zinc oxide nanorod coating: and (3) putting the sample forming the zinc oxide seed layer into a hydrothermal kettle, and treating the sample in an aqueous solution containing 0.025mol/L zinc nitrate and 0.025mol/L hexamethylenetetramine at 90 ℃ for 5 hours to obtain the zinc oxide nanorod coating.
9. A zinc oxide/zinc phosphate nanorod composite antibacterial coating, characterized in that, the zinc oxide/zinc phosphate nanorod composite antibacterial coating prepared by the method for preparing the zinc oxide/zinc phosphate nanorod composite antibacterial coating of any one of claims 1 to 8.
10. The use of the zinc oxide/zinc phosphate nanorod composite antibacterial coating of claim 9 in the field of medical materials.
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| CN112226767A (en) * | 2020-09-29 | 2021-01-15 | 西安交通大学 | Hydroxyapatite nanorod biological coating and preparation method thereof |
| WO2022157638A1 (en) * | 2021-01-19 | 2022-07-28 | Universita' Degli Studi Di Roma "La Sapienza" | Removable, waterproof multi-layer coating having antibacterial properties for contact surfaces and method for the preparation thereof |
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| CN102793948A (en) * | 2012-08-22 | 2012-11-28 | 浙江大学 | Biomedical calcium phosphate/zinc oxide nano-rod array composite coating on surface of medical metal and preparation method thereof |
| CN106563176A (en) * | 2016-10-14 | 2017-04-19 | 湖北大学 | Atomic layer deposition-based preparation method for zinc oxide/carbon nanotube nano-antibacterial coating |
| CN112226767A (en) * | 2020-09-29 | 2021-01-15 | 西安交通大学 | Hydroxyapatite nanorod biological coating and preparation method thereof |
| WO2022157638A1 (en) * | 2021-01-19 | 2022-07-28 | Universita' Degli Studi Di Roma "La Sapienza" | Removable, waterproof multi-layer coating having antibacterial properties for contact surfaces and method for the preparation thereof |
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