Ultrasonic-induced inorganic afterglow luminescent material for promoting repair of tissue organ defects, and preparation method and application thereof

Abstract

The application belongs to the technical field of biomedical materials, and relates to an ultrasonic-induced inorganic afterglow luminescent material for promoting repair of tissue and organ defects as well as a preparation method and application thereof, and comprises the following steps: S1, dispersing an afterglow luminescent material and citric acid in an aqueous solution to obtain a precursor solution for hydrothermal reaction; and S2, adding a titanium oxide-based material to the precursor solution provided in S1 to perform hydrothermal reaction in a reaction kettle to obtain a titanium oxide-based luminescent material loaded with the afterglow material; wherein the afterglow material is one or more of an aluminate-based afterglow luminescent material and a titanate afterglow luminescent material. Compared with the prior art, the ultrasonic-induced inorganic afterglow luminescent material prepared in the application is composed of titanium oxide and the afterglow material, and can produce afterglow luminescence under ultrasonic excitation. By loading microalgae with photosynthesis, oxygen supply to an oxygen-deficient bone defect site is controlled by ultrasonic waves, blood vessel regeneration is promoted, and efficient repair of the bone defect is realized.

Description

Technical Field

[0001] This invention relates to the field of biomedical materials technology, specifically to an ultrasound-induced inorganic afterglow luminescent material that promotes the repair of tissue and organ defects, its preparation method, and its application. Background Technology

[0002] Tissue healing is a dynamic process. Oxygen plays a crucial role in tissue healing and regeneration by participating in aerobic glucose metabolism, the synthesis of glycoproteins and extracellular matrix components, and the synthesis and stabilization of collagen. In tissue engineering, in the absence of a vascular system, molecular diffusion alone is insufficient to meet the oxygen demand of damaged areas. Utilizing tissue-engineered biomaterials or scaffolds to achieve in-situ O2 delivery is a current challenge, particularly for the repair and regeneration of tissues and organs such as bone, cartilage, teeth, blood vessels, skin, muscles, nerves, intestines, biliary tract, and heart. Taking bone defects as an example, the repair of large bone defects has always been a major challenge in orthopedic clinical treatment. Due to the limitations of autologous and allogeneic bone transplantation in clinical treatment, including high postoperative complication rates, limited donor sources, and unsatisfactory bone reconstruction results, the development of intelligent responsive bone tissue engineering materials offers a new approach to solving this clinical problem. Bone is a highly vascularized tissue. Many studies have shown that transplanting stem cells or growth factors can effectively stimulate angiogenesis and osteogenic formation, but their widespread application is limited by their short half-life, high cost, and limited resources. Therefore, there is an urgent need to develop a cytokine-free material that can provide a favorable microenvironment to significantly promote the regeneration of vascularized bone and accelerate bone reconstruction and regeneration at defect sites.

[0003] During bone tissue injury, vascular disruption leads to insufficient oxygen supply, resulting in a localized hypoxic state. Under hypoxic microenvironment conditions, tissue cells release a large number of angiogenic factors (such as vascular endothelial growth factor VEGF), initiating angiogenesis. Once initiated, timely and sufficient oxygen supply plays a crucial role in promoting vascular maturation, enhancing cell viability, and preventing tissue necrosis. Traditional oxygen delivery strategies are facing numerous challenges; how to initiate oxygen delivery at the appropriate time and avoid prolonged hypoxia leading to apoptosis and exacerbated inflammation is a critical issue that urgently needs to be addressed.

[0004] Microalgae, as autotrophic primitive microorganisms, can generate oxygen through photosynthesis under light conditions. Given their spontaneous oxygen production characteristics, photosynthetic microalgae have been widely used in various functional composite material systems and applied in biomedical applications such as tissue regeneration. However, applying oxygen production from photosynthetic microalgae to orthopedic implants faces two major challenges: First, while organic and inorganic afterglow luminescent materials, after being energized, can serve as light sources to promote oxygen production in microalgae, their inherent properties limit their application in medical diagnosis and treatment. For example, organic afterglow materials have characteristics such as weak light intensity, short afterglow time, easy quenching, and complex synthesis steps, making it difficult to achieve controllable biological effects and large-scale industrialization. Inorganic afterglow materials, while possessing advantages such as high afterglow intensity, long duration, and strong stability, have poor solubility, making it difficult to functionalize and composite with other materials. Second, light has limited penetration in human tissues, and dense tissues such as bone weaken its energy, preventing optical signals from being used as an effective external field control mechanism on the surface of orthopedic implants. Summary of the Invention

[0005] To address the aforementioned issues, this invention first constructs a hydrothermal reaction system of citric acid, aluminate-based / titanium-based afterglow materials, and titanium dioxide. Citric acid can chelate cations in aluminates and adsorb them onto the surface of titanium dioxide, successfully solving the problem that insoluble aluminate-based / titanium-based afterglow materials are difficult to combine with other materials. Second, it proposes using ultrasound as an external field control method to induce luminescence in the afterglow material through an ultrasound-responsive titanium dioxide coating or titanium dioxide nanomaterials. The emitted light further stimulates microalgae to produce oxygen, promotes angiogenesis, and achieves efficient repair of bone defects.

[0006] Specifically, titanium dioxide has excellent biocompatibility, chemical stability and acoustic properties, and is a widely used inorganic acoustic sensitizer (DOI: https: / / doi.org / 10.1016 / j.apmt.2021.101215). Current research indicates that titanium dioxide micro / nanomaterials, or thin films, coatings, and scaffolds containing titanium dioxide micro / nanomaterials (DOI: https: / / doi.org / 10.1002 / anbr.202400060, DOI: https: / / doi.org / 10.1002 / smll.202206253), as well as porous structures containing titanium dioxide, such as titanium dioxide nanotube array coatings prepared by anodic oxidation (DOI: https: / / doi.org / 10.1002 / adfm.202313553) and titanium dioxide coatings with a "honeycomb" superstructure prepared by micro-arc oxidation (DOI: https: / / doi.org / 10.1002 / adfm.202316093), all possess acoustic response characteristics. Citric acid, due to its origin in the tricarboxylic acid cycle, exhibits excellent biocompatibility and metabolizability. Furthermore, the multiple carboxyl and hydroxyl groups in its molecular structure enable it to act as a multidentate ligand, forming stable complexes with metal ions. Microalgae, as autotrophic organisms, can generate oxygen through photosynthesis under light conditions. Given their spontaneous oxygen production characteristics, photosynthetic microalgae have been widely used in various functional composite material systems and applied in biomedical applications such as tissue regeneration. This invention grafts titanium dioxide and a luminescent material (afterglow luminescence material) using citric acid. Ultrasonic triggering of the afterglow material's luminescence further drives the photosynthesis of microalgae, supplying oxygen to hypoxic bone defects, promoting angiogenesis, and achieving bone defect repair.

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] One objective of this invention is a method for preparing an ultrasound-induced inorganic afterglow luminescent material that promotes the repair of tissue and organ defects, comprising:

[0009] S1. Disperse the afterglow material and citric acid in an aqueous solution to obtain a precursor solution for the hydrothermal reaction;

[0010] S2. Add the titanium oxide-based material to the precursor solution provided in S1 and carry out a hydrothermal reaction in a reactor to obtain a titanium oxide-based luminescent material loaded with afterglow material.

[0011] The afterglow material is one or more of aluminate-based afterglow luminescent materials and titanate afterglow luminescent materials.

[0012] Furthermore, the aluminate-based afterglow luminescent material is M. x Al2O4:Y1-x Wherein, element M is one or more of Ca, Sr, Ba, Cu, Mg, and Zn, element Y is one or more of Eu, Nd, Dy, Pr, Sm, Cr, and Tb, and x = 0.001-1. Preferably, the aluminate-based afterglow luminescent material comprises CaAl2O4:Eu 2+ ,Nd 3+ and SrAl2O4:Eu 2+ ,Nd 3+ One or more of them.

[0013] Furthermore, the titanate afterglow luminescent material includes rare earth element-doped M. x TiO3:Y 1-x Wherein, M = one or more of Ca, Sr, Ba, Mg, and Zn, and the rare earth element Y is one or more of Eu, Nd, Dy, Sm, Gd, and Pr, and x = 0.001-1. Preferably, the titanate afterglow luminescent material comprises CaTiO3:Pr 3+ .

[0014] Furthermore, the molar ratio of citric acid to the metal element in the afterglow material described in S1 is 1:10 to 10:1.

[0015] Furthermore, the titanium oxide-based material mentioned in S2 is one of titanium oxide matrix, titanium oxide coating, or titanium oxide micro / nanomaterials.

[0016] Furthermore, the hydrothermal reaction temperature in S2 is 100~300℃, and the reaction time is 1~24 hours. Preferably, the reaction temperature is 140℃, 180℃, and 220℃, and the reaction time is 2h, 4h, 6h, 9h, and 24h.

[0017] The second objective of this invention is to provide an ultrasound-induced inorganic afterglow luminescent material that promotes tissue and organ repair, which is prepared by the method described above.

[0018] A third objective of this invention is the application of an ultrasound-induced inorganic afterglow luminescent material, as described above, for promoting tissue and organ defect repair. Specifically, this involves loading a microalgae solution onto the surface of the afterglow luminescent material, inducing luminescence in the inorganic afterglow material through ultrasound, and inducing O2 production through microalgae photosynthesis, thereby promoting tissue and organ repair. The tissues and organs include bones, cartilage, teeth, blood vessels, skin, muscles, nerves, intestines, bile ducts, and the heart.

[0019] Furthermore, the microalgae include one or more of Synechococcus, Chlorella, and diatoms.

[0020] Compared with the prior art, the present invention has the following advantages:

[0021] (1) The ultrasonic-induced inorganic afterglow luminescent material prepared in this invention is composed of titanium oxide and afterglow material, and can generate afterglow under ultrasonic excitation.

[0022] (2) The luminescent material has good biocompatibility. By loading microalgae with photosynthetic ability, it can continuously supply oxygen to hypoxic tissue defects under selective ultrasound control, promote angiogenesis, and achieve tissue and organ repair and regeneration.

[0023] (3) The ultrasound-induced inorganic afterglow luminescence material prepared by the present invention has high biocompatibility, wide applicability, and strong controllability of preparation method, and is suitable for large-scale production. Attached Figure Description

[0024] Figure 1 The afterglow material CaAl2O in Examples 1-3, Example 7, and Comparative Example 1 4: Eu 2+ ,Nd 3+ Scanning electron microscope (SEM) images of titanium oxide coatings after being composited under different reaction conditions.

[0025] Figure 2 This is the elemental analysis energy spectrum of the luminescent material MAO-CAO4 in Example 2.

[0026] Figure 3 These are luminescence imaging images of the MAO-CAO luminescent material after ultrasonic excitation in Examples 1-2.

[0027] Figure 4 This is the emission spectrum of the luminescent material MAO-CAO4 in Example 2.

[0028] Figure 5 This is the excitation spectrum of the luminescent material MAO-CAO4 in Example 2.

[0029] Figure 6 This is a graph showing the citric acid content of the MAO material obtained in Example 1 after different treatments.

[0030] Figure 7 These are cell proliferation diagrams of the luminescent material MAO-CAO in Examples 1-2, as well as the control groups Ti and titanium dioxide (MAO).

[0031] Figure 8 This is a graph showing the oxygen production performance of MAO-CAO4 loaded with Synechococcus 7942 under ultrasonic conditions, obtained in Example 2.

[0032] Figure 9 This is a transmission electron microscope (TEM) image of the luminescent material TO-CAO in Example 8.

[0033] Figure 10This is the elemental analysis energy spectrum of the luminescent material TO-CAO in Example 8.

[0034] Figure 11 These are luminescence imaging images of TiO2 and the luminescent material TO-CAO in Example 8 and the luminescent material TO-CAO-N in Comparative Example 2 after ultrasonic excitation.

[0035] Figure 12 The images show the SEM morphology of the non-honeycomb titanium oxide coating in Example 10 and the ABDA diagram of NAO ultrasonically degraded.

[0036] Figure 13 These are luminescence imaging images of the luminescent materials after ultrasonic excitation in Examples 3, 7, and 10.

[0037] Figure 14 The images show the SEM morphology and luminescence imaging of the MAO-SAO-EG material in Comparative Example 3.

[0038] Figure 15 These are the luminescence imaging images of CaAl2O4:EuNd loaded on titanium oxide using electrodeposition and adsorption methods in Comparative Examples 4 and 5 after ultrasonic excitation. Detailed Implementation

[0039] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0040] Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of this invention. Unless otherwise specified, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0041] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0042] Example 1

[0043] This embodiment provides a load of CaAl2O 4: Eu 2+ ,Nd 3+The method for preparing a titanium dioxide coating includes the following steps:

[0044] (1) Preparation of micro-arc titanium oxide coating (MAO)

[0045] First, pure titanium was subjected to micro-arc oxidation experiments in an electrolyte composed of potassium hydroxide (0.25 M) and sodium tetraborate (0.1 M). During the experiment, a constant voltage mode, a duty cycle of 10%, a frequency of 600 Hz, and circulating water cooling were used for temperature reduction. The reaction time was 4 minutes. This micro-arc oxidized titanium coating was named MAO.

[0046] (2) Loading CaAl2O4:Eu 2+ ,Nd 3+ Preparation of titanium dioxide coating

[0047] First, CaAl2O4:Eu was synthesized via a high-temperature solid-state method. 2+ ,Nd 3+ Powder materials (DOI: https: / / doi.org / 10.1016 / j.bioactmat.2021.08.030), then citric acid and CaAl2O4:Eu 2+ ,Nd 3+ A precursor solution was prepared by stirring and dispersing the precursor solution in water at a molar ratio of 2:1. Then, the micro-arc titanium dioxide coating (MAO) and the precursor solution were placed in a reaction vessel (the solution volume accounted for 60%) and reacted at 180℃ for 2 h. After the reaction was completed, the coating was taken out, washed with deionized water and dried to obtain the sample MAO-CAO2.

[0048] Example 2

[0049] This embodiment is basically the same as Embodiment 1, except that in this embodiment, citric acid and CaAl2O4:Eu are used. 2+ ,Nd 3+ A precursor solution was prepared by stirring and dispersing the precursor solution in water at a molar ratio of 2:1. The precursor solution and the micro-arc titanium dioxide coating were then placed in a reaction vessel (the solution volume accounted for 60%) and reacted at 180°C for 4 hours. After the reaction was completed, the coating was removed, washed with deionized water, and dried to obtain the sample MAO-CAO4.

[0050] Example 3

[0051] This embodiment is basically the same as Embodiment 1, except that in this embodiment, citric acid and CaAl2O4:Eu are used. 2+ ,Nd 3+A precursor solution was prepared by stirring and dispersing the precursor solution in water at a molar ratio of 2:1. Then, the micro-arc titanium dioxide coating (MAO) and the precursor solution were placed in a reaction vessel (the solution volume accounted for 60%) and reacted at 180℃ for 9 h. After the reaction was completed, the coating was taken out, washed with deionized water and dried to obtain the sample MAO-CAO9.

[0052] Example 4

[0053] This embodiment is basically the same as Embodiment 1, except that in this embodiment, citric acid and CaAl2O4:Eu are used. 2+ ,Nd 3+ A precursor solution was prepared by stirring and dispersing the precursor solution in water at a molar ratio of 2:1. Then, the micro-arc titanium dioxide coating (MAO) and the precursor solution were placed in a reaction vessel (the solution volume accounted for 60%) and reacted at 180℃ for 6 h. After the reaction was completed, the coating was taken out, washed with deionized water and dried to obtain the sample MAO-CAO6.

[0054] Example 5

[0055] This embodiment is basically the same as Embodiment 1, except that in this embodiment, citric acid and CaAl2O4:Eu are used. 2+ ,Nd 3+ A precursor solution was prepared by stirring and dispersing the precursor solution in water at a molar ratio of 2:1. Then, the micro-arc titanium dioxide coating (MAO) and the precursor solution were placed in a reaction vessel (the solution volume accounted for 60%) and reacted at 140°C for 24 hours. After the reaction was completed, the coating was removed, washed with deionized water and dried to obtain the sample MAO-CAO-LT.

[0056] Example 6

[0057] This embodiment is basically the same as Embodiment 1, except that in this embodiment, citric acid and CaAl2O4:Eu are used. 2+ ,Nd 3+ A precursor solution was prepared by stirring and dispersing the precursor solution in water at a molar ratio of 2:1. Then, the micro-arc titanium dioxide coating (MAO) and the precursor solution were placed in a reaction vessel (the solution volume accounted for 60%) and reacted at 220℃ for 2 hours. After the reaction was completed, the coating was removed, washed with deionized water and dried to obtain the sample MAO-CAO-HT.

[0058] Example 7

[0059] This embodiment is basically the same as Embodiment 1, except that in this embodiment, citric acid and CaAl2O4:Eu are used. 2+ ,Nd 3+A precursor solution was prepared by stirring and dispersing the precursor solution in water at a molar ratio of 1:10. The micro-arc titanium oxide coating (MAO) and the precursor solution were then placed in a reaction vessel (the solution volume accounted for 60%) and reacted at 180℃ for 4 h. After the reaction was completed, the coating was removed, washed with deionized water, and dried to obtain the sample MAO-CAO-LCA4.

[0060] Comparative Example 1

[0061] This comparative example is basically the same as Example 1, except that in this comparative example, CaAl2O4:Eu 2+ ,Nd 3+ A precursor solution (without citric acid) was prepared by stirring and dispersing in water. The micro-arc titanium dioxide coating (MAO) and the precursor solution were then placed in a reaction vessel (the solution volume accounted for 60%) and reacted at 180℃ for 4 h. After the reaction was completed, the coating was removed, washed with deionized water, and dried to obtain the sample MAO-CAO-NCA4.

[0062] Example 8

[0063] This embodiment provides a load of CaAl2O 4: Eu 2+ ,Nd 3+ The preparation method of titanium dioxide nanomaterials includes the following steps:

[0064] (1) Preparation of TiO2 nanosheets

[0065] 3 mL of 40% hydrofluoric acid was added to the lining of a 25 mL reactor, and 10 mL of tetrabutyl titanate was added dropwise while stirring. After stirring for 2 h, the reaction was carried out at 200 °C for 24 h. After the reaction was completed, the supernatant was discarded, and the collected precipitate was washed three times by centrifugation with water and ethanol at 12000 rpm / min for 20 min each time. Then, it was dried in a vacuum drying oven at 50 °C for 18 h to obtain TiO2 nanosheets.

[0066] (2) Loading CaAl2O4:Eu 2+ ,Nd 3+ Preparation of titanium dioxide nanomaterials

[0067] First, citric acid is reacted with CaAl2O4:Eu 2+ ,Nd 3+ A precursor solution was prepared by stirring and dispersing TiO2 nanosheets in water at a molar ratio of 2:1. Then, TiO2 nanosheets were combined with CaAl2O4:Eu... 2+ ,Nd 3+ The precursor solution was placed in a 1:1 molar ratio and reacted in a reactor at 180°C for 6 h. After the reaction was completed, the coating was removed, washed with deionized water and dried to obtain the sample TO-CAO.

[0068] Comparative Example 2

[0069] This comparative example is basically the same as Example 8, except that CaAl2O4:Eu 2+ ,Nd 3+ A precursor solution was prepared by stirring and dispersing titanium dioxide nanosheets in water at a molar ratio of 1:1. The solution was then reacted in a reactor at 180°C for 6 h. After the reaction was completed, the coating was removed, washed with deionized water, and dried to obtain the sample TO-CAO-N without the addition of citric acid.

[0070] Example 9

[0071] This embodiment is basically the same as Embodiment 1, except that in this embodiment, citric acid and CaTiO3:Pr are used. 3+ (The synthesis method is referenced in DOI:10.1021 / acsomega.7b00761.) The precursor solution was prepared by stirring and dispersing in water at a molar ratio of 2:1. The precursor solution and the micro-arc titanium dioxide coating were then placed in a reactor (the solution volume accounted for 60%) and reacted at 180℃ for 4 h. After the reaction was completed, the coating was removed, washed with deionized water and dried to obtain the sample MAO-CTO4.

[0072] Example 10

[0073] This embodiment provides a method for preparing a non-honeycomb titanium oxide coating (NAO), comprising the following steps:

[0074] (1) Preparation of NAO coating

[0075] First, pure titanium was subjected to micro-arc oxidation experiments in an electrolyte composed of calcium acetate (0.1 M) and sodium glycerophosphate (0.05 M). During the experiment, a constant current mode with a duty cycle of 10% and a frequency of 800 Hz was used, with circulating water cooling for a reaction time of 2 minutes. This titanium oxide coating was named NAO.

[0076] (2) Loading CaAl2O4:Eu 2+ ,Nd 3+ Preparation of titanium dioxide coating

[0077] Citric acid and CaAl2O4:Eu 2+ ,Nd 3+ A precursor solution was prepared by stirring and dispersing the precursor solution in water at a molar ratio of 1:1. Then, the non-honeycomb titanium oxide coating (NAO) and the precursor solution were placed in a reaction vessel (the solution volume accounted for 60%) and reacted at 180℃ for 6 h. After the reaction was completed, the coating was removed, washed with deionized water and dried to obtain the sample NAO-CAO6.

[0078] Example 11

[0079] This embodiment is basically the same as Embodiment 1, except that in this embodiment, citric acid and CaAl2O4:Eu are used. 2+ ,Nd 3+ A precursor solution was prepared by stirring and dispersing the precursor solution in water at a molar ratio of 10:1. The micro-arc titanium dioxide coating (MAO) and the precursor solution were then placed in a reaction vessel (the solution volume accounted for 60%) and reacted at 180°C for 4 h. After the reaction was completed, the coating was removed, washed with deionized water, and dried to obtain the sample MAO-CAO-HCA4.

[0080] Comparative Example 3

[0081] This comparative example is basically the same as Example 1, except that SrAl2O4:Eu 2+ ,Nd 3+ A precursor solution was prepared by dispersing the precursor solution in ethylene glycol. The micro-arc titanium dioxide coating (MAO) and the precursor solution were then placed in a reactor (the solution volume accounted for 60%) and reacted at 180°C for 4 h. After the reaction was completed, the coating was removed, washed with deionized water, and dried to obtain the sample MAO-SAO-EG.

[0082] Comparative Example 4

[0083] This comparative example is basically the same as Example 1, except that citric acid and CaAl2O4:Eu are used in this comparative example. 2+ ,Nd 3+ The sample was dispersed in water at a molar ratio of 2:1. Titanium oxide flakes and graphite were used as the cathode and anode, respectively. Electrodeposition was performed at a current of 5-10 mA for 5 minutes. After the reaction was completed, the coating was removed, washed with deionized water, and dried to obtain the sample MAO-CAO-EPD.

[0084] Comparative Example 5

[0085] In this comparative example, 20 mg of CaAl2O4:Eu was weighed out. 2+ ,Nd 3+ Disperse the MAO sample in 1 mL of water or ethanol. Place the sample in a 24-well plate, add 1 mL of the dispersed material, and let it stand in the dark for 24 hours. Then wash twice with water, air dry, and name the sample MAO-CAO-AD.

[0086] Testing and Characterization

[0087] (1) SEM characterization

[0088] The microstructure of the MAO-CAO luminescent materials prepared in Examples 1-3 and Comparative Examples 1-2 was observed using a scanning electron microscope (SEM), and the results are as follows: Figure 1As shown, only when reacting with citric acid under suitable molar ratio conditions can the CaAl2O4:Eu ratio be achieved. 2 + ,Nd 3+ Only then can the nanosheet structure be uniformly loaded onto the MAO coating surface (as shown in the SEM images of Examples 1-3). Correspondingly, when citric acid is not added to the reaction system (see Comparative Example 1), the CaAl2O4:Eu... 2+ ,Nd 3+ The agglomerates mainly exist on the coating surface in the form of aggregated particles, and their distribution is uneven; the agglomeration is improved under conditions of lower citric acid molar ratio (see Comparative Example 2).

[0089] (2) Elemental analysis energy spectrum of MAO-CAO luminescent materials

[0090] Elemental analysis and energy dispersive spectroscopy were performed on the MAO-CAO4 luminescent material prepared in Example 2, and the results are as follows: Figure 2 As shown, Al, Ca, Eu, and Nd elements are uniformly distributed on the surface of the MAO coating, demonstrating that this method can achieve CaAl2O4:Eu 2+ ,Nd 3+ Effective combination with TiO2.

[0091] (3) Luminescence imaging characterization of MAO-CAO luminescent materials

[0092] The luminescent materials MAO-CAO2 and MAO-CAO4 prepared in Examples 1-2 were characterized by luminescence imaging. Different MAO-CAO luminescent materials were irradiated with 365 nm ultraviolet light for 10 min, and the luminescence intensity was measured at 0 min and 16 min after irradiation. Then, the luminescent materials MAO-CAO2 and MAO-CAO4 were ultrasonicated for 2 min using an ultrasonic probe (1 MHz, 1.5 W / cm²). 2 (Duty cycle 50%), the luminescence intensity of the material was measured after ultrasonication. Results are as follows: Figure 3 As shown, MAO-CAO luminescent materials can all produce long afterglow under ultrasonic treatment.

[0093] (4) Luminescence imaging characterization of MAO-CAO luminescent materials

[0094] The excitation and emission spectra of the luminescent material MAO-CAO4 prepared in Example 2 were characterized. The results are as follows: Figure 4 and Figure 5 As shown, the maximum excitation wavelength of the luminescent material MAO-CAO4 is 354 nm, and the maximum emission wavelength is 406 nm. It can be seen that CaAl2O4:Eu 2+ ,Nd 3+ It retains its luminescent properties even after being loaded onto the coating surface.

[0095] (5) Citric acid bridging titanium dioxide and CaAl2O4:Eu 2+ ,Nd 3+ The representation

[0096] Citric acid was dispersed in water, and a portion of the solution was collected and named CA. Then, a micro-arc titanium dioxide coating (MAO) and citric acid were placed in a reaction vessel (solution volume 60%) and reacted at 180°C for 6 hours. After the reaction, the solution was collected and named CA-MAO. Citric acid was then reacted with CaAl₂O₄:Eu 2+ ,Nd 3+ A precursor solution was prepared by stirring and dispersing the precursor solution in water at a molar ratio of 2:1. Then, the micro-arc titanium dioxide coating (MAO) and the precursor solution were placed in a reaction vessel (solution volume 60%) and reacted at 180℃ for 6 hours. After the reaction, the solution was collected and named CA-MCAO. The citric acid content of these three samples was determined, and the results are as follows: Figure 6 As shown, the citric acid content of the micro-arc titanium dioxide coating decreased significantly after 6 hours of reaction with citric acid, indicating that the coating can significantly adsorb citric acid. The further reduction in citric acid content in the CA-MCAO sample also indicates that citric acid can chelate titanium dioxide and CaAl2O4:Eu, respectively. 2+ ,Nd 3+ Two inorganic materials are combined together.

[0097] (6) Characterization of cell proliferation activity of MAO-CAO luminescent materials

[0098] Ti, MAO, MAO-CAO2, and MAO-CAO4 were placed in a 24-well plate with 4 × 10⁻⁶ cells per well. 4 Mouse bone marrow mesenchymal stem cells (BMSCs) were seeded at a specific density. On days 1, 4, and 7, the old culture medium was discarded, and 500 μL of fresh complete culture medium was added to each well. Then, 50 μL of cell counting reagent CCK-8 was added to each well, and the cells were incubated for 1.5 h. Afterward, 100 μL of the supernatant was collected and the absorbance at 450 nm was recorded using a microplate reader. Results are as follows: Figure 7 The results show that BMSC cells can proliferate effectively on the surface of MAO-CAO luminescent material, indicating that the luminescent material has good biocompatibility.

[0099] (7) Determination of oxygen production performance of MAO-CAO4 luminescent material loaded with Synechococcus faecium

[0100] The MAO-CAO4 luminescent material prepared in Example 2 was placed in a 6-well plate, and 5 mL of a 5×10⁻⁶ concentration was added. 7The sample was soaked in *Synechococcus 7942* at a concentration of 1.5 W / cm² for 4 hours and named MAO-CAO-CB. The liquid was then subjected to ultrasonic treatment at 1.5 W / cm². 2 Under the specified conditions, ultrasound was administered for 2 minutes (1 MHz, 50% duty cycle), and oxygen production was measured using a dissolved oxygen analyzer. Results are as follows: Figure 8 As shown, ultrasound can effectively promote oxygen production in cyanobacteria.

[0101] (8) TEM characterization

[0102] TEM images were taken of the TO-CAO luminescent material prepared in Example 8, and the results are as follows: Figure 9 As shown, CaAl2O4:Eu 2+ ,Nd 3+ The loading did not change the surface morphology of the titanium dioxide nanosheets.

[0103] (9) Elemental analysis energy spectrum of TO-CAO luminescent materials

[0104] Elemental analysis and energy dispersive spectroscopy were performed on the TO-CAO luminescent material prepared in Example 8, and the results are as follows: Figure 10 As shown, Ca and Al elements are uniformly distributed on the surface of titanium dioxide nanosheets, and it can be seen that CaAl2O4:Eu 2+ ,Nd 3+ It can be uniformly loaded onto titanium dioxide nanomaterials.

[0105] (10) Luminescence imaging characterization of TO-CAO luminescent materials

[0106] The TO-CAO luminescent materials prepared in Example 8 were characterized by luminescence imaging. Different TO-CAO luminescent materials were irradiated with 365 nm ultraviolet light for 10 min, and the luminescence intensity of the materials was measured after irradiation. The results are as follows: Figure 11 As shown, the TO-CAO luminescent material with added citric acid produces a long afterglow, while the TO-CAO-N sample prepared from the reaction system without citric acid does not produce a long afterglow luminescence after ultrasonication, instead displaying the white color of the TO-CAO-N sample itself. This indicates that CaAl2O4:Eu 2 + ,Nd 3+ It can be grafted onto the surface of titanium dioxide nanosheets using citric acid as a multidentate ligand and maintain long afterglow properties. In contrast, in Comparative Example 2, under conditions without citric acid, CaAl₂O₄:Eu, as a poorly soluble aluminate,... 2+ ,Nd 3+ It is difficult to uniformly load titanium dioxide nanosheets.

[0107] (11) Characterization of acoustic sensitivity of NAO materials

[0108] The NAO material prepared in Example 10 was placed in a 24-well plate, and 1.5 mL of 0.5 mmol / L 9,10-anthratridiyl-bis(methylene)dicarboxylic acid (ADBA) reagent was added. The liquid was ultrasonically amplified at 1.5 W / cm². 2 Under ultrasound conditions of 0, 2, and 4 minutes (1 MHz, 50% duty cycle), the absorbance changes were measured using a microplate reader. The results are as follows: Figure 12 As shown, non-honeycomb titanium oxide coatings also exhibit certain acoustic properties.

[0109] (12) Luminescence imaging characterization of luminescent materials MAO-CAO9, MAO-CAO-LCA4, and NAO-CAO6

[0110] MAO-CAO9, MAO-CAO-LCA4, and NAO-CAO6 from Examples 3, 7, and 10 were irradiated with 365 nm ultraviolet light for 10 min, and then sonicated with an ultrasonic probe for 2 min (1 MHz, 1.5 W / cm²) 30 min after the irradiation ended. 2 (Duty cycle 50%), the luminescence intensity of the material was measured after the ultrasonic treatment. Results are as follows: Figure 13 As shown, reducing the proportion of citric acid and using a non-honeycomb titanium dioxide coating can both maintain certain long afterglow characteristics.

[0111] (13) SEM characterization and luminescence imaging characterization of MAO-SAO-EG materials

[0112] The microstructure of the MAO-SAO-EG material in Comparative Example 3 was observed using a scanning electron microscope (SEM), and the results are as follows: Figure 14 As shown, under the condition of ethylene glycol as solvent, SrAl2O4:Eu 2+ ,Nd 3+ The coating surface of the material mainly exists in the form of agglomerates. However, when the MAO-SAO-EG material was irradiated with 365 nm ultraviolet light for 10 minutes, the luminescence intensity was measured after the irradiation was completed, and no obvious luminescence was found.

[0113] (14) Luminescence imaging characterization of the materials prepared in Comparative Examples 4 and 5

[0114] The MAO-CAO-EPD and MAO-CAO-AD materials in Comparative Examples 4-5 were irradiated with 365 nm ultraviolet light for 10 min, and the luminescence intensity of the materials was measured after irradiation. The results are as follows: Figure 15 As shown, the surface of MAO-CAO-EPD prepared by electrodeposition technology has no obvious luminescence, while the surface of MAO-CAO-AD prepared by adsorption method has very uneven luminescence, indicating that these methods cannot uniformly load afterglow materials onto titanium oxide-based materials.

[0115] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A method for preparing an ultrasound-induced inorganic afterglow luminescent material that promotes the repair of tissue and organ defects, characterized in that, include: S1. Disperse the afterglow material and citric acid in an aqueous solution to obtain a precursor solution for the hydrothermal reaction; S2. Add the titanium oxide-based material to the precursor solution provided in S1 and carry out a hydrothermal reaction in a reactor to obtain a titanium oxide-based luminescent material loaded with afterglow material. The afterglow material is one or more of aluminate-based afterglow luminescent materials and titanate afterglow luminescent materials.

2. The method for preparing an ultrasound-induced inorganic afterglow luminescent material for promoting tissue and organ defect repair according to claim 1, characterized in that, The aluminate-based afterglow luminescent material is M. x Al2O4:Y 1-x Where M is one or more of Ca, Sr, Ba, Cu, Mg, and Zn, Y is one or more of Eu, Nd, Dy, Pr, Sm, Cr, and Tb, and x = 0.001-1.

3. The method for preparing an ultrasound-induced inorganic afterglow luminescent material for promoting tissue and organ defect repair according to claim 1, characterized in that, The titanate afterglow material includes rare earth element-doped M. x TiO3:Y 1-x Where M = one or more of Ca, Sr, Ba, Mg, and Zn, and the rare earth element Y is one or more of Eu, Nd, Dy, Sm, Gd, and Pr, and x = 0.001-1.

4. The method for preparing an ultrasound-induced inorganic afterglow luminescent material for promoting tissue and organ defect repair according to claim 1, characterized in that, The molar ratio of citric acid to the metal element in the afterglow material described in S1 is 1:10 to 10:

1.

5. The method for preparing an ultrasound-induced inorganic afterglow luminescent material for promoting tissue and organ defect repair according to claim 1, characterized in that, The titanium oxide-based material mentioned in S2 is one of titanium oxide matrix, titanium oxide coating, or titanium oxide micro / nanomaterial.

6. The method for preparing an ultrasound-induced inorganic afterglow luminescent material for promoting tissue and organ defect repair according to claim 1, characterized in that, The hydrothermal reaction in S2 takes place at a temperature of 100~300℃ for 1~24 hours.

7. The method for preparing an ultrasound-induced inorganic afterglow luminescent material for promoting tissue and organ defect repair according to claim 1, characterized in that, The hydrothermal reaction temperature in S2 is 140℃, 180℃ or 220℃, and the reaction time is 2h, 4h, 6h, 9h or 24h.

8. An ultrasound-induced inorganic afterglow luminescence material for promoting the repair of tissue and organ defects, characterized in that, It is prepared by the preparation method described in any one of claims 1-7.

9. The application of the ultrasound-induced inorganic afterglow luminescence material as described in claim 8 in the preparation of materials that promote the repair of tissue and organ defects, characterized in that, In promoting tissue and organ repair, the method involves loading a microalgae solution onto the surface of a luminescent material, inducing the inorganic luminescent material to emit light through ultrasound, and inducing the microalgae to photosynthesize and produce O2, thereby promoting tissue and organ repair. The tissues and organs include bones, cartilage, teeth, blood vessels, skin, muscles, nerves, intestines, bile ducts, and heart.

10. The application of the ultrasound-induced inorganic afterglow luminescent material according to claim 9 in the preparation of materials that promote the repair of tissue and organ defects, characterized in that, The microalgae include one or more of Synechococcus, Chlorella, and diatoms.

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