WO2021008092A1 - 一种在圆柱形钛钉表面的近红外响应功能涂层的制备方法及应用 - Google Patents

一种在圆柱形钛钉表面的近红外响应功能涂层的制备方法及应用 Download PDF

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WO2021008092A1
WO2021008092A1 PCT/CN2019/129998 CN2019129998W WO2021008092A1 WO 2021008092 A1 WO2021008092 A1 WO 2021008092A1 CN 2019129998 W CN2019129998 W CN 2019129998W WO 2021008092 A1 WO2021008092 A1 WO 2021008092A1
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titanium
titanium nail
nail
gold nanoparticles
nails
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French (fr)
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吴水林
金晨
刘想梅
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湖北大学
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
    • A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
    • A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • 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
    • A61L31/02—Inorganic materials
    • A61L31/022—Metals or alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • 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
    • A61L31/084—Carbon; Graphite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • 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
    • A61L31/088—Other specific inorganic materials not covered by A61L31/084 or A61L31/086
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/06—Coatings containing a mixture of two or more compounds
    • 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

Definitions

  • the invention relates to a method for preparing a functional composite material, and more particularly, to a method for preparing a near-infrared response functional coating on the surface of a cylindrical titanium nail and its application.
  • Biomedical materials are materials that are used for clinical diagnosis, treatment of lesions, repair or replacement of tissues and organs, or for functional enhancement of existing tissues and organs, and do not have other negative effects on the organism.
  • Biomedical materials can be divided into medical metal materials, medical polymer materials, medical ceramics and medical composite materials.
  • medical metal materials titanium metal has good mechanical properties, strong corrosion resistance, elastic modulus close to human bones, and biological inertness. It is currently a commonly used implant material in orthopedics, especially in orthopedic internal fixation surgery. The load position in the middle has been widely used.
  • used antibacterial materials include inorganic metal ions and organic antibiotics, but metal ions are often accompanied by more serious toxicity, and the abuse of organic antibiotics can make bacteria resistant.
  • Near-infrared light is widely used in photodynamic therapy and photothermal therapy because of its deep penetration. Therefore, photodynamic and photothermal therapy can be applied in the field of antibacterial, which can achieve rapid sterilization through light response. This rapid sterilization function is applied to titanium implants, which can solve the problem of bacterial infection.
  • Traditional anodized titanium dioxide coatings can basically only be produced on flat titanium metal due to technological limitations, which limits the growth of titanium dioxide coatings on conventional cylindrical titanium nails.
  • the present invention provides a preparation method and application of a near-infrared response functional coating on the surface of cylindrical titanium nails.
  • the method of the present invention can be used to prepare gold nanoparticles and carbon quantum on the surface of cylindrical titanium nails.
  • Dotted titanium dioxide nanotubes, the resulting titanium nails with functional coatings have a good photothermal effect and produce active oxygen after 15 minutes of infrared radiation at 808nm. They have better antibacterial effects against Staphylococcus aureus and Escherichia coli. Good cell compatibility and osteogenic properties.
  • the present invention a method for preparing a near-infrared response functional coating on the surface of a cylindrical titanium nail, includes the following steps:
  • step S2 Growth of titanium dioxide nanotubes on titanium nails: Put the titanium nails processed in step S1 into the electrolyte and connect them to the anode, and connect the cathode to a customized tubular graphite electrode, and the titanium nails are just placed on the tubular graphite electrode.
  • the anodic oxidation reaction voltage is 35-45V
  • the reaction is 170-190min at room temperature, after ultrasonic, drying and calcination, the titanium nail/titania nanotube is obtained;
  • step S4 Load the gold nanoparticles and carbon quantum dots described in step S3 on the titanium dioxide nanotubes on the surface of the titanium nails to obtain titanium nails/titanium dioxide nanotubes/gold nanoparticles/carbon quantum dots.
  • step S4 the solution of gold nanoparticles and carbon quantum dots in step S3 is mixed in a volume ratio of 1:2 to obtain a mixed solution, and the titanium nail/titanium dioxide nanoparticle obtained in step S2 The tube was placed vertically in the mixed solution, loaded in a vacuum environment for 24 hours, and then dried at 50° C. for 24 hours.
  • the preparation method of the electrolyte in step S2 weigh 0.34 g of ammonium fluoride, dissolve it in 5 mL of water to prepare an ammonium fluoride solution, measure 95 mL of deionized water, and combine the deionized water with The prepared ammonium fluoride solution is mixed as electrolyte;
  • the titanium nail is sonicated in ethanol and dried to remove the silica gel and copper wire on the titanium nail, and calcined at 450° C. for 2 hours.
  • the titanium nail pretreatment method in step S1 is: after the surface of the titanium nail with a diameter of 1 mm and a length of 6 mm is sanded with sandpaper, it is washed with acetone, ethanol and deionized water, and the titanium nail is dried. Then use an etching solution to etch for 2 minutes, then wrap one end of the titanium nail with a copper wire, wrap one end of the copper wire wrapped around the titanium nail with silica gel, and dry for 6 hours at room temperature;
  • the etching solution is a mixed solution with a volume ratio of nitric acid, hydrofluoric acid and deionized water of 4:1:5.
  • the preparation method of the gold nanoparticles in step S3 heating and stirring 0.01 wt.% chloroauric acid solution in an oil bath, and adding 3 mL of 1 wt.% sodium citrate when the temperature reaches 100°C The solution, keep the temperature and stir for 20min, stop heating and cool to room temperature, add 400mg PVP and stir for 24h, centrifuge at 13000rpm for 30min, collect the precipitate and wash it with deionized water 3 times, finally concentrate the gold nanoparticles in 8mL deionized water to avoid light save;
  • step S3 The preparation method of carbon quantum dots described in step S3: dissolve 2g ethylenediamine and 2g citric acid in 20mL ethanol and put them in a reaction kettle, react at 180°C for 3h, centrifuge at 3000rpm for 15min to remove large particles in the reaction solution, It was dialyzed with a 1000 Da dialysis membrane for 48 hours to remove ions and small molecular impurities, and stored at 4°C in the dark.
  • the application of a near-infrared response functional coating on the surface of cylindrical titanium nails prepared by the above method in medical implanted titanium nails is characterized in that: the titanium nails with the near-infrared corresponding functional coatings on the surface are irradiated with 808nm laser 15min.
  • Cylindrical titanium nails are anodized by customized graphite electrodes, so that the titanium dioxide nanotube coating can be uniformly grown on the surface of the titanium nails. This method requires less equipment investment, is simple and easy to implement, is cost-effective, and has no impact on the environment ;
  • the titanium dioxide can be excited to generate active oxygen and heat under near-infrared 808 nm light;
  • the functional coating prepared by the technology of the present invention has good photocatalytic performance and photothermal performance, can kill bacteria within 15 minutes, and the coating also has good cell compatibility and osteogenic performance. Conducive to the proliferation and differentiation of osteoblasts.
  • Fig. 1 is a SEM image of titanium dioxide nanotubes formed by anodizing the surface of a cylindrical titanium nail prepared by the method of the present invention.
  • Fig. 2 is an SEM image of titanium dioxide nanotubes after gold nanoparticles and carbon quantum dots are loaded on the surface of the cylindrical titanium nail prepared by the method of the present invention.
  • Figure 3 is a cross-sectional SEM image of a titanium dioxide coating loaded with gold nanoparticles and carbon quantum dots prepared by the method of the present invention, where a is a low-magnification image and b is a high-magnification image.
  • Figure 4 is an XPS diagram of a titanium nail with a coating of near infrared response function prepared by the method of the present invention.
  • Figure 5a shows the explanation of DCFH dyes on the titanium nails with near-infrared response coating prepared by the method of the present invention.
  • Figure 5b shows the temperature rise of a sample of titanium nails with near-infrared response function prepared by the method of the present invention under 808 nm laser irradiation.
  • Fig. 6a shows the antibacterial rate of Staphylococcus aureus for 15 minutes of the coated titanium nail with near-infrared response function prepared by the method of the present invention.
  • Fig. 6b shows the antibacterial rate of the coated titanium nail with near-infrared response function against Escherichia coli prepared by the method of the present invention for 15 minutes.
  • Fig. 7a shows the cytocompatibility test of osteoblasts prepared by the method of the present invention with a titanium nail coated with a near-infrared response function.
  • Figure 7b shows the bone formation performance test of the titanium nail with near-infrared response function coating prepared by the method of the present invention.
  • the steps are the same as in Example 1, except for steps (4), (5) and (6).
  • the titanium nail with functional coating of titanium dioxide nanotube is obtained.
  • Example 2 The procedure is the same as in Example 1, except that the mixed solution prepared by not using 5 mL of gold nanoparticle particle solution and 10 mL of carbon quantum dot solution in step (6), only the solution of carbon quantum dots is used to obtain titanium dioxide nanotubes/carbon quantum Point functional coated titanium nails.
  • Example 2 The procedure is the same as in Example 1, except that the mixed solution prepared by not using 5 mL of gold nanoparticle particle solution and 10 mL of carbon quantum dot solution in step (6), only the gold nano particle solution is used to obtain titanium dioxide nanotube/gold Titanium nails with nano-particle functional coating.
  • the steps are the same as the step (1) of Example 1 to obtain pure titanium nails.
  • Example 1 and Comparative Examples 1 to 3 were tested by SEM respectively, and the experimental results are shown in Figures 1 to 3.
  • the tube in Figure 1 is the titanium dioxide nanotube grown from the titanium nail through the anodization reaction. It can be seen from the figure that the titanium dioxide nanotube grown after the anodization is more uniform in appearance and grows perfectly on the cylindrical titanium nail. Above; the nanoparticles in Figure 2 are gold nanoparticles and carbon quantum dots after being loaded by vacuum, indicating that the gold nanoparticles and carbon quantum dots have been successfully loaded on it; from Figure 3, it can be seen that the coating can be uniformly prepared to On the cylindrical titanium nail, the coating thickness is about 5 nanometers.
  • Example 1 and Comparative Examples 1 to 3 were tested by XPS. The results are shown in Figure 4. From the figure, it can be seen that Example 1 loaded with gold nanoparticles and carbon quantum dots (titanium dioxide nanotubes/gold nanoparticles/carbon Quantum dots) have O1s, Ti2p, C1s and Au4f peaks, and the C1s peak is stronger than the peak of Comparative Example 3 (titanium dioxide nanotube/gold nanoparticle) loaded with gold nanoparticles, which also shows that gold Nanoparticles and carbon quantum dots were successfully loaded on titanium dioxide nanotubes.
  • gold nanoparticles and carbon quantum dots titanium dioxide nanotubes/gold nanoparticles/carbon Quantum dots
  • DCFH 2',7'-dichlorodihydrofluoroalkane diacetate
  • Example 1 and Comparative Examples 1 to 4 were immersed in 200 ⁇ L of DCFH solution in a 96-well plate. Check every two minutes to obtain the fluorescence of the DCF solution after 808nm near infrared radiation.
  • Example 1 titanium dioxide nanotubes/nanoparticles/carbon quantum dots
  • Example 1 and Comparative Examples 1 to 4 were respectively placed in a 96-well plate with 150 microliters of PBS, and each sample was irradiated with 808 nm near-infrared light for 15 minutes, and an infrared imager (E50) was used to obtain the temperature every 2 minutes.
  • E50 infrared imager
  • the photothermal performance of Comparative Example 4 (titanium nail) and Comparative Example 1 (titanium dioxide nanotube) are both poor, that is, after 15 minutes of 808nm near infrared light irradiation, the surface temperature can only be increased to 40°C. And 43.1°C.
  • titanium dioxide nanotubes/carbon quantum dots, titanium dioxide nanotubes/gold nanoparticles and titanium dioxide nanotubes/gold nanoparticles/carbon quantum dots Due to the inherent photo-thermal properties of carbon quantum dots and gold nanoparticles, after 15 minutes of 808nm illumination, titanium dioxide nanotubes/carbon quantum dots, titanium dioxide nanotubes/gold nanoparticles and titanium dioxide nanotubes/gold nanoparticles/carbon quantum dots have obvious effects.
  • the photothermal characteristics of the photothermal properties are 47.6°C, 50°C and 52.5°C respectively.
  • the photothermal effect of titanium dioxide nanotubes/gold nanoparticles/carbon quantum dots is the best, which is due to the combination of carbon quantum dots and gold nanoparticles and The SPR effect of gold nanoparticles is enhanced.
  • composition and concentration of PBS 0.24g/L Na 2 HPO 4 , 1.44g/L KH 2 PO 4 , 8g/L NaCl and 0.2g/L KCl, the pH is 7.4.
  • Example 1 titanium dioxide nanotubes/gold nanoparticles/carbon quantum dots
  • the 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide (MTT, Aladdin) method was used to detect MC3T3-E1 cell samples (provided by Tongji Medical College) Cell viability.
  • remove the cell nutrient solution from each well Add 200 ⁇ L of 0.5mg/mL MTT solution to each well, then soak at 37°C for 4 hours.
  • DMSO dimethyl sulfoxide
  • the alkaline phosphatase (ALP) test was used to study the osteogenic differentiation of cells.
  • MC3T3-E1 cells were seeded on samples in 96-well plates, and a professional kit (abcam, ab83369) was used for osteogenic testing at set times of 3, 7 and 14 days. After incubation, the cells were lysed with 1% Triton X-100 solution at 37° C. for 1 h, and then a professional alp kit (abcam, ab83369) was used for osteogenic test at 405 nm with a microplate reader.
  • Figure 7a shows the cell viability results.
  • Example 1 titanium dioxide nanotubes/gold nanoparticles/carbon quantum dots
  • Figure 7b shows the results of the osteogenic performance test. It can be seen that Example 1 (titanium dioxide nanotubes/gold nanoparticles/carbon quantum dots) exhibits better osteogenic performance.

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Abstract

一种在圆柱形钛钉表面的近红外响应功能涂层的制备方法，包括以下步骤：钛钉预处理；钛钉上生长二氧化钛纳米管：将处理好的钛钉放入电解液中并接在阳极上，阴极接定制的管状石墨电极，反应电压为40V，常温下反应3h，乙醇超声后干燥，450℃煅烧2h，得到钛钉/TNT；合成金纳米粒子和碳量子点；将金纳米粒子和碳量子点负载至钛钉表面二氧化钛纳米管上，得到钛钉/TNT/AU/CQDS。采用该方法可制备在圆柱形钛钉表面负载金纳米粒子和碳量子点的二氧化钛纳米管，所得具备功能涂层的钛钉在红外线808nm照射15min后具备良好的光热效应并且产生活性氧，对于金黄色葡萄球菌和大肠杆菌都有着更加优良的抗菌效果，同时还有很好的细胞相容性和成骨性能。

Description

一种在圆柱形钛钉表面的近红外响应功能涂层的制备方法及应用 技术领域
本发明涉及一种功能复合材料的制备方法，更具体地，涉及一种在圆柱形钛钉表面的近红外响应功能涂层的制备方法及应用。
背景技术
生物医用材料是用来临床诊断、治疗病损、修复或替换组织器官修复或者对现有组织和器官进行功能增进，而且不会对生物体产生其他的负面影响的材料。生物医用材料可以被划分为医用金属材料，医用高分子材料，医用陶瓷以及医用复合材料。在医用金属材料中钛金属因为具有良好的的力学性能，抗腐蚀性强，弹性模量接近于人体骨骼，生物惰性等优良特性，是目前骨科常用的植入体材料，尤其在骨科内固定手术中的负载部位得到了广泛的应用。
但是因为医用植入体所造成的细菌感染已经被越来越多内社会所重视,这种感染的发生不仅会给患者带来更多的痛苦和经济负担,甚至还会威胁到患者的生命。医用钛基植入体的植入过程中也会有被细菌感染的情况发生，而且一般的钛植入体材料的形状并不是平面状的，例如钛钉是圆柱体的，传统工艺很难在形状不平的表面做出完美的二氧化钛纳米管薄膜。为了解决细菌感染和对材料加工工艺的问题，我们希望在保留植入体优良性能的前提下对其进行改性和工艺的升级，让我们的涂层可以做到圆柱体的钛钉上使植入体有抗菌性能，同时还也可以达到促进成骨细胞的增值分化。
传统的常用抗菌材料包括无机的金属离子和有机的抗生素，但是金属离子往往伴随着比较严重的毒性，有机抗生素的滥用则会使得细菌产生耐药性。近红外光因为它的深穿透性被广泛的应用于光动力治疗和光热治疗当中，所以说光动力和光热治疗可以被应用在抗菌领域，可以通过光响应达到快速杀菌的作用，把这种快速杀菌的功能应用在钛植入体上，可以解决细菌感染这个问题。传统的阳极氧化二氧化钛涂层由于工艺的限制基本上只能在平面的钛金属上进行制作，这就限制了在常规的圆柱形钛钉上进行二氧化钛涂层的生长。
发明内容
为解决上述问题，本发明提供了一种在圆柱形钛钉表面的近红外响应功能涂层的制备方法及应用，采用本发明的方法可制备在圆柱形钛钉表面负载金纳米粒子和碳量子点的二氧化钛纳米管，所得具备功能涂层的钛钉在红外线808nm照射15min后具备良好的光热效应并且产生活性氧，对于金黄色葡萄球菌和大肠杆菌都有着更加优良的抗菌效果，同时还有很好的细胞相容性和成骨性能。
本发明，一种在圆柱形钛钉表面的近红外响应功能涂层的制备方法，包括以下步骤：
S1、钛钉预处理；
S2、钛钉上生长二氧化钛纳米管：将步骤S1中处理好的钛钉放入电解液中并接在阳极上，阴极接定制的管状石墨电极，所述钛钉正好置于所述管状石墨电极的中间，阳极氧化反应电压为35～45V，常温下反应170～190min，经过超声、干燥和煅烧后得到钛钉/二氧化钛 纳米管；
S3、合成金纳米粒子和碳量子点；
S4、将步骤S3中所述金纳米粒子和碳量子点负载至钛钉表面二氧化钛纳米管上，得到钛钉/二氧化钛纳米管/金纳米粒子/碳量子点。
进一步地，步骤S4中所述负载方法：步骤S3中所述金纳米粒子和碳量子点的溶液按照体积比1：2的比例混合得到混合溶液，并将步骤S2中得到的钛钉/二氧化钛纳米管垂直放置在所述混合溶液中，在真空环境中负载24h，之后在50℃下干燥24h。
再进一步地，步骤S2中所述电解液的制备方法：称取0.34g的氟化铵，将其溶解到5mL水中配制成氟化铵溶液，量取95mL的去离子水，将去离子水和配好的氟化铵溶液混合作为电解液；
在所述阳极氧化反应后将钛钉在乙醇中超声后干燥，除去钛钉上面的硅胶和铜丝，在450℃下煅烧2个小时。
还进一步地，步骤S1中所述钛钉预处理方法为：将直径为1mm、长度为6mm的钛钉用砂纸表面打磨后，次用丙酮、乙醇和去离子水清洗，将所述钛钉干燥之后用刻蚀液刻蚀2分钟，再用铜丝把所述钛钉的一端缠绕一圈，用硅胶把所述铜丝缠绕钛钉的一端包裹住，常温下干燥6小时；
所述刻蚀液为硝酸、氢氟酸和去离子水的体积比为4:1:5的混合溶液。
更进一步地，步骤S3中所述金纳米粒子的制备方法：将0.01wt.％的氯金酸溶液油浴锅中加热并搅拌，在温度达到100℃时加入3mL 的1wt.％的柠檬酸钠溶液，保持温度搅拌20min，停止加热冷却到室温，加入400mg的PVP后搅拌24h，以13000rpm离心30min，收集沉淀并用去离子水清洗3次，最后把金纳米粒子浓缩在8mL的去离子水中避光保存；
步骤S3中所述碳量子点的制备方法：将2g乙二胺和2g柠檬酸溶解到20mL的乙醇放入反应釜中，180℃反应3h，以3000rpm离心15min除去反应液中的大颗粒沉淀，并用1000Da的透析膜透析48h除去离子和小分子杂质，避光4℃保存。
采用上述方法制备的一种在圆柱形钛钉表面的近红外响应功能涂层在医用植入钛钉的应用，其特征在于：以808nm激光照射表面具有所述近红外相应功能涂层的钛钉15min。
本发明的有益效果是：
(1)通过定制的石墨电极对圆柱形钛钉进行阳极氧化，使得二氧化钛纳米管涂层可以均匀的生长在钛钉表面，此方法设备投入少，简单易行，成本地，并且对环境无影响；
(2)通过用金纳米粒子和碳量子点对二氧化钛纳米管进行修饰，使得二氧化钛可以近红外808纳米的光下被激发产生活性氧和热量；
(3)本发明技术制备的功能涂层具有很好的光催化性能和光热性能，可以在15分钟杀死细菌，并且该涂层还有很好的细胞相容性和成骨性能，有利于成骨细胞的增值和分化。
附图说明
图1为采用本发明方法制备的圆柱形钛钉表面的阳极氧化生成的 二氧化钛纳米管SEM图。
图2为采用本发明方法制备的圆柱形钛钉表面负载了金纳米粒子和碳量子点之后的二氧化钛纳米管SEM图。
图3为采用本发明方法制备的负载了金纳米粒子和碳量子点的二氧化钛涂层的截面SEM图，其中a是低倍图，b是高倍图。
图4为采用本发明方法制备的具有近红外响应功能涂层钛钉的XPS图。
图5a为采用本发明方法制备的具有近红外响应功能涂层钛钉对DCFH染料讲解情况。
图5b为采用本发明方法制备的具有近红外响应功能涂层钛钉在808纳米的激光照射下样品的升温情况。
图6a为采用本发明方法制备的具有近红外响应功能涂层钛钉对金黄色葡萄球菌15min的抗菌率。
图6b为采用本发明方法制备的具有近红外响应功能涂层钛钉对大肠杆菌15min抗菌率。
图7a为采用本发明方法制备的具有近红外响应功能涂层钛钉的成骨细胞的细胞相容性检测。
图7b为采用本发明方法制备的具有近红外响应功能涂层钛钉的成骨性能检测。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明了，下面结合具体实施方式并参照附图，对本发明进一步详细说明。应该理解，这些 描述只是示例性的，而并非要限制本发明的范围。此外，在以下说明中，省略了对公知结构和技术的描述，以避免不必要地混淆本发明的概念。
实施例1
(1)将直径1mm、长度6mm的金属圆柱体钛钉分别用240目，400目，600目，800目和1200目的砂纸打磨直至表面光滑，之后放入烧杯依次加入丙酮，乙醇和去离子水进行超声清洗，除去钛钉表面的杂质，之后50℃在真空环境下干燥12小时。
(2)将1mL氢氟酸，4mL硝酸和5mL去离子水混合配制成刻蚀液，把打磨好的钛钉浸入刻蚀液2分钟，取出钛钉用去离子水清洗，之后浸泡在乙醇中。10mg/mL的聚苯乙烯乙醇
(3)钛钉表面二氧化钛纳米管的制备：将0.34g氟化铵溶解到5mL的去离子水中，在将氟化铵溶液加入到95mL的乙二醇溶液中配制成电解液，之后将处理后的钛钉浸入电解液中接在阳极上，将定制的管状石墨电极(天津艾达)接在阴极上,使得钛钉正好悬挂在管状的石墨电极中间，在40V的电压下室温反应3个小时，之后将钛钉用乙醇浸泡超声5分钟除去残留的电解液。干燥之后在450℃下将处理后的钛钉表面的二氧化钛纳米管涂层煅烧2小时得到锐钛矿晶型的二氧化钛纳米管涂层。
(4)在烧瓶中配制质量分数0.01％的氯金酸溶液，并保持在油浴锅中加热和搅拌。在温度达到100摄氏度时加入3mL的质量分属为1％的柠檬酸钠溶液，保持温度搅拌20分钟，停止加热冷却到室温， 加入400mg的PVP后搅拌24小时，用13000rpm离心30分钟，收集沉淀并用去离子水清洗3次，最后把金纳米粒子浓缩在8mL的去离子水中避光保存。
(5)将2g乙二胺和2g柠檬酸溶解到20mL的乙醇放入反应釜中，180℃反应3个小时。之后用3000rpm离心15分钟除去大颗粒沉淀，并用1000Da的透析膜来透析48小时来除去离子和小分子杂质。避光4℃保存。
(6)将5mL金纳米粒粒子的溶液和10mL的碳量子点的溶液配制成混合溶液，将煅烧后的钛钉放入烧杯中，然后加入混合溶液使溶液没过钛钉，放入真空干燥箱中并抽真空，在常温下保存24个小时。最后取出负载之后的钛钉，在50℃干燥12小时。
对比例1
步骤同实施例1，去除步骤(4)、(5)和(6)。得到二氧化钛纳米管功能涂层的钛钉。
对比例2
步骤同实施例1，除了步骤(6)中不使用5mL金纳米粒粒子的溶液和10mL的碳量子点的溶液配制成的混合溶液，仅使用碳量子点的溶液，得到二氧化钛纳米管/碳量子点功能涂层的钛钉。
对比例3
步骤同实施例1，除了除了步骤(6)中不使用5mL金纳米粒粒子的溶液和10mL的碳量子点的溶液配制成的混合溶液，仅使用金纳米粒子的溶液，得到二氧化钛纳米管/金纳米粒子功能涂层的钛钉。
对比例4
步骤同实施例1的步骤(1)，得到纯钛钉。
SEM检测：
实施例1与对比例1～3分别进行SEM检测，实验结果如图1～3所示。图1中管状物是钛钉通过阳极氧化反应之后生长出来的二氧化钛纳米管，从图中可以看出通过阳极氧化之后生长出来的二氧化钛纳米管的相貌较为均一，并且完美的生长在圆柱体钛钉上；图2中的纳米粒子是经过真空负载了之后的金纳米颗粒和碳量子点，表明金纳米粒子和碳量子点已经成功负载上面了；从图3可以看出涂层可以均匀的制备到圆柱形的钛钉上面，涂层厚度大概是5纳米。
实施例1与对比例1～3分别进行XPS检测，结果如图4所示，从图中可以看出负载了金纳米粒子和碳量子点的实施例1(二氧化钛纳米管/金纳米粒子/碳量子点)有O1s，Ti2p，C1s和Au4f的峰，而且C1s的峰比只负载了金纳米粒子的对比例3(二氧化钛纳米管/金纳米粒子)的峰要强，也从另一方面说明了金纳米粒子和碳量子点成功负载在二氧化钛纳米管上了。
活性氧测试：
为了检测样品的活性氧产率，用2’，7’-二氯二氢氟烷二乙酸酯(DCFH，碧云天生物)与活性氧反应生成DCF。将实施例1以及对比例1～4浸入96孔板中的200μL DCFH溶液中。每隔两分钟进行一次检查，以获得808nm近红外辐射后DCF溶液的荧光。
当DCFH被活性氧氧化时，其荧光强度会增强。如图5a所示，对 比例1(二氧化钛纳米管)的荧光强度与对比例4(钛钉)相比几乎没有增强，而对比例2(二氧化钛纳米管/碳量子点)和对比例3(二氧化钛纳米管/金纳米粒子)的荧光强度略有增强，表明它们在808nm近红外光照射下的光催化性能较差。相比之下，在808nm近红外光照射15分钟后，实施例1(二氧化钛纳米管/纳米粒子/碳量子点)的荧光强度有明显的增强，表明制备的实施例1的二氧化钛纳米管/纳米粒子/碳量子点表面体系在808nm近红外光下具有增强的光催化性能。
光热性能测试：
实施例1以及对比例1～4分别置于96孔板中加入150微升PBS，每个样品在808nm近红外光照射15分钟，用红外成像仪(E50)每2分钟获取温度。如图5b所示，对比例4(钛钉)和对比例1(二氧化钛纳米管)的光热性能都较差，即经过15分钟808nm近红外光照射后，表面温度分别只能提高到40℃和43.1℃。由于碳量子点和金纳米粒子的的固有光热特性，在15min 808nm光照后，二氧化钛纳米管/碳量子点、二氧化钛纳米管/金纳米粒子和二氧化钛纳米管/金纳米粒子/碳量子点具有明显的光热特性，光热温度分别为47.6℃、50℃和52.5℃，其中二氧化钛纳米管/金纳米粒子/碳量子点的光热效应最佳，这是由于碳量子点和金纳米粒子的结合以及金纳米粒子的SPR效应增强。
PBS的成分以及浓度：0.24g/L Na 2HPO 4、1.44g/L KH 2PO 4、8g/L NaCl和0.2g/L KCl，pH为7.4。
抗菌性测试：
将实施例1以及对比例1～4放置在96个孔板中，在每个孔中加入150μL 1×10 5菌落(金黄色葡萄球菌或者大肠杆菌，均来自翊圣生物科技有限公司)形成单位(cfu)/ml的细菌液体。分别在15分钟808nm近红外光照射、黑暗培养15分钟两种条件下测定各组的抗菌效果，处理后取出样品用酶标仪测试吸光度可以评估抗菌效率(ae)。公式：ae＝1－(实验组的吸光度/黑暗条件下Ti组的吸光度)。
结果如图6a和6b所示，其中对比例2(二氧化钛纳米管/碳量子点)和对比例3(二氧化钛纳米管/金纳米粒子)对金黄色葡萄球菌(分别为28.81±3.1％和38.87±5.2％)和大肠杆菌菌落(分别为45.21±4.3％和56.35±6.2％)的抗菌性能不足，这归因于仅这些组的光热效应较差。与此相反，实施例1(二氧化钛纳米管/金纳米粒子/碳量子点)在15分钟808nm近红外光照射后显示出优良的抗菌性能，在平板上只有很少的菌落，相应的抗菌效率分别为对金黄色葡萄球菌和大肠杆菌的96.19±2.3％和99.89±0.1％。说明实施例1(二氧化钛纳米管/金纳米粒子/碳量子点)在808nm近红外光照下能快速杀灭细菌。
细胞活性、成骨性能测试：
采用3-[4，5-二甲基噻唑-2-基]-2，5-二苯基四唑溴化铵(MTT，阿拉丁)法检测MC3T3-E1细胞(同济医学院提供)样品的细胞活力。将细胞与实施例1以及对比例1～4在37℃下、5％浓度CO 2的培养箱中培养1天、3天和7天，在设定时间，取出每个孔中的细胞营养液，向每个孔中加入200μL 0.5mg/mL MTT溶液，然后在37℃下浸泡4 小时。然后取出每个孔中的MTT溶液，连续摇动15分钟，加入200μL二甲基亚砜(DMSO，阿拉丁)，最后用微板阅读器在570nm处测量96孔板中DMSO的吸光度。
采用碱性磷酸酶(ALP)试验研究细胞的成骨分化。将MC3T3-E1细胞接种在96孔板的样品上，并在设定时间3、7和14天使用专业试剂盒(abcam，ab83369)进行成骨测试。孵育后，用1％Triton X-100溶液在37℃下使细胞溶解1h，然后用专业的alp试剂盒(abcam，ab83369)在405nm处用酶标仪进行成骨测试。
结果如图7a和7b所示，图7a为细胞活性结果，有图可见，实施例1(二氧化钛纳米管/金纳米粒子/碳量子点)在培养1、3、7天都由较好的细胞相容性，图7b为成骨性能测试结果，可见实施例1(二氧化钛纳米管/金纳米粒子/碳量子点)表现出较好的成骨性能。
应当理解的是，本发明的上述具体实施方式仅仅用于示例性说明或解释本发明的原理，而不构成对本发明的限制。因此，在不偏离本发明的精神和范围的情况下所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。此外，本发明所附权利要求旨在涵盖落入所附权利要求范围和边界、或者这种范围和边界的等同形式内的全部变化和修改例。

Claims (6)

  1. 一种在圆柱形钛钉表面的近红外响应功能涂层的制备方法，其特征在于，包括以下步骤：
    S1、钛钉预处理；
    S2、钛钉上生长二氧化钛纳米管：将步骤S1中处理好的钛钉放入电解液中并接在阳极上，阴极接管状石墨电极，所述钛钉正好置于所述管状石墨电极的中间，阳极氧化反应电压为35～45V，常温下反应170～190min，经过超声、干燥和煅烧后得到钛钉/二氧化钛纳米管；
    S3、合成金纳米粒子和碳量子点；
    S4、将步骤S3中所述金纳米粒子和碳量子点负载至钛钉表面二氧化钛纳米管上，得到钛钉/二氧化钛纳米管/金纳米粒子/碳量子点。
  2. 根据权利要求1所述的一种在圆柱形钛钉表面的近红外响应功能涂层的制备方法，其特征在于：
    步骤S4中所述负载方法：步骤S3中所述金纳米粒子和碳量子点的溶液按照体积比1：2的比例混合得到混合溶液，并将步骤S2中得到的钛钉/二氧化钛纳米管垂直放置在所述混合溶液中，在真空环境中负载24h，之后在50℃下干燥24h。
  3. 根据权利要求1所述的一种在圆柱形钛钉表面的近红外响应功能涂层的制备方法，其特征在于：
    步骤S2中所述电解液的制备方法：称取0.34g的氟化铵，将其溶解到5mL水中配制成氟化铵溶液，量取95mL的去离子水，将去离子水和配好的氟化铵溶液混合作为电解液；
    在所述阳极氧化反应后将钛钉在乙醇中超声后干燥，除去钛钉上 面的硅胶和铜丝，在450℃下煅烧2个小时。
  4. 根据权利要求1所述的一种在圆柱形钛钉表面的近红外响应功能涂层的制备方法，其特征在于：
    步骤S1中所述钛钉预处理方法为：将直径为1mm、长度为6mm的钛钉用砂纸表面打磨后，依次用丙酮、乙醇和去离子水清洗，将所述钛钉干燥之后用刻蚀液刻蚀2分钟，再用铜丝把所述钛钉的一端缠绕一圈，用硅胶把所述铜丝缠绕钛钉的一端包裹住，常温下干燥6小时；
    所述刻蚀液为硝酸、氢氟酸和去离子水的体积比为4:1:5的混合溶液。
  5. 根据权利要求1所述的一种在圆柱形钛钉表面的近红外响应功能涂层的制备方法，其特征在于：
    步骤S3中所述金纳米粒子的制备方法：将0.01wt.％的氯金酸溶液油浴锅中加热并搅拌，在温度达到100℃时加入3mL的1wt.％的柠檬酸钠溶液，保持温度搅拌20min，停止加热冷却到室温，加入400mg的PVP后搅拌24h，以13000rpm离心30min，收集沉淀并用去离子水清洗3次，最后把金纳米粒子浓缩在8mL的去离子水中避光保存；
    步骤S3中所述碳量子点的制备方法：将2g乙二胺和2g柠檬酸溶解到20mL的乙醇放入反应釜中，180℃反应3h，以3000rpm离心15min除去反应液中的大颗粒沉淀，并用1000Da的透析膜透析48h除去离子和小分子杂质，避光4℃保存。
  6. 采用权利要求1至5中任一权利要求所述的方法制备的一种在圆柱形钛钉表面的近红外响应功能涂层在医用植入钛钉的应用，其特征在于：以808nm激光照射表面具有所述近红外相应功能涂层的钛钉15min。
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