Rare earth hydroxide micro-nano material with rough surface as well as preparation method and application of rare earth hydroxide micro-nano material

Abstract

The invention relates to a rare earth hydroxide micro-nano material with a rough surface as well as a preparation method and application of the rare earth hydroxide micro-nano material. The whole rare earth hydroxide micro-nano material is a spherical particle of 200-800 nm, and a plurality of protruding structures grow on the surface of the rare earth hydroxide micro-nano material from inside to outside. The preparation method specifically comprises the following steps: dissolving a structure-directing agent, rare earth chloride, a regulator, an additive and a catalyst in water to obtain a precursor solution; adding cyclohexane into the precursor solution, uniformly stirring to form a water-cyclohexane emulsion system, and reacting under a heating condition; and after the reaction is finished, centrifuging and washing the product. Compared with the prior art, the rare earth hydroxide micro-nano material with the rough surface has excellent biocompatibility and dispersion stability, the unique surface rough topological structure improves the biological adhesion capacity, and the rare earth hydroxide micro-nano material can be applied to the fields of biological medicine, daily chemical beauty makeup and the like.

Description

Technical Field

[0001] This invention relates to the field of micro- and nanomaterials technology, and in particular to a rare earth hydroxide micro- and nanomaterial with a rough surface, its preparation method, and its application. Background Technology

[0002] The continuous advancements and innovations in materials science and nanobiotechnology have opened up new avenues for the application of functional nanomaterials in biomedicine and daily chemistry. Among these, rare earth materials, due to their unique optical, thermal, and magnetic properties, have wide applications in special devices, catalysis, and biomedicine. For example, nano-cerium oxide, as an excellent ultraviolet absorber, can be used in sunscreen cosmetics; simultaneously, cerium oxide also possesses various enzyme activities, capable of decomposing hydrogen peroxide to alleviate tumor hypoxia or scavenging reactive oxygen species to reduce inflammatory responses.

[0003] Currently, micro- and nano-scale rare earth materials often possess smooth and regular surface structures or porous structures. For example, CN112811458A discloses a mesoporous rare earth hydroxide nanomaterial with a centrally divergent mesoporous channel with an adjustable size of 100-600 nm and an adjustable pore size of 3-15 nm, which can load enzymes, nanoparticles, or other desired substances. However, such micro- and nano-scale rare earth materials often lack good bioadhesion properties, failing to enhance their interaction with biological host interfaces (such as skin or tumor lesions), and thus failing to fully realize the biological activity of the rare earth materials themselves.

[0004] Therefore, novel micro- and nano-scale rare earth materials with excellent bioadhesion capabilities still need to be developed. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing technologies, such as poor bioadhesion performance and inability to exert the biological activity of rare earth materials, and to provide a rare earth hydroxide micro / nano material with a rough surface, its preparation method, and its application.

[0006] This invention constructs rare earth hydroxide micro / nanomaterials with rough surfaces by topologically modifying the surface of rare earth nanoparticles, thereby enhancing their bio-optical properties and catalytic activity. At the same time, their good bio-adhesion properties increase the interaction with the host interface, ultimately resulting in functional nanomaterials with enhanced bioactivity.

[0007] Specifically, the objective of this invention can be achieved through the following technical solutions: The present invention first provides a rare earth hydroxide micro / nanomaterial with a rough surface. The rare earth hydroxide micro / nanomaterial is a spherical particle with an overall diameter of 200-800 nm, and its surface has a number of protrusion structures growing from the inside to the outside. The length of the protrusion structure is 30-100 nm and the diameter of the protrusion structure is 10-45 nm.

[0008] Furthermore, the protruding structure is a columnar protruding structure.

[0009] Furthermore, the components of the rare earth hydroxide are specifically any one of lanthanum hydroxide, cerium hydroxide, praseodymium hydroxide, neodymium hydroxide, promethium hydroxide, samarium hydroxide, europium hydroxide, gadolinium hydroxide, terbium hydroxide, dysprosium hydroxide, holmium hydroxide, erbium hydroxide, thulium hydroxide, ytterbium hydroxide, lutetium hydroxide, or yttrium hydroxide.

[0010] This invention also provides a method for preparing rare earth hydroxide micro / nanomaterials with rough surfaces, the preparation method specifically including the following steps: S1: Dissolve the structure-directing agent, rare earth chloride, regulator, additive, and catalyst in water to obtain a precursor solution; S2: Add cyclohexane to the precursor solution and stir until homogeneous to form a water-cyclohexane emulsion system, and carry out the reaction under heating conditions; S3: After the reaction is complete, the product is centrifuged and washed to obtain rare earth hydroxide micro / nanomaterials with rough surfaces.

[0011] Further, in step S1, the rare earth chloride is any one of lanthanum chloride, cerium chloride, praseodymium chloride, neodymium chloride, promethium chloride, samarium chloride, europium chloride, gadolinium chloride, terbium chloride, dysprosium chloride, holmium chloride, erbium chloride, thulium chloride, ytterbium chloride, lutetium chloride, or yttrium chloride.

[0012] Further, in step S1, the structure directing agent is 1-hexadecyl-3-methylimidazolium chloride. 1-Hexadecyl-3-methylimidazolium chloride forms micelles through hydrophilic-hydrophobic interactions, and the cationic imidazolium groups can modulate the hydrophilic interactions through electrostatic and π-π conjugation interactions.

[0013] Further, in step S1, the regulator is citric acid. Citric acid is used to chelate rare earth precursors and electrostatically adsorb onto the imidazole cationic groups of micelles, acting as a linker to enhance the interaction between the rare earth precursors and micelles.

[0014] Further, in step S1, the additive is sodium salicylate. The carboxylic acid anion in sodium salicylate interacts electrostatically with the positively charged imidazole group, and there is π-π conjugation between the phenyl group and the imidazole ring. By adjusting the sodium salicylate content, the interaction between the hydrophilic imidazole head groups of the structure-directing agent 1-hexadecyl-3-methylimidazolium chloride can be controlled.

[0015] Furthermore, in step S1, the catalyst is hexamethylenetetramine. As a weak base, hexamethylenetetramine can slowly decompose under thermal stimulation to produce NH3, which catalyzes the hydrolysis of rare earth ions, thereby enabling the controlled deposition of rare earth precursors on micelles.

[0016] Further, in step S1, the mass ratio of the structure directing agent, rare earth chloride, regulator, additive, and catalyst is (0.01-1): (0.005-0.5): (0.005-0.5): (0.01-0.5): (0.01-0.5).

[0017] Furthermore, the concentration of the structure-directing agent is 0.01~1wt%. If the concentration is too low, it is insufficient to generate enough micelles for assembly and structure formation, and the rare earth precursor cannot form nanoparticles; if the concentration is too high, it mainly forms oil-in-water micelles to obtain mesoporous spherical particles.

[0018] Furthermore, the concentration of the rare earth chloride is 0.005~0.5wt%. If the concentration is too low, the precursor content is insufficient to form spherical particles; if the concentration is too high, the cross-linking rate is too fast and solid particles are formed directly.

[0019] Furthermore, the concentration of the regulator is 0.005~0.5wt%. If the concentration is too low, the precursor cannot interact well with the micelles and cannot form nanoparticles; if the concentration is too high, the acidity of the system increases, resulting in the formation of random particles with larger particle sizes.

[0020] Furthermore, the concentration of the additive is 0.01~0.5wt%. If the concentration is too low, it will mainly consist of water-in-oil micelles, forming mesoporous spherical particles; if the concentration is too high, the system viscosity will be too high, resulting in irregular products.

[0021] Furthermore, the concentration of the catalyst is 0.01~0.5wt%. If the concentration is too low, the system has insufficient alkali content, resulting in oligomerized products; if the concentration is too high, the system has excessive alkali content, resulting in rapid cross-linking and solid particles.

[0022] Furthermore, in step S1, the mass ratio of the structure-directing agent to the additive is 5:(1-3), preferably 5:2. The benzene ring of sodium salicylate can increase the interaction with the imidazole group in 1-hexadecyl-3-methylimidazolium chloride through π-π conjugation. Therefore, the ratio of 1-hexadecyl-3-methylimidazolium chloride to sodium salicylate directly affects the interaction of the hydrophilic portion of 1-hexadecyl-3-methylimidazolium chloride, thereby regulating the micelle morphology and the surface morphology of nanoparticles.

[0023] Further, in step S2, the volume ratio of water to cyclohexane is 1:(0.1-2).

[0024] Furthermore, in step S2, the reaction temperature is 60-80 °C.

[0025] Furthermore, in step S2, the reaction time is 4-7 h.

[0026] Furthermore, in step S2, the reaction is carried out at a stirring rate of 150-500 rpm.

[0027] In the water-oil two-phase system of this invention, a structure-directing agent, such as 1-hexadecyl-3-methylimidazolium chloride, is used to form micelles, while an additive, such as sodium salicylate, regulates the morphology of the micelles through π-π conjugation with the imidazole groups. A regulator, such as citric acid, acts as a linker, binding the rare earth precursor and micelles through chelation and electrostatic interactions, respectively. Upon heating, the catalyst hexamethylenetetramine decomposes and slowly releases NH3, catalyzing the controlled deposition of the rare earth precursor onto the micelles, thereby preparing a rare earth hydroxide with a rough surface structure. The π-π interaction between sodium salicylate and the hydrophilic imidazole head group of 1-hexadecyl-3-methylimidazolium chloride plays a crucial role in driving the micelles from an oil-in-water structure to a water-in-oil structure, enabling the rare earth precursor to deposit in the hydrophilic region of the inverted micelles, ultimately forming a unique rough surface topology.

[0028] The present invention also provides the application of rare earth hydroxide micro / nano materials with rough surfaces in the preparation of cosmetics and personal care products.

[0029] The present invention also provides the application of rare earth hydroxide micro / nanomaterials with rough surfaces in the preparation of anti-inflammatory and anti-tumor drugs.

[0030] Compared with the prior art, the present invention has the following technical advantages: (1) This invention innovatively prepares a class of rare earth hydroxide micro-nano materials with rough surfaces. The rough protrusion structure is morphologically a spherical nanoparticle with columnar protrusions from the inside out, with high protrusion density and small particle size. In terms of composition, it is a rare earth hydroxide material with nanoenzyme activity. In terms of function, the rough protrusions increase the specific surface area and increase the active sites of the material. Furthermore, the excellent adhesion properties of the rough surface enhance the interaction between the nano-biological interface.

[0031] (2) Through precise control and coordination of multiple components such as structure-directing agents, additives, and catalysts, the present invention ultimately forms a unique rough surface topology on the surface of rare earth hydroxide particles.

[0032] (3) This invention innovatively modifies the surface topology of rare earth nanoparticles to construct rare earth hydroxide micro-nano materials with rough surfaces, which enhances their biological properties. At the same time, the good bioadhesion properties increase the interaction with the host interface, increase cell uptake efficiency and tissue penetration ability, and can be widely used in cosmetics, personal care products, drug delivery and other fields. Attached Figure Description

[0033] Figure 1 This is a scanning electron microscope image of cerium hydroxide prepared in Example 1 of the present invention.

[0034] Figure 2 This is a transmission electron microscope (TEM) image of cerium hydroxide prepared in Example 1 of the present invention.

[0035] Figure 3 This is a transmission electron microscope (TEM) image of cerium hydroxide prepared in Example 2 of the present invention.

[0036] Figure 4 This is a transmission electron microscope (TEM) image of cerium hydroxide prepared in Example 3 of the present invention.

[0037] Figure 5 This is a scanning electron microscope image of cerium hydroxide prepared in Example 4 of the present invention.

[0038] Figure 6 This is a scanning electron microscope image of cerium hydroxide prepared in Example 5 of the present invention.

[0039] Figure 7 This is a scanning electron microscope image of cerium hydroxide prepared in Example 6 of the present invention.

[0040] Figure 8 This is a scanning electron microscope image of cerium hydroxide prepared in Example 7 of the present invention.

[0041] Figure 9 This is a scanning electron microscope image of cerium hydroxide prepared in Example 8 of the present invention.

[0042] Figure 10 This is a scanning electron microscope image of cerium hydroxide prepared in Example 9 of the present invention.

[0043] Figure 11 This is a transmission electron microscope (TEM) image of cerium hydroxide prepared in Example 10 of the present invention.

[0044] Figure 12 This is a transmission electron microscope (TEM) image of cerium hydroxide prepared in Example 11 of the present invention.

[0045] Figure 13 This is a scanning electron microscope image of cerium hydroxide prepared in Comparative Example 1.

[0046] Figure 14 This is a graph showing the results of the biocompatibility test.

[0047] Figure 15 This is a graph showing the results of a cell uptake test.

[0048] Figure 16 This is a diagram showing the results of a skin tissue penetration test. Detailed Implementation

[0049] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0050] Unless otherwise specified, the reagents, methods, instruments, and equipment used in this invention are conventional in the art. Unless otherwise specified, the reagents and materials used in the following examples are all commercially available.

[0051] Compared to biochemical surface modification of nanomaterials, topological modification of the surface structure of nanomaterials is a more direct and effective approach. The ingenious design of biological structures in nature offers valuable lessons; to enhance their affinity with hosts, many organisms have evolved spikes or rough structures through natural selection. By employing biomimetic techniques to precisely design micro- and nanomaterials with rough surfaces, unique adhesive properties can be developed in addition to their original functions, thus attracting widespread attention in fields such as biomedicine and cosmetics.

[0052] Based on this, the present invention provides a rare earth hydroxide micro / nanomaterial with a rough surface. The material is a rare earth hydroxide, and a controllable number of protrusion structures are grown on its surface from the inside out, forming nanoparticles with a rough topological structure. The size of the rare earth hydroxide micro / nanomaterial particles is 200-800 nm, the length of the protrusion structures is 30-100 nm, and the diameter of the protrusion structures is 10-45 nm.

[0053] This invention further provides a method for preparing rare earth hydroxide micro / nanomaterials with rough surfaces. In a water-cyclohexane emulsion system, using 1-hexadecyl-3-methylimidazolium chloride as a structure-directing agent, and adjusting the interaction between the rare earth chloride precursor and the structure-directing agent with citric acid, and using hexamethylenetetramine as a catalyst and sodium salicylate as an additive, rare earth hydroxide nanoparticles with rough surfaces are prepared by reaction under water bath heating.

[0054] Example 1: This embodiment provides a rare earth hydroxide micro / nanomaterial with a rough surface, and its preparation method is as follows: 1-Hexadecyl-3-methylimidazolium chloride (0.2 wt%), cerium chloride heptahydrate (0.1 wt%), citric acid (0.02 wt%), sodium salicylate (0.08 wt%), and hexamethylenetetramine (0.2 wt%) were dissolved thoroughly in water to form a clear solution. Cyclohexane (40% by volume of water) was added and stirred until homogeneous. The solution was transferred to a 70 °C water bath and reacted at a stirring rate of 450 rpm for 7 hours.

[0055] After the reaction was completed, the product was collected by centrifugation and washed three times with ethanol. The product was then extracted at 70 °C to remove 1-hexadecyl-3-methylimidazolium chloride, thus obtaining the desired rare earth hydroxide micro / nanomaterials with rough surfaces.

[0056] The SEM image of the rare earth hydroxide micro / nanomaterials prepared in this embodiment is shown below. Figure 1 As shown, the TEM image is as follows Figure 2 As shown in the figure, the overall particle size of the rare earth hydroxide micro / nanomaterial is about 280 nm, the length of the protrusion is about 35 nm, and the diameter of the protrusion is about 17 nm.

[0057] Example 2: This embodiment provides a rare earth hydroxide micro / nano material with a rough surface. The difference from Embodiment 1 is that the cerium chloride concentration in this embodiment is 0.075 wt%, while other conditions remain unchanged.

[0058] TEM images of the rare earth hydroxide micro / nanomaterials with rough surfaces prepared in this embodiment are shown below. Figure 3 It has a distinct surface protrusion structure.

[0059] Example 3: This embodiment provides a rare earth hydroxide micro / nano material with a rough surface. The difference from Embodiment 1 is that the cerium chloride concentration in this embodiment is 0.125 wt%, while other conditions remain unchanged.

[0060] TEM images of the rare earth hydroxide micro / nanomaterials with rough surfaces prepared in this embodiment are shown below. Figure 4 It has a distinct surface protrusion structure.

[0061] Example 4: This embodiment provides a rare earth hydroxide micro / nanomaterial with a rough surface. The difference from Embodiment 1 is that the ratio of 1-hexadecyl-3-methylimidazolium chloride to sodium salicylate in this embodiment is 5:2, the concentration of 1-hexadecyl-3-methylimidazolium chloride is 0.15%, the concentration of sodium salicylate is 0.06%, and the concentrations of other components remain unchanged.

[0062] The SEM image of the rare earth hydroxide micro / nanomaterials with rough surfaces prepared in this embodiment is shown below. Figure 5 It has a distinct surface protrusion structure.

[0063] Example 5: This embodiment provides a rare earth hydroxide micro / nanomaterial with a rough surface. The difference from Embodiment 1 is that the ratio of 1-hexadecyl-3-methylimidazolium chloride to sodium salicylate in this embodiment is 5:2, the concentration of 1-hexadecyl-3-methylimidazolium chloride is 0.25%, the concentration of sodium salicylate is 0.1%, and the concentrations of other components remain unchanged.

[0064] The SEM image of the rare earth hydroxide micro / nanomaterials with rough surfaces prepared in this embodiment is shown below. Figure 6 It has a distinct surface protrusion structure.

[0065] Example 6: This embodiment provides a rare earth hydroxide micro / nanomaterial with a rough surface. The difference from Embodiment 1 is that the concentration of citric acid in this embodiment is 0.01 wt%, while the concentrations of other components remain unchanged.

[0066] The SEM image of the rare earth hydroxide micro / nanomaterials with rough surfaces prepared in this embodiment is shown below. Figure 7 It has a distinct surface protrusion structure.

[0067] Example 7: This embodiment provides a rare earth hydroxide micro / nanomaterial with a rough surface. The difference from Embodiment 1 is that the concentration of citric acid in this embodiment is 0.04 wt%, while the concentrations of other components remain unchanged.

[0068] The SEM image of the rare earth hydroxide micro / nanomaterials with rough surfaces prepared in this embodiment is shown below. Figure 8 It has a distinct surface protrusion structure.

[0069] Example 8: This embodiment provides a rare earth hydroxide micro / nano material with a rough surface. The difference from Embodiment 1 is that the concentration of sodium salicylate in this embodiment is 0.02 wt%, while the concentrations of other components remain unchanged.

[0070] The SEM image of the rare earth hydroxide micro / nanomaterials with rough surfaces prepared in this embodiment is shown below. Figure 9 It has a distinct surface protrusion structure.

[0071] Example 9: This embodiment provides a rare earth hydroxide micro / nanomaterial with a rough surface. The difference from Embodiment 1 is that the concentration of sodium salicylate in this embodiment is 0.05 wt%, while the concentrations of other components remain unchanged.

[0072] The SEM image of the rare earth hydroxide micro / nanomaterials with rough surfaces prepared in this embodiment is shown below. Figure 10 It has a distinct surface protrusion structure.

[0073] Example 10: This embodiment provides a rare earth hydroxide micro / nanomaterial with a rough surface. The difference from Embodiment 1 is that the concentration of hexamethylenetetramine in this embodiment is 0.01 wt%, while the concentrations of other components remain unchanged.

[0074] TEM images of the rare earth hydroxide micro / nanomaterials with rough surfaces prepared in this embodiment are shown below. Figure 11 It has a distinct surface protrusion structure.

[0075] Example 11: This embodiment provides a rare earth hydroxide micro / nanomaterial with a rough surface. The difference from Embodiment 1 is that the concentration of hexamethylenetetramine in this embodiment is 0.4 wt%, while the concentrations of other components remain unchanged.

[0076] TEM images of the rare earth hydroxide micro / nanomaterials with rough surfaces prepared in this embodiment are shown below. Figure 12 It has a distinct surface protrusion structure.

[0077] Example 12: This embodiment provides a rare earth hydroxide micro / nano material with a rough surface. The difference from Embodiment 1 is that the rare earth chloride in this embodiment is gadolinium chloride.

[0078] Example 13: This embodiment provides a rare earth hydroxide micro / nano material with a rough surface. The difference from Embodiment 1 is that the rare earth chloride in this embodiment is europium chloride.

[0079] Example 14: This embodiment provides a rare earth hydroxide micro / nano material with a rough surface. The difference from Embodiment 1 is that the rare earth chloride in this embodiment is erbium chloride.

[0080] Example 15: This embodiment provides a rare earth hydroxide micro / nano material with a rough surface. The difference from Embodiment 1 is that the rare earth chloride in this embodiment is neodymium chloride.

[0081] Comparative Example 1: This comparative example provides rare earth hydroxide nanoparticles with smooth surfaces and no rough protrusions, and the specific preparation method is as follows: 1-Hexadecyl-3-methylimidazolium chloride (0.2%), cerium chloride heptahydrate (0.1%), citric acid (0.02%), sodium salicylate (0.08%), and hexamethylenetetramine (0.2%) were dissolved thoroughly in water to form a clear solution. The solution was transferred to a 70 °C water bath and reacted at a stirring rate of 450 rpm for 7 hours. After the reaction was completed, the product was collected by centrifugation and washed three times with ethanol. The product was then extracted at 70 °C to remove 1-hexadecyl-3-methylimidazolium chloride, yielding rare earth hydroxide micro / nanomaterials.

[0082] SEM images of rare earth hydroxide nanoparticles prepared in pure aqueous phase in this comparative example are shown below. Figure 13 As shown in the figure, the rare earth hydroxide nanoparticles prepared in this comparative example have a smooth surface and do not have the protruding structure specific to this invention.

[0083] Based on the successful preparation of rare earth hydroxide micro / nanomaterials in the above embodiments, this invention takes the rare earth hydroxide micro / nanomaterials prepared in Example 1 as an example and performs the following performance tests together with the rare earth hydroxide nanoparticles prepared in Comparative Example 1: (1) Biocompatibility experiment: The in vitro cytotoxicity of rare earth hydroxide nanoparticles with rough and smooth surfaces was studied by CCK-8 assay. HaCaT cells were seeded in 96-well plates (10 cells per well). 4 Cells were cultured in DMEM medium for 24 hours. Then, the medium was replaced with fresh DMEM medium containing different concentrations of rare earth nanoparticles with rough (Example 1) and smooth (Comparative Example 1) surfaces (0, 25, 50, 100, 200, 300 μg / mL) and co-incubated with the cells for 24 hours. The medium was removed, and the cells were washed three times with PBS. Fresh medium containing 10% CCK-8 solution was added to each well. Finally, cell viability was assessed by measuring absorbance at 450 nm.

[0084] (2) Cell uptake experiment: HaCaT cells were seeded into 6-well plates (10 cells per well). 5 HaCaT cells were cultured for 24 hours, and then incubated with fresh DMEM medium containing 200 μg / mL of fluorescein isothiocyanate-labeled surface-roughened and surface-smoothened rare earth nanoparticles, respectively, in the dark for 6 hours and washed three times with PBS. Cells were then collected by trypsin and dispersed with PBS for further quantitative analysis of fluorescence signals by flow cytometry.

[0085] (3) Skin tissue penetration experiment: 7.5 mg of fluorescein isothiocyanate-labeled rare earth nanoparticles with rough and smooth surfaces were applied to the hairless back skin of mice, once every 12 hours for a total of two applications. During this period, the mice were placed in a dark environment. After the mice were sacrificed, the back skin was collected, washed with formalin solution and fixed. Subsequently, the skin tissue was sectioned and stained with DAPI. Fluorescence images were observed by confocal laser scanning microscopy, and the fluorescence intensity in the dermis and epidermis was measured.

[0086] The preparation method of fluorescein isothiocyanate-labeled rare earth nanoparticles in the above test is as follows: First, 10.0 mg of rare earth hydroxide nanoparticles were dispersed in 20 mL of ethanol, and then 50 μL of 3-aminopropyltriethoxysilane was added. The mixture was stirred at 60 °C for 12 hours. The product was collected by centrifugation and washed repeatedly with water and ethanol. Subsequently, the obtained amino-functionalized nanoparticles were dispersed in 10.0 mL of ethanol containing 2.0 mg of fluorescein isothiocyanate and stirred overnight under light-protected conditions. Afterward, the fluorescein isothiocyanate-labeled rare earth hydroxide nanoparticles were washed repeatedly with water and ethanol and dried in an oven at 60 °C for 12 hours.

[0087] Depend on Figure 14 The cytotoxicity test results showed that rare earth hydroxide nanoparticles with rough or smooth surfaces maintained cell viability of over 90% even at concentrations as high as 300 µg / mL, highlighting their good biocompatibility during treatment.

[0088] Depend on Figure 15 Cellular uptake tests showed that the average fluorescence intensity of rough-surfaced rare earth hydroxide nanoparticles was 2.6 times higher than that of smooth-surfaced particles, confirming that the rough surface of the particles can enhance the uptake efficiency of cells.

[0089] Depend on Figure 16 Skin tissue penetration tests revealed that for smooth-surfaced rare-earth hydroxide nanoparticles, most were confined to the epidermis, with only a small amount of fluorescence signal detected in the dermis. In contrast, rare-earth hydroxide nanoparticles with rough surfaces exhibited greater fluorescence penetration into the dermis, and the total fluorescence content was higher than that of the smooth-surfaced particle treatment group. This result confirms that the rough surface morphology of the particles has the ability to adhere to and accumulate in skin tissue, thus possessing stronger skin tissue penetration capabilities.

[0090] In summary, the rare earth hydroxide micro / nanomaterials with rough surfaces provided by this invention have excellent biocompatibility and dispersion stability. Their unique rough surface topology enhances bioadhesion ability and has broad application prospects in fields such as biomedicine and daily chemical cosmetics.

[0091] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A rare earth hydroxide micro-nano material with a rough surface, characterized in that, The rare earth hydroxide micro-nano material is a spherical particle with a size of 200-800 nm, and a plurality of protruding structures grow on the surface thereof from inside to outside; The length of the protruding structure is 30-100 nm, and the diameter of the protruding structure is 10-45 nm. 2.The rare earth hydroxide micro-nano material with rough surface according to claim 1, wherein, The component of the rare earth hydroxide is any one of lanthanum hydroxide, cerium hydroxide, praseodymium hydroxide, neodymium hydroxide, promethium hydroxide, samarium hydroxide, europium hydroxide, gadolinium hydroxide, terbium hydroxide, dysprosium hydroxide, holmium hydroxide, erbium hydroxide, thulium hydroxide, ytterbium hydroxide, lutetium hydroxide or yttrium hydroxide.

3. The method for preparing the rare earth hydroxide micro-nano material with rough surface according to claim 1 or 2, characterized in that, The preparation method specifically comprises the following steps: S1: dissolving a structure directing agent, a rare earth chloride, a regulator, an additive and a catalyst in water to obtain a precursor solution; S2: adding cyclohexane to the precursor solution and stirring uniformly to form a water-cyclohexane emulsion system, and performing a reaction under heating; S3: after the reaction is completed, centrifuging and washing the product to obtain the rare earth hydroxide micro-nano material with a rough surface.

4. The method for preparing rare earth hydroxide micro / nanomaterials with rough surfaces according to claim 3, characterized in that, In step S1, the rare earth chloride is any one of lanthanum chloride, cerium chloride, praseodymium chloride, neodymium chloride, promethium chloride, samarium chloride, europium chloride, gadolinium chloride, terbium chloride, dysprosium chloride, holmium chloride, erbium chloride, thulium chloride, ytterbium chloride, lutetium chloride or yttrium chloride; The structure directing agent is 1-hexadecyl-3-methyl imidazole chloride; The regulator is citric acid; The additive is sodium salicylate; The catalyst is urotropine.

5. The method for preparing rare earth hydroxide micro / nanomaterials with rough surfaces according to claim 3, characterized in that, In step S1, the mass ratio of the structure directing agent, the rare earth chloride, the regulator, the additive and the catalyst is (0.01-1):(0.005-0.5):(0.005-0.5):(0.01-0.5):(0.01-0.5).

6. The method for preparing the rare earth hydroxide micro-nano material with rough surface according to claim 5, characterized in that, The mass ratio of the structure directing agent to the additive is 5:(1-3).

7. The method according to claim 3, wherein the method is characterized by, In step S2, the volume ratio of water to cyclohexane is 1:(0.1-2).

8. The method for preparing rare earth hydroxide micro / nanomaterials with rough surfaces according to claim 3, characterized in that, In step S2, the temperature of the reaction is 60-80 °C, the time of the reaction is 4-7 h, and the reaction is performed at a stirring rate of 150-500 rpm.

9. Use of the rare earth hydroxide micro-nano material with a rough surface according to claim 1 or 2 in the preparation of cosmetics, washing and caring products.

10. Use of the rare earth hydroxide micro-nano material with a rough surface according to claim 1 or 2 in the preparation of anti-inflammatory and anti-tumor drugs.

Images