CN114031112A - Titanium oxide photo-thermal material, preparation method thereof and application thereof in photo-thermal tumor treatment under second biological infrared window - Google Patents
Titanium oxide photo-thermal material, preparation method thereof and application thereof in photo-thermal tumor treatment under second biological infrared window Download PDFInfo
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Abstract
The invention provides a titanium oxide photo-thermal material, wherein the crystal form of the titanium oxide photo-thermal material is a rutile phase; the titanium oxide photo-thermal material is blue-gray. Compared with the prior art, the titanium oxide photo-thermal material provided by the invention has high free electron concentration, so that the band gap is narrowed, the spectral range which can be absorbed and utilized by the material is effectively widened, the absorption range and the intensity of the material to infrared light are enhanced, particularly, the material is enhanced to absorb and utilize the light energy in a second biological near-infrared window, the non-radiative energy loss is reduced, and finally, the efficient photo-thermal conversion under the efficient second biological infrared window is realized; the titanium oxide photo-thermal material has excellent biological safety, can not damage normal biological tissues, is used for photo-thermal treatment of cancer under a second biological infrared window, and has remarkable effect.
Description
Technical Field
The invention belongs to the technical field of photothermal treatment, and particularly relates to a titanium oxide photothermal material, a preparation method thereof and application thereof in photothermal tumor treatment under a second biological infrared window.
Background
Photothermal therapy of cancer is becoming an attractive minimally invasive tumor treatment technique with significant therapeutic effects and is gradually becoming a potential alternative to chemotherapy, radiotherapy, gene therapy and immunotherapy in traditional cancer treatment. However, the lack of recognition of tumor prevention, occurrence, metastasis and angiogenesis, and the limitations of current diagnostic methods have prevented the development of clinical cancer treatment technologies, and cancer remains one of the important diseases worldwide threatening human health. In principle, phototherapy for cancer is primarily photothermal therapy (PTT), whereby due to the high permeability of the capillaries and the insufficient endothelial and lymphatic drainage, photothermal agents (PTAs) can be administered and accumulate in the tumor tissue via enhanced permeability and retention Effects (EPR). When tumor tissue is locally irradiated with near infrared light of a specific wavelength, electrons in nano-PTAs are excited by light, which can release heat by non-radiative vibrational relaxation to cause thermal damage to tumor cells.
The design of nano-PTAs with significant photothermal conversion efficiency at the atomic level is of great significance for tumor hyperthermia. The PTAs materials that have been widely reported so far include noble metals, graphene, transition metal dichalcogenides, MXene, polymers, and inorganic-organic hybrid materials. Some of the advanced techniques have begun to be applied in clinical trials, bringing new eosins to cancer patients, and they are still under investigation and improvement. It is noteworthy that a significant portion of these PTAs can typically only absorb and utilize near infrared light in the first biological window (NIR-I, λ 780-1000 nm), and little attention has been paid to developing PTAs materials with infrared light illumination that can work effectively in the second biological window (NIR-ii, λ 1000-1350 nm). However, NIR-II light can provide greater tissue penetration depth and the maximum allowable exposure of the skin to NIR-II laser light is higher.
Semiconductors are one of the well-studied functional nanomaterials, and they are also promising candidates for PTAs materials with excellent biocompatibility. Among them, metal oxides are particularly attractive because of their combination of various cations and anions, stoichiometry, and tunability of crystal phases, and their conduction and valence bands have strong reducing and oxidizing abilities, and can convert absorbed electromagnetic waves into thermal energy for various fields. However, most of the research on photothermal therapies based on metal oxide-PTAs has focused only on the NIR-I region due to the inherently wide band gap structure of semiconductors resulting in low infrared light absorption, low photothermal efficiency, and high electron-hole recombination velocity. In order to expand the optical response range of metal oxide PTAs to the NIR-ii range, the leading strategies of introducing impurities for doping, oxygen vacancy, heterojunction construction, sensitization treatment of composite dye molecules, or composite upconversion nanoparticles are generally adopted, but the low doping content, low free carrier concentration and residual wide energy band gap make the electronic transition process of metal oxides occurring in the NIR-ii biological window still difficult to obtain.
TiO2Is a classical metal oxide semiconductor material, which not only has multifunctionality, but also has low cost, expandability and biosafety. TiO 22Have been demonstrated to affect certain microorganisms, bacteria, viruses, cancer cells, etc., including the regulation of lipid hyperoxidation of biological membranes, as well as interactions between proteins leading to altered cell internal conditions and ultimately, the process of apoptosis in cell metabolism. It has also been shown that TiO2As a disinfectant, chemical substances such as ozone, ultraviolet radiation, chlorine and the like can be used for sewage treatment and disinfection, and safe water is provided for life and production of human beings in modern society. However, TiO in stoichiometric ratio2(atomic ratio of Ti to O is 1:2) has a large energy band gap of about 3.2eV, which results in TiO2The material has low energy utilization efficiency on visible light and infrared light, can only absorb and utilize ultraviolet light with the light wavelength of 380nm or less, and is not suitable for being used as a PTAS material medium to perform infrared response photo-thermal application. Therefore, developProduce novel TiO2Materials, and having high infrared light absorption and utilization capabilities and being applied to near infrared photothermal therapy of cancer, remain a formidable challenge.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a titanium oxide photo-thermal material, a preparation method thereof, and an application thereof in photo-thermal tumor treatment in a second biological infrared window, wherein the titanium oxide photo-thermal material has a high free electron concentration, which causes a band gap to narrow, so that a spectral range in which the material can be absorbed and utilized is effectively widened, thereby enhancing an absorption range and intensity of infrared light, especially, the enhancement material absorbs and utilizes light energy in the second biological near-infrared window, and simultaneously reduces non-radiative energy loss, and finally, efficient photo-thermal conversion in the second biological infrared window is realized.
The invention provides a titanium oxide photo-thermal material, wherein the crystal form of the titanium oxide photo-thermal material is rutile phase; the titanium oxide photo-thermal material is blue-gray.
Preferably, the carrier concentration of the titanium oxide photothermal material is 4.9 × 1020cm-3(ii) a The conductivity of the titanium oxide photo-thermal material is 2.5 multiplied by 10-2S/m; the particle size of the titanium oxide photo-thermal material is 50-200 nm.
The invention also provides a preparation method of the titanium oxide photo-thermal material, which comprises the following steps:
mixing titanium dioxide powder and magnesium powder in an acid solution for reaction to obtain a titanium oxide photo-thermal material; the particle size of the titanium dioxide powder is less than 200 nm.
Preferably, the titanium dioxide powder is prepared according to the following method:
s1) mixing titanium trichloride, an alcohol solvent and a nonionic surfactant, and heating to perform a solvothermal reaction to obtain an intermediate product;
s2) subjecting the intermediate product to high-temperature calcination in an oxidizing atmosphere to obtain a titanium dioxide powder.
Preferably, the volume ratio of the titanium trichloride to the alcohol solvent is 1: (10-20); the ratio of the titanium trichloride to the surfactant is 1 mL: (0.1-0.5) g;
the alcohol solvent is ethanol; the nonionic surfactant is polyvinylpyrrolidone; the molecular weight of the nonionic surfactant is 8000-58000.
Preferably, the mixing time in the step S1) is 30-90 min; the temperature of the solvothermal reaction is 130-150 ℃; the solvothermal reaction time is 20-30 h;
after the solvothermal reaction in the step S1), centrifuging, washing and drying to obtain an intermediate product; the speed of the centrifugation is not lower than 10000 rpm; the centrifugation time is not less than 3 min.
Preferably, the high-temperature calcination temperature is 600-750 ℃; the high-temperature calcination time is 3-5 h.
Preferably, the concentration of the acid in the acid solution is 0.5-1 mol/L; the acid solution is selected from one or more of dilute sulfuric acid, dilute perchloric acid and dilute phosphoric acid.
Preferably, the mass ratio of the titanium dioxide powder to the magnesium powder is 1: (0.5 to 1); the mixing reaction time is 10-60 min.
The invention also provides a photothermal agent capable of carrying out photothermal tumor treatment under a second biological infrared window, which comprises the titanium oxide photothermal material.
The invention provides a titanium oxide photo-thermal material, wherein the crystal form of the titanium oxide photo-thermal material is rutile phase; the titanium oxide photo-thermal material is blue-gray. Compared with the prior art, the titanium oxide photo-thermal material provided by the invention has high free electron concentration, so that the band gap is narrowed, the spectral range which can be absorbed and utilized by the material is effectively widened, the absorption range and the intensity of the material to infrared light are enhanced, especially, the material is enhanced to absorb and utilize the light energy in a second biological near-infrared window, meanwhile, the non-radiative energy loss is reduced, and finally, the efficient photo-thermal conversion under the efficient second biological infrared window is realized; and the titanium oxide photo-thermal material has excellent biological safety, can not damage normal biological tissues, is used for photo-thermal treatment of cancer under a second biological infrared window, and has remarkable effect.
Experiments show that the titanium oxide photo-thermal material with high NIR-II photo-thermal effect integrates the advantages of all excellent photo-thermal materials, the material has no toxicity to normal physiological cells, and the material is irradiated by 1064nm infrared light (the irradiation power is 1.0W/cm)2) The photothermal conversion efficiency is 35%, when the dosage is 200 mug/mL, and the dosage is matched with 1064nm illumination, the significant killing effect can be caused on mouse breast cancer 4T1 cells, and the effective killing efficiency is 90.5%.
Drawings
FIG. 1 shows white TiO prepared in example 1 of the present invention2A picture of the powder and the titanium oxide photo-thermal material;
FIG. 2 shows white TiO prepared in example 1 of the present invention2SEM scanning electron microscope appearance photos of the powder and the titanium oxide photo-thermal material;
FIG. 3 is an XRD spectrum of a titanium oxide photothermal material obtained in example 1 of the present invention;
FIG. 4 is an absorption spectrum of a titanium oxide photothermal material obtained in example 1 of the present invention;
FIG. 5 is a theoretical calculation graph of the DOS band structure of the titanium oxide photothermal material obtained in example 1 of the present invention;
FIG. 6 shows the power of the titanium oxide photo-thermal material obtained in example 1 of the present invention at 1064nm near-infrared light at different aqueous solution concentrations and 1W/cm2A graph of the temperature of the solution as a function of time under the irradiation conditions of (1);
FIG. 7 is a graph showing the temperature change with time and the photothermal imaging of the titanium oxide photothermal material obtained in example 1 of the present invention after irradiation with infrared light through a 1064nm second biological window under different concentration conditions;
FIG. 8 is a graph showing a toxicity test (cell survival test) of the titanium oxide photothermal material obtained in example 1 of the present invention against mouse 4T1 breast cancer cells;
FIG. 9 is a graph showing the survival rate of mouse breast cancer 4T1 cells of the titanium oxide photothermal material obtained in example 1 of the present invention under different concentrations of administration conditions in combination with NIR-II photothermal therapy at 1064 nm;
FIG. 10 is a photograph of calcein AM/PI staining of cancer cells after incubation of mouse breast cancer 4T1 cells with different formulations.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a titanium oxide photo-thermal material, wherein the crystal form of the titanium oxide photo-thermal material is rutile phase; the titanium oxide photo-thermal material is blue-gray.
The titanium oxide photo-thermal material provided by the invention is a nano material, and the particle size of the nano material is preferably 50-200 nm, more preferably 50-150 nm, and further preferably 100 nm; the titanium oxide photo-thermal material has high free electron concentration, and preferably, the carrier concentration is 4.9 multiplied by 1020cm-3(ii) a The titanium oxide photo-thermal material preferably has an electrical conductivity of 2.5X 10-2S/m。
The titanium oxide photo-thermal material provided by the invention has high free electron concentration, so that the band gap is narrowed, the spectral range which can be absorbed and utilized by the material is effectively widened, the absorption range and the intensity of the material to infrared light are enhanced, particularly, the enhancement material absorbs and utilizes the light energy in a second biological near-infrared window, the non-radiative energy loss is reduced, and finally, the high-efficiency photo-thermal conversion under the high-efficiency second biological infrared window is realized; and the titanium oxide photo-thermal material has excellent biological safety, can not damage normal biological tissues, is used for photo-thermal treatment of cancer under a second biological infrared window, and has remarkable effect.
The invention also provides a preparation method of the titanium oxide photo-thermal material, which comprises the following steps: mixing titanium dioxide powder and magnesium powder in an acid solution for reaction to obtain a titanium oxide photo-thermal material; the particle size of the titanium dioxide powder is less than 200 nm.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
In the present invention, the titanium dioxide powder is preferably prepared according to the following method: s1) mixing titanium trichloride, an alcohol solvent and a nonionic surfactant, and heating to perform a solvothermal reaction to obtain an intermediate product; s2) subjecting the intermediate product to high-temperature calcination in an oxidizing atmosphere to obtain a titanium dioxide powder.
Mixing titanium trichloride, an alcohol solvent and a nonionic surfactant; the titanium trichloride is liquid, and the density of the titanium trichloride relative to water is 2.64, namely the density of the titanium trichloride is 2.64 g/ml; (ii) a The volume ratio of the titanium trichloride to the alcohol solvent is preferably 1: (10-20), more preferably 1: (10-15), and more preferably 1: (10-13), most preferably 1: (10-12.5); in the embodiment provided by the invention, the volume ratio of the titanium trichloride to the alcohol solvent is specifically 1: 10. 1: 15. 1: 12.5 or 3: 40; the alcohol solvent is preferably ethanol; the nonionic surfactant is preferably polyvinylpyrrolidone; the generation size of particles in the reaction can be controlled by adopting polyvinylpyrrolidone, so that the finally synthesized particles have the size of less than 200nm and can conveniently enter cells; the molecular weight of the nonionic surfactant is preferably 8000-58000; the ratio of the titanium trichloride to the surfactant is preferably 1 mL: (0.1-0.5) g, more preferably 1 mL: (0.1-0.3) g; in the embodiment provided by the invention, the ratio of the titanium trichloride to the surfactant is specifically 1 mL: 0.2g, 1 mL: 0.3g, 1 mL: 0.25g or 1 mL: 0.17 g; the mixing method is preferably stirring; the mixing time is preferably 30-90 min, more preferably 50-80 min, and still more preferably 60 min.
After mixing, heating for solvothermal reaction; the temperature of the solvothermal reaction is preferably 130-150 ℃; the solvothermal reaction time is preferably 20-30 h.
After the solvothermal reaction, preferably centrifuging, washing and drying to obtain an intermediate product; the centrifugation speed is preferably not lower than 10000rpm, more preferably 10000-13000 rpm, and further preferably 10000-12000 rpm; the time for centrifugation is preferably not less than 3min, and more preferably 3-5 min; preferably, deionized water and ethanol are adopted for washing, and more preferably, deionized water and ethanol are respectively used for washing for 2-4 times; the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 60 ℃ to 70 ℃.
Calcining the intermediate product at high temperature in an oxidizing atmosphere to obtain titanium dioxide powder; the oxidizing atmosphere is not particularly limited, and may be air or pure oxygen; the high-temperature calcination temperature is preferably 600-750 ℃, and more preferably 650-750 ℃; the high-temperature calcination time is preferably 3-5 h.
Mixing titanium dioxide powder and magnesium powder in an acid solution for reaction; the work function of the magnesium powder is less than that of titanium dioxide, electrons can be given to the titanium dioxide, the concentration of free carriers in the material is improved, and the energy band gap of the titanium oxide material is reduced; the mass ratio of the titanium dioxide powder to the magnesium powder is preferably 1: (0.5 to 1); in the embodiment provided by the invention, the mass ratio of the titanium dioxide to the magnesium powder is specifically 1: 1. 1: 0.8, 1: 0.5 or 1: 0.7; the concentration of acid in the acid solution is preferably 0.5-1 mol/L; in the embodiment provided by the invention, the concentration of the acid in the acid solution is specifically 1mol/L, 0.5mol/L or 0.8 mol/L; the acid solution is preferably one or more of dilute sulfuric acid, dilute perchloric acid and dilute phosphoric acid; the mixing reaction is preferably carried out under stirring; the mixing reaction time is preferably 10-60 min, and more preferably; in the examples provided by the present invention, the mixing reaction time is specifically 45min, 30min, 15min or 25 min. The invention is realized by adding TiO into rutile phase2A large amount of electrons are introduced, the free carrier concentration of the material is improved, and the phase transition process from an insulating phase to a semi-metal phase is finally induced, so that a new energy level state appears in the middle of a titanium oxide energy band, and meanwhile, the band gap is narrowed in contraction, so that the response range of the rutile phase titanium oxide material to infrared light can be enlarged, and the second biological infrared window photo-thermal property of the material is improved.
After mixing reaction, washing and drying are preferably carried out to obtain the titanium oxide photo-thermal material; the washing is preferably carried out by adopting deionized water and methanol, and more preferably, the washing is carried out by adopting deionized water and methanol for 2-4 times respectively.
The raw materials used in the invention are all bulk chemicals, are cheap and easily available, meanwhile, the synthesis method is non-toxic to human bodies and does not cause pollution to the environment, and the solvothermal method, the high-temperature calcination method and the wet chemical synthesis are mature industrial process flows, are simple and convenient to operate, and can enlarge equipment and fields for industrial production; the obtained titanium oxide photo-thermal material has strong infrared light absorption capacity on a second biological infrared window, high photo-thermal conversion efficiency and obvious anti-cancer treatment effect, and the material is non-toxic to biological normal tissues, so the titanium oxide photo-thermal material has good clinical application prospect.
The invention also provides a photothermal agent capable of carrying out photothermal tumor treatment under a second biological infrared window, which comprises the titanium oxide photothermal material.
In order to further illustrate the present invention, the following detailed description will be made with reference to the examples of the titanium oxide photothermal material, the preparation method thereof and the application thereof in the treatment of photothermal tumor under the second biological infrared window.
The reagents used in the following examples are all commercially available.
Example 1
The TiCl was measured in a volume of 1mL3Dissolving the liquid in 10mL of ethanol, adding 0.2g of Polyvinylpyrrolidone (PVP) powder with the molecular weight of 58000, stirring for 1 hour until the PVP powder is completely dissolved, transferring the mixed solution into a hydrothermal reaction kettle with the volume of 50mL, putting the hydrothermal reaction kettle into a high-temperature oven, heating to 140 ℃, and preserving the heat for 20 hours.
Transferring the precipitate and the solution in the hydrothermal reaction kettle into a centrifuge tube, centrifuging at the speed of 11000rpm for 3 minutes, washing with ethanol and deionized water for three times respectively, drying at 60 ℃ in a vacuum drying oven after centrifuging to obtain powder, placing the dried powder into a ceramic crucible, calcining in a muffle furnace at 650 ℃ in air, and preserving heat for 4 hours to obtain white TiO2And (3) powder.
20mL of 1M sulfuric acid aqueous solution was prepared, and 0.1 g of white TiO was added2The powder is mixed with 0.1 g of Mg powder and ground uniformly, thenAnd then adding the mixed powder into a dilute sulfuric acid solution, stirring and reacting for 45 minutes by using a magnetic stirrer, washing for 3 times by using deionized water and methanol respectively to remove redundant unreacted impurity ions, and drying to obtain a target product, namely the titanium oxide photo-thermal material.
The white TiO obtained in example 1 was added2The powder was subjected to Hall test with a titania photo-thermal material to obtain test results shown in table 1. As can be seen from Table 1, the titanium oxide photo-thermal material prepared in example 1 has a high free electron concentration, which is much higher than that of normal white TiO2Free electron concentration in (c).
TABLE 1 Hall test results
| Sample (I) | Concentration of carriers (cm)-3) |
| |
1.8×1017 |
| Titanium oxide photo-thermal material | 4.9×1020cm-3 |
The white TiO obtained in example 1 was added2The powder and the titanium oxide photothermal material were subjected to room temperature electrical conductivity test, and the test results thereof are shown in table 2. As shown in Table 2, the titanium oxide photo-thermal material prepared in example 1 has high carrier concentration and high mobility, so that the conductivity is much higher than that of normal white TiO2The electrical conductivity of (a).
TABLE 2 conductivity test results
| Sample (I) | Conductivity (S/m) |
| |
8.6×10-6 |
| Titanium oxide photo-thermal material | 2.5×10-2 |
FIG. 1 shows white TiO prepared in example 12A picture of a powder (figure a) and a titanium oxide photo-thermal material (figure b); as can be seen from FIG. 1, the photo-thermal material of titanium oxide is blue-gray, and the light absorption capability of the photo-thermal material of titanium oxide is comparable to that of white TiO in comparison with that of visible light and near-infrared light2And comparing the samples to obtain great promotion.
Scanning Electron microscope was used to examine the white TiO obtained in example 12The powder and the titanium oxide photo-thermal material are analyzed to obtain an SEM (scanning Electron microscope) morphology picture as shown in figure 2, wherein a is white TiO2Powder, graph b is titanium oxide photo-thermal material. From fig. 2, it can be seen that the morphology and appearance of the two samples are not changed, and the size of the particles is about 100 nm.
The titanium oxide photothermal material obtained in example 1 was analyzed by X-ray diffraction, and the XRD pattern thereof was as shown in fig. 3. As can be seen from fig. 3, the lattice structure of the titanium oxide photo-thermal material is in the rutile phase.
The absorption properties of the titanium oxide photothermal material obtained in example 1 were analyzed, and the absorption spectra at different concentrations in an aqueous solution thereof were obtained as shown in fig. 4. As can be seen from FIG. 4, the light absorption capacity is very strong in the whole solar spectrum range, and especially the near infrared light in the NIR-II range has strong absorption.
FIG. 5 shows an embodiment1, a DOS energy band structure theoretical calculation chart of the prepared titanium oxide photo-thermal material; the band gap of the titanium oxide photo-thermal material is illustrated as compared to white TiO2The titanium oxide photo-thermal material belongs to a semi-metal phase, and the electronic structure is favorable for the material to absorb visible light and infrared light with smaller photon energy.
FIG. 6 shows the power of the titanium oxide photo-thermal material prepared in example 1 at 1064nm near-infrared light in different aqueous solution concentrations and at 1W/cm2Under the irradiation condition, the curve graph of the solution temperature along with the time change shows that the maximum temperature difference reaches 20 ℃, and the titanium oxide photo-thermal material can effectively capture NIR-II near infrared light and convert the NIR-II near infrared light into heat, and has an obvious photo-thermal conversion effect.
FIG. 7 is a graph showing the temperature change with time and the photothermal imaging of the titanium oxide photothermal material prepared in example 1 under different concentrations of aqueous solutions after irradiation with infrared light through a second biological window of 1064 nm; the titanium oxide photo-thermal material prepared in example 1 has good NIR-II infrared photo-thermal imaging function, and the photo-thermal conversion efficiency of the material at 1064nm is calculated to be 35%.
FIG. 8 is a graph showing the toxicity of the photo-thermal titanium oxide material prepared in example 1 after 24 hours of the administration treatment to mouse 4T1 breast cancer cells (cell survival test); it is shown that the photo-thermal material of titanium oxide prepared in example 1 is non-toxic to cells, and the survival rate of cells is more than 70% even when the amount of the photo-thermal material is 200. mu.g/mL.
FIG. 9 is a graph showing the survival rate of mouse breast cancer 4T1 cells after being administered with NIR-II photothermal therapy at 1064nm under different concentrations of the photothermal material prepared in example 1. The titanium oxide photo-thermal material is matched with photo-thermal treatment, when the dosage is 200 mug/mL, the death rate of cancer cells is as high as 90.5%.
FIG. 10 shows the cancer cell density after incubation of mouse breast cancer 4T1 cells with different formulations (the dosage of the titanium oxide photothermal material prepared in example 1 was 200. mu.g/mL)Photograph of cells after calcein AM/PI staining. It is shown that only three factors of PBS buffer solution, titanium oxide photo-thermal material and NIR-II act alone, which cannot kill cancer cells, and when the titanium oxide photo-thermal material and NIR-II (1064 nm, 1.0W/cm)25 minutes of irradiation) the cancer cells were effectively killed and the tumors appeared to be severely damaged after laser irradiation, including a large amount of free debris and a large amount of nucleolysis zone.
Example 2
The TiCl was measured in a volume of 1mL3Dissolving in 15mL of ethanol, adding 0.3g of Polyvinylpyrrolidone (PVP) powder with the molecular weight of 40000, stirring for 1 hour until the PVP powder is completely dissolved, transferring the mixed solution into a hydrothermal reaction kettle with the volume of 50mL, putting the hydrothermal reaction kettle into a high-temperature oven, heating to 130 ℃, and preserving heat for 30 hours.
Transferring the precipitate and the solution in the hydrothermal reaction kettle into a centrifugal tube, centrifuging at 10000rpm for 4 minutes, washing with ethanol and deionized water for three times respectively, drying at 60 ℃ in a vacuum drying oven after centrifuging to obtain powder, placing the dried powder into a ceramic crucible, calcining in a muffle furnace at 700 ℃ in air, and preserving heat for 3 hours to obtain white TiO2And (3) powder.
20mL of a 0.8M sulfuric acid aqueous solution was prepared, and 0.1 g of white TiO was added2The powder and 0.08 g of Mg powder are mixed and ground uniformly, then the mixed powder is added into a dilute sulfuric acid solution, stirred and reacted for 30 minutes by using a magnetic stirrer, then deionized water and methanol are used for washing for 3 times respectively to remove redundant unreacted impurity ions, and a target product, namely the titanium oxide photo-thermal material, is obtained after drying.
Example 3
The TiCl was measured in a volume of 2mL3Dissolving in 25mL of ethanol, adding 0.5 g of Polyvinylpyrrolidone (PVP) powder with the molecular weight of 24000, stirring for 1 hour until the PVP is completely dissolved, transferring the mixed solution into a hydrothermal reaction kettle with the volume of 50mL, putting the hydrothermal reaction kettle into a high-temperature oven, heating to 150 ℃, and preserving the heat for 25 hours.
Transferring the precipitate and the solution in the hydrothermal reaction kettle into a centrifuge tube, centrifuging at 12000rpm for 5 minutes, washing with ethanol and deionized water for three times respectively, drying at 60 ℃ in a vacuum drying oven after centrifuging to obtain powder, placing the dried powder into a ceramic crucible, calcining at 750 ℃ in a muffle furnace in air, and preserving heat for 3.5 hours to obtain white TiO2And (3) powder.
20mL of a 0.5M sulfuric acid aqueous solution was prepared, and 0.1 g of white TiO was added2The powder and 0.05 g of Mg powder are mixed and ground uniformly, then the mixed powder is added into a dilute sulfuric acid solution, stirred and reacted for 15 minutes by using a magnetic stirrer, then deionized water and methanol are used for washing for 3 times respectively to remove redundant unreacted impurity ions, and a target product, namely the titanium oxide photo-thermal material, is obtained after drying.
Example 4
The TiCl was measured in a volume of 3mL3Dissolving in 40mL of ethanol, adding 0.5 g of Polyvinylpyrrolidone (PVP) powder with molecular weight of 8000, stirring for 1 hour until the PVP powder is completely dissolved, transferring the mixed solution into a hydrothermal reaction kettle with the volume of 50mL, putting the hydrothermal reaction kettle into a high-temperature oven, heating to 135 ℃, and preserving heat for 20 hours.
Transferring the precipitate and the solution in the hydrothermal reaction kettle into a centrifugal tube, centrifuging at 10000rpm for 5 minutes, washing with ethanol and deionized water for three times respectively, drying at 60 ℃ in a vacuum drying oven after centrifuging to obtain powder, placing the dried powder into a ceramic crucible, calcining at 680 ℃ in a muffle furnace in the air, and preserving heat for 5 hours to obtain white TiO2And (3) powder.
20mL of 1M sulfuric acid aqueous solution was prepared, and 0.1 g of white TiO was added2The powder and 0.07 g of Mg powder are mixed and ground uniformly, then the mixed powder is added into dilute sulfuric acid solution, a magnetic stirrer is used for stirring and reacting for 25 minutes, then deionized water and methanol are used for washing for 3 times respectively to remove redundant unreacted impurity ions, and a target product, namely the titanium oxide photo-thermal material, is obtained after drying.
Claims (10)
1. The titanium oxide photo-thermal material is characterized in that the crystal form of the titanium oxide photo-thermal material is rutile phase; the titanium oxide photo-thermal material is blue-gray.
2. The titanium oxide photothermal material of claim 1 wherein said titanium oxide photothermal material has a carrier concentration of 4.9 x 1020cm-3(ii) a The conductivity of the titanium oxide photo-thermal material is 2.5 multiplied by 10-2S/m; the particle size of the titanium oxide photo-thermal material is 50-200 nm.
3. A method for preparing a titanium oxide photo-thermal material, which is characterized by comprising the following steps:
mixing titanium dioxide powder and magnesium powder in an acid solution for reaction to obtain a titanium oxide photo-thermal material; the particle size of the titanium dioxide powder is less than 200 nm.
4. The production method according to claim 3, wherein the titanium dioxide powder is produced by:
s1) mixing titanium trichloride, an alcohol solvent and a nonionic surfactant, and heating to perform a solvothermal reaction to obtain an intermediate product;
s2) subjecting the intermediate product to high-temperature calcination in an oxidizing atmosphere to obtain a titanium dioxide powder.
5. The preparation method according to claim 4, wherein the volume ratio of the titanium trichloride to the alcohol solvent is 1: (10-20); the ratio of the titanium trichloride to the surfactant is 1 mL: (0.1-0.5) g;
the alcohol solvent is ethanol; the nonionic surfactant is polyvinylpyrrolidone; the molecular weight of the nonionic surfactant is 8000-58000.
6. The method according to claim 4, wherein the mixing time in the step S1) is 30-90 min; the temperature of the solvothermal reaction is 130-150 ℃; the solvothermal reaction time is 20-30 h;
after the solvothermal reaction in the step S1), centrifuging, washing and drying to obtain an intermediate product; the centrifugation speed is not lower than 10000 rpm; the centrifugation time is not less than 3 min.
7. The preparation method according to claim 4, wherein the temperature of the high-temperature calcination is 600 ℃ to 750 ℃; the high-temperature calcination time is 3-5 h.
8. The method according to claim 1, wherein the acid concentration in the acid solution is 0.5 to 1 mol/L; the acid solution is selected from one or more of dilute sulfuric acid, dilute perchloric acid and dilute phosphoric acid.
9. The production method according to claim 1, wherein the mass ratio of the titanium dioxide powder to the magnesium powder is 1: (0.5 to 1); the mixing reaction time is 10-60 min.
10. A photo-thermal agent for photo-thermal tumor therapy in a second biological infrared window, comprising the titanium oxide photo-thermal material according to any one of claims 1 to 2 or the titanium oxide photo-thermal material prepared by the preparation method according to any one of claims 3 to 9.
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