CN115737923B - Photodynamic antibacterial coating for implant surface and preparation method thereof - Google Patents
Photodynamic antibacterial coating for implant surface and preparation method thereof Download PDFInfo
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- CN115737923B CN115737923B CN202211521840.3A CN202211521840A CN115737923B CN 115737923 B CN115737923 B CN 115737923B CN 202211521840 A CN202211521840 A CN 202211521840A CN 115737923 B CN115737923 B CN 115737923B
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- 238000000576 coating method Methods 0.000 title claims abstract description 52
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- 238000002360 preparation method Methods 0.000 title claims description 10
- MXSJNBRAMXILSE-UHFFFAOYSA-N [Si].[P].[B] Chemical compound [Si].[P].[B] MXSJNBRAMXILSE-UHFFFAOYSA-N 0.000 claims abstract description 48
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- 238000000034 method Methods 0.000 claims abstract description 27
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- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical class CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 claims abstract description 15
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000002390 rotary evaporation Methods 0.000 claims description 14
- 238000004090 dissolution Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
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- 238000005086 pumping Methods 0.000 claims description 5
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 claims description 4
- -1 diethyl phosphate compound Chemical class 0.000 claims description 4
- GZNJJEODYYLYSA-UHFFFAOYSA-N diethyl prop-2-enyl phosphate Chemical compound CCOP(=O)(OCC)OCC=C GZNJJEODYYLYSA-UHFFFAOYSA-N 0.000 claims description 4
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 3
- QBNZQTCUABQLNJ-UHFFFAOYSA-N 3-aminopropyl diethyl phosphate Chemical compound CCOP(=O)(OCC)OCCCN QBNZQTCUABQLNJ-UHFFFAOYSA-N 0.000 claims description 3
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- 208000015181 infectious disease Diseases 0.000 abstract description 6
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- 229940088710 antibiotic agent Drugs 0.000 description 2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a photodynamic antibacterial coating for the surface of an implant, wherein the antibacterial coating is hyperbranched boron phosphorus silicon ternary polymer prepared from boric acid, diethyl phosphate compounds and diethoxysilane compounds. According to the invention, the polymer is prepared by a one-pot method, a catalyst is not used, the polymer is sprayed on the surface of the implant, the binding force between the coating and the implant is enhanced by utilizing the rich functional groups on the surface of the hyperbranched structure of the polymer, so that the polymer is prevented from falling off, and meanwhile, the active oxygen generated by photoluminescence of the polymer coating is utilized to kill bacteria, so that the effect of preventing infection is achieved.
Description
Technical Field
The invention belongs to the technical field of antibacterial coatings, and particularly relates to a photodynamic antibacterial coating for an implant surface and a preparation method thereof.
Background
Bacteria are widely present in the human living and working environment, bacterial infection is one of the most serious health problems worldwide, causing millions of people to become ill each year, and being the leading cause of death before the beginning of the 20 th century. Bone repair and replacement surgery is performed in an atmospheric environment, and pathogenic microorganisms such as staphylococcus, pseudomonas aeruginosa and the like in the air, on the body surface of a patient or an operator are easily brought into the operation part, so that implant related infection is induced. Once infection occurs, it can cause great pain to the patient and will face revision surgery. In order to prevent bone implant related infections, more and more research is focused on the antimicrobial properties of implants. In particular, the advent of surface design strategies provides an effective alternative to antibiotics, thereby preventing the possible development of bacterial resistance. To better treat infections caused by drug resistant bacteria, various antibacterial drugs (e.g., antibacterial peptides and amphiphiles) and antibacterial materials (e.g., nanoparticles, hydrogels, engineered surfaces and surface coatings) have been developed. The antibacterial material has lower binding force with the substrate due to the self property of the antibacterial material and the limitation of the traditional coating process, so that the release of antibacterial particles is influenced, and the antibacterial performance is further influenced.
Due to the overuse of antibiotics, bacterial resistance has become increasingly serious in recent years, resulting in an increasing mortality rate of infectious diseases. Thus, there is an urgent need to find new drugs and new means that can effectively alleviate the problem of drug resistance. With the advancement of optical technology and the development of novel photosensitizers, photodynamic antibacterial treatment (Photodynamic Antibacterial Therapy, PDAT) has become one of the most promising treatment modes for drug-resistant bacteria infection because of the advantage of difficulty in drug resistance. PDAT mainly adopts a light source with proper wavelength to excite photosensitizer molecules to generate Reactive Oxygen Species (ROS) to oxidize and destroy biological macromolecules such as phospholipid, enzyme, protein, DNA and the like, thereby realizing effective inactivation of pathogenic microorganisms. In practical antibacterial application, the traditional small molecule photosensitizer generally has the problems of poor water solubility, easy photobleaching, weak selective identification, poor treatment effect and the like. In view of the above problems, researchers at home and abroad have designed and developed some novel antibacterial photosensitizers in recent years, which can be summarized into four types: (1) aromatic organic small molecules, (2) non-self-quenching organic small molecules, (3) conjugated polymers and (4) nanometer photosensitizers. The novel antibacterial photosensitizers can realize efficient sterilization by optimizing in-vivo delivery to improve pharmacokinetics, increasing the permeability at focus positions, improving the drug concentration of target tissues and the like, and reduce toxic and side effects and improve bioavailability, and the progress provides higher feasibility for the clinical application of PDAT.
Therefore, how to provide a composite antibacterial coating layer having excellent antibacterial properties and being firmly combined with a substrate plays an important role in the wide application of antibacterial materials.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a photodynamic antibacterial coating for the surface of an implant aiming at the defects of the prior art. The coating just carries out polycondensation dealcoholization reaction by controlling the molar ratio of boric acid, diethyl phosphate and diethoxysilane to generate hyperbranched boron phosphorus silicon terpolymer, the bonding strength of the implant and the coating is improved by utilizing rich functional groups on the surface of the hyperbranched boron phosphorus silicon terpolymer, and the effective antibacterial time is prolonged by utilizing the photocatalysis of the hyperbranched boron phosphorus silicon terpolymer, so that the excellent antibacterial effect is achieved.
In order to solve the technical problems, the invention adopts the following technical scheme: the photodynamic antibacterial coating for the surface of the implant is characterized in that the antibacterial coating is a hyperbranched boron-phosphorus-silicon terpolymer prepared by taking boric acid, diethyl phosphate compounds and diethoxysilane compounds as raw materials according to the molar ratio of 2-4:1-2:1-2.
According to the invention, the molar ratio of boric acid, diethyl phosphate compounds and diethoxysilane compounds is controlled to enable the boric acid, diethyl phosphate compounds and diethoxysilane compounds to just perform polycondensation dealcoholization reaction to prepare the hyperbranched boron-phosphorus-silicon terpolymer, the bonding strength of the implant and the coating is improved by utilizing rich functional groups on the surface of the hyperbranched boron-phosphorus-silicon terpolymer, and in addition, the effective antibacterial time can be prolonged by utilizing the photocatalysis of the hyperbranched boron-phosphorus-silicon terpolymer, so that the excellent antibacterial effect is achieved.
The photodynamic antibacterial coating for the implant surface is characterized in that the diethyl phosphate compound is diethyl phosphate, (3-aminopropyl) diethyl phosphate or allyl diethyl phosphate. The raw materials adopted by the invention have excellent photophysical properties after polymerization, achieve the photodynamic antibacterial property, and the phosphorus element is a bioactive element, thereby being beneficial to biocompatibility and osteogenesis.
The photodynamic antibacterial coating for the implant surface is characterized in that the diethoxysilane compound is diethoxysilane, (3-glycidoxy) methyldiethoxysilane or 3-aminopropyl methyldiethoxysilane. The raw materials adopted by the invention have excellent photophysical properties after polymerization, achieve the photodynamic antibacterial property, and the silicon element is a bioactive element, thereby being beneficial to biocompatibility and osteogenesis.
In addition, the invention also provides a method for preparing a photodynamic antibacterial coating for the surface of an implant, which is characterized in that the method comprises the following steps:
step one, mixing boric acid, diethyl phosphate compounds and diethoxysilane compounds to obtain raw materials;
heating and dissolving the raw materials obtained in the first step under stirring, and then distilling to obtain a product;
dialyzing the product obtained in the step two, and sequentially performing rotary evaporation and vacuum drying to obtain the hyperbranched boron-phosphorus-silicon ternary polymer;
and step four, adding the hyperbranched boron-phosphorus-silicon ternary polymer obtained in the step three into a high-pressure airless sprayer to spray the surface of the implant, and obtaining the photodynamic antibacterial coating on the surface of the implant.
According to the invention, boric acid, diethyl phosphate compounds and diethoxysilane compounds are mixed, so that subsequent reaction balance is facilitated, powder raw materials are dissolved by heating under stirring conditions for uniform mixing, subsequent liquid-liquid reaction is more complete, the raw materials are subjected to liquid-liquid reaction by distillation, transesterification polycondensation reaction is carried out between the raw materials to obtain a primary product, unreacted small molecular substances and oligomers with molecular weight not reaching standards are removed by dialysis, solvent during dialysis is removed by rotary evaporation, and sufficient solvent volatilization is facilitated by vacuum drying, so that the pure hyperbranched boron-phosphorus-silicon terpolymer is obtained; according to the invention, the hyperbranched boron-phosphorus-silicon terpolymer is added into a high-pressure airless sprayer to spray the surface of the implant, so that the photodynamic antibacterial coating is obtained on the surface of the implant.
The method is characterized in that the temperature of heating and dissolving in the second step is 80-100 ℃, the temperature of distillation is 140-160 ℃ and the time is 6-24 hours, the distillation is carried out under the nitrogen atmosphere, the product is subjected to vacuum pumping treatment for 30-60 min, and the heating and dissolving and the distillation are carried out under the oil bath condition. The invention ensures that the raw materials can be melted into liquid by controlling the heating temperature, ensures that the raw materials fully react to generate hyperbranched boron phosphorus silicon ternary polymer by controlling the distillation temperature and time, simultaneously prevents the raw materials from decomposing and not fully reacting, removes impurities in the product by vacuumizing treatment, ensures the full removal of the impurities and prevents the product from becoming gel by controlling the vacuumizing time, and ensures the uniform heating temperature by adopting an oil bath.
The method is characterized in that the dialysis process in the third step is as follows: adding absolute ethyl alcohol into the product, stirring and dissolving, and then adding the product into a dialysis bag for dialysis for 24-48 hours, wherein the molecular weight of the dialysis bag is 3000-5000; the temperature of the rotary evaporation is 45-60 ℃, the temperature of the vacuum drying is 60-100 ℃ and the time is 6-12 h. The invention adopts a dialysis bag with the molecular weight of 3000-5000 to remove the raw materials and impurities with small molecular weight, ensures the purity of the hyperbranched boron-phosphorus-silicon terpolymer, ensures the dissolution of the product to facilitate the dialysis to remove the raw materials and impurities by adding absolute ethyl alcohol, ensures the sufficient removal of the raw materials and impurities by controlling the dialysis time, prevents the hydrolysis of the product, and fully removes the absolute ethyl alcohol and prevents the gel of the hyperbranched boron-phosphorus-silicon terpolymer by controlling the temperature of rotary evaporation and the temperature and time of vacuum drying.
The method is characterized in that in the fourth step, the implant is titanium, and the implant is washed by acetone, absolute ethyl alcohol and deionized water in sequence before being used, and then vacuum drying is carried out. The titanium implant is widely used, the application range is wide, acetone, absolute ethyl alcohol and deionized water are sequentially used for cleaning the implant before the implant is used, and then vacuum drying is carried out to remove impurities on the surface of the implant.
The method is characterized in that the spraying process in the fourth step is as follows: adding the hyperbranched boron-phosphorus-silicon ternary polymer into a preparation tank of a high-pressure airless sprayer under the condition of low-speed stirring, stirring and dispersing, and then performing pressurized spraying under medium-speed stirring; the rotating speed of low-speed stirring is 200-400 r/min, the rotating speed of stirring dispersion is 800-1000 r/min, the time is 20-30 min, the rotating speed of medium-speed stirring is 600-800 r/min, the pressurizing pressure is 9.8-29.4 MPa, a nozzle with olive-shaped holes is adopted for spraying, and the distance between the nozzle and an implant is 10-50 cm. The hyperbranched boron-phosphorus-silicon ternary polymer coating with different thicknesses is firmly prepared on the surface of the implant by controlling the spraying process.
The method is characterized in that the thickness of the photodynamic antibacterial coating in the fourth step is 200 nm-1400 nm. The thickness of the photodynamic antibacterial coating is controlled to be suitable for different requirements, and the specific thickness can be determined according to actual requirements.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the molar ratio of boric acid, diethyl phosphate compounds and diethoxysilane compounds is controlled to enable the boric acid, diethyl phosphate compounds and diethoxysilane compounds to just perform polycondensation dealcoholization reaction to prepare the hyperbranched boron-phosphorus-silicon terpolymer, the bonding strength of the implant and the coating is improved by utilizing rich functional groups on the surface of the hyperbranched boron-phosphorus-silicon terpolymer, and in addition, the effective antibacterial time can be prolonged by utilizing the photocatalysis of the hyperbranched boron-phosphorus-silicon terpolymer, so that the excellent antibacterial effect is achieved.
2. The invention adopts the high-pressure airless spraying technology, has high controllability, low deposition temperature and less influence on the performance of implants, and the preparation process of the coating is green and environment-friendly, does not generate waste water and waste gas, and has wide application prospect.
3. The molecular weight of the hyperbranched boron phosphorus silicon ternary polymer fluorescent material prepared by the invention is 5000-30000, the molecular weight distribution of a typical high polymer material is met, the quantum yield of the prepared hyperbranched boron phosphorus silicon ternary polymer fluorescent material is 30% -48%, the problem of low luminous intensity of a non-conjugated fluorescent polymer is effectively improved, a foundation is laid for the biological imaging field, the fluorescence intensity of the prepared fluorescent material for the change of metal ions, pH, polar solvents and reducing agents is changed, and the fluorescent material has a multi-stimulus response characteristic.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a schematic diagram of the synthesis of hyperbranched boron-phosphorus-silicon terpolymers according to the invention.
FIG. 2 is a GPC curve of hyperbranched boron phosphorus silicon ternary polymer obtained in example 1 of the present invention.
FIG. 3 is a fluorescence spectrum of hyperbranched boron-phosphorus-silicon ternary polymer obtained in example 1 of the invention.
FIG. 4 is a graph showing the morphological characteristics of bacteria when the antibacterial coating obtained in example 1 of the present invention is co-cultured with bacteria for 0 h.
FIG. 5 is a graph showing the morphological characteristics of bacteria when the antibacterial coating obtained in example 1 of the present invention is co-cultured with bacteria for 2 hours.
FIG. 6 is a graph showing the morphological characteristics of bacteria in 4 hours of co-cultivation of the antibacterial coating obtained in example 1 of the present invention with bacteria.
FIG. 7 is a graph showing the morphological characteristics of bacteria when the antibacterial coating obtained in example 1 of the present invention is co-cultured with bacteria for 8 hours.
FIG. 8 is a graph showing the morphological characteristics of bacteria when the antibacterial coating obtained in example 1 of the present invention is co-cultured with bacteria for 12 hours.
Detailed Description
FIG. 1 is a schematic diagram of the synthesis of the hyperbranched boron-phosphorus-silicon terpolymer of the invention, and from FIG. 1, it can be seen that boric acid, diethyl phosphate and diethoxysilane react by transesterification polycondensation to produce the hyperbranched boron-phosphorus-silicon terpolymer.
Example 1
The embodiment comprises the following steps:
step one, mixing 1mol of boric acid, 0.5mol of diethyl allylphosphate and 0.5mol of 3-aminopropyl methyldiethoxysilane to obtain a raw material;
heating and dissolving the raw materials obtained in the first step under stirring, and then distilling to obtain a product; the temperature of the heating dissolution is 90 ℃, the temperature of the distillation is 150 ℃ and the time is 12 hours, the distillation is carried out under the nitrogen atmosphere, the product is subjected to vacuum pumping treatment for 30 minutes, and the heating dissolution and the distillation are carried out under the oil bath condition;
dialyzing the product obtained in the step two, and sequentially performing rotary evaporation and vacuum drying to obtain the hyperbranched boron-phosphorus-silicon ternary polymer; the molecular weight of the dialysis bag is 5000, and the dialysis process is as follows: adding absolute ethyl alcohol into the product, stirring and dissolving, and then adding the product into a dialysis bag for dialysis for 48 hours; the temperature of the rotary evaporation is 45 ℃, the temperature of the vacuum drying is 60 ℃ and the time is 6 hours;
step four, adding the hyperbranched boron-phosphorus-silicon ternary polymer obtained in the step three into a high-pressure airless sprayer to spray the surface of the implant, and obtaining a photodynamic antibacterial coating on the surface of the implant; the implant is made of titanium, and is sequentially cleaned by acetone, absolute ethyl alcohol and deionized water before being used, and then vacuum-dried; the spraying process comprises the following steps: adding the hyperbranched boron-phosphorus-silicon ternary polymer into a preparation tank of a high-pressure airless sprayer under the condition of low-speed stirring, stirring and dispersing, and then performing pressurized spraying under medium-speed stirring; the low-speed stirring rotating speed is 300r/min, the stirring dispersing rotating speed is 900r/min, the stirring dispersing time is 25min, the medium-speed stirring rotating speed is 700r/min, the pressurizing pressure is 9.8MPa, the spraying adopts a nozzle with olive-shaped holes, and the distance between the nozzle and an implant is 10cm.
The thickness of the photodynamic antimicrobial coating obtained on the implant surface in this example was 500nm as measured.
Fig. 2 is a GPC curve of the hyperbranched boron phosphorus silicon ternary polymer obtained in this example, and from the data obtained in fig. 2, the number average molecular weight mw=9570 and the weight average molecular weight mn=9740 of the hyperbranched boron phosphorus silicon ternary polymer obtained in this example can be calculated, which illustrates that the hyperbranched boron phosphorus silicon ternary polymer obtained in this example is a high molecular material.
Fig. 3 is a fluorescence spectrum of the hyperbranched boron phosphorus silicon ternary polymer obtained in this example, and as can be seen from fig. 3, the excitation wavelength ex=430 nm and the emission wavelength em=498 nm illustrate that the hyperbranched boron phosphorus silicon ternary polymer obtained in this example is a fluorescent material.
FIG. 4 is a graph showing the morphological characteristics of bacteria in 0h co-culture with the antibacterial coating obtained in this example, and it can be seen from FIG. 4 that the bacteria have full spheres and complete structures.
FIG. 5 is a graph showing the morphological characteristics of bacteria in 2 hours of co-culture of the antibacterial coating and bacteria obtained in this example, and it can be seen from FIG. 5 that the bacterial cell membrane exhibits a wrinkled and recessed morphology.
FIG. 6 is a graph showing the morphological characteristics of bacteria in 4 hours of co-culture of the antibacterial coating and bacteria obtained in the present example, and it can be seen from FIG. 6 that a few membrane structures of bacterial cell membranes are broken and deformed.
FIG. 7 is a graph showing the morphological characteristics of bacteria in 8h of co-culture of the antibacterial coating and bacteria obtained in this example, and it can be seen from FIG. 7 that the large-area membrane structure of the bacterial cell membrane is broken and deformed.
FIG. 8 is a graph showing the morphological characteristics of bacteria in the case of co-cultivation of the antibacterial coating obtained in this example with the bacteria for 12 hours, and it can be seen from FIG. 8 that the bacteria are all killed and the membrane structure is broken and deformed.
As can be seen from fig. 4 to 8, the antibacterial coating obtained in this example has an excellent antibacterial effect.
Example 2
The embodiment comprises the following steps:
step one, mixing 1.5mol of boric acid, 0.75mol of diethyl allylphosphate and 0.75mol of (3-glycidoxy) methyldiethoxysilane to obtain a raw material;
heating and dissolving the raw materials obtained in the first step under stirring, and then distilling to obtain a product; the temperature of the heating dissolution is 100 ℃, the temperature of the distillation is 160 ℃, the time is 6 hours, the distillation is carried out under the nitrogen atmosphere, the product is vacuumized for 40 minutes, and the heating dissolution and the distillation are carried out under the oil bath condition;
dialyzing the product obtained in the step two, and sequentially performing rotary evaporation and vacuum drying to obtain the hyperbranched boron-phosphorus-silicon ternary polymer; the molecular weight of the dialysis bag is 3000, and the dialysis process is as follows: adding absolute ethyl alcohol into the product, stirring and dissolving, and then adding the product into a dialysis bag for dialysis for 36 hours; the temperature of the rotary evaporation is 50 ℃, the temperature of the vacuum drying is 80 ℃ and the time is 12 hours;
step four, adding the hyperbranched boron-phosphorus-silicon ternary polymer obtained in the step three into a high-pressure airless sprayer to spray the surface of the implant, and obtaining a photodynamic antibacterial coating on the surface of the implant; the implant is made of titanium, and is sequentially cleaned by acetone, absolute ethyl alcohol and deionized water before being used, and then vacuum-dried; the spraying process comprises the following steps: adding the hyperbranched boron-phosphorus-silicon ternary polymer into a preparation tank of a high-pressure airless sprayer under the condition of low-speed stirring, stirring and dispersing, and then performing pressurized spraying under medium-speed stirring; the low-speed stirring rotating speed is 400r/min, the stirring dispersing rotating speed is 800r/min, the stirring dispersing time is 30min, the medium-speed stirring rotating speed is 600r/min, the pressurizing pressure is 15.2MPa, the spraying adopts a nozzle with olive-shaped holes, and the distance between the nozzle and an implant is 20cm.
According to detection, the thickness of the photodynamic antibacterial coating obtained on the surface of the implant in the embodiment is 200nm, and the antibacterial coating obtained in the embodiment has excellent antibacterial effect.
Example 3
The embodiment comprises the following steps:
step one, mixing 2mol of boric acid, 1mol of diethyl (3-aminopropyl) phosphate and 1mol of (3-glycidoxy) methyldiethoxysilane to obtain a raw material;
heating and dissolving the raw materials obtained in the first step under stirring, and then distilling to obtain a product; the temperature of the heating dissolution is 80 ℃, the temperature of the distillation is 140 ℃ and the time is 24 hours, the distillation is carried out under the nitrogen atmosphere, the product is subjected to vacuum pumping treatment for 60 minutes, and the heating dissolution and the distillation are carried out under the oil bath condition;
dialyzing the product obtained in the step two, and sequentially performing rotary evaporation and vacuum drying to obtain the hyperbranched boron-phosphorus-silicon ternary polymer; the molecular weight of the dialysis bag is 4000, and the dialysis process is as follows: adding absolute ethyl alcohol into the product, stirring and dissolving, and then adding the product into a dialysis bag for dialysis for 24 hours; the temperature of the rotary evaporation is 60 ℃, the temperature of the vacuum drying is 100 ℃, and the time is 8 hours;
step four, adding the hyperbranched boron-phosphorus-silicon ternary polymer obtained in the step three into a high-pressure airless sprayer to spray the surface of the implant, and obtaining a photodynamic antibacterial coating on the surface of the implant; the implant is made of titanium, and is sequentially cleaned by acetone, absolute ethyl alcohol and deionized water before being used, and then vacuum-dried; the spraying process comprises the following steps: adding the hyperbranched boron-phosphorus-silicon ternary polymer into a preparation tank of a high-pressure airless sprayer under the condition of low-speed stirring, stirring and dispersing, and then performing pressurized spraying under medium-speed stirring; the low-speed stirring rotating speed is 200r/min, the stirring dispersing rotating speed is 1000r/min, the stirring dispersing time is 20min, the medium-speed stirring rotating speed is 800r/min, the pressurizing pressure is 29.4MPa, the spraying adopts a nozzle with olive-shaped holes, and the distance between the nozzle and an implant is 50cm.
According to detection, the thickness of the photodynamic antibacterial coating obtained on the surface of the implant in the embodiment is 1400nm, and the antibacterial coating obtained in the embodiment has excellent antibacterial effect.
Example 4
The embodiment comprises the following steps:
step one, mixing 1mol of boric acid, 1mol of diethyl phosphate and 1mol of diethoxysilane to obtain a raw material;
heating and dissolving the raw materials obtained in the first step under stirring, and then distilling to obtain a product; the temperature of the heating dissolution is 90 ℃, the temperature of the distillation is 150 ℃ and the time is 12 hours, the distillation is carried out under the nitrogen atmosphere, the product is subjected to vacuum pumping treatment for 30 minutes, and the heating dissolution and the distillation are carried out under the oil bath condition;
dialyzing the product obtained in the step two, and sequentially performing rotary evaporation and vacuum drying to obtain the hyperbranched boron-phosphorus-silicon ternary polymer; the molecular weight of the dialysis bag is 5000, and the dialysis process is as follows: adding absolute ethyl alcohol into the product, stirring and dissolving, and then adding the product into a dialysis bag for dialysis for 48 hours; the temperature of the rotary evaporation is 45 ℃, the temperature of the vacuum drying is 60 ℃ and the time is 6 hours;
step four, adding the hyperbranched boron-phosphorus-silicon ternary polymer obtained in the step three into a high-pressure airless sprayer to spray the surface of the implant, and obtaining a photodynamic antibacterial coating on the surface of the implant; the implant is made of titanium, and is sequentially cleaned by acetone, absolute ethyl alcohol and deionized water before being used, and then vacuum-dried; the spraying process comprises the following steps: adding the hyperbranched boron-phosphorus-silicon ternary polymer into a preparation tank of a high-pressure airless sprayer under the condition of low-speed stirring, stirring and dispersing, and then performing pressurized spraying under medium-speed stirring; the low-speed stirring rotating speed is 300r/min, the stirring dispersing rotating speed is 900r/min, the stirring dispersing time is 25min, the medium-speed stirring rotating speed is 700r/min, the pressurizing pressure is 13.4MPa, the spraying adopts a nozzle with olive-shaped holes, and the distance between the nozzle and an implant is 30cm.
The thickness of the photodynamic antimicrobial coating obtained on the implant surface in this example was measured to be 600nm.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (7)
1. The photodynamic antibacterial coating for the surface of the implant is characterized in that the antibacterial coating is a hyperbranched boron phosphorus silicon terpolymer prepared by taking boric acid, diethyl phosphate compounds and diethoxysilane compounds as raw materials in a molar ratio of 2:1:1 or 1:1:1; the diethyl phosphate compound is diethyl phosphate, (3-aminopropyl) diethyl phosphate or allyl diethyl phosphate; the diethoxy silane compound is diethoxy silane, (3-glycidoxy) methyl diethoxy silane or 3-aminopropyl methyl diethoxy silane.
2. A method of preparing a photodynamic antimicrobial coating for an implant surface as claimed in claim 1, characterised in that the method comprises the steps of:
step one, mixing boric acid, diethyl phosphate compounds and diethoxysilane compounds to obtain raw materials;
heating and dissolving the raw materials obtained in the first step under stirring, and then distilling to obtain a product;
dialyzing the product obtained in the step two, and sequentially performing rotary evaporation and vacuum drying to obtain the hyperbranched boron-phosphorus-silicon ternary polymer;
and step four, adding the hyperbranched boron-phosphorus-silicon ternary polymer obtained in the step three into a high-pressure airless sprayer to spray the surface of the implant, and obtaining the photodynamic antibacterial coating on the surface of the implant.
3. The method according to claim 2, wherein the temperature of the heating dissolution in the second step is 80 ℃ to 100 ℃, the temperature of the distillation is 140 ℃ to 160 ℃ and the time is 6 hours to 24 hours, the distillation is performed under a nitrogen atmosphere, the product is subjected to vacuum pumping treatment for 30 minutes to 60 minutes, and the heating dissolution and the distillation are performed under an oil bath condition.
4. The method according to claim 2, wherein the dialysis procedure in step three is: adding absolute ethyl alcohol into the product, stirring and dissolving, and then adding the product into a dialysis bag for dialysis for 24-48 hours, wherein the molecular weight of the dialysis bag is 3000-5000; the temperature of rotary evaporation is 45-60 ℃, the temperature of vacuum drying is 60-100 ℃ and the time is 6-12 h.
5. The method of claim 2, wherein in step four the implant is titanium, and the implant is washed sequentially with acetone, absolute ethanol, and deionized water before use, and then vacuum dried.
6. The method according to claim 2, wherein the spraying in the fourth step is performed by: adding the hyperbranched boron-phosphorus-silicon ternary polymer into a preparation tank of a high-pressure airless sprayer under the condition of low-speed stirring, stirring and dispersing, and then performing pressurized spraying under medium-speed stirring; the low-speed stirring rotating speed is 200-400 r/min, the stirring dispersing rotating speed is 800-1000 r/min, the stirring dispersing rotating speed is 20-30 min, the medium-speed stirring rotating speed is 600-800 r/min, the pressurizing pressure is 9.8-29.4 MPa, the spraying adopts a nozzle with olive-shaped holes, and the distance between the nozzle and an implant is 10-50 cm.
7. The method of claim 2, wherein the thickness of the photodynamic antimicrobial coating in step four is 200nm to 1400nm.
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| CN106636211A (en) * | 2016-12-23 | 2017-05-10 | 北京化工大学 | Method for constructing hyperbranched gene vector with antibacterial performance on basis of ring-opening reaction |
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| US6844028B2 (en) * | 2001-06-26 | 2005-01-18 | Accelr8 Technology Corporation | Functional surface coating |
| DK3194508T3 (en) * | 2014-09-16 | 2020-11-30 | Zorg Innovaties Nederland B V | PROCEDURE FOR PROVIDING A SUBSTRATE WITH AN ANTIMICROBIAL COATING AND COATED SUBSTRATES THAT CAN BE OBTAINED |
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| CN106636211A (en) * | 2016-12-23 | 2017-05-10 | 北京化工大学 | Method for constructing hyperbranched gene vector with antibacterial performance on basis of ring-opening reaction |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis and characterization of surface-active antimicrobial hyperbranched polyurethane coatings based on oleo-ethers of boric acid;Younes Ahmadi et al.;《Arabian Journal of Chemistry》;第13卷(第1期);第2689-2701页 * |
| 生物可降解超支化聚合物的研究进展;黄玉等;《高分子学报》(第2期);第245-254页 * |
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