CN113755828B - Method for antibacterial modification of titanium surface and improvement of biological activity of titanium surface, coating and implant - Google Patents
Method for antibacterial modification of titanium surface and improvement of biological activity of titanium surface, coating and implant Download PDFInfo
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- CN113755828B CN113755828B CN202111027277.XA CN202111027277A CN113755828B CN 113755828 B CN113755828 B CN 113755828B CN 202111027277 A CN202111027277 A CN 202111027277A CN 113755828 B CN113755828 B CN 113755828B
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- 239000010936 titanium Substances 0.000 title claims abstract description 118
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 114
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000007943 implant Substances 0.000 title claims abstract description 39
- 230000004048 modification Effects 0.000 title claims abstract description 34
- 238000012986 modification Methods 0.000 title claims abstract description 34
- 230000004071 biological effect Effects 0.000 title claims abstract description 28
- 238000000576 coating method Methods 0.000 title claims abstract description 19
- 239000011248 coating agent Substances 0.000 title claims abstract description 16
- 230000006872 improvement Effects 0.000 title claims description 6
- 239000000463 material Substances 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 16
- 238000002444 silanisation Methods 0.000 claims abstract description 14
- -1 silicon quaternary ammonium salt Chemical class 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 238000009832 plasma treatment Methods 0.000 claims description 19
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 17
- 230000000845 anti-microbial effect Effects 0.000 claims description 13
- 150000003608 titanium Chemical class 0.000 claims description 11
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000006884 silylation reaction Methods 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910003089 Ti–OH Inorganic materials 0.000 claims description 4
- 239000004599 antimicrobial Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000003100 immobilizing effect Effects 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 9
- 239000003814 drug Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 229940079593 drug Drugs 0.000 description 7
- 230000001737 promoting effect Effects 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229940124350 antibacterial drug Drugs 0.000 description 4
- 230000021164 cell adhesion Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003937 drug carrier Substances 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 244000052616 bacterial pathogen Species 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 210000001185 bone marrow Anatomy 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 210000002901 mesenchymal stem cell Anatomy 0.000 description 3
- 230000002503 metabolic effect Effects 0.000 description 3
- 230000004060 metabolic process Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 210000004513 dentition Anatomy 0.000 description 2
- 229910001651 emery Inorganic materials 0.000 description 2
- 230000004054 inflammatory process Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000036346 tooth eruption Effects 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 208000037408 Device failure Diseases 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033115 angiogenesis Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 210000002919 epithelial cell Anatomy 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 210000001616 monocyte Anatomy 0.000 description 1
- 238000010883 osseointegration Methods 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000004537 potential cytotoxicity Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
-
- 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
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/216—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with other specific functional groups, e.g. aldehydes, ketones, phenols, quaternary phosphonium groups
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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
- 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
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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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
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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
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
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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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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- Chemical & Material Sciences (AREA)
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- Medicinal Chemistry (AREA)
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- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Dermatology (AREA)
- Transplantation (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention belongs to the technical field of medicine, and discloses a method for performing antibacterial modification on a titanium surface and improving the bioactivity of the titanium surface, a coating and an implant, wherein the titanium surface is polished and cleaned; the low-temperature oxygen plasma is used for treating the titanium surface, improving the surface bioactivity of the titanium material and forming the titanium surface with a large number of hydroxyl groups; constructing a silanization reaction system; and placing the titanium implant material sample in a silanization reaction system to form the titanium surface with the organic silicon quaternary ammonium salt and hydroxyl covalently bonded. According to the invention, the titanium surface is treated by low-temperature oxygen plasma, so that the surface hydrophilicity of the material is increased, the surface bioactivity of the material is improved, a large number of hydroxyl groups are introduced, and then the antibacterial agent and the hydroxyl groups are subjected to covalent bonding by a chemical method to form a non-release antibacterial coating, so that the defects of burst release, easiness in degradation and the like of the antibacterial agent are avoided to a certain extent, and the long-acting property of the antibacterial effect is improved. Meanwhile, the invention realizes the purposes of improving the biological activity of the titanium surface and endowing the material with long-acting antibacterial capability.
Description
Technical Field
The invention belongs to the technical field of medicine, and particularly relates to a method for antibacterial modification of a titanium surface and improving the bioactivity of the titanium surface, a coating and an implant.
Background
Currently, dental implantation is recognized as the treatment of choice for current dentition defects and dentition-deficient patients. Peri-implant inflammation is one of the main causes of implant failure. The use of the surface modified implant material is one of effective ways for preventing and treating peri-implant inflammation, can endow the implant material with biological functions such as antibiosis and the like, and becomes a hot spot for the research and development of novel implant materials.
Most of clinically used and newly developed antibacterial modified implant coatings divide drug carriers and antibacterial drugs into mutually independent components, the two components are required to be selected respectively, and meanwhile, the factors such as drug carrying efficiency of the carriers, whether the drug carriers are degraded, drug release rate, release time and the like are also required to be considered, so that the design and synthesis processes of the drug carriers and the antibacterial drugs are complicated. The antibacterial coating formed by the combination way is difficult to stably and slowly release the effective dose of the antibacterial drug in a local part, and the high-concentration drug is suddenly released in an initial stage, so that the residual drug is difficult to maintain the effective antibacterial concentration, and the long-term effectiveness of the antibacterial effect is poor.
The antibacterial agent is fixed on the surface of the implant in a chemical connection mode, so that the technical difficulties of abrupt release of the drug and short antibacterial effect time can be overcome, and the stable and long-acting antibacterial effect can be exerted. The prior researches show that the antibacterial coating material has good antibacterial function, but also has potential cytotoxicity, and influences the growth and the function of host cells. Therefore, it is necessary to study a surface coating material for implant surfaces, which is technically simple and easy to implement, has long-acting antibacterial effect and biological activity, and achieves the effects of inhibiting pathogenic bacteria and promoting growth and function of host cells.
Through the above analysis, the problems and defects existing in the prior art are as follows:
(1) The existing implant coating has complex design and synthesis scheme, poor popularization and low effectiveness. The existing methods for loading the antibacterial agent mostly use embedding, electrostatic attraction and other physical modes, the physical modes have the defect of unstable systems, the formed antibacterial coating is difficult to maintain the concentration of the antibacterial agent with effective dosage in a local stable manner, a large amount of the antibacterial agent is suddenly released in the initial stage, and the residual antibacterial agent is difficult to maintain the effective antibacterial concentration.
(2) The prior art faces the dilemma that it is difficult to balance the contradiction between antibacterial and biological activity. Antibacterial modification of titanium implant materials often affects the biocompatibility of the materials, and shows a certain degree of cytotoxicity due to the introduction of antibacterial agents, which becomes an obstacle for cell adhesion and functional expression.
The difficulty of solving the problems and the defects is as follows:
(1) The coating method for chemically fixing the antibacterial component is designed, so that the antibacterial agent is stably existing on the surface of the titanium implant material, and the searching of a proper chemical reaction and a substrate is difficult.
(2) The biological reactivity of the material needs to be improved on the basis of antibacterial modification, and the difficulty is that the antibacterial modification and the improvement of the biological reactivity of the material are combined.
(3) The design with relatively simplified and more generalized performance is required on the basis of ensuring the antibacterial property and the biological reactivity of the material.
The meaning of solving the problems and the defects is as follows:
(1) The modified implant material has long-term stable antibacterial property.
(2) The biological reactivity of the material is improved while the antibacterial property of the implant material is endowed, the purposes of preventing pathogenic bacteria infection and promoting the smooth formation of biological sealing and osseointegration are achieved, and the success rate of implant repair is improved.
(3) The design scheme is simple and feasible, and is more beneficial to the application and popularization in the later stage.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a method for antibacterial modification of a titanium surface and improving the biological activity of the titanium surface, a coating and an implant.
The invention is realized in such a way that a titanium surface is subjected to antibacterial modification and the biological activity is improved, and the method comprises the following steps:
step one, polishing and cleaning the titanium surface;
treating the titanium surface by low-temperature oxygen plasma to form a titanium surface with high biological activity and a large number of hydroxyl groups;
step three, constructing a silanization reaction system;
and fourthly, placing the titanium material into a silanization reaction system to realize chemical anchoring of the organosilicon quaternary ammonium salt.
Further, in the first step, the polishing and cleaning of the titanium surface comprises:
the titanium material was polished to a specular surface using different grit emery papers (280, 320, 400, 600, 800, 1000, 1200 grit) in order of coarse to fine grit. Respectively using acetone, alcohol and deionized water to ultrasonically shake and clean for 30 min.
Further, in the second step, the low-temperature oxygen plasma treatment is performed on the titanium surface to form a titanium surface with high bioactivity and a large number of hydroxyl groups, and the method comprises the following steps:
pure oxygen is used as treatment gas, the pressure in a plasma treatment bin is kept at 0.08 TORR, and the polished and cleaned titanium material surface is subjected to low-temperature oxygen plasma treatment for 5-60min according to the technical parameters of 720V,25mA and 18W.
Further, in the third step, the construction of the silylation reaction system includes:
the antibacterial component is octadecyl dimethyl trimethoxy silane ammonium chloride, catalyst propylamine and solvent cyclohexane. The amount of the reaction system is determined according to the titanium material to be treated, so that the reaction system can be completely immersed in the material, and each component is added into the system according to the corresponding volume fraction: 4% octadecyl dimethyl trimethoxy silane ammonium chloride (Octadecyldimethyl- (3-trimethoxycilylpropyl) -ammonium chloride, ODDMAC), 2% propylamine, 94% cyclohexane.
Further, in the fourth step, the placing the titanium sheet sample in the silylation reaction system to realize chemical anchoring of the organosilicon quaternary ammonium salt includes:
and (3) placing the titanium implant sample subjected to the low-temperature oxygen plasma treatment in a silanization reaction system to react for 1-2 hours under the water bath condition of 80 ℃, and stirring liquid in the reaction system by using a magnetic stirrer in the reaction process to ensure uniform reaction and smooth discharge of gas generated in the reaction process. Further, the reaction system is-SiOCH in the organosilicon quaternary ammonium salt 3 The group and the Ti-OH group on the surface of the hydroxylated titanium are subjected to dehydration reaction, and an Si-O-Ti covalent bond is formed on the surface of the titanium, so that covalent connection of the organosilicon quaternary ammonium salt serving as an antibacterial component is realized. Then sequentially cleaning the treated titanium implant material by using isopropanol, deionized water and acetone to remove residual reaction substrates on the surface of the material, and then placing the material in a muffle furnace with the temperature of 110℃ highAnd drying at a temperature for 1 hour.
It is another object of the present invention to provide an antibacterial modified implant coating prepared using the method of antibacterial modification of titanium surface and improving its biological activity.
It is another object of the present invention to provide an antimicrobial modified implant having the antimicrobial modified implant coating deposited thereon.
By combining all the technical schemes, the invention has the advantages and positive effects that:
1. the method for antibacterial modification of the titanium surface and improving the biological activity of the titanium surface provided by the invention uses a low-temperature oxygen plasma treatment technology on the titanium surface, utilizes ionized substances such as high-energy molecules, ions and the like in oxygen plasma to destroy C-C and C-H chemical bonds on the titanium implant material surface to form hydrophilic O-H bonds, and the research results in the invention show that the method for antibacterial modification and improving the biological activity of the titanium surface successfully increases the hydrophilicity of the titanium surface, and a great deal of researches prove that the increase of the hydrophilicity is favorable for the adhesion of monocytes and the activation of platelets in the bone-joining formation process, can promote the osteogenesis and the angiogenesis, and effectively improves the biological activity of the material surface. The results of the research prove that the method can promote the adhesion and growth metabolism activity of human bone marrow mesenchymal stem cells, and has the potential of promoting the formation of biological sealing and promoting bone union. In addition, the research result of the X-ray photoelectron spectroscopy on the surface of the material shows that a large number of hydroxyl groups are formed on the surface of the titanium after the oxygen plasma treatment, a large number of reactive groups are provided for the subsequent chemical fixation, and a foundation is laid for realizing the dual-function modified titanium implant.
2. utilizing-SiOCH in organosilicon quaternary ammonium salt on the basis of oxygen plasma treatment of titanium implant surface 3 The group and the Ti-OH group on the surface of the hydroxylated titanium are subjected to dehydration reaction, a Si-O-Ti covalent bond is formed on the surface of the titanium, and the quaternary ammonium group with positive charges is covalently bonded to the surface of the titanium, so that the release of the antibacterial agent and the rapid reduction of the concentration of the agent are avoided, and a non-release antibacterial material is formed, so that the stable antibacterial modified titanium implant surface is formed. Results of the studyThe plasma/quaternary ammonium salt composite modified titanium material provided by the invention has the advantages that the formation of staphylococcus aureus biological film on the surface of the material and the metabolic activity of the biological film can be effectively reduced, the adhesion of cells can be promoted, and the effect of the dual-function modified titanium implant material is achieved.
3. The invention realizes the simplification of the modification technology and the reduction of the technical threshold on the premise of promoting the cell adhesion and effectively improving the antibacterial effect, and has good popularization and application prospect. The organosilicon quaternary ammonium salt used in the invention is a common cationic antibacterial agent, has been widely applied to clinic and life, has great potential in the research of antibacterial modified titanium materials, and has good acquisition convenience, and meanwhile, the antibacterial agent has been commercialized. The low temperature plasma treatment technique is used as a simple and efficient method. Therefore, the invention has simple design and synthesis process, high safety coefficient and convenient operation, and overcomes the defects of complexity and poor realizability of the prior art.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for antimicrobial modification of a titanium surface and improving its biological activity according to an embodiment of the present invention.
FIG. 2 is a schematic diagram of a method for antimicrobial modification of a titanium surface and increasing its bioactivity according to an embodiment of the present invention.
FIG. 3 is a schematic chemical reaction diagram of a method for antimicrobial modification of a titanium surface and improving its biological activity according to an embodiment of the present invention.
FIG. 4 is a schematic diagram showing experimental results of the method for proving antibacterial modification of a titanium surface and improving the bioactivity of the titanium surface, which is provided by the embodiment of the invention, to reduce the water contact angle of the surface of the titanium implant material;
FIG. 5 is a schematic diagram of experimental results showing that the method for antibacterial modification of the surface of titanium and improving the biological activity of the surface of the titanium can inhibit the metabolic activity of Staphylococcus aureus biological membrane on the surface of the material;
fig. 6 to fig. 7 are schematic diagrams of experimental results showing that the method for performing antibacterial modification on the surface of titanium and improving the biological activity of the titanium can promote adhesion and growth metabolism activity of human bone marrow mesenchymal stem cells on the surface of a material;
in the figure: ti, polishing the cleaned titanium surface; ti-PLA, the surface of titanium after 10min oxygen plasma treatment; ti-POC, plasma/organosilicon quaternary ammonium salt compound modifies the surface of titanium.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In view of the problems of the prior art, the present invention provides a method for antibacterial modification of a titanium surface and improving the bioactivity of the titanium surface, and the present invention is described in detail below with reference to the accompanying drawings.
As shown in fig. 1, the method for antibacterial modification and improvement of biological activity of a titanium surface provided by the embodiment of the invention comprises the following steps:
s101, polishing and cleaning the titanium surface;
s102, treating the titanium surface by low-temperature oxygen plasma to form a titanium surface with a large number of hydroxyl groups;
s103, constructing a silanization reaction system;
and S104, placing the titanium sheet sample in a silanization reaction system to form the titanium surface with the organic silicon quaternary ammonium salt and hydroxyl covalently bonded.
The schematic diagram of the method for antibacterial modification of the titanium surface and improving the biological activity of the titanium surface provided by the embodiment of the invention is shown in fig. 2, and the schematic diagram of the chemical reaction of the method for antibacterial modification of the titanium surface and improving the biological activity of the titanium surface provided by the embodiment of the invention is shown in fig. 3.
The technical scheme of the invention is further described below by combining the embodiments.
Example 1
The invention aims to provide a method for compositely modifying the titanium surface by low-temperature oxygen plasma treatment and organic silicon quaternary ammonium salt, which solves the problems in the prior art. The invention relates to a method for modifying the surface properties of titanium implants by using low temperature plasma treatment techniques on the titanium surface and covalently bonding quaternary ammonium salt molecules to the titanium surface by means of a silylation reaction.
In one aspect, the low-temperature plasma treatment technology is used as a simple and efficient method, provides feasibility for material surface modification, and has certain potential. Early studies showed that oxygen plasma treatment of titanium surfaces enhances the bioactivity of titanium materials, has the ability to promote epithelial cell adhesion, shorten healing time and increase bone integration levels. The quaternary ammonium salt is a common cationic antibacterial agent and has good application prospect in antibacterial modified titanium materials. The low-temperature plasma technology and the organic silicon quaternary ammonium salt are effectively combined, and the aim of enabling the titanium surface to have bioactivity and long-acting antibacterial capability is fulfilled.
On the other hand, the organosilicon quaternary ammonium salt and the hydroxyl on the surface of the titanium treated by the low-temperature oxygen plasma carry out silanization reaction, so that the defect that most of antibacterial coatings divide a drug carrier and an antibacterial drug into two mutually independent components is overcome, the method for modifying and modifying the surface of the titanium material is effectively simplified, and the factors such as drug carrying efficiency, drug release rate, release time and the like do not need to be considered, so that the design and synthesis process are simple, the safety coefficient is high, and the operation is convenient.
Research results prove that the plasma/quaternary ammonium salt composite modified titanium material can effectively reduce the colonization of pathogenic bacteria on the surface of the material and promote cell adhesion.
The invention can improve the biological activity of the titanium surface and endow the material with long-acting antibacterial capability on the premise of simplifying the technology and effectively improving the efficiency.
Example 2
The method comprises the following complete steps:
polishing and cleaning the titanium surface: the titanium material was polished to a specular surface using different grit emery papers (280, 320, 400, 600, 800, 1000, 1200 grit) in order of coarse to fine grit. Respectively using acetone, alcohol and deionized water to ultrasonically shake and clean for 30 min.
Oxygen plasma treatment: performing plasma treatment (720V, 25mA, 18W) on the polished and cleaned titanium material surface for 5-60min by using pure oxygen as a treatment gas to form a titanium surface with a large number of hydroxyl groups;
constructing a silanization reaction system: 4% by volume of octadecyl dimethyl trimethoxy silane ammonium chloride, 2% propylamine, 94% cyclohexane.
The titanium implant sample is placed in a silanization reaction system and treated for 1-2 hours at the temperature of 80 ℃ so as to covalently bond the organosilicon quaternary ammonium salt to the titanium surface rich in hydroxyl groups.
In another embodiment of the present invention, elements that may replace technical features: the components in the silanization reaction system can be changed according to the modification purpose, for example, the solvent can be replaced by deionized water, the reaction temperature can be selected to be room temperature, and the reaction time is correspondingly prolonged to 24 hours.
In another embodiment of the invention, a large amount of hydroxyl groups are introduced into the titanium surface treated by low-temperature oxygen plasma, and then the antibacterial agent and the hydroxyl groups are covalently combined by a chemical method to form a non-release antibacterial material, so that the defects of abrupt release, easy degradation and the like of the antibacterial agent are avoided to a certain extent, and the long-acting property of the antibacterial effect is improved.
The titanium material is treated by low-temperature plasma to improve the surface bioactivity of the material, so that the material has the potential of promoting biological seal formation and bone bonding, and the surface modified titanium material with dual functions is synthesized by combining the antibacterial property of quaternary ammonium salt.
In another embodiment of the invention, the surface of the titanium treated by the oxygen plasma is rich in hydroxyl groups, so that the biological activity of the titanium material is improved.
SiOCH in organosilicon quaternary ammonium salt 3 The groups form hydrogen bonds with Ti-OH groups on the surface of the titanium which is hydroxylated, and then the Si-O-Ti covalent bond is formed by heating and dehydratingAnd a bond to effect covalent attachment of the antimicrobial agent to exert a long-acting antimicrobial effect.
In another embodiment of the invention, ti: polishing the cleaned titanium surface; ti-PLA: the surface of titanium after 10min oxygen plasma treatment; ti-POC: plasma/organosilicon quaternary ammonium salt compound modification of titanium surface.
FIG. 4 is a graph showing the detection of Ti-POC capable of reducing the water contact angle of the surface of a material, namely, the method for confirming the antibacterial modification of the surface of titanium and improving the biological activity of the surface of the material can increase the hydrophilicity of the surface of the material and improve the biological activity of the material.
FIG. 5 is a graph showing the metabolic activity of Ti-POC in inhibiting Staphylococcus aureus on the surface of the material.
FIG. 6 and FIG. 7 are graphs showing the activity of Ti-POC in promoting adhesion, growth and metabolism of human bone marrow mesenchymal stem cells on the surface of material.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.
Claims (6)
1. A method for antimicrobial modification of a titanium surface and increasing its biological activity, characterized by chemically immobilizing an antimicrobial agent in combination with oxygen plasma treatment and silylation reaction for the first time, the method for antimicrobial modification of a titanium surface and increasing its biological activity comprising the steps of:
step one, polishing and cleaning the titanium surface;
step two, treating the titanium surface by low-temperature oxygen plasma;
step three, constructing a silanization reaction system;
step four, placing a titanium implant sample in a silanization reaction system to form a titanium surface with organic silicon quaternary ammonium salt and hydroxyl covalently bonded;
in the second step, the low-temperature oxygen plasma is used for treating the titanium surface to form the titanium surface with high surface bioactivity and a large number of hydroxyl groups, and the method comprises the following steps:
pure oxygen is used as a treatment gas, and the polished and cleaned titanium material surface is subjected to low-temperature oxygen plasma treatment for 5-60 min;
the plasma treatment conditions are as follows: 720V,25mA,18W.
2. The method for antibacterial modification of a titanium surface and for increasing its bioactivity according to claim 1, wherein in the third step, the construction of the silylation reaction system comprises:
4% by volume of octadecyl dimethyl trimethoxy silane ammonium chloride ODDMAC,2% propylamine, 94% cyclohexane.
3. The method for antimicrobial modification of a titanium surface and for increasing its biological activity according to claim 1, wherein in step four, the placing the titanium sheet sample in a silylation reaction system forms a titanium surface with covalently bonded organosilicon quaternary ammonium salt and hydroxyl groups, comprising:
the titanium sheet sample is placed in a silanization reaction system and treated for 1-2 hours at the temperature of 80 ℃ to covalently bond the organosilicon quaternary ammonium salt to the titanium surface rich in hydroxyl groups.
4. The method of antimicrobial modification of a titanium surface and increasing its biological activity according to claim 3, wherein-SiOCH in said silicone quaternary ammonium salt 3 The groups form hydrogen bonds with Ti-OH groups on the surface of the hydroxylated titanium, and then the hydroxyl groups are dehydrated by heating to form Si-O-Ti covalent bonds, so that covalent connection of the antibacterial agent is realized.
5. An antibacterial modified implant coating, which is characterized in that the antibacterial modified implant coating is prepared by the method for antibacterial modification of the titanium surface and improvement of the biological activity of the titanium surface according to any one of claims 1-4.
6. An antimicrobial modified implant, wherein the antimicrobial modified implant is deposited with the antimicrobial modified implant coating of claim 5.
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| CN104846354A (en) * | 2015-05-12 | 2015-08-19 | 中国船舶重工集团公司第七二五研究所 | Antifouling and antibacterial treatment method for titanium and titanium alloy surface |
| CN106902396A (en) * | 2017-01-05 | 2017-06-30 | 华南理工大学 | A kind of method that antimicrobial surface is prepared on medical material surface |
| CN113171498A (en) * | 2021-05-08 | 2021-07-27 | 西南大学 | SDS-LA/PLGA/APTES antibacterial coating |
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| CN104846354A (en) * | 2015-05-12 | 2015-08-19 | 中国船舶重工集团公司第七二五研究所 | Antifouling and antibacterial treatment method for titanium and titanium alloy surface |
| CN106902396A (en) * | 2017-01-05 | 2017-06-30 | 华南理工大学 | A kind of method that antimicrobial surface is prepared on medical material surface |
| CN113171498A (en) * | 2021-05-08 | 2021-07-27 | 西南大学 | SDS-LA/PLGA/APTES antibacterial coating |
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