阅读说明：本技术 一种银铋硒光热转换纳米材料的制备方法 (Preparation method of silver bismuth selenium photo-thermal conversion nano material ) 是由 哈恩娜 张京歌 李丹阳 胡俊青 于 2021-08-09 设计创作，主要内容包括：本发明公开了一种银铋硒光热转换纳米材料的制备方法,涉及光热材料技术领域。该制备方法包括步骤：S1、制备0.1-1mol/L的硒原液；S2、制备银盐、铋盐反应混合液,其中,银盐、铋盐的摩尔比为1:0.1-10；S3、对银盐、铋盐反应混合液在90-120℃下抽真空,除去体系中的氧气和水,通入氮气,制得前驱体溶液；S4、将硒原液在90-120℃下注入所述前驱体溶液中反应,得到产物银铋硒纳米颗粒。本发明采用湿热法合成银铋硒光热转换纳米材料,操作简单,反应条件温和。本发明得到的银铋硒光热转换纳米材料,具有窄的能量带隙,对1064nm处有的近红外光很好的吸收效果,具有良好的光热转换效率；并能够在光热下杀死癌细胞,可作为光敏剂在癌症诊断或癌症治疗领域中应用。(The invention discloses a preparation method of a silver bismuth selenium photothermal conversion nano material, and relates to the technical field of photothermal materials. The preparation method comprises the following steps: s1, preparing 0.1-1mol/L selenium stock solution; s2, preparing a silver salt and bismuth salt reaction mixed solution, wherein the molar ratio of silver salt to bismuth salt is 1: 0.1-10; s3, vacuumizing the reaction mixed solution of the silver salt and the bismuth salt at 90-120 ℃, removing oxygen and water in the system, and introducing nitrogen to prepare a precursor solution; and S4, injecting the selenium stock solution into the precursor solution at 90-120 ℃ for reaction to obtain the product silver bismuth selenium nano-particles. The invention adopts a wet-heat method to synthesize the silver bismuth selenium photo-thermal conversion nano material, and has simple operation and mild reaction conditions. The silver bismuth selenium photothermal conversion nanomaterial obtained by the invention has a narrow energy band gap, has a good absorption effect on near infrared light at 1064nm, and has good photothermal conversion efficiency; can kill cancer cells under photothermal conditions, and can be used as photosensitizer in the field of cancer diagnosis or cancer treatment.)

1. The preparation method of the silver bismuth selenium photo-thermal conversion nano material is characterized by comprising the following steps of:

s1, preparing 0.1-1mol/L selenium stock solution;

s2, preparing a silver salt and bismuth salt reaction mixed solution, wherein the molar ratio of silver salt to bismuth salt is 1: 0.1-10;

s3, vacuumizing the reaction mixed solution of the silver salt and the bismuth salt at 90-120 ℃, removing oxygen and water in the system, and introducing nitrogen to prepare a precursor solution;

and S4, injecting the selenium stock solution into the precursor solution at 90-120 ℃ for reaction to obtain the product silver bismuth selenium nano-particles.

2. The method of preparing silver bismuth selenium photothermal conversion nanomaterial of claim 1, wherein in S1, selenium powder is dispersed in a mixed solution of oleylamine and 1-dodecanethiol to prepare a selenium stock solution.

3. The method for preparing silver bismuth selenium photothermal conversion nanomaterial according to claim 2, wherein the mass ratio of 1-dodecanethiol to oleylamine is 1-10: 1.

4. The method for preparing silver bismuth selenium photothermal conversion nanomaterial of claim 1, wherein silver salt and bismuth salt are dissolved in oleylamine solution to obtain silver salt and bismuth salt reaction mixture.

5. The method for preparing the silver bismuth selenium photothermal conversion nanomaterial according to claim 1, wherein the silver salt is one or a combination of silver acetate, silver carbonate, silver nitrate, silver nitrite, silver oxalate and silver chloride.

6. The method for preparing the silver bismuth selenium photothermal conversion nanomaterial of claim 1, wherein the bismuth salt is one or a combination of bismuth acetate, bismuth carbonate, bismuth nitrate, bismuth nitrite, bismuth oxalate and bismuth chloride.

7. The method for preparing silver bismuth selenium photothermal conversion nanomaterial of claim 1, wherein in S4, the molar ratio of selenium: silver: and bismuth is in a ratio of 1:0.1-10:1-10, and the selenium stock solution is injected into the precursor solution for reaction.

8. A silver bismuth selenium photothermal conversion nanomaterial, characterized by being prepared by the method of any one of claims 1 to 7.

9. The use of the silver bismuth selenium photothermal conversion nanomaterial of claim 8 as a photosensitizer in the field of cancer diagnosis or cancer treatment.

10. The silver bismuth selenium photothermal conversion nanomaterial of claim 8 has a good near infrared light absorption effect at a wavelength of 1064 nm.

Technical Field

The invention relates to the technical field of photo-thermal materials, in particular to a preparation method of a silver bismuth selenium photo-thermal conversion nano material.

Background

Cancer is still one of the most fatal diseases threatening the lives of people all over the world, however, traditional tumor treatment methods (surgery, chemotherapy, radiotherapy and the like) often face key obstacles such as nonspecific, multidrug resistance and excessive radiation, and near infrared light-mediated Photothermal therapy (PTT) is a new cancer treatment method and is greatly concerned due to the advantages of high specificity, small invasiveness, small side effects and the like on tumor tissues. In the PTT process, the light absorber can absorb near infrared light energy and convert it into local heat energy, resulting in cancer cell death in a short time.

At present, a plurality of ternary nano materials are applied to the field of cancer diagnosis and treatment, but have some defects, mainly comprising the following aspects: 1) most of the nanometer materials have complex synthesis methods; 2) the tissue penetration force of 808nm laser used as a treatment light source is not enough, so that the tumor treatment effect is not good enough; 3) the distribution and change of materials in the organism cannot be monitored in real time; 4) usually has a great toxicity to normal tissue cells. Recent researches show that the I-V-VI nano material has a narrow band gap and a high absorption coefficient, and has good response to near infrared light, particularly some nano selenides. In addition, the bismuth-based nano material has good X-ray attenuation capability and is beneficial to imaging observation, so that the synthesis of ternary nano particles by selecting three elements of silver, bismuth and selenium is expected to solve the difficult problem of the nano material in the aspect of cancer diagnosis and treatment.

CN201410571388.0 discloses a synthetic AgBiSe₂A method for preparing block thermoelectric material features that the fast thermal explosion synthesis reaction is combined with spark plasma activating sintering process to prepare AgBiSe with ZT up to 0.85(550 deg.C) in 30min₂Bulk thermoelectric material, process for its preparation and use thereofThe reaction conditions are severe and the operation is complex.

CN201910758011.9 discloses a ternary composite nano heterojunction photocatalyst and a preparation method thereof, which is prepared by AgI/Bi₂MoO₆/AgBi(MoO₄)₂Three phases are compounded and can be adjusted by AgI and Bi₂MoO₆And AgBi (MoO)₄)₂The catalytic performance of the catalyst is optimized by the proportion of the components, and the product synthesized by the method has good catalytic effect, but the photothermal effect is not systematically researched and is limited in application.

CN201910225814.8 discloses a bismuth silver sulfide hollow nanosphere and a preparation method thereof, wherein a monodisperse ZnS precursor and thiourea are uniformly dispersed in an alcohol solution, the mixture is stirred at the temperature of 90-130 ℃ for 10min, then a mixed alcohol solution of bismuth salt and silver salt is rapidly injected, and the reaction is continued for 10-30 min, so that AgBiS is obtained₂Hollow nanospheres formed by stacking nanocrystals, AgBiS prepared in this example₂The hollow nanosphere has excellent photothermal conversion properties and can be used as a photothermal therapeutic agent.

CN201911046464.5 discloses a semiconductor photosensitizer AgBiS with controllable size, less surface defects and wide photoresponse range₂Preparation method of quantum dot and semiconductor photosensitizer AgBiS prepared by using same₂The quantum dots can improve the application effect in the quantum dot sensitized solar cell.

Disclosure of Invention

The invention aims to solve the technical problem of how to more simply synthesize the ternary nano material of silver, bismuth and selenium so as to apply the ternary nano material to the photothermal therapy of cancer.

In order to solve the above problems, the present invention proposes the following technical solutions:

a preparation method of a silver bismuth selenium photo-thermal conversion nano material comprises the following steps:

s1, preparing 0.1-1mol/L selenium stock solution;

s2, preparing a silver salt and bismuth salt reaction mixed solution, wherein the molar ratio of silver salt to bismuth salt is 1: 0.1-10;

s3, vacuumizing the reaction mixed solution of the silver salt and the bismuth salt at 90-120 ℃, removing oxygen and water in the system, and introducing nitrogen to prepare a precursor solution;

and S4, injecting the selenium stock solution into the precursor solution at 90-120 ℃ for reaction to obtain the product silver bismuth selenium nano-particles.

In the step S1, selenium powder is dispersed in a mixed solution of oleylamine and 1-dodecanethiol to prepare a selenium stock solution.

The further technical scheme is that the mass ratio of the 1-dodecyl mercaptan to the oleylamine is 1-10: 1.

The further technical scheme is that silver salt and bismuth salt are dissolved in oleylamine solution to obtain silver salt and bismuth salt reaction mixed solution.

The further technical proposal is that the silver salt is one or the combination of a plurality of silver acetate, silver carbonate, silver nitrate, silver nitrite, silver oxalate and silver chloride.

The further technical scheme is that the bismuth salt is one or a combination of more of bismuth acetate, bismuth carbonate, bismuth nitrate, bismuth nitrite, bismuth oxalate and bismuth chloride.

The further technical proposal is that in the step S4, the selenium content is calculated according to the molar ratio of selenium: silver: and bismuth is in a ratio of 1:0.1-10:1-10, and the selenium stock solution is injected into the precursor solution for reaction.

The invention also provides a silver bismuth selenium photothermal conversion nano material which is prepared by the method and is a nano cubic phase and has a narrow energy band gap.

The silver bismuth selenium photothermal conversion nano material provided by the invention is used as a photosensitizer in the field of cancer diagnosis or cancer treatment.

The silver bismuth selenium photothermal conversion nano material provided by the invention has a good near infrared light absorption effect at 1064 nm.

Compared with the prior art, the invention can achieve the following technical effects:

the preparation method of the silver bismuth selenium photothermal conversion nanomaterial adopts a hydrothermal synthesis method, is simple to operate, mild in reaction conditions, low in cost, stable in product appearance and high in product purity, and is an efficient and controllable synthesis method.

The silver bismuth selenium photothermal conversion nano material obtained by the method is a cubic phase, has a narrow energy band gap, has a good absorption effect on near infrared light at 1064nm, and has good photothermal conversion efficiency; the compound can successfully kill 4T1 breast cancer cells under the action of laser, the good photothermal performance promotes the research and development of the compound as a photothermal agent in the aspect of photothermal treatment of cancer, and the compound can be used as a photosensitizer in the field of cancer diagnosis or cancer treatment.

The silver bismuth selenium photo-thermal conversion nano material prepared by the invention has the small size of nano particles, so that the silver bismuth selenium photo-thermal conversion nano material has good dispersibility in water and is easy to be metabolized and discharged in organisms, and the used materials are low in toxicity, so that the safety in biological application is improved.

Drawings

FIG. 1 is a graph showing the ultraviolet absorption curve of the silver bismuth selenium photothermal conversion nanomaterial prepared in example 1 of the present invention;

FIG. 2 is an XRD representation of the silver bismuth selenium photothermal conversion nanomaterial prepared in example 1 of the present invention;

FIG. 3 is an EDS diagram of the silver bismuth selenium photothermal conversion nanomaterial prepared in example 1 of the present invention;

FIG. 4 is a TEM image of the silver bismuth selenium photothermal conversion nanomaterial prepared in example 1 of the present invention;

FIG. 5 is a temperature rise curve of an aqueous solution of silver bismuth selenium photothermal conversion nanomaterial prepared in example 1 of the present invention at 1064nm near-infrared laser irradiation with different concentrations;

FIG. 6 shows the cell killing effect of the silver bismuth selenium photothermal conversion nanomaterial prepared in example 1 of the present invention in photothermal cancer therapy; wherein (a) is a blank group containing only cancer cells; (b) adding silver bismuth selenium photo-thermal conversion nano material into cancer cells; (c) irradiating cancer cells with 1064nm laser; (d) silver, bismuth and selenium photothermal conversion nano materials are added into cancer cells, and 1064nm laser is used for irradiation.

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. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. 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.

It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.

It is also to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the invention. As used in the description of embodiments of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

The embodiment of the invention provides a preparation method of a silver bismuth selenium photothermal conversion nano material, which comprises the following steps:

s1, dispersing selenium powder in a mixed solution of oleylamine and 1-dodecanethiol to prepare 0.1-1mol/L selenium stock solution;

s2, dissolving silver salt and bismuth salt into oleylamine solution to prepare silver salt and bismuth salt reaction mixed solution, wherein the molar ratio of the silver salt to the bismuth salt is 1: 0.1-10;

s3, vacuumizing the reaction mixed solution of the silver salt and the bismuth salt at 90-120 ℃, removing oxygen and water in the system, and introducing nitrogen to prepare a precursor solution;

s4, selenium according to molar ratio: silver: bismuth is in a ratio of 1:0.1-10:1-10, selenium stock solution is injected into the precursor solution at a temperature of 90-120 ℃ for reaction, and the product silver bismuth selenium nano-particles are obtained.

In a specific embodiment, the mass ratio of the 1-dodecanethiol to the oleylamine of S1 is 1-10: 1.

For example, in one embodiment, the mass ratio of 1-dodecanethiol to oleylamine of S1 is 3: 1.

In one embodiment, the mass ratio of 1-dodecanethiol to oleylamine of S1 is 6: 1.

In one embodiment, the mass ratio of 1-dodecanethiol to oleylamine of S1 was 9: 1.

In other embodiments, the molar ratio of the silver salt to the bismuth salt in the mixed reaction solution is 1: 0.1-10.

For example, in one embodiment, the molar ratio of the silver salt to the bismuth salt in the reaction mixture of silver salt and bismuth salt is 1: 0.6.

In one embodiment, the molar ratio of the silver salt to the bismuth salt in the mixed reaction solution is 1: 1.5.

In one embodiment, the molar ratio of the silver salt to the bismuth salt in the mixed reaction solution is 1: 4.

In one embodiment, the molar ratio of the silver salt to the bismuth salt in the mixed reaction solution is 1: 7.

In one embodiment, the molar ratio of the silver salt to the bismuth salt in the mixed reaction solution is 1: 9.

In other embodiments, the silver salt is a combination of one or more of silver acetate, silver carbonate, silver nitrate, silver nitrite, silver oxalate, silver chloride.

For example, in one embodiment, the silver salt is silver acetate.

In one embodiment, the silver salt is silver chloride.

In one embodiment, the silver salt is a mixture of silver nitrate and silver nitrite.

In other embodiments, the bismuth salt is a combination of one or more of bismuth acetate, bismuth carbonate, bismuth nitrate, bismuth nitrite, bismuth oxalate, bismuth chloride.

For example, in one embodiment, the bismuth salt is bismuth carbonate.

In one embodiment, the bismuth salt is bismuth oxalate.

The technical solution of the present invention is specifically described below by taking example 1 as an example:

example 1

The embodiment of the invention provides a silver bismuth selenium photothermal conversion nano material and a preparation method thereof, and the preparation method specifically comprises the following steps: ultrasonically dispersing 0.395g of selenium powder (molecular formula Se,1mmol) in a mixed solution of oleylamine and 1-dodecanethiol (the mass ratio of 1-dodecanethiol to oleylamine is 1: 1) to prepare a selenium source; mixing silver nitrate (molecular formula AgNO)₃0.5mmol)0.085g and bismuth acetate (formula C)₆H₉BiO₆0.5mmol) of 0.193g of the precursor solution is added into the oleylamine solution, the mixture is vacuumized and stirred uniformly, the vacuumizing is stopped after a period of time, the temperature is raised to 90 ℃, nitrogen is introduced, the temperature is raised to 120 ℃ under the protection of the nitrogen, and a reaction precursor solution A of silver and bismuth is prepared; selenium raw liquid is prepared by mixing selenium: silver: injecting bismuth into the solution A in a ratio of 1:1:2 for reaction for 10min, cooling to room temperature after the reaction is finished, washing the product with ethanol, centrifuging, drying, and finally collecting to obtain the silver bismuth selenium nanoparticles.

The silver bismuth selenium nanoparticles prepared in example 1 were prepared into an aqueous solution with a concentration of 150ug/mL, and ultraviolet spectrum absorption was performed to obtain fig. 1, which shows that the silver bismuth selenium nanoparticles synthesized in this example have a narrow energy band gap.

XRD characterization was performed on the silver bismuth selenium nanoparticles prepared in example 1 to obtain FIG. 2.

EDS measurement characterization is carried out on the silver bismuth selenium nano-particles prepared in the example 1, and a graph 3 is obtained, wherein the element proportion is 1:1:2, the distribution is uniform, and the element composition and proportion of the silver bismuth selenium nano-particles are proved to be consistent with those of expected products.

TEM representation is carried out on the silver bismuth selenium nanoparticles prepared in the example 1, and as shown in FIG. 4, the silver bismuth selenium nanoparticles prepared in the example have the size of about 5nm, small size and good dispersibility in water.

1064nm near-infrared laser was used to irradiate aqueous solutions of silver, bismuth and selenium nanoparticles (volume 0.5ml, laser power density 0.8 w/cm) prepared in example 1 at different concentrations²) The concentration is 50ug/mL, 100ug/mL, 150ug/mL, 200ug/mL respectively, and water without Ag, Bi, Se nanoparticles is used as blank control. The obtained temperature rise curve is shown in FIG. 5; show followingThe concentration of the nano material is enhanced, the temperature of the aqueous solution of the silver bismuth selenium nano particles is changed more greatly, and when the concentration is increased to 200 mu g/ml, the temperature is increased by 37 ℃ within 600 seconds, which shows that the silver bismuth selenium nano particles prepared by the invention have good absorption on near infrared light and show good photo-thermal conversion property.

The killing effect of the photothermal effect of the silver bismuth selenium nanoparticles prepared in example 1 on cancer cells is explored:

adding 150 mu g/ml silver bismuth selenium aqueous solution into 4T1 breast cancer cells cultured in a 96-well plate, culturing for a period of time after irradiating for 10min by using near-infrared laser, dyeing by using AM/PI, and observing the survival state of the cells, wherein the result is shown in figure 6, red is dead cells, green is live cells, and the observation of a fluorescence microscope proves that the cells irradiated by the laser are all dead while the silver bismuth selenium nanoparticles are added, and further proves the photothermal effect of the silver bismuth selenium nanoparticles prepared by the invention on a cell level, as shown in (d) in figure 6; meanwhile, bismuth element in the silver, bismuth and selenium has high X-ray attenuation capability and can be used as a reagent for CT imaging.

In conclusion, the silver bismuth selenium photothermal conversion nanomaterial obtained by the method is a cubic phase, has a narrow energy band gap, has a good absorption effect on near-infrared light at 1064nm, and has good photothermal conversion efficiency; and 4T1 breast cancer cells are killed successfully under the action of materials and laser, and the good photothermal performance promotes the research and development of the photothermal therapeutic agent as a photothermal agent for cancer.

The silver bismuth selenium photo-thermal conversion nano material prepared by the invention has the small size of nano particles, so that the silver bismuth selenium photo-thermal conversion nano material has good dispersibility in water and is easy to be metabolized and discharged in organisms, and the used materials are low in toxicity, so that the safety in biological application is improved.

In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.

While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.