CN113998730B - Preparation method of hollow mesoporous tin dioxide applied to tumor diagnosis and treatment oxygen vacancy - Google Patents
Preparation method of hollow mesoporous tin dioxide applied to tumor diagnosis and treatment oxygen vacancy Download PDFInfo
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Abstract
A preparation method of hollow mesoporous tin dioxide applied to tumor diagnosis and treatment oxygen vacancies relates to a preparation method of hollow mesoporous tin dioxide. The invention aims to solve the problems that the existing mesoporous silica cannot realize photothermal treatment due to no obvious characteristic absorption in a near infrared region, has low drug loading rate due to smaller pore size, cannot achieve good chemotherapy effect, can be only used as a drug carrier, and cannot realize the combination of diagnosis and treatment due to single function. The preparation method comprises the following steps: 1. preparing silicon dioxide nano particles by adopting a sol-gel method; 2. synthesizing hollow mesoporous tin dioxide nano particles by adopting an in-situ deposition method; 3. and (3) preparing the oxygen vacancy hollow mesoporous tin dioxide. The preparation method is used for preparing the hollow mesoporous tin dioxide with the oxygen vacancies in tumor diagnosis and treatment.
Description
Technical Field
The invention relates to a preparation method of hollow mesoporous tin dioxide.
Background
Tumors are one of the most important diseases threatening human health at present, with the rapid development of nano medicine, new tumor treatment methods such as near infrared light induced phototherapy (including photodynamic therapy and photothermal therapy) continuously appear, and the unique advantages of deeper tissue penetration depth, relatively high selectivity and tissue specificity for tumor cells, safety, effectiveness, small toxic and side effects and the like have attracted extensive attention of researchers, but the unique microenvironment and heat shock response of tumors limit the phototherapy effect. At present, most of organic photosensitizers are poor in water solubility, and are easy to agglomerate in practical application, so that photosensitization efficiency is low; absorption is mainly distributed in the ultraviolet-visible range, and the limited penetration depth of the tissue can damage normal tissues and skin; in addition, some diagnosis and treatment reagents mainly combine functional components, and the preparation process is complex, so that the application of the diagnosis and treatment reagents in clinical tumor treatment is severely limited.
In recent years, hollow structures have attracted great attention, both in basic research and in practical use. The hollow mesoporous material has the characteristics of good internal cavity and pore canal structure, adjustable pore diameter, pore volume, high specific surface area and the like, and is widely applied to the fields of adsorption, separation, drug transportation, catalysis and the like. Among these hollow structural materials, silica is one of the most popular materials because of its excellent mechanical and thermal stability, ease of modification, low toxicity, and high biocompatibility. In the field of nano biomedicine, the mesoporous silica has no obvious characteristic absorption in the near infrared region, so that photothermal treatment cannot be realized, and the small pore size leads to low drug loading rate, so that a good chemotherapy effect cannot be realized, and the mesoporous silica can be only used as a drug carrier, and has single function, so that the combination of diagnosis and treatment cannot be realized. Therefore, developing a novel hollow mesoporous integrated multifunctional nano diagnosis and treatment reagent with near infrared light response is an urgent problem to be solved at present.
Disclosure of Invention
The invention provides a preparation method of hollow mesoporous tin dioxide for oxygen vacancy in tumor diagnosis and treatment, which aims to solve the problems that the existing mesoporous silicon dioxide cannot realize photothermal treatment due to no obvious characteristic absorption in a near infrared region, has low drug loading rate and cannot achieve good chemotherapy effect due to smaller pore size, can be only used as a drug carrier, and has single function and cannot realize the combination of diagnosis and treatment.
The preparation method of the hollow mesoporous tin dioxide applied to the tumor diagnosis and treatment oxygen vacancy is carried out according to the following steps:
1. silica nanoparticles were prepared using sol-gel method:
adding cetyl trimethyl ammonium chloride and triethylamine into deionized water, ultrasonically obtaining a clear and transparent solution, heating the clear and transparent solution to 85-95 ℃ under magnetic stirring, stirring for 0.5-1.5 h under the condition of 85-95 ℃, then dropwise adding tetraethoxysilane under the condition of 85-95 ℃, reacting for 1.5-2.5 h under the condition of 85-95 ℃, finally centrifugally collecting and washing to obtain white precipitate, and vacuum drying the white precipitate to obtain mesoporous silica;
2. synthesizing hollow mesoporous tin dioxide nano particles by adopting an in-situ deposition method:
adding mesoporous silica into a mixed solution of ethanol and water, uniformly dispersing by ultrasonic, adding urea with the concentration of 2-3 mol/L and sodium stannate trihydrate with the concentration of 0.06-1 mol/L, stirring for 30 min-1 h at room temperature, heating to 160-180 ℃, preserving heat for 1 h-2 h at 160-180 ℃, naturally cooling to room temperature, centrifugally collecting and washing, and finally drying in vacuum to obtain hollow mesoporous tin dioxide;
3. preparing oxygen vacancy hollow mesoporous tin dioxide:
mixing hollow mesoporous tin dioxide with sodium borohydride, grinding for 10-15 min, placing in a tube furnace, heating to 350-450 ℃ under the protection of hydrogen, calcining for 1-1.5 h under the condition of 350-450 ℃, naturally cooling to room temperature, washing to obtain black precipitate, and vacuum drying the black precipitate to obtain the oxygen vacancy hollow mesoporous tin dioxide.
The beneficial effects of the invention are as follows:
(1) the oxygen vacancy hollow mesoporous tin dioxide is black, has uniform particle size, the size of the shell can be adjusted by changing the size of a silicon dioxide template, and the thickness of the shell and the template clearance can be adjusted by changing the amounts of urea and sodium stannate trihydrate in the reaction process, the reaction temperature and the reaction time. Because sodium carbonate is generated in the reaction process, the silicon dioxide template is removed while mesoporous tin dioxide is prepared, the experimental flow is shortened, and the method is simple, convenient and easy to control;
(2) the oxygen vacancy hollow mesoporous tin dioxide has larger specific surface area (290 m 2 /g～295m 2 And/g), internal cavity and mesoporous channel structure (5.5-6 nm), which is beneficial to improving the loading efficiency of anticancer drugs; the method has obvious near infrared light absorption, a large number of defects exist on the surface, which is beneficial to promoting the separation of electron holes, and under the excitation of near infrared light, a large number of reactive oxygen species can be generated for photodynamic therapy and obvious over-high thermal effect for photothermal therapy;
(3) tin is one of essential trace elements for human body, has important effects on various physiological activities and health maintenance of human body, and is simultaneously mixed with clinical CT contrast agent iohexol (0.70 cm) 2 Per kg at 140 keV) with similar element number and attenuation coefficient (0.61 cm) 2 And (3) the oxygen vacancy mesoporous tin dioxide can be used as a contrast agent for computed tomography imaging, so that the anti-tumor treatment effect is monitored.
The invention is used for preparing the hollow mesoporous tin dioxide applied to the tumor diagnosis and treatment oxygen vacancy.
Drawings
FIG. 1 is a schematic diagram of a synthesis process for preparing oxygen vacancy hollow mesoporous tin dioxide according to the first embodiment;
FIG. 2 is a transmission electron microscope image, a is mesoporous silica prepared in the first step of the example, b is hollow mesoporous tin dioxide prepared in the second step of the example, c is oxygen vacancy hollow mesoporous tin dioxide prepared in the first step of the example;
FIG. 3 is a high resolution transmission electron microscope image of the hollow mesoporous tin dioxide with oxygen vacancies prepared in example one;
fig. 4 is an element mapping image of oxygen vacancy hollow mesoporous tin dioxide prepared in embodiment one, e is an oxygen vacancy hollow mesoporous tin dioxide dark field scanning transmission electron microscope image, f is an oxygen element mapping image, g is a tin element mapping image, and h is a composition of different element mapping images;
FIG. 5 is a nitrogen adsorption-desorption isotherm plot of oxygen vacancy hollow mesoporous tin dioxide prepared in example one;
FIG. 6 is a graph showing the pore size distribution of oxygen vacancy hollow mesoporous tin dioxide prepared in example I;
FIG. 7 is a physical diagram, wherein a is hollow mesoporous tin dioxide prepared in the step two of the embodiment, and b is hollow mesoporous tin dioxide with oxygen vacancies prepared in the embodiment one;
FIG. 8 is an absorption spectrum, a is hollow mesoporous tin dioxide prepared in the step two of the embodiment, b is hollow mesoporous tin dioxide with oxygen vacancies prepared in the embodiment one;
FIG. 9 is an X-ray diffraction chart, a is hollow mesoporous tin dioxide prepared in the first step of the embodiment, and b is hollow mesoporous tin dioxide with oxygen vacancies prepared in the first step of the embodiment;
FIG. 10 is a graph of Sn 3d photoelectron spectrum, a is hollow mesoporous tin dioxide prepared in the first step of the embodiment, and b is hollow mesoporous tin dioxide with oxygen vacancies prepared in the first step of the embodiment;
fig. 11 shows the colloidal stability of the oxygen-vacancy-hollow mesoporous tin dioxide prepared in example one in different solutions, 1 is a sodium chloride aqueous solution with a mass percentage of 0.9%, 2 is a phosphate buffer solution with a pH of 7.4, 3 is RPMI 1640 medium, and 4 is fetal bovine serum.
Detailed Description
The first embodiment is as follows: the embodiment relates to a preparation method of hollow mesoporous tin dioxide for tumor diagnosis and treatment oxygen vacancies, which comprises the following steps:
1. silica nanoparticles were prepared using sol-gel method:
adding cetyl trimethyl ammonium chloride and triethylamine into deionized water, ultrasonically obtaining a clear and transparent solution, heating the clear and transparent solution to 85-95 ℃ under magnetic stirring, stirring for 0.5-1.5 h under the condition of 85-95 ℃, then dropwise adding tetraethoxysilane under the condition of 85-95 ℃, reacting for 1.5-2.5 h under the condition of 85-95 ℃, finally centrifugally collecting and washing to obtain white precipitate, and vacuum drying the white precipitate to obtain mesoporous silica;
2. synthesizing hollow mesoporous tin dioxide nano particles by adopting an in-situ deposition method:
adding mesoporous silica into a mixed solution of ethanol and water, uniformly dispersing by ultrasonic, adding urea with the concentration of 2-3 mol/L and sodium stannate trihydrate with the concentration of 0.06-1 mol/L, stirring for 30 min-1 h at room temperature, heating to 160-180 ℃, preserving heat for 1 h-2 h at 160-180 ℃, naturally cooling to room temperature, centrifugally collecting and washing, and finally drying in vacuum to obtain hollow mesoporous tin dioxide;
3. preparing oxygen vacancy hollow mesoporous tin dioxide:
mixing hollow mesoporous tin dioxide with sodium borohydride, grinding for 10-15 min, placing in a tube furnace, heating to 350-450 ℃ under the protection of hydrogen, calcining for 1-1.5 h under the condition of 350-450 ℃, naturally cooling to room temperature, washing to obtain black precipitate, and vacuum drying the black precipitate to obtain the oxygen vacancy hollow mesoporous tin dioxide.
The embodiment prepares the multifunctional diagnosis and treatment integrated nano reagent with uniform and adjustable size distribution, stronger near infrared light absorption and oxygen vacancy hollow mesoporous tin dioxide for the nano biomedical fields such as imaging tumor treatment and the like, and adopts mesoporous silicon dioxide as a template and sodium stannate trihydrate as a tin source to construct an oxygen vacancy hollow mesoporous structure through a simple hydrothermal method.
The beneficial effects of this embodiment are:
(1) the oxygen vacancy hollow mesoporous tin dioxide is black, has uniform particle size, the size of the shell can be adjusted by changing the size of a silicon dioxide template, and the thickness of the shell and the template clearance can be adjusted by changing the amounts of urea and sodium stannate trihydrate in the reaction process, the reaction temperature and the reaction time. Because sodium carbonate is generated in the reaction process, the silicon dioxide template is removed while mesoporous tin dioxide is prepared, the experimental flow is shortened, and the method is simple, convenient and easy to control;
(2) the oxygen vacancy hollow mesoporous tin dioxide has larger specific surface area (290 m 2 /g～295m 2 And/g), internal cavity and mesoporous channel structure (5.5-6 nm), which is beneficial to improving the loading efficiency of anticancer drugs; the method has obvious near infrared light absorption, a large number of defects exist on the surface, which is beneficial to promoting the separation of electron holes, and under the excitation of near infrared light, a large number of reactive oxygen species can be generated for photodynamic therapy and obvious over-high thermal effect for photothermal therapy;
(3) tin is one of essential trace elements for human body, has important effects on various physiological activities and health maintenance of human body, and is simultaneously mixed with clinical CT contrast agent iohexol (0.70 cm) 2 Per kg at 140 keV) with similar element number and attenuation coefficient (0.61 cm) 2 And (3) the oxygen vacancy mesoporous tin dioxide can be used as a contrast agent for computed tomography imaging, so that the anti-tumor treatment effect is monitored.
The second embodiment is as follows: the second difference between this embodiment and the second embodiment is that: the washing in the first step is three times of washing with ethanol; the washing in the second step is to wash with ethanol three times to remove unreacted substances; and step three, washing with hydrochloric acid and deionized water with the mass percentage of 1-3% to remove excessive sodium borohydride. The other is the same as in the second embodiment.
And a third specific embodiment: this embodiment differs from one or both of the embodiments in that: the vacuum drying in the first to third steps is vacuum drying at 50-60 ℃. The other is the same as the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: the mass ratio of the hexadecyl trimethyl ammonium chloride to the triethylamine in the first step is 1g (75-85 mg); the volume ratio of the cetyl trimethyl ammonium chloride to the deionized water in the first step is 1g (75-85 mL). The other embodiments are the same as those of the first to third embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: the mass ratio of the cetyl trimethyl ammonium chloride to the tetraethoxysilane in the first step is 1 (5-7). The other embodiments are the same as those of the first to fourth embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: the volume ratio of the ethanol to the water in the mixed solution of the ethanol and the water in the second step is 1 (0.5-1.5). The other embodiments are the same as those of the first to fifth embodiments.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: the volume ratio of the mass of the mesoporous silica to the mixed solution of ethanol and water in the second step is 1mg (0.7-0.8) mL. The other embodiments are the same as those of the first to sixth embodiments.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: the volume ratio of the mass of the mesoporous silica to the urea with the concentration of 2mol/L to 3mol/L in the second step is 1mg (0.05 to 0.07) mL. The other is the same as in embodiments one to seven.
Detailed description nine: this embodiment differs from one to eight of the embodiments in that: the volume ratio of the mesoporous silica to the sodium stannate trihydrate solution with the concentration of 0.06 mol/L-1 mol/L is 1mg (0.08-0.09) mL. The others are the same as in embodiments one to eight.
Detailed description ten: this embodiment differs from one of the embodiments one to nine in that: and step three, the mass ratio of the hollow mesoporous tin dioxide to the sodium borohydride is 1 (0.4-0.6). The others are the same as in embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
embodiment one, specifically described with reference to fig. 1:
the preparation method of the hollow mesoporous tin dioxide applied to the tumor diagnosis and treatment oxygen vacancy is carried out according to the following steps:
1. silica nanoparticles were prepared using sol-gel method:
adding 1g of hexadecyl trimethyl ammonium chloride and 80mg of triethylamine into 80mL of deionized water, carrying out ultrasonic treatment to obtain a clear and transparent solution, heating the clear and transparent solution to 90 ℃ under magnetic stirring, stirring for 1h under the condition of 90 ℃, then adding 6g of tetraethoxysilane dropwise under the condition of 90 ℃, reacting for 2h under the condition of 90 ℃, finally centrifugally collecting and washing to obtain white precipitate, and carrying out vacuum drying on the white precipitate to obtain mesoporous silica;
2. synthesizing hollow mesoporous tin dioxide nano particles by adopting an in-situ deposition method:
adding 20mg of mesoporous silica into 15mL of mixed solution of ethanol and water, uniformly dispersing by ultrasonic, adding 1.2mL of urea with the concentration of 2mol/L and 1.75mL of sodium stannate trihydrate with the concentration of 0.08mol/L, stirring for 30min at room temperature, heating to 170 ℃, preserving heat for 1.5h under the condition of 170 ℃, naturally cooling to room temperature, centrifugally collecting and washing, and finally drying in vacuum to obtain hollow mesoporous tin dioxide;
3. preparing oxygen vacancy hollow mesoporous tin dioxide:
mixing the hollow mesoporous tin dioxide with sodium borohydride, grinding for 10min, then placing in a tube furnace, heating to 400 ℃ under the protection of hydrogen, calcining for 1h under the condition of 400 ℃, naturally cooling to room temperature, washing to obtain black precipitate, and vacuum drying the black precipitate to obtain the oxygen vacancy hollow mesoporous tin dioxide.
The washing in the first step is three times of washing with ethanol; the washing in the second step is to wash with ethanol three times to remove unreacted substances; the washing in the third step is to wash with hydrochloric acid and deionized water with the mass percentage of 2% to remove excessive sodium borohydride.
The vacuum drying described in the steps one to three is vacuum drying at a temperature of 60 ℃.
And in the second step, the volume ratio of the ethanol to the water in the mixed solution of the ethanol and the water is 1:1.
And step three, the mass ratio of the hollow mesoporous tin dioxide to the sodium borohydride is 1:0.5.
FIG. 2 is a transmission electron microscope image, a is mesoporous silica prepared in the first step of the example, b is hollow mesoporous tin dioxide prepared in the second step of the example, c is oxygen vacancy hollow mesoporous tin dioxide prepared in the first step of the example; as can be seen from the graph, the average particle diameter of the prepared mesoporous silica with good dispersibility is 55.6nm, mesoporous tin dioxide is prepared by an in-situ deposition method by taking the mesoporous silica as a template, the particle size is not obviously changed, but the particle surface is obviously roughened and hollow inner cavities exist, and the mesoporous tin dioxide shell layer is formed by stacking 3-4 nm ultra-small tin dioxide. The oxygen vacancy hollow mesoporous tin dioxide is further prepared by sodium borohydride reduction, the average size is 60.1nm, and the appearance is not obviously changed compared with the tin dioxide.
FIG. 3 is a high resolution transmission electron microscope image of the hollow mesoporous tin dioxide with oxygen vacancies prepared in example one; as can be seen from the graph, the lattice fringe spacing was 0.33nm, which was equivalent to SnO 2-x And keeping the consistency, and proving that the oxygen vacancy hollow mesoporous tin dioxide is successfully prepared.
Fig. 4 is an element mapping image of oxygen vacancy hollow mesoporous tin dioxide prepared in embodiment one, e is an oxygen vacancy hollow mesoporous tin dioxide dark field scanning transmission electron microscope image, f is an oxygen element mapping image, g is a tin element mapping image, and h is a composition of different element mapping images; from the graph, the nano structure of the oxygen vacancy hollow mesoporous tin dioxide is proved, and the uniform distribution of tin and oxygen elements in SnO can be observed 2-x A surface.
FIG. 5 is a nitrogen adsorption-desorption isotherm plot of oxygen vacancy hollow mesoporous tin dioxide prepared in example one; FIG. 6 is a graph showing the pore size distribution of oxygen vacancy hollow mesoporous tin dioxide prepared in example I; as can be seen from the figure, the specific surface area of the oxygen vacancy hollow mesoporous tin dioxide is 293m 2 And/g, the average pore size is 5.88nm.
FIG. 7 is a physical diagram, wherein a is hollow mesoporous tin dioxide prepared in the step two of the embodiment, and b is hollow mesoporous tin dioxide with oxygen vacancies prepared in the embodiment one; as can be seen, the color of the sample changed from white to black after the sodium borohydride was reduced.
FIG. 8 is an absorption spectrum, a is hollow mesoporous tin dioxide prepared in the step two of the embodiment, b is hollow mesoporous tin dioxide with oxygen vacancies prepared in the embodiment one; from the figure, it is clear that the oxygen vacancy hollow mesoporous tin dioxide has a significant absorption in the ultraviolet visible as well as near infrared light region, compared with the mesoporous tin dioxide.
FIG. 9 is an X-ray diffraction chart, a is hollow mesoporous tin dioxide prepared in the first step of the embodiment, and b is hollow mesoporous tin dioxide with oxygen vacancies prepared in the first step of the embodiment; the figure shows that the characteristic diffraction peak of the prepared oxygen vacancy hollow mesoporous tin dioxide is consistent with that of a standard card, and the oxygen vacancy hollow mesoporous tin dioxide with a square rutile structure is successfully prepared.
FIG. 10 is a graph of Sn 3d photoelectron spectrum, a is hollow mesoporous tin dioxide prepared in the first step of the embodiment, and b is hollow mesoporous tin dioxide with oxygen vacancies prepared in the first step of the embodiment; from the figure, it is seen that the hollow mesoporous tin dioxide has lower electron binding energy due to the presence of oxygen defects in the black oxygen vacancies compared to the white mesoporous tin dioxide.
FIG. 11 shows the colloidal stability of the oxygen vacancy hollow mesoporous tin dioxide prepared in example I in different solutions, 1 is 0.9% sodium chloride aqueous solution by mass, 2 is phosphate buffer solution with pH of 7.4, 3 is RPMI 1640 medium, and 4 is fetal bovine serum; as can be seen from the graph, the size of the oxygen-vacancy hollow mesoporous tin dioxide does not change significantly with the extension of the culture time, and the nano particles still have good dispersibility in different solvents even on the 14 th day, which indicates that the oxygen-vacancy hollow mesoporous tin dioxide has good colloid stability and dispersibility.
Claims (10)
1. The preparation method of the hollow mesoporous tin dioxide applied to the tumor diagnosis and treatment oxygen vacancy is characterized by comprising the following steps of:
1. silica nanoparticles were prepared using sol-gel method:
adding cetyl trimethyl ammonium chloride and triethylamine into deionized water, ultrasonically obtaining a clear and transparent solution, heating the clear and transparent solution to 85-95 ℃ under magnetic stirring, stirring for 0.5-1.5 h under the condition of 85-95 ℃, then dropwise adding tetraethoxysilane under the condition of 85-95 ℃, reacting for 1.5-2.5 h under the condition of 85-95 ℃, finally centrifugally collecting and washing to obtain white precipitate, and vacuum drying the white precipitate to obtain mesoporous silica;
2. synthesizing hollow mesoporous tin dioxide nano particles by adopting an in-situ deposition method:
adding mesoporous silica into a mixed solution of ethanol and water, uniformly dispersing by ultrasonic, adding urea with the concentration of 2-3 mol/L and sodium stannate trihydrate with the concentration of 0.06-1 mol/L, stirring for 30 min-1 h at room temperature, heating to 160-180 ℃, preserving heat for 1 h-2 h at 160-180 ℃, naturally cooling to room temperature, centrifugally collecting and washing, and finally drying in vacuum to obtain hollow mesoporous tin dioxide;
3. preparing oxygen vacancy hollow mesoporous tin dioxide:
mixing hollow mesoporous tin dioxide with sodium borohydride, grinding for 10-15 min, placing in a tube furnace, heating to 350-450 ℃ under the protection of hydrogen, calcining for 1-1.5 h under the condition of 350-450 ℃, naturally cooling to room temperature, washing to obtain black precipitate, and vacuum drying the black precipitate to obtain the oxygen vacancy hollow mesoporous tin dioxide.
2. The method for preparing hollow mesoporous tin dioxide for tumor diagnosis and treatment according to claim 1, wherein the washing in the first step is three times of washing with ethanol; the washing in the second step is to wash with ethanol three times to remove unreacted substances; and step three, washing with hydrochloric acid and deionized water with the mass percentage of 1-3% to remove excessive sodium borohydride.
3. The method for preparing hollow mesoporous tin dioxide for tumor diagnosis and treatment according to claim 1, wherein the vacuum drying in the first to third steps is performed at a temperature of 50-60 ℃.
4. The preparation method of the hollow mesoporous tin dioxide for tumor diagnosis and treatment oxygen vacancies, which is characterized in that the mass ratio of the cetyltrimethylammonium chloride to the triethylamine in the first step is 1g (75-85 mg); the volume ratio of the cetyl trimethyl ammonium chloride to the deionized water in the first step is 1g (75-85 mL).
5. The preparation method of the hollow mesoporous tin dioxide for tumor diagnosis and treatment oxygen vacancies according to claim 1, wherein the mass ratio of the cetyltrimethylammonium chloride to the tetraethoxysilane in the step one is 1 (5-7).
6. The method for preparing hollow mesoporous tin dioxide for tumor diagnosis and treatment according to claim 1, wherein the volume ratio of ethanol to water in the mixed solution of ethanol and water in the second step is 1 (0.5-1.5).
7. The preparation method of the hollow mesoporous tin dioxide for tumor diagnosis and treatment oxygen vacancies according to claim 1, wherein the volume ratio of the mass of the mesoporous silicon dioxide to the mixed solution of ethanol and water in the second step is 1mg (0.7-0.8) mL.
8. The preparation method of the hollow mesoporous tin dioxide for tumor diagnosis and treatment oxygen vacancies, which is characterized in that the volume ratio of the mass of mesoporous silicon dioxide to the urea with the concentration of 2 mol/L-3 mol/L in the second step is 1mg (0.05-0.07) mL.
9. The preparation method of the hollow mesoporous tin dioxide for tumor diagnosis and treatment oxygen vacancies according to claim 1, wherein the volume ratio of the mesoporous silicon dioxide in the second step to the sodium stannate trihydrate solution with the concentration of 0.06 mol/L-1 mol/L is 1mg (0.08-0.09) mL.
10. The preparation method of the hollow mesoporous tin dioxide for tumor diagnosis and treatment oxygen vacancies according to claim 1, wherein the mass ratio of the hollow mesoporous tin dioxide to sodium borohydride in the third step is 1 (0.4-0.6).
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