Flower-shaped chiral aluminum hydroxide nanomaterial and preparation method thereof

Abstract

The present invention belongs to the field of inorganic chemical technology, and specifically relates to a flower-shaped chiral aluminum hydroxide nanomaterial and a preparation method thereof. The present invention is to add a chiral ligand into the formation process of aluminum hydroxide precipitation, and induce the target product, flower-shaped chiral aluminum hydroxide, by means of a solvent dispersion method. The chiral aluminum hydroxide nanomaterial is a flower-shaped structure formed by stacking chiral sheets. The flower-shaped chiral aluminum hydroxide nanomaterial of the present invention has high safety, good dispersibility in water, CD activity in the near-infrared region, and can be used for the recognition and detection of polarized light. At the same time, the material has an obvious chiral configuration that is more adaptable to the biological environment, and can not only be used as an adjuvant to prolong the action time of antigens, but also promote the response of local macrophages.

Description

Technical Field

[0001] The invention belongs to the technical field of inorganic chemistry, and in particular relates to a flower-shaped chiral aluminum hydroxide nano material and a preparation method thereof. Background Art

[0002] The term chirality refers to the inability of an object to overlap with its mirror image. Chirality refers to the phenomenon that an object cannot overlap with its mirror image, and exists at all scales from microscopic to macroscopic. Chirality is widely present in nature. Since the discovery of chiral optical activity in the early 19th century, chiral materials have been continuously developed. They are of great significance in promoting the development of biomarkers, chiral analysis and detection, enantiomer selective separation, polarization-dependent photonics and optoelectronics. Chirality is of great significance to the origin of life and life systems. It is well known that life chooses small molecules such as left-handed amino acids and right-handed sugars to build biological macromolecules such as proteins and nucleic acids.

[0003] Aluminum-based materials are widely used in the biomedical field due to their excellent biocompatibility and biodegradability. Aluminum adjuvants are one of the new immunopotentiators, which have multiple functions such as promoting specific reactions between the human body and antigens and antibodies, immunosuppression, and anti-tumor. However, current studies have found that there are serious cross-reaction problems when aluminum adjuvants induce the production of antibodies, which affects their clinical application. The use of chiral ligands to induce the preparation of chiral aluminum hydroxide nanomaterials can improve the dispersibility of the prepared nanoparticles in the solvent by changing their external surface morphology or internal surface functional groups, thereby increasing the range of influence of the material on cells and improving its bioavailability, providing new ideas and methods for the further development of more efficient and stable aluminum adjuvants in the future. Summary of the invention

[0004] In order to solve the above-mentioned technical problems, this application provides the following technical solutions:

[0005] The present invention provides a method for preparing a flower-shaped chiral aluminum hydroxide nanomaterial, comprising the following steps:

[0006] S1: mixing an aluminum ion aqueous solution, a chiral ligand aqueous solution, an alkaline aqueous solution and an organic solvent and reacting them for 12-24 hours to obtain a mixed reactant;

[0007] S2: Centrifuge, wash and dry the mixed reactants to obtain the flower-shaped chiral aluminum hydroxide nanomaterial; the chiral ligand is one or more of cysteine, tartaric acid, mannose, aspartic acid and serine; the cysteine, tartaric acid, mannose, aspartic acid and serine all include L-type and D-type.

[0008] Preferably, the solute of the aluminum ion aqueous solution is one or more of aluminum sulfate, aluminum chloride and aluminum nitrate.

[0009] Preferably, in step S1, the reaction speed is 400-800 rpm.

[0010] Preferably, in step S1, the reaction temperature is 20-30°C.

[0011] Preferably, the solute in the alkaline aqueous solution is one or more of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate.

[0012] Preferably, the organic solvent is one or more of ethanol, methanol, ethylene glycol, isopropanol and ethylenediamine.

[0013] Preferably, the volume ratio of the aluminum ion compound aqueous solution, the organic solvent, the chiral ligand aqueous solution and the alkaline aqueous solution is 1-4:10-15:1-4:0.5-2.

[0014] Preferably, the concentration ratio of the aqueous solution of aluminum ion compound, the aqueous solution of chiral ligand and the aqueous alkaline solution is 0.1-0.4:0.1-0.4:0.05-0.2.

[0015] The present invention also provides a flower-shaped chiral aluminum hydroxide nano material prepared by the above preparation method.

[0016] Preferably, the particle size of the flower-shaped chiral aluminum hydroxide nanomaterial is 5-6 μm.

[0017] Specifically, the characteristic peak of the circular dichroism spectrum signal of the flower-shaped chiral aluminum hydroxide (Al(OH)3) nanomaterial is 600-900nm, and the chiral configuration g value is 0.002-0.003.

[0018] The present invention provides a flower-shaped chiral aluminum hydroxide nanomaterial and a preparation method thereof. The chiral ligand is added into the formation process of aluminum hydroxide precipitation, and the target product, flower-shaped chiral Al(OH)3, is obtained by means of a solvent dispersion method. The product has good dispersibility in water, presents a flower-shaped structure formed by stacking chiral sheets with a particle size of 5-6 μm, and has a near-infrared chiral signal.

[0019] The technical solution of the present invention has the following advantages over the prior art:

[0020] (1) The flower-shaped chiral aluminum hydroxide nanomaterial described in the present invention is easy to prepare, has a distinct chiral configuration, excellent optical activity, and CD activity in the near-infrared region. By utilizing near-infrared CD, it can be used for the identification and detection of polarized light.

[0021] (2) The flower-shaped chiral aluminum hydroxide nanomaterial described in the present invention has good dispersibility in water, high biocompatibility, strong safety, and is more adaptable to the biological environment. It can not only be used as an adjuvant to prolong the action time of antigens, but also promote the response of local macrophages. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a scanning electron microscope image (SEM) of flower-like chiral aluminum hydroxide nanomaterials;

[0023] Figure 2 This is the X-ray powder diffraction pattern (XRD) of flower-like chiral aluminum hydroxide nanomaterials;

[0024] Figure 3 This is the CD image of flower-like chiral aluminum hydroxide nanomaterials;

[0025] Figure 4 This is the UV image of flower-like chiral aluminum hydroxide nanomaterials;

[0026] Figure 5 This is the g-factor diagram of flower-like chiral aluminum hydroxide nanomaterials. DETAILED DESCRIPTION

[0027] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention.

[0028] Example 1

[0029] The present invention discloses a flower-shaped chiral aluminum hydroxide nanomaterial and a preparation method thereof. The preparation is carried out according to the following processes: preparing an aqueous solution containing aluminum sulfate, the concentration of which is 0.1-0.4M; preparing an aqueous solution containing L-cysteine, the concentration of which is 0.1M; preparing an aqueous solution containing ammonia water, the concentration of which is 0.05M; adding them to 10mL of ethanol in sequence, wherein the amount of the aqueous solution containing aluminum ion compounds is 1mL, the amount of the aqueous solution containing chiral ligands is 1mL, and the amount of the aqueous solution containing alkaline substances is 0.5mL, stirring evenly at room temperature (25±5°C) at a speed of 400rpm for 12h, centrifuging, washing, and drying after the reaction is completed, and finally obtaining the flower-shaped chiral aluminum hydroxide nanomaterial.

[0030] Example 2

[0031] The present invention discloses a flower-shaped chiral aluminum hydroxide nanomaterial and a preparation method thereof. The materials are prepared according to the following processes: preparing an aqueous solution containing aluminum chloride with a concentration of 0.2M; preparing an aqueous solution containing L-type tartaric acid with a concentration of 0.2M; preparing an aqueous solution containing sodium hydroxide with a concentration of 0.1M; adding them to 12mL of methanol in sequence, wherein the amount of the aqueous solution containing aluminum ion compounds is 2mL, the amount of the aqueous solution containing chiral ligands is 2mL, and the amount of the aqueous solution containing alkaline substances is 1mL, stirring uniformly at room temperature at a speed of 500rpm for 16h, centrifuging, washing, and drying after the reaction is completed, and finally obtaining the flower-shaped chiral aluminum hydroxide nanomaterial.

[0032] Example 3

[0033] The present invention discloses a flower-shaped chiral aluminum hydroxide nanomaterial and a preparation method thereof. The preparation is carried out according to the following processes: preparing an aqueous solution containing aluminum nitrate with a concentration of 0.3M; preparing an aqueous solution containing L-mannose with a concentration of 0.3M; preparing an aqueous solution containing potassium hydroxide with a concentration of 0.2M; adding them to 14mL of ethylene glycol in sequence, wherein the amount of the aqueous solution containing aluminum ion compounds is 3mL, the amount of the aqueous solution containing chiral ligands is 3mL, and the amount of the aqueous solution containing alkaline substances is 1.5mL, stirring uniformly at room temperature at a speed of 600rpm for 20h, centrifuging, washing, and drying after the reaction is completed, and finally obtaining the flower-shaped chiral aluminum hydroxide nanomaterial.

[0034] Example 4

[0035] The present invention discloses a flower-shaped chiral aluminum hydroxide nanomaterial and a preparation method thereof. The materials are prepared according to the following processes: preparing an aqueous solution containing aluminum chloride with a concentration of 0.4M; preparing an aqueous solution containing D-aspartic acid with a concentration of 0.4M; preparing an aqueous solution containing sodium carbonate with a concentration of 0.2M; adding them to 15mL of isopropanol in sequence, wherein the amount of the aqueous solution containing aluminum ion compounds is 4mL, the amount of the aqueous solution containing chiral ligands is 4mL, and the amount of the aqueous solution containing alkaline substances is 2mL; stirring them uniformly at room temperature at a speed of 800rpm for 24h, centrifuging, washing, and drying after the reaction is completed, and finally obtaining the flower-shaped chiral aluminum hydroxide nanomaterial.

[0036] Example 5

[0037] The present invention discloses a flower-shaped chiral aluminum hydroxide nanomaterial and a preparation method thereof. The materials are prepared according to the following processes: preparing an aqueous solution containing aluminum sulfate with a concentration of 0.4M; preparing an aqueous solution containing L-serine with a concentration of 0.4M; preparing an aqueous solution containing sodium bicarbonate with a concentration of 0.2M; adding them to 15mL of ethylenediamine in sequence, wherein the amount of the aqueous solution containing aluminum ion compounds is 4mL, the amount of the aqueous solution containing chiral ligands is 4mL, and the amount of the aqueous solution containing alkaline substances is 2mL; stirring them uniformly at room temperature at a speed of 800rpm for 24h, centrifuging, washing, and drying after the reaction is completed, and finally obtaining the flower-shaped chiral aluminum hydroxide nanomaterial.

[0038] Effect evaluation

[0039] The flower-shaped chiral aluminum hydroxide nanomaterial prepared in Example 1 was subjected to a scanning electron microscope (SEM) circular dichroism instrument characterization test, and the results are as follows: Figures 1 to 5 As shown. Figure 1 As shown, the flower-shaped chiral aluminum hydroxide nanomaterial has a flower-shaped structure formed by stacking chiral sheets, and the particle size is 5-6 μm. Figure 2 As shown, the flower-like chiral aluminum hydroxide nanomaterial corresponds to (010), (100), (111), (110) and (111) crystal planes at 18.56°, 21.72°, 29.03°, 35.60° and 35.53°, respectively (PDF#97-005-0581). Figure 3 The results show that the characteristic peak of the circular dichroism spectrum signal of the flower-shaped chiral aluminum hydroxide nanomaterial is 600-900nm. Figures 2 to 5 Images and calculations show that the chiral configuration g value of the flower-shaped chiral aluminum hydroxide nanomaterial is 0.002-0.003.

[0040] The flower-shaped chiral aluminum hydroxide nanomaterial of the present invention has high safety, good dispersibility in water, CD activity in the near-infrared region, and can be used for the recognition and detection of polarized light. At the same time, the material has a distinct chiral configuration and is more adaptable to the biological environment. It can not only be used as an adjuvant to prolong the action time of the antigen, but also promote the response of local macrophages.

[0041] Obviously, the above embodiments are merely examples for clear explanation and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from these are still within the protection scope of the invention.

Claims

1. A method for preparing a flower-shaped chiral aluminum hydroxide nanomaterial, characterized in that: The steps include: S1: mixing an aluminum ion aqueous solution, a chiral ligand aqueous solution, an alkaline aqueous solution and an organic solvent and reacting them for 12-24 hours to obtain a mixed reactant; S2: Centrifuge the mixed reactants, wash, and dry to obtain the flower-shaped chiral aluminum hydroxide nanomaterial; the chiral ligand is one or more of cysteine, tartaric acid, mannose, aspartic acid, and serine; the cysteine, tartaric acid, mannose, aspartic acid, and serine all include L-type and D-type; the flower shape is formed by stacking chiral sheets; the organic solvent is one or more of ethanol, methanol, ethylene glycol, isopropanol, and ethylenediamine; the volume ratio of the aluminum ion aqueous solution, the organic solvent, the chiral ligand aqueous solution, and the alkaline aqueous solution is 1-4:10-15:1-4:0.5-2; the concentration ratio of the aluminum ion aqueous solution, the chiral ligand aqueous solution, and the alkaline aqueous solution is 0.1-0.4:0.1-0.4:0.05-0.

2.

2. The preparation method according to claim 1, characterized in that The solute of the aluminum ion aqueous solution is one or more of aluminum sulfate, aluminum chloride and aluminum nitrate.

3. The preparation method according to claim 1, characterized in that: In the step S1, the reaction speed is 400-800 rpm.

4. The preparation method according to claim 1, characterized in that: In the step S1, the reaction temperature is 20-30°C.

5. The preparation method according to claim 1, characterized in that: The solute in the alkaline aqueous solution is one or more of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate.

6. A flower-shaped chiral aluminum hydroxide nanomaterial prepared by the preparation method according to any one of claims 1 to 5.

7. The flower-shaped chiral aluminum hydroxide nanomaterial according to claim 6, characterized in that: The particle size of the flower-shaped chiral aluminum hydroxide nanomaterial is 5-6 μm.

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