CN110217819B - One-step synthesis method of spherical hollow mesoporous bismuth sulfide/silicon dioxide nano material - Google Patents
One-step synthesis method of spherical hollow mesoporous bismuth sulfide/silicon dioxide nano material Download PDFInfo
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Abstract
The invention relates to the technical field of preparation of hollow nano biomaterials, in particular to a one-step synthesis method of a spherical hollow mesoporous bismuth sulfide/silicon dioxide nanomaterial. Taking ethyl orthosilicate, surfactant, albumin, inorganic bismuth source, dilute nitric acid, sodium hydroxide, ammonium nitrate and absolute ethyl alcohol as raw materials, and preparing the hollow mesoporous Bi through constant temperature crystallization, template removal and centrifugal separation2S3/SiO2Nano material to greatly increase Bi2S3/SiO2Purity of nano material, enlarging Bi2S3/SiO2The application range of the nanometer material. The technological process is one fast and controllable synthesis of hollow mesoporous Bi2S3/SiO2The process of the nano material can realize the preparation of the hollow mesoporous Bi by changing the addition amounts of the surfactant, the ethyl orthosilicate and the albumin in a synthesis system2S3/SiO2The particle size of the microsphere and the thickness of the hollow layer of the nano material can be controllably adjusted. The hollow mesoporous Bi prepared by the method of the invention2S3/SiO2The properties of the nano material are as follows: the particle size is 80-150 nm, the thickness of the hollow outer layer is 10-20 nm, and the purity of the product reaches 99.9%.
Description
Technical Field
The invention relates to the technical field of preparation of hollow nano biomaterials, in particular to a one-step synthesis method of a spherical hollow mesoporous bismuth sulfide/silicon dioxide nanomaterial.
Background
Cancer is one of major diseases mainly overcome by accurate medical treatment at present, early diagnosis and boundary accuracy are carried out on tumors by utilizing a molecular imaging technology, and personalized treatment is constructed, so that efficient and accurate diagnosis and treatment of cancer are expected to be realized under the influence of low side effects. With the rise of the nanotechnology, the application field of the molecular imaging technology is expanded by utilizing the characteristics of the nanomaterials, the application of the nanomaterials in the aspect of disease treatment is realized, the molecular imaging technology is significant, and a new era is provided for developing novel cancer treatment means.
At present, various nanoprobes realize clinical transformation, and as the blood vessels in tumor tissues are rich, the gaps of the blood vessel walls are wide, and the structural integrity is poor, the nano-materials can be enriched in tumor parts through high permeability and long retention (EPR). Researchers find that the nanoparticles with the size of 50-100nm have a good passive targeting effect, the circulation time of the nanoparticles in vivo is relatively long, the nanoparticles can enter a focus part through a gap generated by 'intermittent eruption' of a dynamic orifice of a blood vessel, and then the gap is gradually closed, so that the large-size nanoparticles are kept in the interior, the removal rate is reduced, and the deposition amount of the nanoparticles on the focus part is greatly increased.
The mesoporous silica (HMSN) with the hollow structure has a large specific surface area and an internal hollow structure, can greatly improve the drug loading capacity, and meanwhile, the density of an external shell layer is low, so that the mesoporous silica is beneficial to rapid degradation and metabolism in a living body, and effectively reduces the toxicity accumulated in the body. Silicon oxide has been regarded as "generally recognized by the FDA in the united states as" GRAS ", and is widely used in drugs such as oral agents, and HMSN is a preferred material, providing a new concept for research and development of nano-materials in biomedicine. However, the currently constructed hollow mesoporous silica nanoparticles mostly adopt a step-by-step synthesis mode, the preparation process is complex, the number of variable factors is large, and the large-scale production is difficult, so that the deep research and clinical transformation of the hollow mesoporous silica nanoparticles are greatly limited.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the spherical hollow mesoporous Bi which has simple synthesis steps, easily controlled product structure and greatly improved product purity2S3/SiO2A one-step synthesis method.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a one-step synthesis method of spherical hollow mesoporous bismuth sulfide/silicon dioxide nano material comprises the following steps:
s1, mixing deionized water: surfactant (b): the albumin is prepared according to the following steps of 277.778-555.556: 0.082-0.329: 2.257.10-3～6.020·10-3Preparing a mixed solution according to the molar ratio, and stirring for 5-15 min at 30 ℃;
s2, dissolving an inorganic bismuth source in dilute nitric acid with the concentration of 2mol/L, dropwise adding the solution into the mixed solution in the S1 after full dissolution and dispersion, and stirring at a high speed for 10-20 min; the molar ratio of the inorganic bismuth source to the dilute nitric acid is 0.024-0.198: 1.6 to 2.4
S3, dropwise adding a sodium hydroxide solution with the concentration of 2mol/L into the mixed solution in the S2, adjusting the pH value to 12, and stirring at the constant temperature of 37 ℃ for 10-30 h;
s4, slowly dropwise adding ethyl orthosilicate into the mixed solution in the S3, sealing, and stirring at the constant temperature of 37 ℃ for 20-40 hours; the molar ratio of the ethyl orthosilicate to the surfactant is 1.307-6.533: 0.082-0.329;
s5, washing the mixed solution in the S4 by deionized water, centrifuging, freezing and drying to obtain the hollow mesoporous Bi without removing the template agent2S3/SiO2A nanomaterial;
s6 hollow mesoporous Bi without removing template agent2S3/SiO2: ammonium nitrate: 0.5-1% of absolute ethyl alcohol: 5-25: 1000-2000, adding ammonium nitrate into absolute ethyl alcohol to form a mixed solution, and adding hollow mesoporous Bi without removing the template agent2S3/SiO2After fully dissolving and dispersing, stirring for 2-6 h at 60 ℃ to prepare a mixture;
s7, sequentially carrying out solid-liquid separation, deionized water washing and drying on the mixture in the S6, and repeating the steps for three times to obtain the hollow mesoporous Bi2S3/SiO2And (3) nano materials.
Preferably, the surfactant is cetyltrimethylammonium bromide.
Preferably, the albumin is bovine serum albumin.
Preferably, the inorganic bismuth source is bismuth nitrate pentahydrate.
Preferably, the high-speed stirring in S2 is performed by using an ultrasonic disperser with a frequency of 59 KHz.
Preferably, an ultrasonic disperser is used for dissolving and dispersing in S6, the frequency is 59KHz, and the dispersing time is 5 min.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a one-step synthesis method of spherical hollow mesoporous bismuth sulfide/silicon dioxide nano material, which takes albumin and surfactant as template agents, modulates the addition amounts of the surfactant, ethyl orthosilicate and albumin in a synthesis system, thereby achieving the structural optimization of hollow nano particles, making up the defects of complicated multiple steps and difficult regulation and control of crystal grain structure of the preparation process for preparing hollow mesoporous silicon dioxide by the conventional method, ensuring simple and easy synthesis method, and greatly improving Bi2S3/SiO2Purity of nano material, enlarging Bi2S3/SiO2The application range of the nano material is very ideal one-step rapid and controllable preparation of the hollow mesoporous Bi2S3/SiO2A method of preparing a nanomaterial.
Drawings
FIG. 1 shows a hollow mesoporous Bi2S synthesized in example 1 of the present invention3/SiO2XRD spectrum of the nano material.
FIG. 2 shows the hollow mesoporous Bi2S synthesized in example 1 of the present invention3/SiO2TEM images of nanomaterials.
FIG. 3 shows the hollow mesoporous Bi2S synthesized in example 1 of the present invention3/SiO2Nitrogen adsorption-desorption spectrogram of the nano material.
FIG. 4 shows the hollow mesoporous Bi2S synthesized in example 1 of the present invention3/SiO2Pore size distribution of nanomaterials.
FIG. 5 shows the hollow mesoporous Bi2S synthesized in example 1 of the present invention3/SiO2XPS spectrum of nanometer material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the 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.
Example 1
138.6mL of 65% nitric acid and 806mL of deionized water are taken and added into a beaker together for full mixing, and the mixed solution is transferred into a volumetric flask to prepare a nitric acid solution with the concentration of 2moL/L for standby;
taking 83.33g of sodium hydroxide and 1L of deionized water, adding the sodium hydroxide and the deionized water into a beaker, fully mixing, transferring the mixed solution into a volumetric flask, and preparing a sodium hydroxide solution with the concentration of 2moL/L for later use;
adding 120mL of deionized water, 3.750g of bovine serum albumin and 1.05g of hexadecyl trimethyl ammonium bromide into a beaker together, and stirring for 10min at 30 ℃ to form a transparent solution; dissolving 0.36g of bismuth nitrate pentahydrate in 15mL of 2moL/L nitric acid solution, adding the solution into the mixed solution, and placing the mixed solution in an ultrasonic dispersion instrument for dissolution and dispersion with the frequency of 59KHz and the dispersion time of 10 min; adjusting the pH value of the mixed solution to 12 by using a prepared sodium hydroxide solution, heating to 37 ℃, stirring at a constant temperature for 15 hours, and changing the solution from transparent to brownish black;
taking 15mL of tetraethoxysilane, slowly dropwise adding the tetraethoxysilane into the brownish black mixed solution, sealing, and stirring at the constant temperature of 37 ℃ for 30 hours; washing the product with deionized water, centrifuging, and freeze-drying to obtain hollow mesoporous Bi without removing the template agent2S3/SiO2And (3) nano materials.
Weighing the dried hollow mesoporous Bi without removing the template agent2S3/SiO21.0g of nano material, 25g of ammonium nitrate and 2.5L of ethanol are added into a beaker together, and the beaker is placed in an ultrasonic dispersion instrument for dissolution and dispersion, wherein the frequency is 59KHz, and the dispersion time is 5 min. Then heating to 60 ℃ and stirring for 3h at constant temperature to obtain hollow mesoporous Bi2S3/SiO2And (3) nano materials.
FIG. 1 shows the hollow mesoporous Bi2S synthesized in this example3/SiO2The nano material synthesized by the XRD spectrogram of the nano material shows a characteristic diffraction peak.
FIG. 2 shows the hollow mesoporous Bi2S synthesized in this example3/SiO2TEM images of the nanomaterials, in which a is a TEM image on a scale of 100nm and b is a TEM image on a scale of 50 nm. The figure shows that the synthesized nano material is uniformly distributed and has a hollow spherical shape.
FIG. 3 shows the hollow mesoporous Bi2S synthesized in this example3/SiO2Nitrogen adsorption-desorption spectrogram of the nano material. The adsorption-desorption isotherms show a type IV curve in the region of relatively low partial pressure (P/P)00.08-0.21) has capillary condensation phenomenon, and the material is proved to have uniform pore channels.
FIG. 4 shows the hollow mesoporous Bi2S synthesized in this example3/SiO2Pore size distribution of nanomaterials. The pore size distribution calculated by a BJH model in the adsorption branch is narrow, and the average pore size is about 3.1 nm.
FIG. 5 shows the hollow mesoporous Bi2S synthesized in this example3/SiO2XPS spectrum of nanometer material. As can be seen, the XPS peaks at 159.0 and 164.1eV correspond to Bi2S3Bi4F7/2 and 4F5/2 peaks of nanoparticles, the 2p peak of S at 163.5eV being stabilized by BSA2S3Bi and S are combined in the nanoparticles.
Example 2
138.6mL of 65% nitric acid and 806mL of deionized water are taken and added into a beaker together for full mixing, and the mixed solution is transferred into a volumetric flask to prepare a nitric acid solution with the concentration of 2moL/L for standby;
taking 83.33g of sodium hydroxide and 1L of deionized water, adding the sodium hydroxide and the deionized water into a beaker, fully mixing, and transferring the mixed solution into a volumetric flask to prepare a sodium hydroxide solution with the concentration of 2moL/L for later use;
taking 75mL of deionized water, 2.250g of bovine serum albumin and 0.45g of hexadecyl trimethyl ammonium bromide, adding the deionized water, the bovine serum albumin and the hexadecyl trimethyl ammonium bromide into a beaker together, and stirring the mixture for 5min at the temperature of 30 ℃ to form a transparent solution; dissolving 0.18g of bismuth nitrate pentahydrate in 12mL of 2moL/L nitric acid solution, adding the solution into the mixed solution, and placing the mixed solution in an ultrasonic dispersion instrument for dissolution and dispersion with the frequency of 59KHz and the dispersion time of 10 min; adjusting the pH value of the mixed solution to 12 by using a prepared sodium hydroxide solution, heating to 37 ℃, stirring at a constant temperature for 10 hours, and changing the solution from transparent to brownish black;
4.5mL of tetraethoxysilane is taken, slowly dripped into the brownish black mixed solution, sealed and stirred for 20 hours at the constant temperature of 37 ℃; washing the product with deionized water, centrifuging, and freeze-drying to obtain hollow mesoporous Bi without removing the template agent2S3/SiO2And (3) nano materials.
Weighing the dried hollow mesoporous Bi without removing the template agent2S3/SiO20.5g of nano material and 6g of ammonium nitrate are added into a beaker together with 1.5L of ethanol, and the beaker is placed into an ultrasonic dispersion instrument for dissolution and dispersion, wherein the frequency is 59KHz, and the dispersion time is 5 min. Then heating to 60 ℃ and stirring for 2h at constant temperature to obtain hollow mesoporous Bi2S3/SiO2And (3) nano materials.
Example 3
138.6mL of 65% nitric acid and 806mL of deionized water are taken and added into a beaker together for full mixing, and the mixed solution is transferred into a volumetric flask to prepare a nitric acid solution with the concentration of 2moL/L for standby;
taking 83.33g of sodium hydroxide and 1L of deionized water, adding the sodium hydroxide and the deionized water into a beaker, fully mixing, transferring the mixed solution into a volumetric flask, and preparing a sodium hydroxide solution with the concentration of 2moL/L for later use;
adding 150mL of deionized water, 6.000g of bovine serum albumin and 1.80g of hexadecyl trimethyl ammonium bromide into a beaker together, and stirring for 15min at 30 ℃ to form a transparent solution; dissolving 1.44g of bismuth nitrate pentahydrate in 18mL of 2moL/L nitric acid solution, adding the solution into the mixed solution, and placing the mixed solution in an ultrasonic dispersion instrument for dissolution and dispersion with the frequency of 59KHz and the dispersion time of 10 min; adjusting the pH value of the mixed solution to 12 by using a prepared sodium hydroxide solution, heating to 37 ℃, stirring at a constant temperature for 30 hours, and changing the solution from transparent to brownish black;
taking 22.5mL of tetraethoxysilane, slowly dropwise adding the tetraethoxysilane into the brownish black mixed solution, sealing, and stirring at the constant temperature of 37 ℃ for 40 hours; washing the product with deionized water, centrifuging, and coolingFreeze drying to obtain hollow mesoporous Bi without template agent removal2S3/SiO2And (3) nano materials.
Weighing the dried hollow mesoporous Bi without removing the template agent2S3/SiO21.5g of nano material, 40g of ammonium nitrate and 4.0L of ethanol are added into a beaker, and the beaker is placed into an ultrasonic dispersion instrument for dissolution and dispersion, wherein the frequency is 59KHz, and the dispersion time is 5 min. Then heating to 60 ℃ and stirring for 6h at constant temperature to obtain hollow mesoporous Bi2S3/SiO2And (3) nano materials.
Example 4
138.6mL of 65% nitric acid and 806mL of deionized water are taken and added into a beaker together for full mixing, and the mixed solution is transferred into a volumetric flask to prepare a nitric acid solution with the concentration of 2moL/L for standby;
taking 83.33g of sodium hydroxide and 1L of deionized water, adding the sodium hydroxide and the deionized water into a beaker, fully mixing, transferring the mixed solution into a volumetric flask, and preparing a sodium hydroxide solution with the concentration of 2moL/L for later use;
adding 120mL of deionized water, 3.750g of bovine serum albumin and 1.05g of hexadecyl trimethyl ammonium bromide into a beaker together, and stirring for 10min at 30 ℃ to form a transparent solution; dissolving 0.36g of bismuth nitrate pentahydrate in 15mL of 2moL/L nitric acid solution, adding the solution into the mixed solution, and placing the mixed solution in an ultrasonic dispersion instrument for dissolution and dispersion with the frequency of 59KHz and the dispersion time of 10 min; adjusting the pH value of the mixed solution to 12 by using a prepared sodium hydroxide solution, heating to 37 ℃, stirring at a constant temperature for 15 hours, and changing the solution from transparent to brownish black;
taking 18mL of tetraethoxysilane, slowly dropwise adding the tetraethoxysilane into the brownish black mixed solution, sealing, and stirring at the constant temperature of 37 ℃ for 30 hours; washing the product with deionized water, centrifuging, and freeze-drying to obtain hollow mesoporous Bi without removing the template agent2S3/SiO2And (3) nano materials.
Weighing the dried hollow mesoporous Bi without removing the template agent2S3/SiO21.2g of nano material, 35g of ammonium nitrate and 3.1L of ethanol are added into a beaker together, and the beaker is placed in an ultrasonic dispersion instrument for dissolution and dispersion, wherein the frequency is 59KHz, and the dispersion time is 5 min. Then heating to 60 ℃ and stirring at constant temperatureObtaining hollow mesoporous Bi after 3 hours2S3/SiO2And (3) nano materials.
Example 5
138.6mL of 65% nitric acid and 806mL of deionized water are taken and added into a beaker together for full mixing, and the mixed solution is transferred into a volumetric flask to prepare a nitric acid solution with the concentration of 2moL/L for standby;
taking 83.33g of sodium hydroxide and 1L of deionized water, adding the sodium hydroxide and the deionized water into a beaker, fully mixing, transferring the mixed solution into a volumetric flask, and preparing a sodium hydroxide solution with the concentration of 2moL/L for later use;
adding 120mL of deionized water, 3.750g of bovine serum albumin and 0.6g of hexadecyl trimethyl ammonium bromide into a beaker together, and stirring for 10min at 30 ℃ to form a transparent solution; dissolving 0.36g of bismuth nitrate pentahydrate in 15mL of 2moL/L nitric acid solution, adding the solution into the mixed solution, and placing the mixed solution in an ultrasonic dispersion instrument for dissolution and dispersion with the frequency of 59KHz and the dispersion time of 10 min; adjusting the pH value of the mixed solution to 12 by using a prepared sodium hydroxide solution, heating to 37 ℃, stirring at a constant temperature for 15 hours, and changing the solution from transparent to brownish black;
taking 15mL of tetraethoxysilane, slowly dropwise adding the tetraethoxysilane into the brownish black mixed solution, sealing, and stirring at the constant temperature of 37 ℃ for 30 hours; washing the product with deionized water, centrifuging, and freeze-drying to obtain hollow mesoporous Bi without removing the template agent2S3/SiO2And (3) nano materials.
Weighing the dried hollow mesoporous Bi without removing the template agent2S3/SiO20.8g of nano material, 20g of ammonium nitrate and 2L of ethanol are added into a beaker, and the beaker is placed in an ultrasonic dispersion instrument for dissolution and dispersion, wherein the frequency is 59KHz, and the dispersion time is 5 min. Then heating to 60 ℃ and stirring for 3h at constant temperature to obtain hollow mesoporous Bi2S3/SiO2And (3) nano materials.
Example 6
138.6mL of 65% nitric acid and 806mL of deionized water are taken and added into a beaker together for full mixing, and the mixed solution is transferred into a volumetric flask to prepare a nitric acid solution with the concentration of 2moL/L for standby;
taking 83.33g of sodium hydroxide and 1L of deionized water, adding the sodium hydroxide and the deionized water into a beaker, fully mixing, transferring the mixed solution into a volumetric flask, and preparing a sodium hydroxide solution with the concentration of 2moL/L for later use;
adding 120mL of deionized water, 4.500g of bovine serum albumin and 1.2g of hexadecyl trimethyl ammonium bromide into a beaker together, and stirring for 10min at 30 ℃ to form a transparent solution; dissolving 0.36g of bismuth nitrate pentahydrate in 15mL of 2moL/L nitric acid solution, adding the solution into the mixed solution, and placing the mixed solution in an ultrasonic dispersion instrument for dissolution and dispersion with the frequency of 59KHz and the dispersion time of 10 min; adjusting the pH value of the mixed solution to 12 by using a prepared sodium hydroxide solution, heating to 37 ℃, stirring at a constant temperature for 15 hours, and changing the solution from transparent to brownish black;
taking 10mL of tetraethoxysilane, slowly dropwise adding the tetraethoxysilane into the brownish black mixed solution, sealing, and stirring at the constant temperature of 37 ℃ for 30 hours; washing the product with deionized water, centrifuging, and freeze-drying to obtain hollow mesoporous Bi without removing the template agent2S3/SiO2And (3) nano materials.
Weighing the dried hollow mesoporous Bi without removing the template agent2S3/SiO21.0g of nano material, 20g of ammonium nitrate and 2.2L of ethanol are added into a beaker together, and the beaker is placed in an ultrasonic dispersion instrument for dissolution and dispersion, wherein the frequency is 59KHz, and the dispersion time is 5 min. Then heating to 60 ℃ and stirring for 3h at constant temperature to obtain hollow mesoporous Bi2S3/SiO2And (3) nano materials.
The hollow mesoporous Bi prepared by the method of the invention2S3/SiO2The properties of the nano material are as follows: the particle size is 80-150 nm, the thickness of the hollow outer layer is 10-20 nm, and the purity of the product reaches 99.9%.
Although only the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art, and all changes are encompassed in the scope of the present invention.
Claims (4)
1. A one-step synthesis method of spherical hollow mesoporous bismuth sulfide/silicon dioxide nano material is characterized by comprising the following steps:
s1, mixing deionized water: surfactant (b): the albumin is prepared according to the following steps of 277.778-555.556: 0.082-0.329: 2.257.10-3~6.020·10-3Preparing a mixed solution according to the molar ratio, and stirring for 5-15 min at 30 ℃;
s2, according to the molar ratio of the inorganic bismuth source to the nitric acid being 0.024-0.198: 1.6-2.4, dissolving an inorganic bismuth source in dilute nitric acid with the concentration of 2mol/L, dropwise adding the solution into the mixed solution in S1 after the inorganic bismuth source is fully dissolved, and stirring at a high speed for 10-20 min;
s3, dropwise adding a sodium hydroxide solution with the concentration of 2mol/L into the mixed solution in the S2, adjusting the pH value of the mixed solution to 12, and stirring at the constant temperature of 37 ℃ for 10-30 h;
s4, according to the molar ratio of ethyl orthosilicate to surfactant of 1.307-6.533: 0.082-0.329, slowly dripping ethyl orthosilicate into the mixed solution in the S3, sealing, and stirring for 20-40 h at the constant temperature of 37 ℃;
s5, washing the mixed solution in the S4 by deionized water, centrifuging, freezing and drying to obtain the hollow mesoporous Bi without removing the template agent2S3/SiO2A nanomaterial;
s6 hollow mesoporous Bi without removing template agent2S3/SiO2: ammonium nitrate: absolute ethyl alcohol = 0.5-1: 5-25: 1000-2000, adding ammonium nitrate into absolute ethyl alcohol to form a mixed solution, and adding hollow mesoporous Bi without removing the template agent2S3/SiO2After fully dissolving and dispersing, stirring for 2-6 h at 60 ℃ to prepare a mixture;
s7, sequentially carrying out solid-liquid separation, deionized water washing and drying on the mixture in the S6, and repeating the steps for three times to obtain the hollow mesoporous Bi2S3/SiO2A nanomaterial;
the surfactant is cetyl trimethyl ammonium bromide; the albumin is bovine serum albumin.
2. The one-step synthesis method of spherical hollow mesoporous bismuth sulfide/silica nano material according to claim 1 is characterized in that: the inorganic bismuth source is bismuth nitrate pentahydrate.
3. The one-step synthesis method of spherical hollow mesoporous bismuth sulfide/silica nano material according to claim 1 is characterized in that: and an ultrasonic disperser is adopted for high-speed stirring in the S2, and the frequency is 59 KHz.
4. The one-step synthesis method of spherical hollow mesoporous bismuth sulfide/silica nano material according to claim 1 is characterized in that: and an ultrasonic disperser is adopted for dissolving and dispersing in the S6, the frequency is 59KHz, and the dispersion time is 5 min.
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| CN103446595A (en) * | 2013-08-01 | 2013-12-18 | 华中科技大学 | Multifunctional probe for CT (Computed Tomography) and dual-mode fluorescent imaging based on nanometer bismuth sulfide |
| CN106252661A (en) * | 2016-10-14 | 2016-12-21 | 成都理工大学 | Bismuth sulfide/carbon nano tube compound material and its preparation method and application |
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| CN103446595A (en) * | 2013-08-01 | 2013-12-18 | 华中科技大学 | Multifunctional probe for CT (Computed Tomography) and dual-mode fluorescent imaging based on nanometer bismuth sulfide |
| CN106252661A (en) * | 2016-10-14 | 2016-12-21 | 成都理工大学 | Bismuth sulfide/carbon nano tube compound material and its preparation method and application |
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| "BSA-Mediated Synthesis of Bismuth Sulfide Nanotheranostic Agents for Tumor Multimodal Imaging and Thermoradiotherapy";Yong Wang et al.;《ADVANCED FUNCTIONAL MATERIALS》;20161231;第26卷(第29期);第5335-5344页，支持信息 * |
| "Enhancing Osteosacoma Killing and CT Imaging Using Ultrahigh Drug Loading and NIR-Responsive Bismuth;Lu Yao et al.;《ADVANCED HEALTHCARE MATERIALS》;20181231;第7卷(第19期);第1-12页，支持信息 * |
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