CN114031112B - 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, the crystal form of which 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 of the material which can be absorbed and utilized is effectively widened, the absorption range and intensity of the material to infrared light are enhanced, especially the light energy in a second biological near infrared window is enhanced and utilized by the enhanced material, the non-radiation energy loss is reduced, and the high-efficiency photo-thermal conversion under the high-efficiency second biological infrared window is finally realized; the titanium oxide photo-thermal material has excellent biological safety, can not damage normal biological tissues, and has obvious effect when being used for photo-thermal treatment of cancers under a second biological infrared window.
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 becoming a potential alternative to chemotherapy, radiation therapy, gene therapy and immunotherapy in traditional cancer therapies. However, the lack of knowledge of tumor prevention, development, metastasis and angiogenesis, as well as the limitations of current diagnostic methods, have long prevented the development of clinical cancer treatment techniques, resulting in cancer which remains one of the important diseases worldwide threatening human health. In principle, phototherapy of cancer mainly refers to phototherapy (photothermal therapy, PTT), and due to high permeability of capillaries and insufficient endothelial and lymphatic drainage, photothermal agents (photothermal agents, PTAs) can be administered and accumulated in tumor tissue by enhanced permeability and retention effects (enhanced permeability and retention effect, 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 to cause thermal damage to tumor cells by a non-radiative vibratory relaxation mode.
The design of nano PTAs with remarkable photo-thermal conversion efficiency on the atomic level has important significance for tumor hyperthermia. PTAs materials that have been widely reported to date 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, which bring new dawn to cancer patients, and they are still under investigation and improvement. Notably, a significant portion of these PTAs are typically only able to absorb and utilize near infrared light in a first biological window (NIR-I, λ=780-1000 nm), and little attention has been paid to developing PTAs materials with infrared light that can operate effectively in a second biological window (NIR-II, λ=1000-1350 nm). But NIR-II light may provide greater tissue penetration depth and the maximum allowable exposure of the skin to the NIR-II laser is higher.
Semiconductors are one of the well-studied functional nanomaterials, which are also promising PTAs material candidates with excellent biocompatibility. Among them, metal oxides are particularly attractive because of their adjustability of various combinations of cations and anions, stoichiometry and crystalline phases, and their strong reducing and oxidizing abilities of conduction and valence bands, which can convert absorbed electromagnetic waves into heat 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 low infrared light absorption, low photothermal efficiency and high electron hole recombination velocity caused by the inherent wide bandgap structure of semiconductors. In order to expand the optical response range of metal oxide PTAs to NIR-II region, the dominant strategies of doping by introducing impurities, oxygen vacancy, constructing heterojunction, sensitizing compound dye molecules or up-converting compound nano-particles are generally adopted, but the electronic transition process of metal oxide occurring in NIR-II biological window is still difficult to obtain due to low doping content, low free carrier concentration and residual wide energy band gap.
TiO 2 Is a classical metal oxide semiconductor material which has not only versatility but also low cost, scalability and biosafety. TiO (titanium dioxide) 2 The biological effects of (a) have been demonstrated on certain microorganisms, bacteria, viruses, cancer cells, etc., including the regulation of lipid peroxidation of biological membranes, as well as interactions between proteins leading to altered intracellular conditions and ultimately the metabolic apoptosis process of cells. Studies have also shown that TiO 2 As a disinfectant, the sewage can be treated and disinfected by utilizing chemical substances such as ozone, ultraviolet radiation, chlorine and the like, and safe water is provided for the life and production of human beings in the modern society. However, stoichiometric TiO 2 The band gap (atomic ratio of Ti to O1:2) is about 3.2eV, which results in TiO 2 The material has low energy utilization efficiency on visible light and infrared light, can only absorb and utilize ultraviolet light with the wavelength of 380nm or less, and is not suitable for being used as a PTAs material medium for infrared response photo-thermal application. Therefore, a novel TiO was developed 2 Materials, and having high infrared light absorption and utilization capabilities and being applied to near infrared photothermal treatment of cancer, remain a difficult 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 under a second biological infrared window, wherein the titanium oxide photo-thermal material has a high free electron concentration, which causes a narrowing of a band gap, so that a spectrum range of the material which can be absorbed and utilized is effectively widened, thereby enhancing an absorption range and strength of the material to infrared light, particularly enhancing the absorption of the material to light energy in the second biological near infrared window, reducing non-radiative energy loss, and finally realizing efficient photo-thermal conversion under the efficient second biological infrared window.
The invention provides a titanium oxide photo-thermal material, the crystal form of which is rutile phase; the titanium oxide photo-thermal material is blue-gray.
Preferably, the carrier concentration of the titanium oxide photo-thermal material is 4.9X10 20 cm -3 The method comprises the steps of carrying out a first treatment on the surface of the The conductivity of the titanium oxide photo-thermal material is 2.5X10 -2 S/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 to react to obtain a titanium oxide photo-thermal material; the particle size of the titanium dioxide powder is less than 200nm.
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 solvothermal reaction to obtain an intermediate product;
s2) calcining the intermediate product at high temperature in an oxidizing atmosphere to obtain 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 1mL: (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 hours;
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 10000rpm; the centrifuging time is not less than 3min.
Preferably, the high-temperature calcination temperature is 600-750 ℃; the high-temperature calcination time is 3-5 h.
Preferably, the concentration of 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: (0.5-1); the time of the mixing reaction is 10-60 min.
The invention also provides a photo-thermal agent capable of carrying out photo-thermal tumor treatment under the second biological infrared window, which comprises the titanium oxide photo-thermal material.
The invention provides a titanium oxide photo-thermal material, the crystal form of which 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 of the material which can be absorbed and utilized is effectively widened, the absorption range and intensity of the material to infrared light are enhanced, especially the light energy in a second biological near infrared window is enhanced and utilized by the enhanced material, the non-radiation energy loss is reduced, and the high-efficiency photo-thermal conversion under the high-efficiency second biological infrared window is finally realized; the titanium oxide photo-thermal material has excellent biological safety, can not damage normal biological tissues, and has obvious effect when being used for photo-thermal treatment of cancers under a second biological infrared window.
Experiments show that the titanium oxide photo-thermal material with high NIR-II photo-thermal effect prepared by the invention integrates the advantages of all excellent photo-thermal materials, and the material is nontoxic to normal physiological cells and has the irradiation power of 1.0W/cm under 1064nm infrared light irradiation 2 ) The light-heat conversion efficiency is 35%, when the dosage is 200 mug/mL, the light irradiation of 1064nm is matched, the light-heat conversion efficiency can cause remarkable killing effect on the breast cancer 4T1 cells of mice, and the effective killing efficiency is 90.5%.
Drawings
FIG. 1 shows white TiO according to example 1 of the present invention 2 A physical photograph of the powder and the titanium oxide photo-thermal material;
FIG. 2 shows white TiO according to example 1 of the present invention 2 SEM scanning electron microscope morphology photo of powder and titanium oxide photo-thermal material;
FIG. 3 is an XRD spectrum of a titanium oxide photo-thermal material obtained in example 1 of the present invention;
FIG. 4 is a graph showing the absorbance of the photo-thermal material of titanium oxide obtained in example 1 of the present invention;
FIG. 5 is a theoretical calculation chart of DOS band structure of the titania photo-thermal material obtained in example 1 of the present invention;
FIG. 6 shows the power of the titania photo-thermal material obtained in example 1 of the present invention at 1064nm near infrared light at 1W/cm under different aqueous solution concentrations 2 A graph of the solution temperature over time under irradiation conditions;
FIG. 7 is a graph showing the change of temperature with time and photothermography of the titanium oxide photothermal material obtained in example 1 of the present invention after irradiation with infrared light at a second biological window of 1064nm under different concentration conditions;
FIG. 8 is a graph showing the toxicity test (cell viability test) of the titanium oxide photothermal material obtained in example 1 of the present invention on mouse 4T1 breast cancer cells;
FIG. 9 is a graph showing the survival rate of 4T1 cells of breast cancer in mice by the combination of 1064nm NIR-II photothermal treatment with the titanium oxide photothermal material obtained in example 1 of the present invention under different concentration administration conditions;
FIG. 10 is a photograph of cancer cells stained with calcein AM/PI after incubation of 4T1 cells of breast cancer in mice with different formulations.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a titanium oxide photo-thermal material, the crystal form of which 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 still more preferably 100nm; the titanium oxide photo-thermal material has a relatively high free electron concentration, preferably a carrier concentration of 4.9X10 20 cm -3 The method comprises the steps of carrying out a first treatment on the surface of the The conductivity of the titanium oxide photo-thermal material is preferably 2.5X10 -2 S/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 of the material which can be absorbed and utilized is effectively widened, the absorption range and 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, the non-radiation energy loss is reduced, and finally, the high-efficiency photo-thermal conversion under the high-efficiency second biological infrared window is realized; the titanium oxide photo-thermal material has excellent biological safety, can not damage normal biological tissues, and has obvious effect when being used for photo-thermal treatment of cancers under a second biological infrared window.
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 to react to obtain a titanium oxide photo-thermal material; the particle size of the titanium dioxide powder is less than 200nm.
The source of all the raw materials is not particularly limited, and the raw materials are 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 solvothermal reaction to obtain an intermediate product; s2) calcining the intermediate product at high temperature in an oxidizing atmosphere to obtain 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 2.64g/ml; the method comprises the steps of carrying out a first treatment on the surface of the The volume ratio of the titanium trichloride to the alcohol solvent is preferably 1: (10 to 20), more preferably 1: (10 to 15), and more preferably 1: (10 to 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, a step of performing a; the alcohol solvent is preferably ethanol; the nonionic surfactant is preferably polyvinylpyrrolidone; the polyvinylpyrrolidone can control the generation size of particles in the reaction, so that the finally synthesized particles with the size smaller than 200nm are convenient for entering cells; the molecular weight of the nonionic surfactant is preferably 8000 to 58000; the ratio of the titanium trichloride to the surfactant is preferably 1mL: (0.1 to 0.5) g, more preferably 1mL: (0.1-0.3 g); in the embodiment provided by the invention, the ratio of the titanium trichloride to the surfactant is specifically 1mL:0.2g, 1mL:0.3g, 1mL:0.25g or 1mL:0.17g; the method of mixing is preferably stirring; the mixing time is preferably 30 to 90 minutes, more preferably 50 to 80 minutes, still more preferably 60 minutes.
After mixing, heating to perform solvothermal reaction; the temperature of the solvothermal reaction is preferably 130-150 ℃; the time of the solvothermal reaction is preferably 20 to 30 hours.
After solvothermal reaction, preferably centrifuging, washing and drying to obtain an intermediate product; the speed of the centrifugation is preferably not lower than 10000rpm, more preferably 10000 to 13000rpm, still more preferably 10000 to 12000rpm; the time of centrifugation is preferably not less than 3min, more preferably 3 to 5min; the washing is preferably carried out by adopting deionized water and ethanol, more preferably deionized water and ethanol are used for washing for 2-4 times respectively; 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 an oxidizing atmosphere well known to those skilled in the art, and is not particularly limited, and may be air or pure oxygen; the temperature of the high-temperature calcination is preferably 600-750 ℃, more preferably 650-750 ℃; the high-temperature calcination time is preferably 3 to 5 hours.
Mixing titanium dioxide powder and magnesium powder in an acid solution for reaction; the work function of the magnesium powder is smaller 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: (0.5-1); 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 examples provided by the present invention, the acid concentration in the acid solution is specifically 1mol/L, 0.5mol +.L or 0.8mol/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 to 60 minutes, more preferably; in the embodiment provided by the invention, the time of the mixing reaction is specifically 45min, 30min, 15min or 25min. The invention is realized by the method that the TiO is in the rutile phase 2 And a large number of electrons are introduced, the free carrier concentration of the material is improved, and finally, the phase transformation process from an insulating phase to a semi-metal phase is induced, so that a new energy level state appears in the middle of a titanium oxide energy band, and meanwhile, the band gap is contracted and narrowed, thereby being capable of improving the response range of the rutile phase titanium oxide material to infrared light and improving the photo-thermal performance of a second biological infrared window of the material.
Preferably washing and drying the mixture to obtain the titanium oxide photo-thermal material; the washing is preferably performed with deionized water and methanol, more preferably with deionized water and methanol, respectively, 2 to 4 times.
The raw materials used in the invention are bulk chemicals, are cheap and easy to obtain, the synthesis method is harmless to human bodies and does not pollute the environment, and the solvothermal method, the high-temperature calcination method and the wet chemical synthesis are all mature industrial process flows, so that the operation is simple and convenient, and the industrial production of equipment and sites can be enlarged; the obtained titanium oxide photo-thermal material has strong infrared light absorption capacity to a second biological infrared window, high photo-thermal conversion efficiency and remarkable anticancer treatment effect, and the material is nontoxic to biological normal tissues, so that the titanium oxide photo-thermal material has good clinical application prospect.
The invention also provides a photo-thermal agent capable of carrying out photo-thermal tumor treatment under the second biological infrared window, which comprises the titanium oxide photo-thermal material.
In order to further illustrate the present invention, the following describes in detail a titanium oxide photo-thermal material, a preparation method thereof and an application thereof in photo-thermal tumor treatment under a second biological infrared window.
The reagents used in the examples below are all commercially available.
Example 1
TiCl with a volume of 1mL was measured out 3 The solution was dissolved in 10mL of ethanol, then 0.2g of Polyvinylpyrrolidone (PVP) powder having a molecular weight of 58000 was added, stirred for 1 hour until complete dissolution, and the above mixed solution was transferred to a hydrothermal reaction vessel having a volume of 50mL, placed in a high-temperature oven, heated to 140 ℃ and kept at temperature for 20 hours.
Transferring the precipitate and the solution in the hydrothermal reaction kettle into a centrifuge tube, centrifuging at 11000rpm for 3 minutes, washing with ethanol and deionized water respectively for three times, centrifuging, drying at 60deg.C in a vacuum drying oven to obtain powder, placing the dried powder into a ceramic crucible, calcining at 650deg.C in a muffle furnace in air, and maintaining the temperature for 4 hours to obtain white TiO 2 And (3) powder.
A solution of 0.1 g of white TiO was prepared by preparing 20mL of an aqueous sulfuric acid solution having a concentration of 1M 2 Mixing and grinding the powder with 0.1 g of Mg powder uniformly, adding the mixed powder into a dilute sulfuric acid solution, stirring and reacting for 45 minutes by using a magnetic stirrer, respectively washing for 3 times by using deionized water and methanol to remove excessive unreacted impurity ions, and drying to obtain a target product, namely the titanium oxide photo-thermal material.
The white TiO obtained in example 1 2 The powder and the titanium oxide photothermal material were subjected to Hall test, and the test results are 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 far higher than that of normal white TiO 2 Free electron concentration in (a) is provided.
TABLE 1 Hall test results
| Sample of | Carrier concentration (cm) -3 ) |
| White TiO 2 | 1.8×10 17 |
| Titanium oxide photothermal material | 4.9×10 20 cm -3 |
The white TiO obtained in example 1 2 The powder and the titanium oxide photo-thermal material were subjected to a room temperature conductivity test, and the test results are shown in Table 2. As can be seen from Table 2, the titanium oxide photo-thermal material prepared in example 1 has higher conductivity than normal white TiO due to high carrier concentration and high mobility 2 Is a high-conductivity metal.
Table 2 conductivity test results
| Sample of | Conductivity (S/m) |
| White TiO 2 | 8.6×10 -6 |
| Titanium oxide photothermal material | 2.5×10 -2 |
FIG. 1 is a white TiO prepared in example 1 2 A physical photograph of the powder (a) and the titanium oxide photo-thermal material (b); as can be seen from FIG. 1, the titanium oxide photo-thermal material is blue gray, and has light absorption capability for visible light and near infrared light, compared with white TiO 2 And compared with the sample, the sample is greatly improved.
The white TiO obtained in example 1 was subjected to a scanning electron microscope 2 Powder and oxidationThe titanium photo-thermal material is analyzed, and an SEM scanning electron microscope morphology photo of the titanium photo-thermal material is shown in figure 2, wherein a graph a is white TiO 2 The powder, b is the titanium oxide photo-thermal material. As can be seen from FIG. 2, the morphology and appearance of the two samples were unchanged, and the particle sizes were about 100 nm.
The titanium oxide photothermal material obtained in example 1 was analyzed by X-ray diffraction, and the XRD pattern thereof was shown in fig. 3. As can be seen from fig. 3, the lattice structure of the titanium oxide photo-thermal material is rutile phase.
The absorbance properties of the titanium oxide photothermal material obtained in example 1 were analyzed, and absorbance spectra of different concentrations in aqueous solutions were obtained as shown in fig. 4. As can be seen from fig. 4, the absorption power is very strong in the entire solar spectrum, especially in the NIR-ii region.
FIG. 5 is a theoretical calculation chart of DOS band structure of the photo-thermal material of titanium oxide prepared in example 1; illustrating the energy band gap of the titanium oxide photo-thermal material compared with white TiO 2 The energy band gap is narrowed, new impurity energy level appears, the spin direction of electrons is upward, and electrons with no spin downward are not generated, so that the titanium oxide photo-thermal material belongs to a semi-metal phase, and the electron structure is favorable for absorbing visible light and infrared light with relatively small photon energy.
FIG. 6 shows the power of the titania photo-thermal material prepared in example 1 at 1064nm in various aqueous solutions at 1W/cm 2 Under the irradiation condition, the highest temperature difference reaches 20 ℃ as shown by the graph of the change of the solution temperature along with the time, 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, so that the titanium oxide photo-thermal material has an obvious photo-thermal conversion effect.
FIG. 7 is a graph showing the changes over time of the temperature of the titanium oxide photo-thermal material prepared in example 1 after infrared irradiation at a 1064nm second biological window under different concentration aqueous conditions, and photo-thermal imaging; the titanium oxide photo-thermal material prepared in the embodiment 1 has a 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 shows the toxicity (cell viability test) of the titania photothermal material prepared in example 1 24 hours after treatment with mouse 4T1 breast cancer cells; the titanium oxide photothermal material prepared in example 1 was not toxic to cells, and even when the administration amount was as high as 200. Mu.g/mL, the survival rate of cells was 70% or more.
FIG. 9 shows the survival rate of 4T1 cells of breast cancer in mice after treatment with NIR-II photothermal therapy of 1064nm under different concentrations of the photothermal material prepared in example 1. The result shows that when the administration amount of the titanium oxide photothermal material of the present invention is 200. Mu.g/mL in combination with photothermal treatment, the death rate of cancer cells is as high as 90.5%.
FIG. 10 is a photograph of cancer cells stained with calcein AM/PI after incubation of 4T1 cells of breast cancer in mice with different formulations (200. Mu.g/mL of the titania photothermal material prepared in example 1). It was demonstrated that the three factors, PBS buffer alone, titanium oxide photothermal material, NIR-II, alone, did not cause killing of cancer cells, whereas the three factors, titanium oxide photothermal material and NIR-II (1064 nm,1.0W/cm 2 5 minutes of irradiation) the cancer cells are effectively killed, and it can be seen that the tumor shows a serious lesion state after laser irradiation, including a large amount of free debris and a large amount of nuclear lysis zone.
Example 2
TiCl with a volume of 1mL was measured out 3 Dissolving in 15mL of ethanol, adding 0.3g of Polyvinylpyrrolidone (PVP) powder with molecular weight of 40000, stirring for 1 hour to dissolve completely, transferring the mixed solution into a hydrothermal reaction kettle with volume of 50mL, placing 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 centrifuge tube, centrifuging at 10000rpm for 4 min, washing with ethanol and deionized water respectively for three times, centrifuging, drying at 60deg.C in a vacuum drying oven to obtain powder, placing the dried powder into a ceramic crucible, calcining at 700deg.C in a muffle furnace in air, and maintaining the temperature for 3 hr to obtain white TiO 2 Powder。
A solution of 0.8M sulfuric acid in 20mL was prepared, and 0.1 g of white TiO was added 2 Mixing and grinding the powder with 0.08 g of Mg powder uniformly, adding the mixed powder into a dilute sulfuric acid solution, stirring and reacting for 30 minutes by using a magnetic stirrer, respectively washing for 3 times by using deionized water and methanol to remove excessive unreacted impurity ions, and drying to obtain a target product, namely the titanium oxide photo-thermal material.
Example 3
TiCl with a volume of 2mL was measured out 3 Dissolving in 25mL of ethanol, adding 0.5 g of Polyvinylpyrrolidone (PVP) powder with molecular weight of 24000, stirring for 1 hour to dissolve completely, transferring the mixed solution into a hydrothermal reaction kettle with volume of 50mL, placing into a high-temperature oven, heating to 150 ℃ and preserving heat for 25 hours.
Transferring the precipitate and the solution in the hydrothermal reaction kettle into a centrifuge tube, centrifuging at 12000rpm for 5min, washing with ethanol and deionized water respectively for three times, centrifuging, drying at 60deg.C in a vacuum drying oven to obtain powder, placing the dried powder into a ceramic crucible, calcining at 750deg.C in a muffle furnace in air, and maintaining the temperature for 3.5 hr to obtain white TiO 2 And (3) powder.
An aqueous sulfuric acid solution (20 mL) having a concentration of 0.5M was prepared, and 0.1 g of white TiO was added 2 Mixing and grinding the powder with 0.05 g of Mg powder uniformly, adding the mixed powder into a dilute sulfuric acid solution, stirring and reacting for 15 minutes by using a magnetic stirrer, respectively washing for 3 times by using deionized water and methanol to remove excessive unreacted impurity ions, and drying to obtain a target product, namely the titanium oxide photo-thermal material.
Example 4
TiCl with a volume of 3mL was measured out 3 Dissolving in 40mL of ethanol, adding 0.5 g of Polyvinylpyrrolidone (PVP) powder with molecular weight of 8000, stirring for 1 hour to dissolve completely, transferring the mixed solution into a hydrothermal reaction kettle with volume of 50mL, placing into a high-temperature oven, heating to 135 ℃ and preserving heat for 20 hours.
The hydrothermal reaction is carried outTransferring the precipitate and solution in the reaction kettle into a centrifuge tube, centrifuging at 10000rpm for 5min, washing with ethanol and deionized water respectively for three times, centrifuging, oven drying at 60deg.C in a vacuum drying oven to obtain powder, placing the dried powder into a ceramic crucible, calcining at 680 deg.C in a muffle furnace in air, and maintaining the temperature for 5 hr to obtain white TiO 2 And (3) powder.
A solution of 0.1 g of white TiO was prepared by preparing 20mL of an aqueous sulfuric acid solution having a concentration of 1M 2 Mixing and grinding the powder with 0.07 g of Mg powder uniformly, adding the mixed powder into a dilute sulfuric acid solution, stirring and reacting for 25 minutes by using a magnetic stirrer, respectively washing for 3 times by using deionized water and methanol to remove excessive unreacted impurity ions, and drying to obtain a target product, namely the titanium oxide photo-thermal material.
Claims (1)
1. The preparation method of the titanium oxide photo-thermal material is characterized by comprising the following steps:
mixing titanium dioxide powder and magnesium powder in an acid solution to react to obtain a titanium oxide photo-thermal material; the particle size of the titanium dioxide powder is less than 200nm; the concentration of 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;
the mass ratio of the titanium dioxide powder to the magnesium powder is 1: (0.5-1); the time of the mixing reaction is 10-60 min;
the crystal form of the titanium oxide photo-thermal material is rutile phase; the titanium oxide photo-thermal material is blue-gray;
the carrier concentration of the titanium oxide photo-thermal material is 4.9X10 20 cm -3 The method comprises the steps of carrying out a first treatment on the surface of the The conductivity of the titanium oxide photo-thermal material is 2.5X10 -2 S/m; the particle size of the titanium oxide photo-thermal material is 50-200 nm;
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 solvothermal reaction to obtain an intermediate product;
s2) calcining the intermediate product at high temperature in an oxidizing atmosphere to obtain titanium dioxide powder;
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 1mL: (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;
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 hours;
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 10000rpm; centrifuging for at least 3min;
the high-temperature calcination temperature is 600-750 ℃; the high-temperature calcination time is 3-5 h;
the titanium oxide photo-thermal material is used as a photo-thermal agent for photo-thermal tumor treatment under a second biological infrared window.
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