Preparation method of mesoporous nano long afterglow material

Abstract

The application discloses a preparation method of mesoporous nano long-afterglow material and belongs to the technical field of long-afterglow material preparation. The mesoporous nano long-afterglow material is synthesized by using a hydrothermal method and a high-temperature calcination method. Compared with a traditional method for preparing nano long-afterglow material, the mesoporous nano long-afterglow material prepared by the application has good morphology and mesopores capable of loading functional substances, and the mesoporous nano long-afterglow material does not need to use mesoporous silica as a template to synthesize nano long-afterglow material, so that the application of the mesoporous nano long-afterglow material in the fields of biomedicine and the like is further expanded.

Description

Technical Field

[0001] This invention relates to the field of long afterglow material preparation technology, specifically designing a method for preparing mesoporous nano-long afterglow materials. Background Technology

[0002] Long-afterglow materials are materials capable of storing external radiation energy and continuing to emit light after the excitation light stops, with afterglow lasting for hours or even days. Due to their unique optical properties, long-afterglow materials have wide applications in illumination, emergency safety, and transportation. In recent years, with the emergence of nanomaterials with long afterglow, their advantages, such as long afterglow lifetime, no need for in-situ excitation, non-organic autofluorescence, and high signal-to-noise ratio, have shown great application potential in bioimaging, biosensing, and imaging-mediated tumor therapy. Subsequently, various types of nanomaterials with long afterglow have been synthesized and applied to in vivo imaging.

[0003] Existing long afterglow materials are generally synthesized using high-temperature calcination. Although the synthesized long afterglow materials exhibit good afterglow performance, material aggregation occurs during high-temperature calcination, resulting in excessively large material sizes. While ball milling can produce nanoscale materials, their size and morphology remain difficult to control, ultimately limiting their further biomedical applications. Long afterglow materials synthesized using hydrothermal methods exhibit better water solubility, but their afterglow time is shorter compared to those obtained through high-temperature calcination. To further expand the biomedical applications of long afterglow materials, researchers have synthesized them using mesoporous silica as a template. This method involves pre-adsorbing precursor ions of the long afterglow material into the pores of the mesoporous silica before calcination. This cleverly solves the problem of agglomeration of long afterglow materials during solid-state annealing. However, the precursor ions pre-occupy the mesoporous silica pores, thus affecting the loading of other functional substances. Therefore, the preparation of mesoporous nanoscale afterglow materials is of great significance for their application in the biomedical field. Summary of the Invention

[0004] In view of this, the present invention aims to provide a method for preparing mesoporous nanolong afterglow materials; a second objective of the present invention is to provide mesoporous nanolong afterglow materials prepared by the method; and a third objective of the present invention is to provide the application of the mesoporous nanolong afterglow materials in spectral analysis, bioimaging, or tumor treatment.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] 1. A method for preparing a mesoporous nanolength afterglow material, comprising the following preparation steps:

[0007] (1) Prepare an aqueous solution of ascorbic acid or citric acid and hexadecyltrimethylammonium bromide;

[0008] (2) Under vigorous stirring, add nano-long afterglow material precursor ions to the solution prepared in step (1), then add hexamethylenetetramine, heat the reaction, and collect the product by centrifugation after the reaction is completed; the nano-long afterglow material precursor ions are a mixture of gadolinium, gallium and chromium nitrate or chloride salts; the molar ratio of gadolinium, gallium and chromium is 1:1 to 4:0.001 to 0.006;

[0009] (3) In order to remove the template, the product collected by centrifugation was added to a mixed solution of ethanol-hydrochloric acid, ultrasonically dispersed, refluxed at 60°C for 24 hours, the product was collected by centrifugation, washed with anhydrous ethanol and deionized water, and dried.

[0010] (4) The product dried in step (3) is calcined in air.

[0011] 8. Preferably, the molar ratio of ascorbic acid or citric acid, hexadecyltrimethylammonium bromide and hexamethylenetetramine is 2:3:2.

[0012] Preferably, in step (2) of this invention, the heating reaction is carried out at 60-120°C for 6-24 hours.

[0013] Preferably, in step (3) of the present invention, the volume ratio of ethanol to hydrochloric acid in the ethanol-hydrochloric acid mixed solution is 6:1.

[0014] In a preferred embodiment of the present invention, in step (4), the calcination is carried out in a muffle furnace at 600-700°C for 1-2 hours.

[0015] 2. The mesoporous nanolength afterglow material prepared by the method.

[0016] 3. Applications of the mesoporous nanolength afterglow material in spectral analysis, bioimaging, or tumor treatment.

[0017] The beneficial effects of this invention are as follows: Compared with the prior art, this invention synthesizes mesoporous nanolong afterglow materials. Compared with the traditional method of preparing nanolong afterglow materials using mesoporous silicon as a template, the mesoporous nanolong afterglow materials prepared by this invention have good morphology and mesopores that can be used to load functional substances. It does not require the use of mesoporous silicon as a template to synthesize nanolong afterglow materials, further expanding its application in biomedicine and other fields. Attached Figure Description

[0018] To make the objectives, technical solutions, and beneficial effects of this invention clearer, the following figures are provided for illustration:

[0019] Figure 1This is a transmission electron microscope image of the mesoporous nanolength afterglow material synthesized in this invention;

[0020] Figure 2 This is the elemental mapping diagram of the mesoporous nanolength afterglow material synthesized in this invention;

[0021] Figure 3 The N2 adsorption-desorption isotherm and pore size distribution diagram of the mesoporous nano-long afterglow material synthesized in this invention are shown.

[0022] Figure 4 These are the excitation and emission spectra of the mesoporous nanolength afterglow material synthesized in this invention;

[0023] Figure 5 The afterglow decay curve of the mesoporous nano-long afterglow material synthesized in this invention;

[0024] Figure 6 The images show the afterglow of the solid powder and aqueous solution (2 mg / mL) of the mesoporous nano-long afterglow material synthesized in this invention after irradiation with a 254 nm ultraviolet lamp for 15 min, respectively, over time. Detailed Implementation

[0025] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments described are not intended to limit the present invention.

[0026] Example 1

[0027] 0.02 mmol of ascorbic acid or citric acid and 0.03 mmol of cetyltrimethylammonium bromide (CTAB) were added to 10 mL of deionized water and ultrasonically dispersed. Then, a mixed solution of gadolinium nitrate hexahydrate (1 mmol), gallium nitrate hydrate (2 mmol), and chromium nitrate nonahydrate (0.003 mmol) was added to the above solution under vigorous stirring, followed by the addition of 0.02 mmol of hexamethylenetetramine. The mixture was stirred at room temperature for 15 min. The solution was then placed in an oven and reacted at 60 °C for 6 h. After the reaction was complete, the solution was allowed to cool naturally to room temperature. The product was centrifuged at 12000 rpm at room temperature for 5 min, and then washed three times with deionized water under the same conditions. The final product was refluxed at 85 °C for 24 h in a solution of anhydrous ethanol-hydrochloric acid (6:1 volume ratio). The solution was allowed to cool naturally to room temperature, and the product was collected by centrifugation. The obtained product was then washed with anhydrous ethanol and deionized water under the same conditions, and the final product was dried in an oven. The resulting product was calcined at 600°C for 1 hour in a tube furnace to obtain mesoporous nano-long afterglow materials.

[0028] Example 2

[0029] 0.02 mmol of ascorbic acid or citric acid and 0.03 mmol of hexadecyltrimethylammonium bromide (CTAB) were added to 10 mL of deionized water and ultrasonically dispersed until homogeneous. A mixed solution of gadolinium chloride hexahydrate (1 mmol), gallium chloride (1.5 mmol), and chromium chloride (0.002 mmol) was added to the above solution under vigorous stirring, followed by the addition of 0.02 mmol of hexamethylenetetramine, and the mixture was stirred at room temperature for 15 min. The solution was then placed in an oven and reacted at 60 °C for 8 h. After the reaction was complete, the solution was allowed to cool naturally to room temperature. The product was centrifuged at 12,000 rpm at room temperature for 5 min, and then washed three times with deionized water under the same conditions. The final product was refluxed at 60 °C for 24 h in a solution of anhydrous ethanol-hydrochloric acid (6:1 volume ratio). The solution was allowed to cool naturally to room temperature, and the product was collected by centrifugation. The obtained product was then washed with anhydrous ethanol and deionized water under the same conditions, and the final product was dried in an oven. The resulting product was calcined at 700°C for 2 hours in a tube furnace to obtain mesoporous nano-long afterglow materials.

[0030] Example 3

[0031] 0.02 mmol of ascorbic acid or citric acid and 0.03 mmol of cetyltrimethylammonium bromide (CTAB) were added to 10 mL of deionized water and ultrasonically dispersed until homogeneous. A mixed solution of gadolinium nitrate hexahydrate (1 mmol), gallium nitrate hydrate (2 mmol), and chromium nitrate nonahydrate (0.004 mmol) was added to the above solution under vigorous stirring, followed by the addition of 0.02 mmol of hexamethylenetetramine. The mixture was stirred at room temperature for 15 min. The solution was then placed in an oven and reacted at 90 °C for 10 h. After the reaction was complete, the solution was allowed to cool naturally to room temperature. The product was centrifuged at 12000 rpm at room temperature for 5 min, and then washed three times with deionized water under the same conditions. The final product was ultrasonically dispersed in a solution of anhydrous ethanol and hydrochloric acid at a volume ratio of 6:1 and refluxed at 60 °C for 24 h. The solution was allowed to cool naturally to room temperature, and the product was collected by centrifugation. The obtained product was then washed with anhydrous ethanol and deionized water under the same conditions, and the final product was dried in an oven. The resulting product was calcined at 800°C for 2 hours in a tube furnace to obtain mesoporous nano-long afterglow materials.

[0032] Example 4

[0033] 0.02 mmol of ascorbic acid or citric acid and 0.03 mmol of cetyltrimethylammonium bromide (CTAB) were added to 10 mL of deionized water and ultrasonically dispersed. Then, a mixed solution of gadolinium nitrate hexahydrate (1 mmol), gallium nitrate hydrate (3 mmol), and chromium nitrate nonahydrate (0.003 mmol) was added to the above solution under vigorous stirring, followed by the addition of 0.02 mmol of hexamethylenetetramine. The mixture was stirred at room temperature for 15 min. The solution was then placed in an oven and reacted at 100 °C for 12 h. After the reaction was complete, the solution was allowed to cool naturally to room temperature. The product was centrifuged at 12000 rpm at room temperature for 5 min, and then washed three times with deionized water under the same conditions. The final product was refluxed at 60 °C for 24 h in a solution of anhydrous ethanol-hydrochloric acid (6:1 volume ratio). The solution was allowed to cool naturally to room temperature, and the product was collected by centrifugation. The obtained product was then washed with anhydrous ethanol and deionized water under the same conditions, and the final product was dried in an oven. The resulting product was calcined at 600°C for 2 hours in a tube furnace to obtain mesoporous nano-long afterglow materials.

[0034] Example 5

[0035] 0.02 mmol of ascorbic acid or citric acid and 0.03 mmol of hexadecyltrimethylammonium bromide (CTAB) were added to 10 mL of deionized water and ultrasonically dispersed until homogeneous. A mixed solution of gadolinium chloride hexahydrate (1 mmol), gallium chloride (4 mmol), and chromium chloride (0.006 mmol) was added to the above solution under vigorous stirring, followed by the addition of 0.02 mmol of hexamethylenetetramine, and the mixture was stirred at room temperature for 15 min. The solution was then placed in an oven and reacted at 120 °C for 24 h. After the reaction was complete, the solution was allowed to cool naturally to room temperature. The product was centrifuged at 12000 rpm at room temperature for 5 min, and then washed three times with deionized water under the same conditions. The final product was refluxed at 60 °C for 24 h in a solution of anhydrous ethanol-hydrochloric acid (6:1 volume ratio). The solution was allowed to cool naturally to room temperature, and the product was collected by centrifugation. The obtained product was then washed with anhydrous ethanol and deionized water under the same conditions, and the final product was dried in an oven. The resulting product was calcined at 700°C for 2 hours in a tube furnace to obtain mesoporous nano-long afterglow materials.

[0036] Results and Analysis

[0037] The morphology and microstructure of the synthesized mesoporous nanolength afterglow material were characterized by transmission electron microscopy (TEM). Figure 1 As can be seen, the synthesized mesoporous nano-long afterglow material consists of spherical particles with a particle size of approximately 50 nm. Figure 1 Elemental mapping results confirmed the presence of Gd, Ga, Cr, and O elements in the synthesized mesoporous nanolength afterglow material. Figure 2We further analyzed the pore size of the synthesized mesoporous nanolength afterglow material using N2 adsorption-desorption curves. Based on the Barrett-Joyner-Halenda (BJH) distribution, the pore size was calculated to be approximately 2.5 nm. Figure 3 Therefore, this mesoporous nanoscale afterglow material is advantageous for loading drugs or other functional substances.

[0038] Figure 4 This represents the excitation and emission spectra of mesoporous nanolong afterglow materials. When excited by 254 nm ultraviolet light, these mesoporous nanolong afterglow materials emit near-infrared light at 760 nm, belonging to the gadolinium-gallium-chromium (GGaCh) system. 3+ of 4 T2→ 4 The A2 transition emission band has an almost symmetrical emission spectrum that extends into the near-infrared region.

[0039] Figure 5 The figure shows the near-infrared afterglow decay curves of mesoporous nano-long afterglow material solid powder after irradiation with a 254nm ultraviolet lamp for 5 minutes. It reveals that when excitation stops, the afterglow decays rapidly at the beginning, then the decay becomes slower. This is because some electrons in shallower traps rapidly transition and emit light, resulting in a rapid decay process; while other electrons in deeper traps require certain external disturbances to escape, resulting in a slow decay process.

[0040] To more intuitively illustrate the time-dependent decay of the afterglow of this mesoporous nano-long afterglow material in both solid and aqueous solutions, the afterglow decay was evaluated using a live-in imaging system equipped with a CCD camera. After irradiation with a 254 nm UV lamp for 10 min, the afterglow decay images of the mesoporous nano-long afterglow material solid powder and solution were monitored using a CCD camera. After the excitation light was removed, the afterglow intensity gradually weakened over time, with the afterglow in both solid and solution lasting for more than 2 h and 1.5 h, respectively. Figure 6 ).from Figure 6 As can be seen, under the same UV irradiation time, the afterglow intensity of mesoporous nano-long afterglow materials in the solid state is higher than that in the solution state. This is because the concentration (density) of mesoporous nano-long afterglow materials in aqueous solution is much lower than that in the solid state.

[0041] The above-described embodiments are merely preferred embodiments provided to fully illustrate the present invention, and the scope of protection of the present invention is not limited thereto. Equivalent substitutions or modifications made by those skilled in the art based on the present invention are all within the scope of protection of the present invention. The scope of protection of the present invention is defined by the claims.

Claims

1. A mesoporous nanolength afterglow material, characterized in that, Its preparation method includes the following preparation steps: (1) Prepare an aqueous solution of ascorbic acid or citric acid and hexadecyltrimethylammonium bromide; (2) Under vigorous stirring, add nano-long afterglow material precursor ions to the solution prepared in step (1), then add hexamethylenetetramine, heat at 60~120℃ for 6~24 h, and collect the product by centrifugation after the reaction is completed; the nano-long afterglow material precursor ions are a mixture of gadolinium, gallium and chromium nitrate or chloride salts; the molar ratio of gadolinium, gallium and chromium is 1:1~4:0.001~0.006; the molar ratio of ascorbic acid or citric acid, hexadecyltrimethylammonium bromide and hexamethylenetetramine is 2:3:2; (3) In order to remove the template, the product collected by centrifugation was added to a mixed solution of ethanol and hydrochloric acid, ultrasonically dispersed, refluxed at 60 °C for 24 h, the product was collected by centrifugation, washed with anhydrous ethanol and deionized water, and dried; the volume ratio of ethanol to hydrochloric acid in the mixed solution of ethanol and hydrochloric acid was 6:

1. (4) The product dried in step (3) is calcined in air at 600~800 ℃ in a muffle furnace for 1~2 h.

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