阅读说明：本技术 可提高光热治疗效果的碳基稀土硫氧化物纳米材料及其制备方法和应用 (Carbon-based rare earth oxysulfide nano material capable of improving photothermal treatment effect and preparation method and application thereof ) 是由 杨梅 黄锦海 包必君 黄怡达 谢超然 徐文锦 于 2020-03-03 设计创作，主要内容包括：本发明公开可提高光热治疗效果的碳基稀土硫氧化物纳米材料及其制备方法和应用,其技术方案包括以下步骤：(1)选择介孔碳纳米材料作为前驱物材料；(2)将介孔碳纳米材料分散到分散到硝酸钆(Gd(NO<Sub>3</Sub>)<Sub>3</Sub>·6H<Sub>2</Sub>O)、硝酸镱(Yb(NO<Sub>3</Sub>)<Sub>3</Sub>·6H<Sub>2</Sub>O)和硝酸铒(Er(NO<Sub>3</Sub>)<Sub>3</Sub>·6H<Sub>2</Sub>O)水溶液中,其中Gd：Yb：Er的比例是1-x-y：x＝0～0.2：y＝0～0.02；在搅拌的情况下加入尿素,然后进行保温操作,得到Gd(OH)<Sub>3</Sub>:x％Yb<Sup>3+</Sup>,y％Er<Sup>3+</Sup>包裹的介孔碳前驱物；(3)将步骤(2)所制备的Gd(OH)<Sub>3</Sub>:x％Yb<Sup>3+</Sup>,y％Er<Sup>3+</Sup>包裹的介孔碳前驱物置于高温管式炉中,在N<Sub>2</Sub>/S的混合气氛中于600-800℃下保温1.5-3h,得到稀土硫氧化物包裹的介孔碳纳米材料。本发明的技术方案具有提高光热治疗效果的优点,具有快速,高效的特点。(The invention discloses a carbon-based rare earth oxysulfide nano material capable of improving photothermal treatment effect, and a preparation method and application thereof, and the technical scheme comprises the following steps: (1) selecting a mesoporous carbon nanomaterial as a precursor material; (2) dispersing mesoporous carbon nano material into gadolinium nitrate (Gd (NO) 3 ) 3 ·6H 2 O), ytterbium nitrate (Yb (NO) 3 ) 3 ·6H 2 O) and erbium nitrate (Er (NO) 3 ) 3 ·6H 2 O) aqueous solution, wherein Gd: yb: the proportion of Er is 1-x-y: x is 0-0.2: y is 0-0.02; adding urea while stirring, and performing heat preservation to obtain Gd (OH) 3 :x％Yb 3+ ,y％Er 3+ A coated mesoporous carbon precursor; (3) reacting Gd (OH) prepared in the step (2) 3 :x％Yb 3+ ,y％Er 3+ The wrapped mesoporous carbon precursor is placed in a high temperature tube furnace in N 2 And (3) preserving the heat for 1.5-3h at the temperature of 600-800 ℃ in the mixed atmosphere of/S to obtain the mesoporous carbon nano material wrapped by the rare earth oxysulfide. The technical scheme of the invention has the advantage of improving the photothermal treatment effect and has the characteristics of rapidness and high efficiency.)

1. A preparation method of a carbon-based rare earth oxysulfide nano material capable of improving photothermal treatment effect is characterized by comprising the following steps:

(1) selecting a mesoporous carbon nanomaterial as a precursor material;

(2) dispersing mesoporous carbon precursor nano material into gadolinium nitrate (Gd (NO)₃)₃·6H₂O), ytterbium nitrate (Yb (NO)₃)₃·6H₂O) and erbium nitrate (Er (NO)₃)₃·6H₂O) aqueous solution, wherein Gd: yb: the proportion of Er is 1-x-y: x is 0-0.2: y is 0-0.02; adding urea while stirring, and performing heat preservation to obtain Gd (OH)₃:x％Yb³⁺,y％Er³⁺The coated mesoporous carbon precursor nano material;

(3) reacting Gd (OH) prepared in the step (2)₃:x％Yb³⁺,y％Er³⁺The wrapped mesoporous carbon precursor nano material is placed in a high-temperature tube furnace in N₂And (3) preserving the heat for 1.5-3h at the temperature of 600-800 ℃ in the mixed atmosphere of/S to obtain the mesoporous carbon nano material wrapped by the rare earth oxysulfide.

2. The method for preparing carbon-based rare earth oxysulfide nano-material capable of improving photothermal therapy effect according to claim 1, characterized in that: the mesoporous carbon nano material is prepared by a solvothermal preparation method and a subsequent high-temperature hydrothermal method.

3. The method for preparing a carbon-based rare earth oxysulfide nanomaterial capable of improving photothermal therapy effect according to claim 2, characterized in that the step (1) comprises adding 0.6g of phenol, 2.1ml of formaldehyde and 15ml of 0.1 mol/L NaOH solution into a 100ml flask, stirring uniformly, transferring to a 70 ℃ water bath kettle for reaction for 30min, transferring the flask to a 66 ℃ oil bath kettle, slowly dropping 15ml of an aqueous solution containing 0.96g of Pluronic F-127 into the flask, reacting for 2h, slowly dropping 50ml of deionized water for dilution, continuing to react for 16-18 h, taking 17.8ml of the solution obtained by reaction, dissolving in 56ml of deionized water, stirring uniformly, adding to a 100ml reaction kettle, placing in a 130 ℃ oven for reaction for 24h, and centrifuging and washing to obtain the mesoporous carbon precursor nanomaterial.

4. A carbon-based rare earth oxysulfide nanomaterial prepared by the method of any one of claims 1 to 3.

5. Use of the carbon-based rare earth oxide nanomaterial of claim 4 as a photothermal agent in photothermal treatment of cancer.

Technical Field

The invention belongs to the field of novel materials, and particularly relates to a carbon-based rare earth oxysulfide nano material capable of improving a photothermal treatment effect and a preparation method thereof.

Background

Cancer is one of the leading causes of death in the world population, and traditional cancer therapies all have inevitable drawbacks and limitations, making development of new cancer therapies extremely necessary. The photothermal therapy is a new tumor treatment method which appears in recent years, and under the irradiation of external near infrared light, the photothermal agent at the tumor part absorbs the near infrared light and converts the near infrared light into heat, so that the temperature of the tumor part is rapidly increased, and cancer cells can be killed within a few minutes. The photothermal therapy process has less side effect, low systemic toxicity, no damage to normal tissue and great clinical application potential.

Various nano photothermal agents such as noble metal nano particles, carbon nano materials, organic nano materials, semiconductor nano materials and the like are developed and applied to photothermal therapy, and a better tumor treatment effect is achieved. However, the development of novel photothermal agents with absorption covering the spectroscopy window (700-1500nm) of organisms and the exploration of their application in tumor photothermal therapy remain a great challenge.

Disclosure of Invention

In order to solve the problems and the defects in the prior art, the invention aims to provide a carbon-based (taking mesoporous carbon as an example) rare earth oxysulfide nano material capable of improving the photothermal treatment effect and a preparation method thereof, wherein the carbon-based (taking mesoporous carbon as an example) rare earth oxysulfide nano material has the characteristics of high speed and high efficiency.

According to the invention, the mesoporous carbon nanomaterial coated with the rare earth oxysulfide upconversion nanomaterial is synthesized by a two-step method, besides the photothermal conversion of the mesoporous carbon material, the rare earth oxysulfide upconversion luminescent material can also convert 980nm near infrared light into visible light, and further generate a photothermal effect or convert the visible light emitted by the rare earth oxysulfide into heat energy through mesoporous carbon, so that the purpose of photothermal therapy is realized. Compared with simple mesoporous carbon, the material has the characteristics of high efficiency and high speed. The invention enriches the nanometer materials for tumor photothermal therapy, widens the wavelength selection range of incident light for photothermal therapy, and provides a new idea for tumor diagnosis and treatment.

In order to achieve the above objects, the first aspect of the present invention provides a method for preparing mesoporous carbon nanomaterial precursor by using a solvothermal preparation method and a subsequent high temperature hydrothermal method, for example, adding 0.6g phenol, 2.1ml formaldehyde and 15ml 0.1 mol/L NaOH solution into a 100ml flask, stirring uniformly, transferring to a 70 ℃ water bath for reaction for 30min, transferring the flask to a 66 ℃ oil bath, slowly dropping 15ml Pluronic F-127-containing aqueous solution into the flask, reacting for 2h, slowly dropping 50ml deionized water for dilution, continuing to react for 16-18, taking 17.8ml reaction solution, dissolving in 56ml deionized water, stirring uniformly, adding to a 100ml reaction kettle, reacting for 24h in a 130 ℃ oven, centrifuging, washing to obtain mesoporous carbon nanomaterial precursor, and dispersing the mesoporous carbon nanomaterial precursor into 20-30ml gadolinium nitrate (Gd) (NO) containing different proportions₃)₃·6H₂O), ytterbium nitrate (Yb (NO)₃)₃·6H₂O) and erbium nitrate (Er (NO)₃)₃·6H₂O) (wherein Gd: yb: the proportion of Er is 1-x-y: x is 0-0.2: y 0 to 0.02, and the total amount of substances is about 0.25 to 1mmol), adding urea (2 to 3g) while stirring, and maintaining the temperature at 90 ℃3h to obtain Gd (OH)₃:x％Yb³⁺,y％Er³⁺Encapsulated mesoporous carbon precursors. Finally, the obtained material is placed in a high-temperature tube furnace in N₂And (3) preserving the heat for 1.5-3h at the temperature of 600-800 ℃ in the S mixed atmosphere, wherein the adding amount of sulfur is about 3-5g, so as to obtain the mesoporous carbon nano material coated by the rare earth oxysulfide. And finally, evaluating the photo-thermal performance of the obtained nano material. After the photo-thermal killing effect generated by the 980nm laser is eliminated, the fact that the synthesized mesoporous carbon nano material and the mesoporous carbon nano material wrapped by the rare earth oxysulfide up-conversion material have the obvious photo-thermal treatment effect is found, and compared with the mesoporous carbon nano material with the same concentration, the mesoporous carbon nano material wrapped by the rare earth oxysulfide up-conversion material has the effect of efficiently and quickly killing tumor cells.

The invention has the beneficial effects that: the mesoporous carbon nanomaterial coated with rare earth oxysulfide prepared by the method has an obvious treatment effect under the irradiation of 980nm laser, has an efficient and rapid treatment effect compared with a simple mesoporous carbon material, and has important research significance for expanding the application field of the rare earth nanomaterial.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.

FIG. 1 is a photo of a sample of mesoporous carbon nanomaterial precursor and rare earth oxysulfide coated mesoporous carbon nanomaterial prepared by the present invention;

FIG. 2 is an XRD spectrum of the mesoporous carbon nanomaterial precursor and the rare earth oxysulfide coated mesoporous carbon nanomaterial prepared by the embodiment of the invention;

FIG. 3 is an SEM image of the mesoporous carbon nanomaterial precursor and the rare earth oxysulfide coated mesoporous carbon nanomaterial prepared by the embodiment of the invention;

FIG. 4 is a biological compatibility evaluation of the mesoporous carbon nanomaterial prepared by the embodiment of the present invention and the mesoporous carbon nanomaterial coated with rare earth oxysulfide;

FIG. 5 shows the photo-thermal killing effect of the mesoporous carbon nanomaterial prepared by the embodiment of the present invention and the mesoporous carbon nanomaterial coated with rare earth oxysulfide on cancer cells under 980nm laser irradiation.

FIG. 6 shows the photo-thermal killing effect of the mesoporous carbon nanomaterial with the same concentration and the mesoporous carbon nanomaterial coated with rare earth oxysulfide on cancer cells under 980nm laser irradiation for different irradiation times.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.

Firstly, a solvent thermal preparation method and a subsequent high-temperature hydrothermal method are adopted to prepare a precursor of a mesoporous carbon nano material, for example, 0.6g of phenol, 2.1ml of formaldehyde and 15ml of 0.1 mol/L NaOH solution are added into a 100ml flask, the mixture is stirred uniformly and then transferred into a 70 ℃ water bath kettle to react for 30min, the flask is transferred into a 66 ℃ oil bath kettle, 15ml of aqueous solution containing 0.96g of Pluronic F-127 is slowly added into the flask to react for 2h, then 50ml of deionized water is slowly dropped to dilute the solution, the reaction is continuously carried out for 16-18 h, then 17.8ml of solution obtained by the reaction is taken and dissolved into 56ml of deionized water, the solution is stirred uniformly and then added into a 100ml reaction kettle to be put into a 130 ℃ oven to react for 24h, the precursor of the mesoporous carbon nano material is obtained by centrifugal washing, and then the precursor of the mesoporous carbon nano material is dispersed into 20-30ml of gadolinium (NO) nitric acid (Gd (NO)₃)₃·6H₂O), ytterbium nitrate (Yb (NO)₃)₃·6H₂O) and erbium nitrate (Er (NO)₃)₃·6H₂O) (wherein Gd: yb: the proportion of Er is 1-x-y: x is 0-0.2: y is 0 to 0.02, and the total amount of substances is about 0.25 to 1mmol), adding urea (2 to 3g) while stirring, and then keeping the temperature at 90 ℃ for 3h to obtain Gd (OH)₃:x％Yb³⁺,y％Er³⁺Encapsulated mesoporous carbon precursors. Finally, the obtained material is processedThe material is placed in a high temperature tube furnace at N₂And (3) preserving the heat for 1.5-3h at the temperature of 600-800 ℃ in the S mixed atmosphere, wherein the adding amount of sulfur is about 3-5g, so as to obtain the mesoporous carbon nano material coated by the rare earth oxysulfide.

The left and right photographs of fig. 1 are the mesoporous carbon nanomaterial precursor and the mesoporous carbon nanomaterial wrapped by rare earth oxysulfide.

The presence of rare earth oxysulfide material in the material can be confirmed by the XRD pattern change of the two materials of fig. 2.

From FIG. 3, it can be found that the mesoporous carbon nanomaterial and the mesoporous carbon nanomaterial wrapped by rare earth oxysulfide are both nanomaterials, and the sample has excellent dispersibility

From fig. 4, it can be found that the biocompatibility of the mesoporous carbon nanomaterial wrapped by mesoporous carbon and rare earth oxysulfide is good.

Fig. 5 shows that under the irradiation of 980nm laser, the mesoporous carbon nanomaterial and the mesoporous carbon nanomaterial coated with rare earth oxysulfide both have a detailed killing effect on cancer cells, and compared with the agreed concentration, the mesoporous carbon nanomaterial coated with rare earth oxysulfide has a more obvious killing effect on cancer cells,

fig. 6 shows that under the irradiation of 980nm laser, the killing effect of the mesoporous carbon nanomaterial wrapped by rare earth oxysulfide on cancer cells is higher than that of a pure mesoporous carbon nanomaterial within the same irradiation time, the mesoporous carbon nanomaterial has a good killing effect within 5min, and the killing performance of the irradiation time for tumors is not greatly improved. Therefore, the mesoporous carbon nano material coated by the rare earth oxysulfide prepared by the invention has high-efficiency and quick treatment effect.

The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.