CN114129777A - Preparation and application of photoresponse composite nano coating - Google Patents
Preparation and application of photoresponse composite nano coating Download PDFInfo
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- CN114129777A CN114129777A CN202010916761.7A CN202010916761A CN114129777A CN 114129777 A CN114129777 A CN 114129777A CN 202010916761 A CN202010916761 A CN 202010916761A CN 114129777 A CN114129777 A CN 114129777A
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/082—Inorganic materials
- A61L31/086—Phosphorus-containing materials, e.g. apatite
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- A—HUMAN NECESSITIES
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/16—Biologically active materials, e.g. therapeutic substances
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Abstract
The invention discloses preparation and application of a photoresponse nano-coating. The composite nano coating has good biocompatibility, high safety and strong antibacterial performance, can release active oxygen under near infrared light, and can be applied to the surface of a medical implant.
Description
Technical Field
The invention belongs to the technical field of biomedical material engineering, and particularly relates to preparation and application of a photoresponse composite nano coating.
Background
At present, the main mode of combating bacterial infections is by antibiotic treatment, however, in recent years the development of new antimicrobial materials has become of particular importance due to the emergence of many drug-resistant bacteria, such as carbapenem-resistant enterobacteriaceae and methicillin-resistant staphylococcus aureus, due to the increased tolerance of the bacteria.
Phototherapy has received increasing attention because it does not lead to the development of homologous drug resistance, and is increasingly used as an alternative to antibiotics for antibacterial therapy. Generally, photodynamic therapy (PDT) and photothermal therapy (PTT) are used for tissue disinfection due to their permeability, controllability and excellent antibacterial activity. The photodynamic therapy reacts free photo-generated electrons generated by photocatalysis with oxygen in the air to generate Reactive Oxygen Species (ROS), such as OH,1o2 and. O2 -The active oxygen and membrane protein or phospholipid bilayer on the surface of the bacteria are utilized to play an antibacterial role; while photothermal therapy (PTT) converts light energy absorbed by a material into heat energy, thereby affecting the synthesis of bacterial proteins and RNA/DNA, and the activity of Adenosine Triphosphate (ATP) and membrane structures. By combining the two, phototherapy can achieve a higher efficiency of rapid disinfection.
However, the current photodynamic photothermal antibacterial coating has poor biocompatibility, can generate Phototherapy Tissue Injury (PTI) on normal tissues in the antibacterial process, and generates certain toxic and side effects on blood vessels in the tissues while sterilizing, so that the traditional phototherapy sterilization means is modified.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a photoresponse composite nano-coating, and the composite nano-coating has good biocompatibility, strong antibacterial performance and high safety.
It is another object of the present invention to provide a use of a photo-responsive composite nanocoating on the surface of a medical implant.
The invention is realized by the following technical scheme:
a preparation method of a photoresponse composite nano-coating comprises the following steps:
step 1) preparation of hydroxyapatite/graphene oxide: 0.4 to 0.6mol/L of Ca (NO)3)2·4H2O water solution and 0.2-0.4 mol/L (NH)4)2HPO4The aqueous solution was mixed with Ca: p is 1: 1.6-1: 1.7 to obtain a first solution; adjusting the pH value of the first solution to 7-9; placing the first solution with the pH value of 7-9 in a reactor to react for 10-13 h at 120-150 ℃, centrifugally separating the obtained reaction product, washing the centrifuged precipitate with deionized water, and calcining after freeze drying to obtain hydroxyapatite powder; mixing the hydroxyapatite powder with a graphene oxide solution to obtain a second solution, wherein the mass concentration of hydroxyapatite in the second solution is 0.1-0.4 g/mL, the second solution is subjected to ultrasonic treatment for 20-30 hours, preferably 21-26 hours, and the hydroxyapatite is loaded on the graphene oxide to obtain hydroxyapatite/graphene oxide;
step 2) synthesis of nitrogen-doped carbon quantum dots: dissolving citric acid monohydrate and glycine in water to obtain a third solution, wherein the mass concentration of the citric acid monohydrate in the third solution is 0.2-0.6 g/mL, and the mass concentration of the glycine is 0.10-0.15 g/mL, preferably 0.11-0.14 g/mL; concentrating the third solution at 60-80 ℃, preferably 63-77 ℃ for 10-13 h under a vacuum condition to obtain viscous mixed slurry, placing the viscous mixed slurry in a reactor to react at 180-220 ℃ for 2-3 h, adjusting the pH value of the obtained reaction product to 9-11 after the reaction is finished, and adding water with the volume of 0.2-1 time of that of the reaction product to obtain a carbon quantum dot solution;
step 3) synthesis of a hydroxyapatite/carbon quantum dot/graphene oxide composite nano coating: polishing the substrate step by step to smooth and remove surface impurities, cleaning, then placing the substrate in acid etching liquid at 50-70 ℃, preferably 54-66 ℃ to etch the surface of the substrate to obtain a substrate with hydroxyl active groups, taking out the substrate, and storing the substrate in deionized water; spin-coating the hydroxyapatite/graphene oxide prepared in the step 1) on the surface of the substrate with the hydroxyl active groups at a speed of 2700-3300 rpm, drying, then placing in a tubular furnace in a nitrogen atmosphere, and curing to bond the hydroxyapatite/graphene oxide on the substrate to obtain a hydroxyapatite/graphene oxide coating constructed on the surface of the substrate; and (3) immersing the hydroxyapatite/graphene oxide coating constructed on the surface of the substrate into the carbon quantum dot solution prepared in the step 2), and carrying out vacuum loading for 20-30 h, preferably 21-27 h to obtain the photoresponse composite nano-coating constructed on the surface of the substrate.
In the technical scheme, in the step 1), 25% ammonia water is adopted to adjust the pH value of the first solution to 8.7; the reactor is a Teflon stainless steel kettle; the concentration of the graphene oxide solution is 1 mg/mL.
In the technical scheme, in the step 1), the centrifugal revolution number of the reaction product is 6000-8000 rpm, and the centrifugal time is 5-10 min; the calcining temperature of the precipitate after centrifugation is 360-440 ℃, and the calcining time is 4.5-5.5 h.
In the above technical scheme, in the step 2), the reactor is a stainless steel reactor lined with polytetrafluoroethylene.
In the technical scheme, in the step 2), 1mol/L of sodium hydroxide is adopted to adjust the pH value of the reaction product.
In the technical scheme, in the step 3), the curing temperature of the hydroxyapatite/graphene oxide is 400-600 ℃, and the curing time is 0.9-1.1 h.
In the above technical scheme, in the step 3), the etching solution is a mixed solution of 36 wt% concentrated hydrochloric acid and water in a volume ratio of 1:1.
In the technical scheme, in the step 3), the substrate is a titanium sheet, the titanium sheet is polished under 240 meshes, 400 meshes, 600 meshes, 800 meshes and 1200 meshes in sequence by using a polishing machine, and then ultrasonic cleaning is performed for 3 times by using deionized water and ethanol respectively in sequence.
The application of the photoresponse composite nano-coating constructed on the surface of the substrate in the technical scheme in the surface of the medical implant.
The photoresponse composite nano-coating prepared in the technical scheme.
A photoresponsive composite nanocoating, characterized by: the photoresponse composite nano-coating is an antibacterial nano-coating formed by combining hydroxyapatite, nitrogen-doped graphene quantum dots and graphene oxide through electrostatic interaction.
The invention has the advantages and beneficial effects that:
1. the photoresponse composite nano material prepared on the surface of the substrate utilizes the photoresponse of the photoresponse composite nano material to light, and generates active oxygen capable of killing bacteria under the irradiation of near infrared light (808nm), so that the coating has excellent antibacterial performance.
2. The hydroxyapatite is added into the composite nano material, and the hydroxyapatite can provide a calcium ion source, so that the coating has good osteogenesis performance due to good biocompatibility of the hydroxyapatite under the condition of no illumination.
3. Due to the penetrability of near infrared light, the body can be quickly sterilized by selective illumination, and can be sterilized by illumination when infection does not occur. Therefore, the photoresponse composite nano-coating constructed on the surface of the substrate prepared by the method can be prepared on the surface of a medical implant by a simple method, and has the advantages of low product cost, low implementation difficulty, simple preparation method and good medical application prospect.
4. Hydroxyapatite is a traditional bioactive material that can be used as a coating for implants due to its good thermal stability, biodegradability and osteogenesis. According to the invention, hydroxyapatite is compounded into nitrogen-doped carbon dots (NCD) and Graphene Oxide (GO), so that the overall biocompatibility of the coating can be improved, meanwhile, the photocatalytic performance of the NCD and GO can be enhanced, and the sterilization efficiency is improved. Compared with NCD and GO which are not compounded with hydroxyl phosphorus lime, photogenerated electrons excited by the latter under illumination are basically completely compounded with holes, and the photogenerated electrons cannot be used for photodynamic antibiosis. Meanwhile, as the hydroxyapatite has good biocompatibility, the biocompatibility of the hydroxyapatite can be improved after the hydroxyapatite is compounded with NCD and GO.
5. The photoresponse composite nano-coating constructed on the surface of the substrate combines photodynamic therapy (PDT) and photothermal therapy (PTT) for application, and realizes rapid and efficient sterilization through multiple mechanisms of bacteriostasis.
Drawings
Fig. 1 is an SEM image of the photo-responsive composite nanocoating of example 1.
Fig. 2 is an XRD pattern of the photo-responsive composite nano-coating constructed on the surface of the titanium alloy of example 1.
Fig. 3 is a graph comparing the current of the photo-responsive composite nanocoating of example 1.
FIG. 4 is a photo-thermal contrast spectrum of a photo-responsive composite nanocoating constructed on the surface of the titanium alloy of example 1.
FIG. 5 is a graph comparing the antibacterial performance of the photo-responsive composite nano-coating constructed on the surface of the titanium alloy in example 1 against Staphylococcus aureus.
FIG. 6 is a graph comparing osteogenic properties of photo-responsive composite nanocoatings constructed on the surface of the titanium alloy of example 1;
for a person skilled in the art, other relevant figures can be obtained from the above figures without inventive effort.
Detailed Description
In order to make the technical solution of the present invention better understood, the technical solution of the present invention is further described below with reference to specific examples.
Example one
A preparation method of a photoresponse composite nano-coating constructed on the surface of a titanium alloy comprises the following steps:
1) preparing a hydroxyapatite/graphene oxide coating: 0.5mol/L of Ca (NO)3)2·4H2O aqueous solution and 0.3mol/L (NH)4)2HPO4The aqueous solution was mixed with Ca: p is 1: 1.67 molar ratio to obtain a first solution; adjusting the pH value of the first solution to 8.7 by using 25% ammonia water, placing the first solution with the pH value of 8.7 in a Teflon stainless steel kettle for reaction at 130 ℃ for 12h, centrifuging the obtained reaction product at the rotating speed of 6000rpm for 10min, washing the centrifuged precipitate for 3 times by using deionized water, freeze-drying at-40 ℃ for 12h, taking out, and calcining at 400 ℃ for 5h to obtain hydroxyapatite powder; mixing 1g of hydroxyapatite powder with 5mL of graphene oxide solution (1mg/mL) to obtain a second solution, and carrying out ultrasonic treatment on the second solution for 24h to load hydroxyapatite on the second solutionOxidizing the graphene to obtain hydroxyapatite/graphene oxide;
2) and (3) synthesizing nitrogen-doped carbon quantum dots: dissolving 2g of citric acid monohydrate and 0.62g of glycine in 5mL of water to obtain a third solution; concentrating the third solution at 70 ℃ in vacuum for 12 hours to obtain viscous mixed slurry, placing the viscous mixed slurry in a stainless steel reactor of a polytetrafluoroethylene tank to react for 3 hours at 200 ℃, adjusting the pH value of the obtained reaction product to 10 by using 1mol/L sodium hydroxide after the reaction is finished, and adding water with the volume of 0.2 of the reaction product to obtain a carbon quantum dot solution;
3) synthesizing a hydroxyapatite/carbon quantum dot/graphene oxide composite nano coating: polishing titanium sheets under 240 meshes, 400 meshes, 600 meshes, 800 meshes and 1200 meshes in sequence by using a polishing machine, and ultrasonically cleaning the polished titanium sheets for 3 times by using deionized water and ethanol respectively in sequence; concentrated hydrochloric acid and water were mixed at a ratio of 1:1 to obtain acid etching solution, placing the polished titanium sheet in the acid etching solution at 60 ℃ for 45min, and taking out to obtain the titanium sheet with the surface provided with hydroxyl active groups; coating the hydroxyapatite/graphene oxide prepared in the step 1) on the surface of the titanium sheet with the hydroxyl active groups on the surface in a spinning mode at the speed of 2700rpm, drying, then placing the titanium sheet in a tube furnace in a nitrogen atmosphere, and curing for 1 hour at the temperature of 500 ℃ to adhere the hydroxyapatite/graphene oxide to the titanium sheet to obtain a hydroxyapatite/graphene oxide coating constructed on the surface of the titanium alloy; immersing the hydroxyapatite/graphene oxide coating constructed on the surface of the titanium alloy into the carbon quantum dot solution prepared in the step 2), and carrying out vacuum loading for 24 hours to obtain the photoresponse composite nano coating constructed on the surface of the titanium alloy.
1) SEM experiment of photoresponse composite nano coating
The photoresponse composite nano-coating prepared in the example 1 was subjected to gold spraying for 120s by a gold spraying instrument, taken out, and placed on a sample stage of an SEM electron microscope for observation, and the result is shown in FIG. 1. According to the figure 1, the middle flaky layer is Graphene Oxide (GO) which presents a lamellar structure distribution, the long particles with larger particles are hydroxyapatite (Hap) which is uniformly distributed on the surface and the periphery of the graphene oxide, and the tiny bright white round particles are carbon quantum dots (NCDs) which are uniformly distributed on the surfaces of the graphene oxide and the graphene oxide, so that the hydroxyapatite, the graphene oxide film and the carbon quantum dots are successfully loaded on the surface of the titanium alloy.
2) XRD experiment of photoresponse composite nano coating constructed on titanium alloy surface
The photoresponse composite nano-coating constructed on the surface of the titanium alloy prepared in the example 1 is washed by absolute ethyl alcohol for 2 times, and then is placed on an XRD sample table, the diffraction angle is 5-60 degrees, the speed is 10 degrees/min, and the result is shown in figure 2. As can be seen from fig. 2, peaks of titanium metal, hydroxyapatite, and graphene oxide/carbon quantum dots simultaneously appear in the photoresponse composite nano-coating constructed on the surface of the titanium alloy, which indicates that the photoresponse composite nano-coating constructed on the surface of the titanium alloy has been successfully prepared.
3) Photoelectric experiment of photoresponse composite nano coating
The photoresponse composite nano-coating prepared in the example 1 is clamped on a working electrode of an electrochemical workstation, a standard electrode is connected at the same time, the electrolyte is 1M saturated sodium sulfate solution, then a laser machine (808nm) is aligned to the photoresponse composite nano-coating, the on/off operation of the laser machine is carried out every 20s, the current value of the workstation is recorded, and the time and the current value are used as coordinates for drawing, so that the result is shown in figure 3. As can be seen from fig. 3, compared to a single graphene and carbon quantum dot sample, the photoresponsive composite nano-coating has a higher current variation value, which indicates that it has better photodynamic performance, while the graphene and carbon quantum dot sample has a smaller current value, which indicates that the photodynamic performance of unmodified graphene and carbon quantum dot is weaker and is not suitable for photodynamic antibacterial therapy.
4) Photothermal experiment of photoresponse composite nano coating constructed on titanium alloy surface
Respectively placing the photoresponse composite nano-coating (GO/NCDs/Hap/Ti) constructed on the surface of the titanium alloy prepared in the embodiment 1, the graphene oxide/carbon quantum dot composite nano-coating (GO/NCDs/Ti) constructed on the surface of the titanium alloy, the graphene oxide/hydroxyapatite composite nano-coating (GO/Hap/Ti) constructed on the surface of the titanium alloy, the graphene oxide nano-coating (GO/Ti) constructed on the surface of the titanium alloy and the titanium alloy (Ti) at the bottom of a 96-pore plate,then 200. mu.L of PBS buffer was added thereto at a power of 0.5W/cm2The laser irradiates the 96-well plate, the thermal imager is used for recording the temperature, the temperature change of each sample in the 96-well plate is recorded every 1min, the laser is closed after the irradiation for 10min, the time and the temperature are taken as coordinates for drawing, and the result is shown in figure 4. As can be seen from fig. 4, the temperature of the photoresponsive composite nano-coating constructed on the surface of the titanium alloy is more remarkably changed with time than that of the composite coating constructed on the surface of the titanium alloy and other titanium alloys, which indicates that the photoresponsive composite nano-coating has the best photo-thermal performance.
5) Antibacterial experiment of photoresponse composite nano coating constructed on titanium alloy surface
Respectively adding a photoresponse composite nano coating (GO/NCDs/Hap/Ti) constructed on the surface of a titanium alloy, a graphene oxide/carbon quantum dot composite nano coating (GO/NCDs/Ti) constructed on the surface of the titanium alloy, a graphene oxide/hydroxyapatite composite nano coating (GO/Hap/Ti) constructed on the surface of the titanium alloy, a graphene oxide nano coating (GO/Ti) constructed on the surface of the titanium alloy and titanium alloy (Ti) samples into a 96-pore plate, wherein each group of samples is provided with 3 composite pores, and adding 200 mu L of a sample pore with the order of magnitude of 10 into each sample pore7The bacterial liquid of the staphylococcus aureus of CFU/mL, wherein half of the pore plate is subjected to Light treatment for 15 minutes (Light), and the laser power is 0.5W/cm2(ii) a The other half of the plates were dark treated for 15min (Dark). After the treatment is finished, the liquid in the pore plate is further diluted until the concentration of the staphylococcus aureus is 105CFU/mL, 20. mu.L was taken out onto an agar plate, and then cultured in a bacterial incubator at 37 ℃ for 24 hours, the number of colonies was counted, and the antibacterial efficiency was calculated, and the results are shown in FIG. 5. As can be seen from fig. 5, after the light irradiation treatment, the photoresponse composite nano-coating layer set constructed on the surface of the titanium alloy has the least colony count and the highest antibacterial efficiency, while the antibacterial effect of other samples is poor, which indicates that the grating antibacterial performance of the unmodified graphene and carbon quantum dots is weak, but the intermediate component also has a certain antibacterial property due to the photothermal effect of the titanium alloy surface coating. In the dark condition, the samples except for the pure titanium alloy have smaller antibacterial efficiency due to the self-antibacterial property of the graphene, and the antibacterial effect of the composite coatings is shownFrom synergistic effects of photodynamic and photothermal effects.
6) Osteogenesis experiments
Respectively incubating osteoblasts MC3T3-E1 with a graphene oxide coating (GO/Ti) constructed on the surface of a titanium alloy, a graphene oxide/hydroxyapatite composite coating (GO/Hap/Ti) constructed on the surface of the titanium alloy, a graphene oxide/carbon quantum dot composite coating (GO/NCDs/Ti) constructed on the surface of the titanium alloy, a light-responsive composite nano coating (GO/NCDs/Hap/Ti) constructed on the surface of the titanium alloy and a titanium alloy (Ti) in a carbon dioxide cell incubator for 1 week, replacing a cell culture medium every 2 days, and respectively carrying out light 15min (light) treatment or dark 15min (dark) treatment. After the culture is finished, all groups of cell sap are taken out, alkaline phosphatase (ALP) detection is carried out on adherent cells on the surface of the coating, the result is shown in figure 6, and according to the figure 6, the osteogenesis performance of the coating is obviously improved after hydroxyapatite is added into each sample under the light condition and the dark condition.
Example two
A preparation method of a photoresponse composite nano-coating constructed on the surface of a titanium alloy comprises the following steps:
1) preparing a hydroxyapatite/graphene oxide coating: 0.5mol/L of Ca (NO)3)2·4H2O aqueous solution and 0.3mol/L (NH)4)2HPO4The aqueous solution was mixed with Ca: p is 1: 1.60 to obtain a first solution; adjusting the pH value of the first solution to 7 by using 25% ammonia water, and placing the first solution with the pH value of 7 in a Teflon stainless steel kettle for reaction at 140 ℃ for 11 h; centrifuging the obtained reaction product at 8000rpm for 7min, washing the centrifuged precipitate with deionized water for 3 times, freeze-drying at-40 deg.C for 12h, taking out, and calcining at 370 deg.C for 5.5h to obtain hydroxyapatite powder; mixing 1g of hydroxyapatite powder with 4mL of graphene oxide solution (1mg/mL) to obtain a second solution, and carrying out ultrasonic treatment for 22 hours to load hydroxyapatite on graphene oxide to obtain hydroxyapatite/graphene oxide;
2) and (3) synthesizing nitrogen-doped carbon quantum dots: dissolving 1g of citric acid monohydrate and 0.55g of glycine in 5mL of water to obtain a third solution; concentrating the third solution at 75 ℃ in vacuum for 11h to obtain viscous mixed slurry; placing the viscous mixed slurry in a stainless steel reactor of a polytetrafluoroethylene tank to react for 3 hours at 190 ℃, adjusting the pH value of the obtained reaction product to 10 by using 1mol/L sodium hydroxide after the reaction is finished, and adding water with the volume of 0.5 time that of the reaction product to obtain a carbon quantum dot solution;
3) synthesizing a hydroxyapatite/carbon quantum dot/graphene oxide composite nano coating: polishing titanium sheets under 240 meshes, 400 meshes, 600 meshes, 800 meshes and 1200 meshes in sequence by using a polishing machine, and then respectively ultrasonically cleaning for 3 times by using deionized water and ethanol in sequence; concentrated hydrochloric acid and water were mixed at a ratio of 1:1 to obtain acid etching solution, placing the polished titanium sheet in the acid etching solution at 55 ℃ for 50min, and taking out to obtain the titanium sheet with active groups on the surface; coating the hydroxyapatite/graphene oxide prepared in the step 1) on the surface of the titanium sheet with active groups on the surface in a spin coating manner at the speed of 3000rpm, drying, then placing the titanium sheet in a tubular furnace in a nitrogen atmosphere, and curing for 1.1h at the temperature of 450 ℃ to adhere the hydroxyapatite/graphene oxide to the titanium sheet, so as to obtain the hydroxyapatite/graphene oxide constructed on the surface of the titanium alloy; immersing the hydroxyapatite/graphene oxide constructed on the surface of the titanium alloy into the carbon quantum dot solution prepared in the step 2), and loading for 21 hours in vacuum to obtain the photoresponse composite nano-coating constructed on the surface of the titanium alloy.
EXAMPLE III
A preparation method of a photoresponse composite nano-coating constructed on the surface of a titanium alloy comprises the following steps:
1) preparing a hydroxyapatite/graphene oxide coating: 0.5mol/L of Ca (NO)3)2·4H2O aqueous solution and 0.3mol/L (NH)4)2HPO4The aqueous solution was mixed with Ca: p is 1: 1.7 to obtain a first solution; adjusting the pH value of the first solution to 9 by using 25% ammonia water, and placing the first solution with the pH value of 9 in a Teflon stainless steel kettle for reaction at 150 ℃ for 10 h; centrifuging the obtained reaction product at the rotating speed of 6000rpm for 10min, washing the centrifuged precipitate with deionized water for 3 times, freeze-drying at-40 ℃ for 12h, taking out, and calcining at 440 ℃ for 4.6h to obtain hydroxyapatite powder; taking 1g of hydroxyapatite powder and 3mL of oxygenMixing graphene solution (1mg/mL) to obtain a second solution, and carrying out ultrasonic treatment for 24 hours to load hydroxyapatite on graphene oxide to obtain hydroxyapatite/graphene oxide;
2) and (3) synthesizing nitrogen-doped carbon quantum dots: dissolving 3g of citric acid monohydrate and 0.7g of glycine in 5mL of water to obtain a third solution; concentrating the third solution at 65 ℃ for 13h under vacuum to obtain viscous mixed slurry; placing the viscous mixed slurry in a stainless steel reactor of a polytetrafluoroethylene tank to react for 2 hours at 220 ℃, adjusting the pH value of the obtained reaction product to 10 by using 1mol/L sodium hydroxide after the reaction is finished, and adding water with the volume of 1 time of that of the reaction product to obtain a carbon quantum dot solution;
3) synthesizing a hydroxyapatite/carbon quantum dot/graphene oxide composite nano coating: polishing titanium sheets under 240 meshes, 400 meshes, 600 meshes, 800 meshes and 1200 meshes in sequence by using a polishing machine, and then respectively ultrasonically cleaning for 3 times by using deionized water and ethanol in sequence; concentrated hydrochloric acid and water were mixed at a ratio of 1:1 to obtain acid etching solution, placing the polished titanium sheet in the acid etching solution at 65 ℃ for 60min, and taking out to obtain the titanium sheet with active groups on the surface; coating the hydroxyapatite/graphene oxide prepared in the step 1) on the surface of the titanium sheet with active groups on the surface in a spin coating manner at the speed of 3300rpm, drying, then placing the titanium sheet in a tube furnace in a nitrogen atmosphere, and curing at the temperature of 600 ℃ for 0.9h to adhere the hydroxyapatite/graphene oxide to the titanium sheet, so as to obtain the hydroxyapatite/graphene oxide constructed on the surface of the titanium alloy; and (3) immersing the hydroxyapatite/graphene oxide constructed on the surface of the titanium alloy into the carbon quantum dot solution prepared in the step 2), and loading for 24 hours in vacuum to obtain the photoresponse composite nano-coating constructed on the surface of the titanium alloy.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A preparation method of a photoresponse composite nano coating is characterized by comprising the following steps: the method comprises the following steps:
step 1, preparation of hydroxyapatite/graphene oxide: 0.4 to 0.6mol/L of Ca (NO)3)2·4H2O water solution and 0.2-0.4 mol/L (NH)4)2HPO4The aqueous solution was mixed with Ca: mixing the components in a molar ratio of 1: 1.6-1.7 to obtain a first solution; adjusting the pH value of the first solution to 7-9; placing the first solution into a reactor to react for 10-13 h at 120-150 ℃, carrying out solid-liquid separation on the obtained reaction product, washing the solid precipitate with deionized water, and calcining the solid precipitate after freeze drying to obtain hydroxyapatite powder; mixing the hydroxyapatite powder with a graphene oxide solution to obtain a second solution, wherein the mass concentration of hydroxyapatite in the second solution is 0.1-0.4 g/mL, and carrying out ultrasonic treatment on the second solution for 20-30 hours to load the hydroxyapatite on the graphene oxide to obtain hydroxyapatite/graphene oxide;
step 2, synthesis of nitrogen-doped carbon quantum dots: dissolving citric acid monohydrate and glycine in water to obtain a third solution, wherein the concentration of the citric acid monohydrate in the third solution is 0.2-0.6 g/mL, and the concentration of the glycine is 0.10-0.15 g/mL; evaporating and concentrating the third solution at 60-80 ℃ under a vacuum condition to obtain viscous mixed slurry, placing the viscous mixed slurry in a reactor to react for 2-3 hours at 180-220 ℃, adjusting the pH value of the obtained reaction product to 9-11 after the reaction is finished, and adding water with the volume of 0.2-1 time that of the reaction product to obtain a carbon quantum dot solution;
step 3, synthesis of the hydroxyapatite/carbon quantum dot/graphene oxide composite nano coating: polishing the substrate step by step to smooth and remove surface impurities, cleaning, then placing the substrate in an acid etching solution at 50-70 ℃ to etch the surface of the substrate to obtain a substrate with hydroxyl active groups, taking out the substrate, and storing the substrate in deionized water; coating the hydroxyapatite/graphene oxide prepared in the step 1 on the surface of the substrate with the hydroxyl active groups in a spin coating manner, drying, and then placing the substrate in a nitrogen atmosphere for curing so as to adhere the hydroxyapatite/graphene oxide to the substrate and obtain a hydroxyapatite/graphene oxide coating constructed on the surface of the substrate; and (3) immersing the hydroxyapatite/graphene oxide coating constructed on the surface of the substrate into the carbon quantum dot solution prepared in the step 2), and loading the carbon quantum dot solution for 20-30 h in vacuum to obtain the photoresponse composite nano coating on the surface of the substrate.
2. The method of preparing a photoresponsive composite nanocoating according to claim 1, characterized in that: in step 1, adjusting the pH value of the first solution to 8.7 by using 25% ammonia water; the reactor is a Teflon stainless steel kettle; the concentration of the graphene oxide solution is 1 mg/mL.
3. The method of preparing a photoresponsive composite nanocoating according to claim 1, characterized in that: in the step 1, performing centrifugal solid-liquid separation on the reaction product, wherein the centrifugal revolution is 6000-8000 rpm, and the centrifugal time is 5-10 min; and the calcining temperature of the centrifuged solid precipitate is 360-440 ℃, and the calcining time is 4.5-5.5 h.
4. The method of preparing a photoresponsive composite nanocoating according to claim 1, characterized in that: in step 2, the reactor is a stainless steel reactor lined with polytetrafluoroethylene.
5. The method of preparing a photoresponsive composite nanocoating according to claim 1, characterized in that: in step 2, the pH of the reaction product is adjusted with 1mol/L sodium hydroxide.
6. The method of preparing a photoresponsive composite nanocoating according to claim 1, characterized in that: in the step 3, the curing temperature of the hydroxyapatite/graphene oxide is 400-600 ℃, and the curing time is 0.9-1.1 h.
7. The method of preparing a photoresponsive composite nanocoating according to claim 1, characterized in that: in step 3, the etching solution is a mixed solution of 36 wt% concentrated hydrochloric acid and water in a volume ratio of 1:1.
8. The method of preparing a photoresponsive composite nanocoating according to claim 1, characterized in that: in the step 3), the substrate is a titanium sheet, the titanium sheet is polished under 240 meshes, 400 meshes, 600 meshes, 800 meshes and 1200 meshes in sequence by using a polishing machine, and then ultrasonic cleaning is performed for 3 times by using deionized water and ethanol respectively in sequence.
9. Use of a photo-responsive composite nanocoating according to any one of claims 1 to 8 on the surface of a medical implant.
10. A photoresponsive composite nanocoating, characterized by: the photoresponse composite nano-coating is an antibacterial nano-coating formed by combining hydroxyapatite, nitrogen-doped graphene quantum dots and graphene oxide through electrostatic interaction.
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