CN113952503B - Near-infrared light response type titanium-based material and preparation method and application thereof - Google Patents
Near-infrared light response type titanium-based material and preparation method and application thereof Download PDFInfo
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- CN113952503B CN113952503B CN202111234843.4A CN202111234843A CN113952503B CN 113952503 B CN113952503 B CN 113952503B CN 202111234843 A CN202111234843 A CN 202111234843A CN 113952503 B CN113952503 B CN 113952503B
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 239000010936 titanium Substances 0.000 title claims abstract description 156
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 156
- 239000000463 material Substances 0.000 title claims abstract description 113
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 76
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 72
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- 229910001069 Ti alloy Inorganic materials 0.000 claims description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
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- IZTQOLKUZKXIRV-YRVFCXMDSA-N sincalide Chemical compound C([C@@H](C(=O)N[C@@H](CCSC)C(=O)NCC(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)NC(=O)[C@@H](N)CC(O)=O)C1=CC=C(OS(O)(=O)=O)C=C1 IZTQOLKUZKXIRV-YRVFCXMDSA-N 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The application provides a preparation method of a near-infrared light response type titanium-based material, which comprises the following steps: placing the pretreated titanium-based precursor in an alkali liquor for a first hydrothermal reaction to obtain a titanium-based body, wherein the temperature of the first hydrothermal reaction is 60-300 ℃, the time is 2-24 h, and the concentration of the alkali liquor is 0.5-10M; and (3) placing the titanium-based body in an acid solution to carry out a second hydrothermal reaction to obtain the near-infrared light response type titanium-based material, wherein the near-infrared light response type titanium-based material comprises the titanium-based body and a plurality of titanium oxide nano-rods arranged on the surface of the titanium-based body, the temperature of the second hydrothermal reaction is greater than or equal to 120 ℃, the time is greater than or equal to 3 hours, and the concentration of the acid solution is 0.01M-0.5M. The near infrared light response type titanium-based material prepared by the preparation method has near infrared light absorption and photocatalysis capabilities, an antibacterial effect and excellent biocompatibility. The application also provides a near-infrared light response type titanium-based material and an application thereof.
Description
Technical Field
The application relates to the field of materials, in particular to a near-infrared light response type titanium-based material and a preparation method and application thereof.
Background
The metal or alloy material, especially titanium and titanium alloy, has excellent biocompatibility, mechanical property, corrosion resistance and other advantages, is widely applied to dental implants, artificial joints and bone wounds, and becomes the preferred material for human hard tissue substitutes and restorations. Since titanium and titanium alloys have poor antibacterial properties and cause infection after implantation, there is a need for improvement of the antibacterial properties of implants.
In the related art, the antibacterial effect is directly achieved by adding an antibacterial material into the surface coating of the implant, or the antibacterial effect is achieved by adding a photosensitizer or a photo-thermal agent into the surface coating of the implant and irradiating the surface coating with near infrared light. For example, CN108853604A discloses a method for rapidly eliminating bacterial biofilm on the surface of a bone implant by using near infrared, which is to deposit red phosphorus on the surface of a titanium alloy to form a composite coating, and then further modify the composite coating by using IR780 and RGDC, so that the implant can rapidly remove staphylococcus aureus biofilm under the illumination of the near infrared light; CN109260476A discloses a method for preparing a molybdenum sulfide nano structure with photoresponse on a titanium alloy by hydrothermal treatment, then loading an antibiotic on the nano molybdenum sulfide, and finally spin-coating chitosan on a drug-loaded coating to obtain a 808nm near-infrared excited composite antibacterial coating. However, the antibacterial material, the photosensitizer or the photothermal agent still have certain cytotoxicity and poor biocompatibility, and the surface coating risks peeling off. Therefore, the current technical means improve the antibacterial performance of the implant, but influence the biocompatibility of the plant body.
Therefore, the development of an implant with both biocompatibility and antibacterial properties is an urgent problem to be solved in the biomedical field.
Disclosure of Invention
In view of this, the application provides a near-infrared light response type titanium-based material and a preparation method thereof, the titanium-based material with near-infrared light response is obtained by performing a hydrothermal reaction of an alkali solution and an acid solution, and the titanium-based material has a good antibacterial effect and excellent biocompatibility, and has excellent light absorption and photocatalysis capabilities under the action of near-infrared light, so that the antibacterial capability of the titanium-based material is remarkably improved, and the titanium-based material is beneficial to application of the titanium-based material in the fields of biomedical materials and photocatalysis.
In a first aspect, the present application provides a method for preparing a near-infrared light-responsive titanium-based material, comprising:
placing the pretreated titanium-based precursor in an alkali liquor for a first hydrothermal reaction to obtain a titanium-based body, wherein the temperature of the first hydrothermal reaction is 60-300 ℃, the time is 2-24 h, and the concentration of the alkali liquor is 0.5-10M;
and placing the titanium-based body in an acid solution to carry out a second hydrothermal reaction to obtain a near-infrared light response type titanium-based material, wherein the near-infrared light response type titanium-based material comprises a titanium substrate and a plurality of titanium oxide nano rods arranged on the surface of the titanium substrate, the temperature of the second hydrothermal reaction is greater than or equal to 120 ℃, the time is greater than or equal to 3 hours, and the concentration of the acid solution is 0.01-0.5M.
Optionally, the temperature of the first hydrothermal reaction is 120-150 ℃, and the concentration of the alkali liquor is 3-5M.
Optionally, the temperature of the second hydrothermal reaction is 120-300 ℃, and the time is 3-24 h.
Optionally, the surface of the titanium base body has a fibrous structure of titanate.
Optionally, the first hydrothermal reaction and the second hydrothermal reaction are performed in a reaction kettle, the volume of the alkali liquor is 1/4-3/4 of the volume of the reaction kettle, and the volume of the acid liquor is 1/4-3/4 of the volume of the reaction kettle.
Optionally, the lye comprises at least one of a sodium hydroxide solution, a potassium hydroxide solution, a lithium hydroxide solution and a calcium hydroxide solution.
Optionally, the acid solution comprises at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, formic acid and acetic acid.
Optionally, the pre-treatment comprises washing the titanium-based body with an acid wash.
Further, the acid cleaning solution comprises hydrofluoric acid with the mass fraction of 1.2% -2.2%, nitric acid with the mass fraction of 0.9% -1.6% and the balance of water.
Further, the washing time is 20-60 s.
Carrying out a first hydrothermal reaction on a titanium-based precursor in an alkaline solution and carrying out a second hydrothermal reaction in an acid solution to obtain a titanium-based material with near-infrared light response; the preparation method is simple, convenient to operate, high in biological safety, green and environment-friendly, and capable of performing large-scale generation to obtain the near-infrared light response type titanium-based material with excellent performance.
In a second aspect, the present application provides a near-infrared light-responsive titanium-based material, including a titanium substrate and a plurality of titanium oxide nanorods disposed on a surface of the titanium substrate, wherein the titanium oxide nanorods are formed on the surface of the titanium substrate by in-situ growth.
Optionally, the length of the titanium oxide nanorod is 60nm-120nm, the diameter of the titanium oxide nanorod is 10nm-40nm, and the distribution density of the titanium oxide nanorod is 200/mum 2 600 pieces/. Mu.m 2 。
Optionally, the plurality of titanium oxide nanorods are in a quasi-periodic structure on the surface of the titanium substrate.
Optionally, the titanium substrate is made of titanium or a titanium alloy.
Optionally, the near-infrared light response type titanium-based material is prepared by the preparation method of the first aspect.
The second aspect of the application provides a near-infrared light response type titanium-based material, which has an antibacterial effect, generates light absorption and photocatalysis under the illumination of near-infrared light, can generate hydroxyl radicals and singlet oxygen, and remarkably improves the antibacterial effect; meanwhile, the near-infrared light response type titanium-based material has good biocompatibility and good growth induction capability; the titanium oxide nano rod grows and forms on the surface of the titanium matrix in situ, and no obvious interface exists between the titanium oxide nano rod and the titanium matrix, so that the falling risk is reduced, and the stability and the reliability of the integral structure are ensured.
In a third aspect, the present application provides the near infrared light response type titanium-based material prepared by the preparation method of the first aspect, or the application of the near infrared light response type titanium-based material of the second aspect in biomedical materials and photocatalysis fields.
Optionally, the biomedical material comprises an implant.
The third aspect of the application provides an application of the near-infrared light response type titanium-based material in a biomedical material, so that the antibacterial effect and the biocompatibility of the biomedical material are improved; the near-infrared light response type titanium-based material can perform photocatalysis under the irradiation of near-infrared light, and is beneficial to the application of the material in the field of photocatalysis.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. The specific embodiments described herein are merely illustrative of the present application and are not intended to be limiting of the present application.
Fig. 1 is a schematic flow chart of a method for preparing a near-infrared light-responsive titanium-based material according to an embodiment of the present disclosure.
FIG. 2 is an electron microscope image of the surface morphology of the titanium alloy after acid washing in example 1.
FIG. 3 is an electron micrograph of the surface of the material treated with the NaOH solution of examples 1-9, wherein a, b, c, d, e, f, g, h, i in FIG. 3 correspond to example 2, example 3, example 4, example 5, example 1, example 6, example 7, example 8, example 9, respectively.
FIG. 4 is an electron micrograph of the surface of the materials prepared in examples 1, 10 to 11 and comparative examples 1 to 5, wherein a, b, c, d, e, f, g and h in FIG. 4 correspond to comparative example 1, comparative example 2, comparative example 3, comparative example 4, comparative example 5, example 10, example 11 and example 1, respectively.
Fig. 5 is a graph showing the uv-nir test results of the material prepared in example 1.
FIG. 6 is a graph showing the results of the photocatalytic performance test of the material obtained in example 1.
FIG. 7 is a graph showing the results of an antibacterial experiment of the material obtained in example 1.
FIG. 8 is a graph showing the results of cell proliferation experiments for the material prepared in example 1.
Detailed Description
The following is a preferred embodiment of the present application, and it should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present application, and these improvements and modifications are also considered as the protection scope of the present application.
Referring to fig. 1, a schematic flow chart of a method for preparing a near-infrared light response type titanium-based material according to an embodiment of the present application includes:
s101: and (3) placing the pretreated titanium-based precursor in an alkali liquor to carry out a first hydrothermal reaction to obtain a titanium-based body, wherein the temperature of the first hydrothermal reaction is 60-300 ℃, the time is 2-24 h, and the concentration of the alkali liquor is 0.5-10M.
S102: and (3) placing the titanium-based body in an acid solution to carry out a second hydrothermal reaction to obtain a near-infrared light response type titanium-based material, wherein the near-infrared light response type titanium-based material comprises the titanium-based body and a plurality of titanium oxide nano-rods arranged on the surface of the titanium-based body, the temperature of the second hydrothermal reaction is greater than or equal to 120 ℃, the time is greater than or equal to 3 hours, and the concentration of the acid solution is 0.01-0.5M.
In the application, the titanium oxide nanorods are generated by controlling the process conditions of the first hydrothermal reaction and the second hydrothermal reaction, and the light absorption of the titanium oxide nanorods is regulated from an ultraviolet region to a near-infrared region, so that the titanium oxide nanorods have excellent antibacterial performance and good biocompatibility under near-infrared light. Specifically, in the first hydrothermal reaction, the alkali solution reacts with the titanium-based precursor to form titanate, so as to obtain a titanium-based body with titanate; in the second hydrothermal reaction, by controlling the concentration of the acid solution, the temperature and the time of the second hydrothermal reaction, the titanate and the acid solution are reacted and corroded to dissolve, the dissolved titanate provides a titanium source for the second hydrothermal reaction along with the increase of the reaction time, titanium oxide nano-particles are formed, and finally titanium oxide nano-rods are formed; and the titanium oxide nanorods are better in size uniformity by treating with alkali liquor and then with acid liquor, thereby being beneficial to the improvement of antibacterial property of the titanium oxide nanorods.
The method comprises the steps of obtaining a titanium-based material with near-infrared light response through an alkaline-acid bidirectional hydrothermal treatment; the preparation method is simple, convenient to operate, green and environment-friendly, and capable of performing large-scale generation to obtain the near-infrared light response type titanium-based material with excellent performance. In the related technology, when the antibacterial material is added to improve the antibacterial performance of the titanium-based material, potential toxicity exists and drug resistance is easy to generate, so that the use of the titanium-based material is influenced, and when the photosensitizer and the photothermal agent are added to carry out photodynamic and photothermal treatment to generate the antibacterial effect, the photosensitizer and the photothermal agent have cytotoxicity and need to be combined with the titanium-based material by being attached to the coating, but the coating can be degraded and shed in the using process, so that the antibacterial performance is lost, and even secondary infection can occur. The titanium oxide nano-rods are directly generated on the surface of the titanium matrix through hydrothermal reaction, photodynamic sterilization can be realized under near infrared light, the use of foreign materials is avoided, and the safety is improved; and no obvious interface exists between the titanium oxide nanorod and the titanium substrate, so that the risk of falling off of the titanium oxide nanorod is reduced, the bonding strength between the titanium oxide nanorod and the titanium substrate is ensured, the stability and reliability of the overall structure are improved, the antibacterial capability and the antibacterial aging effect of the near-infrared light response type titanium-based material are improved, and the application of the titanium oxide nanorod and the titanium substrate is facilitated.
In S101, the pretreated titanium precursor is subjected to a first hydrothermal reaction in an alkali solution to produce a titanate.
In the application, the temperature of the first hydrothermal reaction is 60-300 ℃, the time is 2-24 h, and the concentration of the alkali liquor is 0.5-10M; the reaction temperature is too low, the reaction time is too short or the concentration of alkali liquor is too low, so that the titanate content is too low and cannot be used as a titanium source in the second hydrothermal reaction to promote the generation of the titanium oxide nanorods, and the reaction temperature is too high, the reaction time process or the concentration of alkali liquor is too high, so that the generation amount of titanate is too much, the dissolution of titanate in the second hydrothermal reaction is influenced, and the formation of the titanium oxide nanorods with near-infrared response is influenced; within the above range, the formation of titanate is facilitated and preparation is made for the subsequent formation of titanium oxide nanorods. In one embodiment of the present application, the temperature of the first hydrothermal reaction is 100-270 ℃, 120-240 ℃, 130-220 ℃, 150-180 ℃, 130-160 ℃, or 120-150 ℃ and the like; specifically, the temperature of the first hydrothermal reaction may be, but not limited to, 80 ℃, 120 ℃, 135 ℃, 145 ℃, 150 ℃, 170 ℃, 190 ℃, 225 ℃, 270 ℃, or the like. In another embodiment of the present application, the time of the first hydrothermal reaction is 2h-20h, 4h-18h, 5h-15h, 7h-17h, 10h-15h or 2h-4h, etc.; specifically, the first hydrothermal reaction time may be, but is not limited to, 2h, 3h, 5h, 9h, 12h, 15h, 19h, 24h, or the like. In yet another embodiment of the present application, the concentration of the alkaline solution is 1M-5M, 2M-8M, 3M-7M, 4M-10M, or 5M-7M, etc.; specifically, the concentration of the alkali solution can be, but is not limited to, 1M, 3M, 5M, 6M or 9M.
In an embodiment of the present application, the alkali solution includes at least one of a sodium hydroxide solution, a potassium hydroxide solution, a lithium hydroxide solution, and a calcium hydroxide solution. In one embodiment of the present application, the concentration of the lye is between 0.5M and 10M, i.e., OH in the lye - The concentration is 0.5M-10M.
In an embodiment of the application, the surface of the titanium base body has a fibrous structure of titanates. The titanium base body is obtained after the first hydrothermal reaction, the surface of the titanium base body is provided with the titanate with the fibrous structure, and the titanate with the fibrous structure can promote the size and distribution uniformity of the titanium oxide nano-rods in the second hydrothermal reaction, so that the quasi-periodic titanium oxide nano-structure can be obtained, and the antibacterial performance of the near-infrared light response type titanium base material is obviously improved.
In the embodiment of the application, the temperature of the first hydrothermal reaction is 120-150 ℃, and the concentration of the alkali liquor is 3-5M. Therefore, the titanium-based body with the fibrous titanate can be obtained, the quasi-periodic titanium oxide nano structure can be obtained, and the antibacterial property of the near-infrared light response type titanium-based material is improved. Furthermore, the temperature of the first hydrothermal reaction is 120-130 ℃, 125-140 ℃, 130-145 ℃ or 135-150 ℃ and the like, and the concentration of the alkali liquor is 3M-4M, 3.5M-4.5M or 4M-5M and the like. In one embodiment of the present application, the temperature of the first hydrothermal reaction is 120 ℃ to 150 ℃, the time is 2h to 24h, and the concentration of the alkali liquor is 3M to 5M, so that the titanium matrix with the fibrous titanate can be obtained. In a specific embodiment, the temperature of the first hydrothermal reaction is 120 ℃, the time is 4 hours, and the concentration of the alkali liquor is 4M; or the temperature of the first hydrothermal reaction is 130 ℃, the time is 4 hours, and the concentration of the alkali liquor is 5M; or the temperature of the first hydrothermal reaction is 145 ℃, the time is 2 hours, and the concentration of the alkali liquor is 5M; or the temperature of the first hydrothermal reaction is 150 ℃, the time is 3h, the concentration of the alkali liquor is 3M, and the like, so that the titanium matrix with the fibrous titanate can be obtained.
In the embodiment of the application, the first hydrothermal reaction is carried out in a reaction kettle, and the volume of the alkali liquor is 1/4-3/4 of the volume of the reaction kettle. The first hydrothermal reaction is carried out in the reaction kettle, and the volume of the alkali liquor is 1/4-3/4 of the volume of the reaction kettle, so that the pressure intensity of the titanium-based precursor in multiple experiments is further ensured to be the same, formation of titanate with the same morphology is facilitated, and preparation is made for subsequent formation of the titanium oxide nanorod. Specifically, the volume of the alkali liquor accounts for 0.25, 0.28, 0.3, 0.4, 0.5, 0.6 or 0.7 of the volume of the reaction kettle.
In the embodiment of the present application, the material of the titanium-based precursor is titanium or a titanium alloy. The titanium-based precursor becomes a titanium-based body after the first hydrothermal reaction, titanate is generated on the surface of the titanium-based body, and the part except the titanate in the titanium-based body is still titanium or titanium alloy.
In S102, a titanium base body is subjected to a second hydrothermal reaction in acid liquor, titanate reacts with the acid liquor to be corroded and dissolved, the dissolved titanate can serve as a titanium source, titanium oxide nanoparticles are generated on the surface of the titanium base body, and finally titanium oxide nanorods with near infrared light response are grown, so that the near infrared light response type titanium base material has near infrared light absorption, photocatalysis and antibacterial capabilities.
In the application, the temperature of the second hydrothermal reaction is more than or equal to 120 ℃, the time is more than or equal to 3 hours, and the concentration of the acid solution is 0.01M-0.5M; if the reaction temperature is too low, the reaction time is too short or the acid solution concentration is too low, the titanate cannot be completely dissolved, so that titanium oxide cannot be generated, or only titanium oxide nanoparticles are generated, a titanium oxide nanorod structure with near-infrared light response cannot be obtained, and a titanium-based material with an antibacterial effect cannot be obtained; the titanium-based material is corroded and dissolved due to the over-high concentration of the acid liquor, a corroded appearance is formed on the surface, the near infrared response is not available, and the titanium-based material with the antibacterial effect cannot be obtained. Therefore, the second hydrothermal reaction in the above range can obtain the titanium oxide nanorod with near infrared light response, thereby obtaining the near infrared light response type titanium-based material with antibacterial ability.
In the embodiment of the application, the concentration of the acid solution is 0.05M-0.25M, 0.1M-0.5M, 0.2M-0.45M, 0.3M-0.4M or 0.1M-0.35M, etc.; specifically, the concentration of the acid solution may be, but not limited to, 0.02M, 0.09M, 0.12M, 0.25M, 0.3M, 0.45M, 0.5M, or the like.
In the embodiment of the present application, the temperature of the second hydrothermal reaction is 120 ℃ to 300 ℃ and the time is 3h to 24h. Therefore, the uniformity and orientation of the formed titanium oxide nanorod can be improved, the quasi-periodic titanium oxide nanostructure can be obtained, the crystal face of the titanium oxide can be more exposed, and the antibacterial capability of the near-infrared light response type titanium-based material can be further improved. In one embodiment of the application, the temperature of the second hydrothermal reaction is 150-210 ℃, 150-200 ℃, 150-180 ℃, 155-170 ℃, 160-180 ℃, 170-210 ℃ or the like; specifically, the temperature of the second hydrothermal reaction may be, but not limited to, 120 ℃, 150 ℃, 160 ℃, 170 ℃, 190 ℃, 200 ℃, 250 ℃, 280 ℃, or the like. In another embodiment of the present application, the time of the second hydrothermal reaction is 3h to 20h, 5h to 24h, 5h to 18h, 7h to 15h, or the like; specifically, the second hydrothermal reaction time may be, but is not limited to, 3h, 5h, 8h, 10h, 15h, 18h, 20h, 22h, or the like. In a specific embodiment, the temperature of the second hydrothermal reaction is 150-210 ℃ and the time is 3-5 h.
In an embodiment of the present application, the acid solution includes at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, formic acid, and acetic acid. Specifically, the acid solution may be, but not limited to, hydrochloric acid, a mixed solution of hydrochloric acid and sulfuric acid, a mixed solution of nitric acid and phosphoric acid, a mixed solution of formic acid and acetic acid, and the like. In one embodiment of the present application, the acid solution has a concentration of 0.01M to 0.5M, i.e., H in the acid solution + The concentration is 0.01M-0.5M.
In the embodiment of the application, the second hydrothermal reaction is carried out in a reaction kettle, and the volume of the acid solution is 1/4-3/4 of the volume of the reaction kettle. The second hydrothermal reaction is carried out in the reaction kettle, and the volume of the acid liquor is 1/4-3/4 of the volume of the reaction kettle, so that the pressure stability in the second hydrothermal reaction is ensured, the improvement of the uniformity of the size of the titanium oxide nano-rod is facilitated, and the antibacterial performance of the near-infrared light response type titanium-based material can be enhanced. Specifically, the volume of the acid solution accounts for 0.25, 0.28, 0.3, 0.4, 0.5, 0.6 or 0.7 of the volume of the reaction kettle.
In the embodiment of the application, the temperature of the first hydrothermal reaction is 120-150 ℃, the time is 2-24 h, and the concentration of the alkali liquor is 3-5M; the temperature of the second hydrothermal reaction is 120-300 ℃, the time is 3-24 h, and the concentration of the acid liquid is 0.01-0.5M, so that the near-infrared light response type titanium-based material with the quasi-periodic titanium oxide nano structure can be obtained.
In the embodiment of the application, titanium oxide nanorods are arranged on 70% -90% of the surface of the titanium matrix in the near infrared light response type titanium-based material. It is understood that the surface of the titanium substrate on which the first hydrothermal reaction and the second hydrothermal reaction can occur is taken as a reference.
In an embodiment of the present application, the pre-treatment includes washing the titanium-based body with an acid wash. Thus, the oxide film formed on the surface of the titanium base body can be removed. In one embodiment of the present application, the acid cleaning solution includes hydrofluoric acid, nitric acid and water. Optionally, the acid cleaning solution includes hydrofluoric acid with a mass fraction of 1.2% -2.2%, nitric acid with a mass fraction of 0.9% -1.6%, and the balance of water. Further, the acid cleaning solution comprises 1.5-2% by mass of hydrofluoric acid, 1-1.5% by mass of nitric acid and the balance of water. In a specific embodiment, the hydrofluoric acid solution with the mass fraction of 48%, the dilute nitric acid with the mass fraction of 48% and water are mixed and then diluted by 15 times to obtain the acid cleaning solution, wherein the volume ratio of the hydrofluoric acid solution to the dilute nitric acid to the water during mixing is 3. In one embodiment of the present application, the time for cleaning is 20s-60s. Specifically, the washing time may be, but is not limited to, 20s, 25s, 30s, 35s, 40s, 46s, 50s, 55s, 57s, 60s, or the like. In an embodiment of the application, the pre-treatment further includes water cleaning and drying the titanium-based body after the acid cleaning solution is cleaned. Specifically, the water cleaning may be, but not limited to, deionized water cleaning. In a specific embodiment, the titanium substrate is cleaned for 20-60 s by acid cleaning solution, then cleaned for three times by deionized water, and finally dried.
The application provides a near-infrared light response type titanium-based material, which comprises a titanium substrate and a plurality of titanium oxide nanorods arranged on the surface of the titanium substrate, wherein the titanium oxide nanorods are formed on the surface of the titanium substrate through in-situ growth.
In the application, the near-infrared light response type titanium-based material comprises a titanium matrix and a plurality of titanium oxide nanorods arranged on the surface of the titanium matrix, and the titanium oxide nanorods are formed on the surface of the titanium matrix through in-situ growth and have no obvious interface with the titanium matrix, so that the risk of falling off of the titanium oxide nanorods is reduced, the bonding strength between the titanium oxide nanorods and the titanium matrix is ensured, and the stability and reliability of the whole structure are improved; the near-infrared light response type titanium-based material has good antibacterial capacity, good tissue growth induction capacity and biocompatibility; the titanium oxide nanorod has near infrared light response, so that the near infrared light response type titanium-based material has near infrared light response, generates photocatalysis under the irradiation of near infrared light, remarkably improves the antibacterial capability of the near infrared light response type titanium-based material, such as the antibacterial capability to escherichia coli, staphylococcus aureus and the like, and is beneficial to application of the near infrared light response type titanium-based material.
In an embodiment of the present application, the near-infrared light-responsive titanium-based material is prepared by the preparation method according to any one of the above embodiments.
In the embodiment of the present application, the titanium oxide nanorods have a length of 60nm to 120nm, a diameter of 10nm to 40nm, and a distribution density of 200 particles/μm 2 600 pieces/. Mu.m 2 . In one embodiment of the present application, the length of the titanium oxide nanorod is 60nm-80nm, 60nm-100nm, 70nm-110nm, 75nm-115nm, 85nm-100nm, 80nm-105nm, 100nm-120nm, etc. Specifically, the length of the titanium oxide nanorod can be, but is not limited to, 60nm, 75nm, 85nm, 90nm, 95nm, 100nm, 110nm, 120nm, or the like. In another embodiment of the present application, the diameter of the titanium oxide nanorods is 15nm-35nm, 15nm-30nm, 20nm-40nm, 25nm-35nm, or 30nm-40nm, etc. Specifically, the diameter of the titanium oxide nanorods can be, but is not limited toThe wavelength is limited to 10nm, 15nm, 20nm, 22nm, 25nm, 30nm, 35nm, 40nm, or the like. In yet another embodiment of the present application, the titanium oxide nanorods have a distribution density of 250/μm 2 600 pieces/. Mu.m 2 300 pieces/. Mu.m 2 550 pieces/. Mu.m 2 350 pieces/. Mu.m 2 500 pieces/. Mu.m 2 400 pieces/. Mu.m 2 550 pieces/. Mu.m 2 Or 480 pieces/. Mu.m 2 600 pieces/. Mu.m 2 And so on. Specifically, the distribution density of the titanium oxide nanorods can be, but is not limited to, 200/μm 2 300 pieces/. Mu.m 2 350 pieces/. Mu.m 2 400 pieces/. Mu.m 2 450 pieces/. Mu.m 2 500 pieces/. Mu.m 2 Or 600 pieces/. Mu.m 2 And the like.
In the embodiment of the application, the plurality of titanium oxide nanorods are in a quasiperiodic structure on the surface of the titanium matrix. Therefore, the photocatalysis capability and the antibacterial capability of the near-infrared light response type titanium-based material can be obviously improved. As can be understood, the quasi-periodic structure is that the titanium oxide nanorods are aligned and oriented in a certain mode in a local range of the titanium matrix and have a regular appearance in the local range. That is to say, near infrared light response type titanium-based material includes the titanium base body and sets up the quasiperiodic titanium oxide nanometer structure on the titanium base body surface, and quasiperiodic titanium oxide nanometer structure includes a plurality of titanium oxide nanorods, and it can be in a plurality of directions regulation and control, realizes excellent antibiotic effect. In the application, the titanium oxide nanorods in the quasi-periodic titanium oxide nanostructure have better size uniformity and higher distribution density, thereby being beneficial to improving the antibacterial performance of the structure. In an embodiment of the present application, the plurality of titanium oxide nanorods in the quasi-periodic titanium oxide nanostructure are obliquely disposed on the titanium substrate, and the plurality of titanium oxide nanorods are staggered.
In the embodiment of the present application, the material of the titanium substrate is titanium or a titanium alloy. The titanium or the titanium alloy has excellent mechanical property, corrosion resistance and biocompatibility, and is beneficial to the use of the near infrared light response type titanium-based material.
The application also provides application of the near-infrared light response type titanium-based material provided by any one of the above embodiments in biomedical materials and photocatalysis fields. That is, the near-infrared light responsive titanium-based material can be used in biomedical materials, the field of photocatalysis, and the like. In embodiments of the present application, the biomedical material comprises an implant. Specifically, the implant can be used for, but not limited to, a dental implant, a bone implant and the like, has biocompatibility, has excellent antibacterial capability under near infrared light illumination, and prolongs the service life of biomedical materials.
Example 1
A method of preparing a titanium-based material, comprising:
mixing 20mL of deionized water, 6mL of 48% hydrofluoric acid and 4mL of 48% nitric acid, and diluting by 15 times to obtain an acid cleaning solution; cleaning the surface of a titanium alloy (TC 4, junhang Metal materials Co., ltd., baoji city, diameter 15mm, thickness 1 mm) for 30s by using an acid cleaning solution, cleaning for 3 times by using deionized water, and drying for later use; the surface morphology of the titanium alloy after acid cleaning was observed by scanning electron microscopy, and the results are shown in fig. 2.
Putting the acid-cleaned titanium alloy into a reaction kettle with the volume of 150mL, adding 50mL of 3M sodium hydroxide solution to immerse the titanium alloy, screwing the reaction kettle, putting the reaction kettle into an oven, carrying out heat preservation treatment at 150 ℃ for 3 hours, then cleaning the alkali-treated titanium alloy with absolute ethyl alcohol, and drying.
And (3) putting the titanium alloy subjected to alkali treatment into a reaction kettle with the volume of 150mL, adding 50mL of 0.18M hydrochloric acid solution to immerse the titanium alloy, carrying out heat preservation treatment at 150 ℃ for 4h, ultrasonically cleaning the titanium alloy subjected to acid treatment by using deionized water, and drying for later use.
Example 2
The procedure was as in example 1 except that a 1M sodium hydroxide solution was used and the treatment temperature was 120 ℃.
Example 3
The procedure was as in example 1, except that 1M sodium hydroxide solution was used and the treatment temperature was 150 ℃.
Example 4
The procedure was as in example 1 except that a 1M sodium hydroxide solution was used and the treatment temperature was 180 ℃.
Example 5
The procedure was as in example 1, except that 3M sodium hydroxide solution was used and the treatment temperature was 120 ℃.
Example 6
The procedure was as in example 1, except that 3M sodium hydroxide solution was used and the treatment temperature was 180 ℃.
Example 7
The procedure was as in example 1, except that 5M sodium hydroxide solution was used and the treatment temperature was 120 ℃.
Example 8
The procedure was as in example 1, except that 5M sodium hydroxide solution was used and the treatment temperature was 150 ℃.
Example 9
The procedure was as in example 1, except that 5M sodium hydroxide solution was used and the treatment temperature was 180 ℃.
Example 10
The same as in example 1, except that the treatment time of the hydrochloric acid solution was changed to 3 hours.
Example 11
The same as in example 1, except that the treatment time of the hydrochloric acid solution was changed to 3.5 hours.
Comparative example 1
The same as example 1 except that the hydrochloric acid solution was treated for 0.5 hour.
Comparative example 2
The same as in example 1, except that the treatment time of the hydrochloric acid solution was changed to 1 hour.
Comparative example 3
The same as example 1 except that the hydrochloric acid solution was treated for 1.5 hours.
Comparative example 4
The same as example 1, except that the treatment time of the hydrochloric acid solution was changed to 2 hours.
Comparative example 5
The same as example 1 except that the hydrochloric acid solution was treated for 2.5 hours.
Performance detection
(1) Surface topography observation
The surface of the material treated with the sodium hydroxide solution in examples 1 to 9 was observed with a scanning electron microscope, and the results are shown in FIG. 3, in which a, b, c, d, e, f, g, h, and i in FIG. 3 correspond to example 2, example 3, example 4, example 5, example 1, example 6, example 7, example 8, and example 9, respectively, and the scale is 500nm, as shown in i in FIG. 3. As can be seen from a, b and c in fig. 3, with the increase of the treatment temperature, the morphology of the titanium alloy surface is gradually changed from sheet-shaped titanate to a fibrous structure, and the sheet-shaped structure still exists at the treatment temperature of 180 ℃; as can be seen from d, e and f in fig. 3, fibrous structures are formed at the treatment temperatures of 120 ℃ and 150 ℃, and the titanate is changed into sheets from fibrous structures by continuously increasing the treatment temperature; as can be seen from g, h and i in FIG. 3, the surface of the titanium alloy is formed with fibrous titanate.
The surface observation of the materials obtained in examples 1, 10 to 11 and comparative examples 1 to 5 using a scanning electron microscope showed that the results are shown in FIG. 4, in which a, b, c, d, e, f, g and h in FIG. 4 correspond to comparative example 1, comparative example 2, comparative example 3, comparative example 4, comparative example 5, example 10, example 11 and example 1, respectively, and the scale is 100nm, as shown in e in FIG. 4. As can be seen from a and b in fig. 4, fibrous titanate is formed on the surface of the titanium alloy after the alkali treatment, and under the action of hydrochloric acid, the titanate is firstly corroded and dissolved; as can be seen from c-h in FIG. 4, as the hydrochloric acid treatment time increases, the dissolved titanate provides a titanium source for the hydrothermal reaction, so that titanium oxide nanoparticles begin to form on the surface of the titanium alloy, and as the particles grow, titanium oxide nanorods gradually form, even quasi-periodic titanium oxide nanostructures (h in FIG. 4), wherein the average distribution density of the titanium oxide nanorods in f-h in FIG. 4 is 260.32/μm 2 300.43 pieces/. Mu.m 2 383.24 pieces/. Mu.m 2 424.54 pieces/. Mu.m 2 445.27/. Mu.m 2 480.29 pieces/. Mu.m 2 . In the alkali-acid water heat treatment process, titanate is formed firstly, and then is completely dissolved under the acid treatmentDissolving, taking the dissolved titanate as a titanium source, and forming titanium oxide nanorods on the surface of the titanium alloy through hydrothermal reaction, and even forming a quasi-periodic titanium oxide nano structure.
(2) Light absorption Performance test
The material prepared in example 1 was subjected to an ultraviolet-near infrared test at a wavelength of 260nm to 2650nm to evaluate the light absorption property of the material, and the result is shown in fig. 5 using the titanium alloy after acid cleaning as a control. It can be seen that the titanium alloy provided by the titanium alloy in the range of 260nm to 2650nm only has ultraviolet absorption (within 350 nm), titanium oxide nanorods are formed along with the increase of the acid treatment time, the light absorption of the material gradually red shifts to 808nm, and the material prepared in example 1 has remarkable near infrared light absorption, so that the realization of the antibacterial performance of the material under the irradiation of near infrared light is facilitated.
(3) Photocatalytic Performance test
Methylene blue was formulated with deionized water to a concentration of 10ppm as methylene blue solution. The first group is that the titanium alloy after acid cleaning is placed in a 24-hole plate, 1mL of methylene blue solution is added into each hole, the titanium alloy is placed for 0min, 10min, 30min, 60min, 120min, 180min and 240min under the condition of no illumination, and finally, an enzyme-labeling instrument is used for measuring the absorbance value of the solution in each hole under the condition of 664 nm; the second group is that the material prepared in the example 1 is placed in a 24-hole plate, 1mL of methylene blue solution is added into each hole, the materials are respectively placed for 0min, 10min, 30min, 60min, 120min, 180min and 240min under the condition of no illumination, and finally the absorbance value of the solution in each hole is measured by a microplate reader under the condition of 664 nm; the third group is that the titanium alloy after acid cleaning is placed in a 24-hole plate, 1mL of methylene blue solution is added into each hole, then the titanium alloy is respectively irradiated for 0min, 10min, 30min, 60min, 120min, 180min and 240min under near-infrared light of 808nm, and finally the absorbance value of the solution in each hole is measured by an enzyme-labeling instrument under 664 nm; and the fourth group is to put the material prepared in the example 1 into a 24-well plate, add 1mL of methylene blue solution into each well, irradiate the material for 0min, 10min, 30min, 60min, 120min, 180min and 240min under the near infrared light of 808nm respectively, measure the absorbance value of the solution in each well by a microplate reader at 664nm, and evaluate the degradation condition of the methylene blue, wherein the result is shown in figure 6.
It can be seen that the titanium alloy has no strong ability to catalyze methylene blue degradation no matter whether the titanium alloy is illuminated or not, the material prepared in example 1 has the ability to catalyze methylene blue degradation, and the ability to catalyze methylene blue degradation is significantly improved under 808nm illumination, which indicates that the titanium-based material provided by the application has significant photocatalytic ability under near-infrared light illumination.
(4) Antibacterial experiments
The material obtained in example 1 and the acid-washed titanium alloy were autoclaved at 121 ℃ for 20min, placed in a 24-well plate, and Escherichia coli (E.coli) and Staphylococcus aureus (S.aureus) were each applied at a density of 1X 10 7 CFU/mL was inoculated on the material and incubated in an incubator at 37 ℃ for 24h, wherein the first group used acid-washed titanium alloy, the second group used the material prepared in example 1, and the third group used acid-washed titanium alloy and used 808nm (0.5W/cm) after incubation for 24h 2 ) The well plate was irradiated with near infrared light for 10min, and the fourth group was prepared using the material prepared in example 1 and using 808nm (0.5W/cm) after incubation for 24h 2 ) Irradiating the orifice plate for 10min by near infrared light; then, the material was washed three times with a phosphate buffer solution, and the activity of the bacteria was measured with thiazole blue (MTT), and the activity of the bacteria was evaluated by the OD value at a wavelength of 570nm in a microplate reader to evaluate the antibacterial property of the material, and the result is shown in FIG. 7.
It can be seen that there is no significant difference in bacterial activity and bacterial amount on the titanium alloy, whether or not it is illuminated, and even if it is illuminated by near infrared light, the titanium alloy still has no antibacterial ability; the nanostructure on the surface of the titanium-based material provided by the embodiment 1 inhibits the adhesion of bacteria to a certain extent, and shows a certain antibacterial ability, and the antibacterial performance of the material is remarkably improved and the bacterial activity is remarkably reduced by near-infrared light illumination, which shows that the titanium-based material provided by the application has a remarkable antibacterial ability under near-infrared light.
(5) Cell proliferation assay
The material prepared in example 1 and the acid-washed titanium alloy were autoclaved at 121 ℃ for 20min, placed in a 24-well plate, and gingival fibroblasts (HGFs) at 5X 10 4 Is smallCell/well density was inoculated onto the material at 37 deg.C, 5% 2 Culturing in an incubator; wherein the first group was made of acid-washed titanium alloy, the second group was made of the material prepared in example 1, cell proliferation was measured by 2- (2-methoxy-4-nitrophenyl) -3- (4-nitrophenyl) -5- (2, 4-disulfophenyl) -2H-tetrazole monosodium salt (CCK-8) for one, three and seven days of culture in the first and second groups, and the cell proliferation was evaluated by OD at a 450nm wavelength using a microplate reader; the third group was made of the acid-washed titanium alloy, the fourth group was made of the material obtained in example 1, and the third and fourth groups were cultured for one day using 808nm (0.5W/cm) 2 ) The cells were irradiated with near infrared light for 10min and then cultured, and the proliferation of the cells on various materials was evaluated by measuring the proliferation of the cells by CCK-8 after the third and fourth groups were cultured for one day and irradiated for 10min, and the proliferation of the cells by three days and seven days of culture, and the results are shown in FIG. 8.
It can be seen that after one day of culture, the proliferation of the cells of the second group is evident, that is to say the material prepared in example 1 promotes the proliferation of the cells; after one day of culture, the fourth group had a lower cell proliferation amount than the second group, but was comparable to the first group; when the culture is continued to the third day and the seventh day, the cell growth level of the fourth group is equivalent to that of the second group, which shows that the damage of the cells caused by illumination can be recovered by the culture, and the cell growth level of the second group and the fourth group is obviously higher than that of the first group and the third group, which shows that the titanium-based material provided by the application has good biocompatibility.
The above-mentioned embodiments only express several implementation modes of the present application, and the description thereof is specific and detailed, but not to be construed as limiting the scope of the present application. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present application shall be subject to the appended claims.
Claims (8)
1. A preparation method of a near-infrared light response type titanium-based material is characterized by comprising the following steps:
placing the pretreated titanium-based precursor in an alkali liquor for a first hydrothermal reaction to obtain a titanium-based body, wherein the temperature of the first hydrothermal reaction is 100-270 ℃, the time is 2-24 h, and the concentration of the alkali liquor is 0.5-10M;
and placing the titanium-based body in an acid solution to carry out a second hydrothermal reaction to obtain a near-infrared light response type titanium-based material, wherein the near-infrared light response type titanium-based material comprises a titanium substrate and a plurality of titanium oxide nano rods arranged on the surface of the titanium substrate, the temperature of the second hydrothermal reaction is greater than or equal to 120 ℃, the time is greater than or equal to 3 hours, and the concentration of the acid solution is 0.01-0.5M.
2. The preparation method according to claim 1, wherein the temperature of the first hydrothermal reaction is 120 ℃ to 150 ℃, and the concentration of the alkali liquor is 3M to 5M;
the temperature of the second hydrothermal reaction is 120-300 ℃, and the time is 3-24 h.
3. The method of claim 1, wherein the surface of the titanium base body has a fibrous structure of titanate.
4. The preparation method according to claim 1, wherein the first hydrothermal reaction and the second hydrothermal reaction are carried out in a reaction kettle, the volume of the alkali liquor is 1/4-3/4 of the volume of the reaction kettle, and the volume of the acid liquor is 1/4-3/4 of the volume of the reaction kettle;
the alkali liquor comprises at least one of sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution and calcium hydroxide solution; the acid solution comprises at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, formic acid and acetic acid.
5. The method of claim 1, wherein the pre-treating comprises washing the titanium-based body with an acid wash; the acid cleaning solution comprises 1.2-2.2% of hydrofluoric acid by mass, 0.9-1.6% of nitric acid by mass and the balance of water; the cleaning time is 20-60 s.
6. The method of claim 1, wherein the titanium oxide nanorods have a length of 60nm to 120nm, a diameter of 10nm to 40nm, and a distribution density of 200 particles/μm 2 600 pieces/. Mu.m 2 。
7. The method according to claim 1, wherein a plurality of the titanium oxide nanorods exhibit a quasi-periodic structure on the surface of the titanium substrate.
8. The method according to claim 1, wherein the titanium substrate is made of titanium or a titanium alloy.
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