CN117959497A - Controllable degradation antibacterial coating with near infrared response, preparation method and application thereof - Google Patents
Controllable degradation antibacterial coating with near infrared response, preparation method and application thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 108
- 239000011248 coating agent Substances 0.000 title claims abstract description 97
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 31
- 230000004044 response Effects 0.000 title claims abstract description 12
- 230000015556 catabolic process Effects 0.000 title claims abstract description 10
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title description 18
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000011777 magnesium Substances 0.000 claims abstract description 31
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 30
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention provides a controllable degradation antibacterial coating with near infrared response, which is prepared by mixing coating dispersion liquid and nano filler to prepare slurry, and then coating and drying the slurry; the coating dispersion liquid is prepared by dissolving a biodegradable material in an organic solvent, wherein the mass-volume ratio of the biodegradable material to the organic solvent is 2-10 w/v%; the nano-filler is in a shell-core structure, wherein the organic polymer is a shell, the photosensitizer is a core, and the mass of the nano-filler is 5% -10% of that of the biodegradable material. The antibacterial coating prepared by the invention is coated on the surface of the magnesium-based material, has antibacterial performance under the near infrared irradiation condition after being dried, and can control the corrosion rate of the magnesium-based material by adjusting the near infrared irradiation condition in the later bone healing period, so as to realize the technical effects of promoting bone healing recovery and avoiding secondary operation extraction.
Description
Technical Field
The invention belongs to the technical field of biomedical functional coatings, and particularly relates to a controllable degradation antibacterial coating with near infrared response, and a preparation method and application thereof.
Background
The biodegradable material can avoid secondary operation, shorten recovery period, and relieve pain of patients, thus becoming one of the research hot spots of medical materials. At present, the biodegradable material mainly comprises a high polymer and a metal material, and compared with the high polymer material, the metal material with better mechanical property is the first choice of the orthopedic implant material. The density and Young modulus of the magnesium-based material are close to those of human bones, so that the stress shielding effect can be effectively relieved, the magnesium-based material has good bearing capacity in the early stage of implantation, bone healing and vascular tissue reconstruction are promoted, and compared with other degradable metals such as zinc matrixes, iron matrixes and the like, the unique biocompatibility and low cytotoxicity of the magnesium matrixes accelerate the adhesion of osteoblasts on the surfaces of the magnesium-based material. At the same time, the alkaline environment generated by local corrosion of magnesium base effectively inhibits bacterial adsorption to avoid bacterial infection, and the advantages make the magnesium base have great potential in bone implant materials.
However, the magnesium matrix has too high corrosion rate, is easy to destroy mechanical properties, is unfavorable for bone healing, has serious hydrogen evolution, is unfavorable for wound healing, and has hidden troubles of bacterial invasion and wound infection. To solve the above problems, the current treatment strategies mainly include the following two methods for improving the corrosion resistance of magnesium substrates and increasing the antibacterial function. (1) antibacterial metal alloying: the addition of strontium chloride particles in a magnesium matrix reported in China patent CN202310204112.8 improves corrosion resistance, and strontium ions released by matrix degradation can promote bone tissue growth; the controllable degradable component gradient Mg Zn Si Gd alloy reported in Chinese patent CN202111241201.7 is prepared by a series of complicated processes such as casting, heat treatment, friction stir, rolling and the like, and the metal doping regulation is complex. In order to improve the antibacterial performance of the controllably degradable magnesium matrix, chinese patent CN201810203593.X reports that nano copper with antibacterial effect synthesized in situ is dispersed in magnesium alloy by a laser selective melting process, and Mg 2 Si and MgO nano reinforced phases are prepared into a high antibacterial performance, and the controllably degradable magnesium matrix implant material, however, nano copper particles are released only to provide short-term antibacterial performance, and cannot meet long-term effective antibacterial performance. (2) The coating is prepared, for example, the micro-arc oxidation self-sealing is realized by adjusting the components of the micro-arc oxidation electrolyte as reported in the specification of CN201210127249.X, the corrosion resistance is improved, the prepared maintenance oxide layer contains calcium and phosphorus elements, and the biocompatibility is improved compared with a metal matrix. However, inorganic coatings have poor biocompatibility, insufficient corrosion resistance, and are challenging to apply in bone implantation.
Disclosure of Invention
In view of this, the present invention provides an antimicrobial coating that does not require complex alloy casting, can be effectively sterilized for a long period of time, and has good biocompatibility.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The coating is prepared by mixing coating dispersion liquid and nano filler to prepare slurry, and then coating and drying the slurry;
the coating dispersion liquid is prepared by dissolving a biodegradable material in an organic solvent, wherein the mass-volume ratio of the biodegradable material to the organic solvent is 2-10 w/v%;
The nano-filler is in a shell-core structure, wherein the organic polymer is a shell, the photosensitizer is a core, and the mass of the nano-filler is 5% -10% of that of the biodegradable material.
Further, the biodegradable material is any one of polylactic acid, polycaprolactone, chitosan, dopamine and polylactic acid-glycolic acid copolymer.
Further, the organic solvent is at least one of dichloromethane, acetone, ethyl acetate, tetrahydrofuran and dimethyl sulfoxide.
Further, the preparation process of the nano-filler comprises the following steps: adding a photosensitizer, a surfactant, a polymer monomer and a polymerization catalyst into deionized water, reacting for 12 hours at normal temperature, washing, centrifuging and drying to obtain the nano filler.
Further, the mass ratio of the photosensitizer to the polymer monomer is 8: (3-7).
Further, the photosensitizer is at least one of CuS and MoS 2,ZnO,TiO2,BiVO4.
Further, the surfactant is any one of polyvinylpyrrolidone and sodium dodecyl sulfate; the polymerization catalyst is any one of ammonium persulfate and ferric chloride.
Further, the polymer monomer is at least one of dopamine, pyrrole and aniline.
The preparation method of the antibacterial coating comprises the following steps: dissolving biodegradable material in organic solvent to obtain coating dispersion, adding nano filler into the coating dispersion, mixing under 200-600W ultrasonic condition for 20-40 min, coating and drying to obtain the antibacterial coating.
The application of the antibacterial coating in bone healing is that the coating is coated on the surface of the magnesium-based material after surface treatment, and the antibacterial coating is formed after drying, and the corrosion rate of the implanted magnesium-based material is regulated and controlled by light and heat so as to realize the effects of promoting bone healing recovery and avoiding secondary operation extraction;
The coating comprises dripping, dipping, brushing or spraying;
the surface treatment comprises acid and alkali solution surface treatment, micro-arc oxidation and sand paper polishing
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method has the advantages of simple preparation process, mild preparation conditions, no need of complex metal treatment processing process, short preparation period and low manufacturing cost.
(2) The coating has no biotoxicity and high biocompatibility, improves the lubricating performance of the magnesium-based implant material, reduces the damage degree of the magnesium-based implant material to human tissues, effectively reduces the immune rejection reaction of organisms to the magnesium-based implant material, and enhances the combination capability of the magnesium-based implant material and the organism tissues; and the corrosion resistance is high, and the protective performance of the coating is still not destroyed after being soaked for 42 days under the non-near infrared triggering condition, so that the long-term service performance of the magnesium-based implant material is ensured.
(3) Near infrared light which can penetrate the superficial skin of a human body and has no damage to cell tissues is used as an external trigger source, the molecular gap of the coating is regulated according to the photo-thermal property of the coating, the protective property of the coating can be destroyed after the near infrared irradiation for 20-40 minutes, the purpose of controlling the corrosion rate of a magnesium matrix implantation material is achieved, the corrosion rate of the magnesium matrix is regulated, and the external regulation can be carried out at any time according to the bone healing condition of a patient.
(4) The coating can regulate the magnesium-based corrosion rate in the near infrared, simultaneously, the photodynamic excitation active oxygen and the photothermal effect cooperate for resisting bacteria, has high efficiency, high speed and broad-spectrum antibacterial property, and can achieve the aim of long-term continuous antibacterial by regulating the near infrared power.
Drawings
FIG. 1 is a schematic diagram of the process flow for preparing the near infrared controllable antibacterial degradable coating.
FIG. 2 is a transmission electron microscope image of the nanofiller prepared in example 1.
FIG. 3 is electrochemical impedance data of soaking experiments for different periods of PCL/PPy@CuS coating prepared in example 1.
FIG. 4 shows the electrochemical impedance profiles of PLGA/PANI@CuS, PLA/PDA@CuS coatings prepared from the coatings of examples 2 and 3 after 1 day and 20 days of immersion.
Fig. 5 and 6 show the electrochemical impedance of the coatings prepared in example 1 and comparative examples 1 and 2 before and after near infrared illumination.
FIG. 7 shows the fluorescence intensity of working fluid at different irradiation times for the antimicrobial coating of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples so as to more clearly understand the present invention by those skilled in the art.
Example 1
The embodiment provides a controllable degradation antibacterial coating with near infrared response, which comprises the following specific steps:
S1, preparation of a photosensitizer: 0.85g of CuCl 2·2H2 O is weighed and dissolved in 50mL of H 2 O, the temperature is heated to 70 ℃, 25mL of 1.8mol/L NaS is dripped into the CuCl 2 solution under the condition of 500rpm, the reaction is carried out for 2 hours, the pH is regulated to 3-4 by 0.099415mol/L citric acid solution after the reaction is finished, and the photosensitizer CuS is prepared by washing, centrifuging, drying and grinding.
S2, preparation of nano filler: adding 0.2g of CuS into 15mL of 0.4mol/L polyvinylpyrrolidone (PVP K30) solution, stirring for 30min, washing, centrifuging, transferring to a 50mL round bottom flask, adding 25mL of deionized water, stirring and reacting 0.075g of pyrrole monomer with 0.9065g of ferric trichloride hexahydrate in an ice-water bath for 12h, washing, centrifuging, drying, and grinding to prepare the PPy@CuS multifunctional core-shell structured nano filler. The transmission electron microscope image is shown in fig. 2, and it can be seen from fig. 2 that the nano-filler prepared by the invention obviously forms a core-shell structure, wherein the darker color of the image is photosensitizer CuS, and a circle of lighter-colored surrounding is surrounded around the darker color, and the surrounding is pyrrole polymer PPy, so that the core-shell structure taking the polymer as a shell and the photosensitizer as a core is formed.
S3, preparation of an antibacterial coating: 5g of Polycaprolactone (PCL) is weighed, dissolved in 50mL of dichloromethane to prepare a coating dispersion liquid, 5% of the nano filler by mass of PCL is added into the coating dispersion liquid, ultrasonic dispersion is carried out for 30min under the condition of 300W, after the nano filler is uniformly dispersed, the nano filler is dripped on a pure magnesium substrate subjected to micro-arc oxidation treatment, and the coating is cured and dried at room temperature, so that the thickness of the coating is about 100 mu m. The coating was named PLC/PPy@CuS.
Example 2
The embodiment provides a controllable degradation antibacterial coating with near infrared response, which comprises the following specific steps:
S1, preparation of a photosensitizer: 0.85g of CuCl 2·2H2 O is weighed and dissolved in 50mL of H 2 O, the temperature is heated to 70 ℃, 25mL of 1.8mol/L NaS is dripped into the CuCl 2 solution under the condition of 500rpm, the reaction is carried out for 2 hours, the pH is regulated to 3-4 by 0.099415mol/L citric acid solution after the reaction is finished, and the photosensitizer CuS is prepared by washing, centrifuging, drying and grinding.
S2, preparation of nano filler: 0.2g of CuS was added to 15mL of 0.4mol/L PVP (K30) solution and stirred for 30min. Transferring the mixture into a 50mL round-bottom flask after water washing and centrifugation, adding 25mL deionized water, stirring and reacting 0.075g aniline monomer and 0.049g ammonium persulfate in an ice-water bath for 12h, water washing and centrifugation, drying, and grinding to prepare the PANI@CuS multifunctional core-shell structured nano filler.
S3, preparation of an antibacterial coating: 2.5g of polylactic acid-glycolic acid copolymer (PLGA) is weighed, dissolved in 50mL of chloroform to prepare a coating dispersion liquid, 10% of the nano filler by mass of PLGA is added into the coating dispersion liquid, ultrasonic dispersion is carried out for 30min under the condition of 500W, after the nano filler is uniformly dispersed, the nano filler is dripped on a pure magnesium substrate subjected to micro-arc oxidation treatment, and the coating is cured and dried at room temperature, wherein the thickness of the coating is about 100 mu m. The coating was designated PLGA/PANI@CuS.
Example 3
The embodiment provides a controllable degradation antibacterial coating with near infrared response, which comprises the following specific steps:
S1, preparation of a photosensitizer: weighing 2.20g of Zn (Ac) 2·2H2 O, dissolving in 100mL of boiled absolute ethanol (80 ℃), vigorously stirring under normal pressure, refluxing for 3 hours, and directly cooling the solution to 0 ℃ in an ice bath; next, dissolving 0.58g of NaOH-H 2 O in 50mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 2 hours, cooling to 0 ℃, mixing Zn (Ac) 2 solution with sodium hydroxide solution, and then vigorously stirring for 120min at 0 ℃ to obtain transparent and uniform zinc oxide solution; then, deionized water is added into the ZnO solution, znO nanocrystals are precipitated under vigorous stirring, the supernatant is removed by centrifugation, and ZnO is dried in an oven at 60 ℃ to obtain photosensitizer ZnO.
S2, preparation of nano filler: adding 0.2g ZnO into 15mL of 0.4mol/L Sodium Dodecyl Sulfate (SDS) solution, stirring for 30min, transferring into a 50mL round bottom flask after washing and centrifuging, adding 25mL deionized water, reacting 0.175g dopamine hydrochloride monomer with 0.053g tris (hydroxymethyl) aminomethane under stirring for 12h, washing and centrifuging, drying and grinding to prepare the PDA@CuS multifunctional core-shell structured nanofiller.
S3, preparation of an antibacterial coating: 2.5g of polylactic acid (PLA) is weighed and dissolved in 50mL of dichloromethane to prepare coating dispersion liquid, 10 percent of the nano filler by mass of the PLA is added into the coating dispersion liquid, ultrasonic dispersion is carried out for 30min under the condition of 300W, after the nano filler is uniformly dispersed, the nano filler is dripped on a pure magnesium matrix subjected to micro-arc oxidation treatment, and the coating is solidified and dried at room temperature, and the thickness of the coating is about 100 mu m. This coating was named PLA/PDA@CuS.
Comparative example 1
This comparative example provides a controllably degradable antimicrobial coating having near infrared response, which is substantially identical to example 1, except that: step S2 is omitted, the prepared photosensitizer CuS is directly added into the coating dispersion liquid in step S3, and the rest is unchanged. This coating was designated PCL/CuS.
Comparative example 2
This comparative example provides a controllably degradable antimicrobial coating with near infrared response, as compared to example 1: 5g of Polycaprolactone (PCL) was directly coated in 50mL of dichloromethane and dried to form an antimicrobial coating without any nanofiller added. This coating was named PCL.
Performance verification
Further, in order to understand the technical effects of the antibacterial coating prepared by the above schemes, a test was also performed.
(1) Corrosion resistance test
The Electrochemical Impedance (EIS) of the long-term immersed coating is tested by adopting a CS350 electrochemical workstation, an electrolyte is physiological saline (0.9% NaCl), a standard three-electrode system is adopted, a counter electrode is a platinum sheet electrode, a reference electrode is a silver/silver chloride electrode, a working electrode is a pure magnesium electrode coated with the coating, a testing device is a quartz electrolytic cell, an impedance test is performed in a Faraday shielding box, and impedance test parameters are as follows: the alternating current amplitude is 20mV, the scanning frequency ranges from 100kHz to 0.01Hz, the electrochemical impedance data of the PCL/PPy@CuS coating prepared in example 1 in different periods of soaking experiments are respectively tested, and the result is shown in FIG. 3; the PLGA/PANI@CuS, PLA/PDA@CuS coatings prepared by the coatings of examples 2 and 3 were immersed for 1 day and 20 days to obtain the result shown in FIG. 4.
As can be seen from fig. 3: when the PCl/PPy@CuS coating is tested on the first day of the 0.01Hz mode value |Z| (|Z|0.01 Hz), 10 9 is reached, the |Z|0.01 Hz gradually decreases with the increase of soaking days, but finally the coating is stabilized by about 10 7, the |Z|0.01 Hz is still higher than 10 7 after soaking for 42 days, and only one time constant is still available after soaking for 42 days, so that the coating performance is not destroyed. The greater the electrochemical impedance |Z|0.01 Hz is, the greater the corrosion resistance of the coating is, and the phase angle only has one time constant, which proves that the metal substrate is not contacted with a corrosive medium, and the protective performance of the coating is not destroyed, so that the corrosion resistance of the coating PCL/PPy@CuS is excellent.
As can be seen from FIG. 4, the initial |Z|0.01Hz of the PLGA/PANI@CuS, PLA/PDA@CuS coatings were not high, all did not reach 10 8, and the PLGA/PANI@CuS coatings were dropped to 10 6 after 20 days of immersion.
(2) Corrosion rate controllability test
The coatings prepared in example 1 and comparative examples 1 and 2 were tested for their electrochemical resistance before and after near infrared illumination, respectively, and as shown in FIGS. 5 and 6, the PCL coating and the PCL/CuS coating did not have a significant order of magnitude difference in the near infrared light before and after |Z|0.01 Hz, demonstrating that the two coatings did not adjust the corrosion rate of the magnesium-based implant material. The PCL/PPy@CuS coating has good protective performance when reaching 10 9 before infrared irradiation (namely befor NIR) and the Z|0.01 Hz, and the magnesium substrate is hardly corroded. After infrared irradiation (i.e., after NIR), the |Z|0.01 Hz of the coating PCL/PPy@CuS rapidly decreased to 10 6; and the phase angle has two time constant trends, so that the corrosion resistance of the coating is damaged, and the corrosion of the magnesium alloy is accelerated. Therefore, the PCL/PPy@CuS coating has the property of adjusting the corrosion of the magnesium alloy matrix in a near infrared response.
(3) Near infrared photodynamic response performance test
The controllable antibacterial degradation coating is soaked in singlet oxygen green fluorescent probe working solution, and after 2min,4min,6min,8min and 10min of irradiation are respectively carried out by using 808nm near infrared light, the fluorescence intensities of the working solutions with different irradiation times are tested by using a fluorescence spectrometer of FP-6500 type (Jasco, japan), and the result is shown in figure 7.
As can be seen from fig. 7: after near infrared irradiation at 808nm, the fluorescence value is increased with the increase of heat, which shows that the active oxygen content generated by the coating is increased with the increase of time, and the antibacterial effect can be effectively shown.
The specific raw materials are not described in the invention, and the raw materials are existing substances and can be directly purchased from the market.
The foregoing is merely a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The controllable degradation antibacterial coating with the near infrared response is characterized in that the coating is prepared into slurry by mixing coating dispersion liquid and nano filler, and the slurry is obtained by coating and drying;
the coating dispersion liquid is prepared by dissolving a biodegradable material in an organic solvent, wherein the mass-volume ratio of the biodegradable material to the organic solvent is 2-10 w/v%;
The nano-filler is in a shell-core structure, wherein the organic polymer is a shell, the photosensitizer is a core, and the mass of the nano-filler is 5% -10% of that of the biodegradable material.
2. The antimicrobial coating of claim 1, wherein the biodegradable material is any one of polylactic acid, polycaprolactone, chitosan, dopamine, polylactic acid-glycolic acid copolymer.
3. The antimicrobial coating of claim 1, wherein the organic solvent is at least one of methylene chloride, acetone, ethyl acetate, tetrahydrofuran, dimethylsulfoxide.
4. The antimicrobial coating of claim 1, wherein the nanofiller is prepared by a process comprising: adding a photosensitizer, a surfactant, a polymer monomer and a polymerization catalyst into deionized water, reacting for 12 hours at normal temperature, washing, centrifuging and drying to obtain the nano filler.
5. The antimicrobial coating of claim 4, wherein the photosensitizer and the polymer monomer are present in a mass ratio of 8: (3-7).
6. The antimicrobial coating of claim 4, wherein the photosensitizer is at least one of CuS, moS 2,ZnO,TiO2,BiVO4.
7. The antimicrobial coating of claim 4, wherein the surfactant is any one of polyvinylpyrrolidone, sodium dodecyl sulfate;
the polymerization catalyst is any one of ammonium persulfate and ferric chloride.
8. The antimicrobial coating of claim 4, wherein the polymer monomer is at least one of dopamine, pyrrole, and aniline.
The polymerization catalyst is any one of ammonium persulfate and ferric chloride.
9. A method of producing an antimicrobial coating according to any one of claims 1 to 8, comprising the steps of: dissolving biodegradable material in organic solvent to obtain coating dispersion, adding nano filler into the coating dispersion, mixing for 20-40 min under 200-600W ultrasonic condition, and coating and drying to obtain the antibacterial coating.
10. Use of an antimicrobial coating according to any one of claims 1-8 in bone healing, characterized in that the coating is applied to the surface of a surface treated magnesium-based material, whereby the corrosion rate of the implant material is regulated by photo-thermal control to achieve promotion of bone healing recovery, avoiding secondary surgical removal;
The coating comprises dripping, dipping, brushing or spraying;
the surface treatment comprises acid and alkali solution surface treatment, micro-arc oxidation and sand paper polishing.
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