CN115501392B - Zinc oxide/zinc phosphate nano rod composite antibacterial coating and preparation method and application thereof - Google Patents
Zinc oxide/zinc phosphate nano rod composite antibacterial coating and preparation method and application thereof Download PDFInfo
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- CN115501392B CN115501392B CN202211191672.6A CN202211191672A CN115501392B CN 115501392 B CN115501392 B CN 115501392B CN 202211191672 A CN202211191672 A CN 202211191672A CN 115501392 B CN115501392 B CN 115501392B
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- zinc oxide
- phosphate
- zinc
- coating
- nano rod
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 209
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 110
- 238000000576 coating method Methods 0.000 title claims abstract description 90
- 239000011248 coating agent Substances 0.000 title claims abstract description 86
- 239000002073 nanorod Substances 0.000 title claims abstract description 71
- 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 52
- 229910000165 zinc phosphate Inorganic materials 0.000 title claims abstract description 52
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000012567 medical material Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 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 15
- 239000010452 phosphate Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 9
- 230000001276 controlling effect Effects 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 16
- 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 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 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
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 238000004528 spin coating Methods 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
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 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
- 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
- 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
- 229940031098 ethanolamine Drugs 0.000 claims 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims 1
- 229910000397 disodium phosphate Inorganic materials 0.000 claims 1
- 235000019800 disodium phosphate Nutrition 0.000 claims 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 13
- 230000015556 catabolic process Effects 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 4
- -1 and then Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 13
- 210000004027 cell Anatomy 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 210000002901 mesenchymal stem cell Anatomy 0.000 description 7
- 210000000963 osteoblast Anatomy 0.000 description 7
- 230000001988 toxicity Effects 0.000 description 7
- 231100000419 toxicity Toxicity 0.000 description 7
- 230000002924 anti-infective effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 102000002260 Alkaline Phosphatase Human genes 0.000 description 5
- 108020004774 Alkaline Phosphatase Proteins 0.000 description 5
- 206010067268 Post procedural infection Diseases 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 210000001185 bone marrow Anatomy 0.000 description 5
- 239000007943 implant Substances 0.000 description 5
- 210000001519 tissue Anatomy 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 102000010834 Extracellular Matrix Proteins Human genes 0.000 description 4
- 108010037362 Extracellular Matrix Proteins Proteins 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000033558 biomineral tissue development Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 210000002744 extracellular matrix Anatomy 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 230000017423 tissue regeneration Effects 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 102000008186 Collagen Human genes 0.000 description 3
- 108010035532 Collagen Proteins 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 229920001436 collagen Polymers 0.000 description 3
- 230000003013 cytotoxicity Effects 0.000 description 3
- 231100000135 cytotoxicity Toxicity 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000004069 differentiation Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 230000035876 healing Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000000399 orthopedic effect Effects 0.000 description 3
- 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
- 239000000758 substrate Substances 0.000 description 3
- BSIUFWMDOOFBSP-UHFFFAOYSA-N 2-azanylethanol Chemical compound NCCO.NCCO BSIUFWMDOOFBSP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004113 cell culture Methods 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004962 physiological condition Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 230000028327 secretion Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010609 cell counting kit-8 assay Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 210000000805 cytoplasm Anatomy 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000001804 debridement Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000004053 dental implant Substances 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 230000004072 osteoblast differentiation Effects 0.000 description 1
- 230000004819 osteoinduction Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 208000037816 tissue injury Diseases 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/606—Coatings
-
- 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
- A61L2420/06—Coatings containing a mixture of two or more compounds
Abstract
The invention provides a zinc oxide/zinc phosphate nano rod composite antibacterial coating, a preparation method and application thereof. The preparation method comprises the steps of firstly preparing a zinc oxide nano rod coating on the surface of a medical material; and then converting the zinc oxide in the zinc oxide nano rod coating into zinc phosphate by a water bath treatment method in a phosphate or hydrogen phosphate solution, thereby preparing the zinc oxide/zinc phosphate nano rod composite antibacterial coating with nano morphology. According to the preparation method, firstly, a zinc oxide nano rod coating is prepared on the surface of a medical material, and then, zinc oxide in the zinc oxide nano rod coating is partially converted into zinc phosphate with lower degradation rate through water bath treatment in a phosphate or hydrogen phosphate solution. The conversion ratio of zinc phosphate can be regulated and controlled by regulating and controlling the parameters of 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 medical materials with complex shapes, has simple technical process and low cost, and is suitable for batch and industrialized production.
Description
Technical Field
The invention relates to the technical field of medical materials, in particular to a zinc oxide/zinc phosphate nano rod composite antibacterial coating, a preparation method and application thereof.
Background
Along with the development of the biological material industry, the clinical medical material has wide application in the aspect of repairing human tissue injury. For example, biomedical metallic materials titanium and titanium alloys have been widely used in the fields of artificial joints, dental implants, orthopedic prostheses, and the like; the biomedical high polymer material polyether-ether-ketone also has wide application in the aspects of intervertebral fusion device and craniofacial injury repair. However, in practical clinical applications, medical materials still face the problem of bacterial infection that needs to be solved. The occurrence of post-operative infections greatly affects the outcome of the procedure, and certain implant post-operative infections tend to be catastrophic. Implant post-operative infections such as artificial joint replacement surgery require a secondary surgical debridement process, placing 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, the biological toxicity of the antibacterial coating needs to be considered when the antibacterial coating is introduced on the surface of the material, so that the antibacterial coating has excellent anti-infection performance and can not delay or even block the tissue repair process.
Therefore, the preparation of the coating with the anti-infection and tissue healing promoting capabilities on the surface of the medical material 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 nano rod composite antibacterial coating, and a preparation method and application thereof.
In order to achieve the above 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 nano rod composite antibacterial coating, which comprises the steps of firstly preparing a zinc oxide nano rod coating on the surface of a medical material; and then converting the zinc oxide in the zinc oxide nano rod coating into zinc phosphate by a water bath treatment method in a phosphate or hydrogen phosphate solution, thereby preparing the zinc oxide/zinc phosphate nano rod composite antibacterial coating with 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 nano rod coating on the zinc oxide seed layer through hydrothermal treatment to obtain the medical material loaded with the zinc oxide nano rod coating; and secondly, immersing the medical material loaded with the zinc oxide nano rod coating into a phosphate or hydrogen phosphate solution for phosphorylation treatment, and controlling the conversion ratio of zinc oxide to zinc phosphate by regulating and controlling reaction conditions to obtain the zinc oxide/zinc phosphate nano rod 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 20-100 ℃, and the reaction time is 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 60 ℃, and the reaction time is 2h.
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 phosphate or hydrogen phosphate 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 first step specifically includes the following steps of preparing a mixed solution: dissolving zinc acetate (Zn (CH 3COO)2·2H2 O) and ethanolamine (ethanolamine) in ethanol, stirring at room temperature for 5 hours to form a mixed solution, wherein the concentration of the zinc acetate, the concentration of the ethanolamine and the concentration of the ethanol are all 0.05mol/L, performing spin coating treatment, namely fixing a sample on a spin coater, dripping more than 60 mu L of the mixed solution on the surface of the sample, then treating the sample in an oven at 120 ℃ for 10 minutes, preparing a sample for forming a zinc oxide seed layer, namely transferring the sample into a muffle furnace for treating at 500 ℃ for 30 minutes after repeating the spin coating treatment three times, thus forming the zinc oxide seed layer on the surface of the sample, preparing a zinc oxide nanorod coating, namely placing the sample for forming the zinc oxide seed layer into a hydrothermal kettle, and treating the sample in an aqueous solution containing 0.025mol/L zinc nitrate (Zn (NO 3)2·6H2 O) and 0.025mol/L hexamethylenetetramine (hexamethylenetetramine) for 5 hours at 90 ℃ to obtain the zinc oxide nanorod coating, wherein the sample is a medical implant material.
The second aspect of the invention provides a zinc oxide/zinc phosphate nano-rod composite antibacterial coating, such as the zinc oxide/zinc phosphate nano-rod composite antibacterial coating prepared by the preparation method of the zinc oxide/zinc phosphate nano-rod composite antibacterial coating.
The third aspect of the invention also provides application of the zinc oxide/zinc phosphate nano rod 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 has at least the following advantages:
The invention provides a zinc oxide/zinc phosphate nano rod composite antibacterial coating, a preparation method and application thereof. According to the preparation method, firstly, a zinc oxide nano rod coating is prepared on the surface of a medical material, and then, zinc oxide in the zinc oxide nano rod coating is partially converted into zinc phosphate with lower degradation rate through water bath treatment in a phosphate or hydrogen phosphate solution. The conversion ratio of zinc phosphate can be regulated and controlled by regulating and controlling the parameters of 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 medical materials with complex shapes, has simple technical process and low cost, and is suitable for batch and industrialized production.
The prepared zinc oxide/zinc phosphate composite coating with the nano morphology has good anti-infection capability, and the biological toxicity of the original zinc oxide nano rod coating is greatly reduced. Wherein, by controlling proper zinc phosphate conversion proportion, proper zinc ions released in the degradation process can be achieved, thereby achieving the purpose of promoting tissue healing.
The zinc oxide/zinc phosphate composite coating is applied to the medical field as an antibacterial coating, so that a medical material with dual functions of resisting infection and promoting healing can be obtained, the occurrence of infection after implantation can be reduced, and particularly, the surface of an orthopedic hard tissue implantation material, such as metal-based titanium and titanium alloy, medical stainless steel and the like, can be reduced. At the same time, the coating imparts anti-infective ability to the surface of the medical material without biological toxicity and can promote tissue repair.
Drawings
One or more embodiments are illustrated by way of example and not limitation in the figures of the accompanying drawings, which are not to be construed as limiting the embodiments unless specifically indicated otherwise.
FIG. 1a is a scanning electron micrograph of the surface of a Ti-ZnO sample of example 1;
FIG. 1b is a scanning electron micrograph of the surface of the Ti-ZnP0.5 sample of example 1;
FIG. 1c is a scanning electron micrograph of the surface of the Ti-ZnP sample of example 1;
FIG. 1d is a scanning electron micrograph of the surface of the Ti-ZnP sample of example 1;
FIG. 1e is a scanning electron micrograph of the surface of the Ti-ZnP sample of example 1;
FIG. 2 is a scanning electron micrograph of a Ti-ZnO sample obtained in example 2 after 2 hours of treatment at 60℃at 70℃and at 80℃in an aqueous solution containing 0.1M dipotassium hydrogen phosphate (K 2HPO4·3H2 O);
FIG. 3a is a transmission electron micrograph of the surface of the Ti-ZnO sample of example 3;
FIG. 3b is a transmission electron micrograph of the surface of the Ti-ZnP sample of example 3;
FIG. 3c is a transmission electron micrograph of the surface of the Ti-ZnP sample of example 3;
FIG. 4a is an X-ray diffraction analysis of each set of samples in example 4;
FIG. 4b is a full spectrum of the X-ray photoelectron spectroscopy for each set of samples in example 4;
FIG. 4c is the atomic percent of the surface elements of each set of treated samples in example 4;
FIG. 4d is the hydrophilicity and hydrophobicity of each set of treated sample surfaces in example 4;
FIG. 5 is a scanning electron micrograph of the surface of each of the samples of example 5 after scratch testing;
FIG. 6 is a graph showing the release trend of zinc ions after 30 days of immersion in Hank's buffer for each group of samples of example 6;
FIG. 7 is a scanning electron micrograph of the surface of each set of samples of example 7 at each time in Hank's buffer soak 30;
FIG. 8 is the proliferation of mesenchymal stem cells of example 8 after surface culture of each group of samples;
FIG. 9a is the activity of alkaline phosphatase after induced differentiation of bone marrow mesenchymal stem cells into osteoblasts on the surface of each set of samples in example 9;
FIG. 9b is the collagen secretion of bone marrow mesenchymal stem cells of example 9 after the differentiation of osteoblasts on the surface of each sample set;
FIG. 9c is the mineralization of the extracellular matrix of the mesenchymal stem cells of example 9 after the induced differentiation of osteoblasts on the surface of each group of samples;
FIG. 10a is a photograph showing the survival of staphylococcus aureus and escherichia coli cultured on the surface of each group of samples detected by the plate coating method in example 10;
FIG. 10b is the antibacterial activity against Staphylococcus aureus and Escherichia coli on the surfaces of each group 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 nano rod coating has the advantages of simple preparation process, low cost, suitability for preparing a large-area complex surface and the like. More importantly, the zinc oxide nano rod 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 believed that the broad spectrum antimicrobial properties of zinc oxide nanorod arrays come from three aspects: 1) Sterilizing the zinc ions released by the degradation of the coating; 2) The destructive effect of Reactive Oxygen Species (ROS) generated by zinc oxide itself as a semiconductor material on the cell membrane, cytoplasm and genetic material of bacteria; 3) Physical penetration of the nanorod morphology into the bacterial cell wall. However, the zinc oxide nano rod coating has too high degradation rate under physiological conditions, a large amount of zinc ions are released suddenly during degradation, and strong toxicity is generated on tissue cells under the combined action of the zinc oxide nano rod coating and ROS generated by zinc oxide. Therefore, in order to improve the antibacterial application prospect of the zinc oxide nano rod coating, the degradation rate of the zinc oxide nano rod coating needs to be regulated, so that the zinc oxide nano rod coating also has a good tissue repair promoting function on the premise of maintaining good antibacterial performance.
The inventor finds that the degradation rate of the coating can be reduced on the premise of maintaining the shape of the nano rod and excellent antibacterial performance by carrying out phosphorylation treatment on the zinc oxide nano rod coating prepared on the surface of the material and converting part of the zinc oxide nano rod coating into zinc phosphate. The zinc ions released at a proper degradation rate can not only not cause biological toxicity, but also 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 shape of the nano rod 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 nano rod composite coating on the surface of a metal-based medical orthopedic implant material pure titanium serving as a substrate.
Example 1
Medical grade pure titanium sheets with the diameter of 14mm and the thickness of 2mm are polished by 2000-mesh sand paper and then sequentially cleaned by ultrasonic cleaning with acetone, alcohol and deionized water. The pretreated sample was labeled Ti.
Zinc acetate (Zn (CH 3COO)2·2H2 O)) and ethanolamine (ethanolamine) were dissolved in ethanol to a concentration of 0.05M and stirred at room temperature for 5 hours, ti was fixed on a spin coater and 60 μl or more of the solution was dropped on the Ti surface, and then the sample was placed in an oven and treated at 120 ℃ for 10 minutes, after repeating the above treatment three times, the sample was transferred to a muffle furnace and treated at 500 ℃ for 30 minutes to form a ZnO "seed layer" on the Ti surface, and then the sample was placed in a hydrothermal kettle and treated at 90 ℃ for 5 hours in an aqueous solution containing 0.025M zinc nitrate (Zn (NO 3)2·6H2 O) and 0.025M hexamethylenetetramine (hexamethylenetetramine) to obtain a zinc oxide nanorod coating.
After further treatment of Ti-ZnO in an aqueous solution containing 0.1M dipotassium hydrogen phosphate (K 2HPO4·3H2 O) at 60℃for several hours, the zinc oxide nanorod arrays can be partially converted to zinc phosphate. The samples obtained are marked as Ti-ZnP0.5, ti-ZnP1, ti-ZnP2, and Ti-ZnP3, respectively, where the numbers represent 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 zinc oxide nanorod coatings, ti-ZnP0.5, ti-ZnP1, ti-ZnP2, and Ti-ZnP3, respectively. It can be seen that the surface morphology was substantially unchanged from the zinc oxide nanorod coating when reacted for 0.5h. After 1h of reaction, the bottom of the nanorod began to transform into a block, and this change was more evident after 2h and 3 h.
Example 2
After treating Ti-ZnO of example 1 in an aqueous solution containing 0.1M dipotassium hydrogen phosphate (K 2HPO4·3H2 O) at 60 ℃, 70 ℃ and 80 ℃ for 2 hours, the surface morphology of the different samples was observed using a Scanning Electron Microscope (SEM) (FIG. 2). The graph shows that the tendency of the bottom of the nano rod to be converted into a block shape is more obvious along with the temperature rise, which proves that the temperature rise is more beneficial to the conversion of zinc oxide into zinc phosphate.
Example 3
The surface of each set of samples was observed using a Transmission Electron Microscope (TEM). FIGS. 3a-c are TEM pictures of zinc oxide nanorod coatings, ti-ZnP1, and Ti-ZnP2, respectively. As can be seen from fig. 3a, a interplanar spacing of 1.92nm corresponds to zinc oxide crystals. Whereas in the samples of reaction 1h (FIG. 3 b) and 2h (FIG. 3 c), the crystal structures of zinc oxide and zinc phosphate can be observed simultaneously. 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 is evident that the coatings on the surfaces of the Ti-ZnP and Ti-ZnP2 samples are in the presence of both zinc oxide and zinc phosphate crystal forms.
X-ray photoelectron spectroscopy (XPS) wide field scanning is performed on the surface of the sample to obtain an XPS full spectrum shown in figure 4 b. Wherein the intensity of the characteristic peak represents the level of the element on the surface. Comparing the patterns of different groups of samples, the characteristic peaks of phosphorus element are added on the surfaces of the Ti-ZnP1 and Ti-ZnP2 samples. Fig. 4c shows the atomic percentages of the individual elements on the surface of the material from XPS results analysis, it can be seen that the Ti and Ti-ZnO sample surfaces are substantially free of phosphorus elements, while the Ti-ZnP1 and Ti-ZnP2 sample surfaces have a greatly increased content of phosphorus elements, demonstrating that the hydrothermal treatment in hydrogen phosphate can successfully convert zinc oxide to zinc phosphate.
The surface wettability of the material was tested using a static water contact angle tester. Fig. 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 about 60 °; after the zinc oxide nano rod coating is prepared on the Ti surface, the contact angle is reduced to about 22 degrees; after conversion of the zinc oxide moiety to zinc phosphate, the contact angle is further reduced.
Example 5
And detecting the bonding force between the formed coating and the substrate by adopting a scratch experiment. After forming scratches on the surface of the sample, the coating on both sides of the scratches was observed for peeling off using SEM. As can be seen from fig. 5, the scratch edges of the three samples are not cracked and fall off in a large area, which indicates that the coating prepared by the invention has good bonding force with the substrate.
Example 6
Each group of samples was immersed in Hank's buffer, stored at 37℃and tested for release of zinc ions under physiological conditions simulating in vivo. As can be seen from fig. 6, each group of samples can continuously release zinc ions in a detection period of 30 days. Wherein the release speed of the Ti-ZnO sample is the fastest, the release speed of the Ti-ZnP sample is the slowest, and the release speed of the Ti-ZnP sample is the slowest. It is demonstrated that the zinc ion release rate can be significantly reduced after conversion of the zinc oxide moiety to zinc phosphate.
Example 7
Samples stored in Hank's buffer for various times as described in example 6 were removed and the surface morphology of the samples was observed using SEM. As shown in fig. 7, after the Ti-ZnO sample was immersed in the solution for 5 days, the nanorod-like structure of the surface began to collapse; after 20 days of soaking, the rod-like structure completely disappeared and a hole-like etch pit was formed. While the Ti-ZnP and Ti-ZnP2 samples had only slight changes in surface morphology during the 30 days of soaking. The above results are consistent with those in example 6, demonstrating that the conversion of zinc oxide to zinc phosphate can greatly slow down the degradation rate of the surface coating.
Example 8
Human-derived bone marrow mesenchymal stem cells were inoculated and cultured on the surfaces of each group of samples. FIG. 8 shows proliferation of cells obtained using CCK-8 assay kit after 1,3, 5 days of cell culture on the surface of sample. Wherein the abscissa represents the number of days of cell culture, and the ordinate represents 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, cells cultured on the Ti surface can proliferate normally with the increase of the culture time, while the cells on the Ti-ZnO surface lose activity completely after 1 day of culture due to the strong cytotoxicity of zinc oxide. The Ti-ZnP1 sample reduced the toxicity of the Ti-ZnO sample but still inhibited the cellular activity to some extent compared to Ti. Whereas the cells on the surface of the Ti-ZnP sample are substantially identical to the cells on the surface of Ti. The results show that as part of zinc oxide in the zinc oxide nano rod coating is converted into zinc phosphate with slower degradation speed, the biotoxicity of the material is greatly reduced, and as the reaction time is prolonged, the conversion proportion of the zinc phosphate is increased, 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 them into osteoblasts, and then the activity of alkaline phosphatase (ALP), a marker enzyme in early stage of osteoblast formation (fig. 9 a), the case of collagen secreted by cells (fig. 9 b), and the case of mineralization of extracellular matrix (fig. 9 c) were examined. The results are plotted on the abscissa as days of cell induction, and the activity of ALP is plotted on the ordinate in FIG. 9a, and normalized to the total intracellular protein content; FIGS. 9b-c are graphs on the ordinate showing that the higher the absorbance at 570nm wavelength of the corresponding well of the detection kit indicates a higher degree of mineralization of the extracellular matrix. The result shows that the Ti-ZnO sample has stronger cytotoxicity, so that osteoblasts are difficult to normally grow on the surface of the sample, and the osteoblasts are more difficult to differentiate into the sample; the cells cultured on the surface of Ti-ZnP1 have a certain osteoblast differentiation trend; the surface culture of Ti-ZnP2 sample has the highest ALP activity, the highest collagen secretion after 21 days of induction and the highest mineralization degree of extracellular matrix. The above results demonstrate that Ti-ZnP2 can promote bone marrow mesenchymal stem cells to differentiate into osteogenesis.
Example 10
Bacteria were cultured on the surfaces of each group of samples to examine the antibacterial properties of the surfaces of the samples. As can be seen from fig. 10a, ti surface has no antibacterial effect, 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-ZnP and Ti-ZnP is slightly poor, but the calculated antibacterial rate is more than 90%. 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 of carrying out the application and that various changes in form and details may be made therein without departing from the spirit and scope of the application. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the application, and the scope of the application is therefore intended to be limited only by the appended claims.
Claims (8)
1. The preparation method of the zinc oxide/zinc phosphate nano rod composite antibacterial coating is characterized by comprising the steps of firstly preparing the zinc oxide nano rod coating on the surface of a medical material; then converting zinc oxide in the zinc oxide nano rod coating into zinc phosphate by a water bath treatment method in phosphate or hydrogen phosphate solution, so as to prepare the zinc oxide/zinc phosphate nano rod composite antibacterial coating with nano morphology; 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 nano rod coating on the zinc oxide seed layer through hydrothermal treatment to obtain the medical material loaded with the zinc oxide nano rod coating;
Immersing the medical material loaded with the zinc oxide nano rod coating into a phosphate or hydrogen phosphate solution for phosphorylation treatment, and controlling the conversion ratio of zinc oxide to zinc phosphate by regulating and controlling reaction conditions to obtain the zinc oxide/zinc phosphate nano rod composite antibacterial coating;
the phosphate or hydrogen phosphate solution is one or more of potassium phosphate, sodium phosphate, dipotassium phosphate, disodium phosphate, monopotassium phosphate or sodium dihydrogen phosphate solution.
2. The method for preparing the zinc oxide/zinc phosphate nano rod composite antibacterial coating according to claim 1, 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 20-100 ℃, and the reaction time is 1-24 h.
3. The method for preparing the zinc oxide/zinc phosphate nano rod 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, the temperature is 60 ℃, and the reaction time is 2h.
4. The method for preparing the zinc oxide/zinc phosphate nano-rod composite antibacterial coating according to claim 1, wherein the concentration of the phosphate or hydrogen phosphate solution is 0.01mol/L-0.5mol/L.
5. The method for preparing a zinc oxide/zinc phosphate nanorod composite antibacterial coating according to claim 4, wherein the concentration of the phosphate or hydrogen phosphate solution is 0.1mol/L.
6. The method for preparing the zinc oxide/zinc phosphate nano-rod composite antibacterial coating according to claim 1, wherein the first step specifically comprises the following steps,
Preparing a mixed solution: zinc acetate and ethanolamine are dissolved in ethanol and stirred for 5 hours at room temperature to form a mixed solution; wherein the concentration of the zinc acetate, the ethanol amine and the ethanol is 0.05mol/L;
Spin coating treatment: fixing a sample on a spin coater, dripping more than 60 mu l of the mixed solution on the surface of the sample, and then placing the sample in an oven for processing at 120 ℃ for 10min;
preparing a sample for forming a zinc oxide seed layer: repeating the spin coating treatment for three times, transferring the sample into a muffle furnace, and treating at 500 ℃ for 30min, so as to form a zinc oxide seed layer on the surface of the sample;
Preparing a zinc oxide nano rod coating: and (3) placing the sample with the zinc oxide seed layer into a hydrothermal kettle, and treating the sample with the zinc oxide seed layer 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 nano rod coating.
7. A zinc oxide/zinc phosphate nano rod composite antibacterial coating, characterized in that the zinc oxide/zinc phosphate nano rod composite antibacterial coating is prepared by the preparation method of the zinc oxide/zinc phosphate nano rod composite antibacterial coating according to any one of claims 1 to 6.
8. The use of the zinc oxide/zinc phosphate nanorod composite antibacterial coating according to claim 7 in the field of medical materials.
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| PCT/CN2022/137052 WO2024066040A1 (en) | 2022-09-28 | 2022-12-06 | Zinc oxide/zinc phosphate nanorod composite antibacterial coating and preparation method therefor and use thereof |
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| 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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| CN105259096B (en) * | 2015-10-19 | 2018-01-12 | 武汉顺可达生物科技有限公司 | Trbasic zinc phosphate nanometer substrate and preparation method thereof and the application in circulating tumor cell captures and discharges |
| CN113117145A (en) * | 2020-01-13 | 2021-07-16 | 中国科学院上海硅酸盐研究所 | Antibacterial coating for surface of implant and preparation method thereof |
| CN113797396B (en) * | 2021-10-08 | 2023-03-03 | 温州医科大学附属口腔医院 | Preparation method of porous zinc biological composite coating for degradable bone scaffold |
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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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