Long afterglow-mannose-BDP composite material, and preparation method and application thereof

Abstract

The invention relates to the technical field of materials, in particular to a long afterglow coated mannose coated BDP composite material, a preparation method and application. The preparation method specifically comprises the following steps: synthesizing ZGGO: Cr long afterglow nanoparticles by adopting a hydrothermal method; carrying out organic synthesis to obtain an amino-functionalized Aza-BODIPY molecule; the preparation method comprises the following steps: carrying out amination modification on long afterglow nano-particles through a silane coupling agent to obtain ZGGO: Cr-NH2; the surface of the ZGGO: Cr-NH2 is connected with a mannose targeting molecule to obtain ZGGO: Cr (at) Man; the preparation method comprises the following steps: covalently linking a carboxyl group to ZGGO: Cr (at) Man to obtain ZGGO: Cr (at) Man-COOH; the preparation method comprises the following steps: amidating ZGGO: Cr (at) Man-COOH, and connecting BDP molecules to obtain a long afterglow (at) mannose (at) BDP composite material; according to the invention, the nano composite material with functions of real-time monitoring of a drug delivery process, targeted photo-thermal antibiosis and sustainable antibiosis is successfully constructed.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of materials, in particular to a long-afterglow mannose BDP composite material, a preparation method and application. BACKGROUND

[0002] In order to avoid the emergence of bacterial drug resistance, in recent years, researchers have developed a new type of antibacterial method, photothermal therapy (PTT). This treatment method can effectively kill bacteria by generating local high temperature under near-infrared light irradiation of a photothermal conversion agent, and is not easy to induce bacterial drug resistance. However, in the actual application of photothermal therapy, there are still several key technical bottlenecks in the single use of organic photothermal agents such as BODIPY (fluoroboron dipyrrin): first, the BODIPY molecule lacks an active targeting function and is difficult to specifically enrich in the infection site, which not only reduces the antibacterial efficiency, but also may cause thermal damage to normal tissues; second, the traditional BODIPY system lacks an integrated imaging platform, and cannot track the distribution and metabolism of the photothermal agent in the body in real time through fluorescence imaging, photoacoustic imaging and other technologies, which seriously restricts the precise regulation of the treatment process; in addition, the single photothermal agent also has problems such as insufficient light stability and limited tissue penetration depth. These defects together limit the conversion application of BODIPY photothermal agents in clinical antibacterial therapy,

[0003] Therefore, it is urgent to develop a new method for preparing a nano-composite material with the functions of real-time monitoring of drug delivery process, targeted photothermal antibacterial and sustainable antibacterial. SUMMARY

[0004] To solve the above problems, the application provides a long-afterglow mannose BDP composite material, a preparation method and application.

[0005] The application is realized by the following technical solutions: A preparation method of a long-afterglow mannose BDP composite material, specifically comprising the following steps: ZGGO:Cr long-afterglow nanoparticles are synthesized by using Zn source, Ga source, Cr source and Ge source as raw materials through a hydrothermal method.

[0006] An amino-functionalized Aza-BODIPY molecule is obtained by organic synthesis.

[0007] ZGGO:Cr-NH2 is obtained by modifying the long-afterglow nanoparticles through amino modification of a silane coupling agent.

[0008] ZGGO:Cr@Man is obtained by connecting a mannose targeting molecule to the surface of ZGGO:Cr-NH2.

[0009] The carboxyl group was covalently attached to ZGGO:Cr@Man to obtain ZGGO:Cr@Man-COOH.

[0010] After amidation of ZGGO:Cr@Man-COOH, Aza-BODIPY molecules were linked to obtain a long afterglow@mannose@BDP composite material.

[0011] The chemical structure of the Aza-BODIPY molecule is shown in 4c: .

[0012] Preferably, the Aza-BODIPY molecule is synthesized through the following steps: Using methanol as a solvent, 4-aminoacetophenone and thiophene-2-carboxaldehyde were subjected to an aldehyde-ketone condensation reaction, and the pH was adjusted to 12-14 to obtain the target product 1c; the molar ratio of 4-aminoacetophenone to thiophene-2-carboxaldehyde was 1:1-1.5.

[0013] Using ethanol as a solvent, 1c and di-tert-butyl dicarbonate were subjected to an amino-protected chemical reaction in the presence of potassium carbonate to obtain the target product 1c-Boc; the molar ratio of 1c, di-tert-butyl dicarbonate and potassium carbonate was 1:2~4:3~5.

[0014] Using methanol as a solvent, 1c-Boc and nitromethane were subjected to a Henry reaction in the presence of diethylamine to obtain the target product 2c-Boc; the molar ratio of 1c-Boc, nitromethane and diethylamine was 1:4~6:4~6.

[0015] Using anhydrous ethanol as a solvent, 2c-Boc was reacted with ammonium acetate via Nef reaction, Paal-Knorr reaction and electrophilic substitution reaction to obtain the target product 3c-Boc; the molar ratio of 2c-Boc to ammonium acetate was 1:25~50.

[0016] Using ultra-dry dichloromethane as a solvent, 3c-Boc and etherified boron trifluoride were subjected to coordination and bonding reactions in the presence of N,N-diisopropylethylamine to obtain the target product 4c, namely the Aza-BODIPY molecule; the molar ratio of 3c-Boc, etherified boron trifluoride and N,N-diisopropylethylamine was 1:20~50:5~20.

[0017] .

[0018] Preferably, the preparation method of the ZGGO:Cr long afterglow nanoparticles specifically includes the following steps: Using water as a solvent, Zn, Ga, Cr, and Ge sources were added, and the pH was adjusted to 8-9. The mixture was then reacted at 200-240℃ for 8-12 hours via a hydrothermal method to obtain ZGGO:Cr long afterglow nanoparticles. The molar ratio of the Zn, Ga, Cr, and Ge sources was 1.2-1.5:1-1.6:0.005-0.01:0.2-0.5.

[0019] Preferably, the silane coupling agent is 3-aminopropyltriethoxysilane; ZGGO:Cr-NH2 is obtained by amylating ZGGO:Cr long afterglow nanoparticles with the 3-aminopropyltriethoxysilane; the reaction temperature is 70℃~90℃, the time is 9h~15h, and the mass-to-volume ratio of ZGGO:Cr long afterglow nanoparticles to 3-aminopropyltriethoxysilane is 100mg:300μL~500μL.

[0020] Preferably, the preparation method of ZGGO:Cr@Man specifically includes the following steps: ZGGO:Cr-NH2 was dispersed in DMSO, mannose was added, and the reaction was carried out at 60℃~80℃ for 9 to 15 hours. After centrifugation and washing, ZGGO:Cr@Man was obtained. The mass ratio of ZGGO:Cr-NH2 to mannose was 100:20~50.

[0021] Preferably, the preparation method of ZGGO:Cr@Man-COOH specifically includes the following steps: ZGGO:Cr@Man, succinic anhydride, and 4-dimethylaminopyridine were reacted in DMF at room temperature for 9 to 14 hours to obtain ZGGO:Cr@Man-COOH; the mass ratio of ZGGO:Cr@Man, succinic anhydride, and 4-dimethylaminopyridine was 1:0.8~1.2:0.8~1.2.

[0022] ZGGO:Cr@Man-COOH was amidated with 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide to obtain activated ZGGO:Cr@Man-COOH. The activated ZGGO:Cr@Man-COOH was then reacted with Aza-BODIPY in a buffer solution at 37°C for 10-14 hours. After centrifugation and washing, a long-afterglow@mannose@BDP composite material was obtained. The mass ratio of ZGGO:Cr@Man-COOH, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and N-hydroxysuccinimide was 1:1.5-2.5:2.5-3.5. The mass ratio of activated ZGGO:Cr@Man-COOH to Aza-BODIPY was 10:1-9. The buffer solution was MES buffer, HEPES buffer, or PBS buffer.

[0023] The long afterglow@mannose@BDP composite material prepared by the aforementioned preparation method.

[0024] The application of the long afterglow@mannose@BDP composite material in bacterial targeted photothermal therapy.

[0025] The long afterglow@mannose@BDP composite material targets mannose-binding proteins on the surface of bacteria with mannose and kills bacteria through a photothermal effect generated by Aza-BODIPY under near-infrared light irradiation.

[0026] Compared with the prior art, the present invention has the following beneficial effects: This invention provides a method for preparing a long-afterglow@mannose@BDP composite material, specifically including the following steps: using Zn source, Ga source, Cr source and Ge source as raw materials, ZGGO:Cr long-afterglow nanoparticles are synthesized by hydrothermal method; the long-afterglow nanoparticles are modified by amination with a silane coupling agent to obtain ZGGO:Cr-NH2; mannose targeting molecules are connected to the surface of ZGGO:Cr-NH2 to obtain ZGGO:Cr@Man; carboxyl groups are covalently connected to ZGGO:Cr@Man to obtain ZGGO:Cr@Man-COOH; after amidation of ZGGO:Cr@Man-COOH, Aza-BODIPY molecules are connected to obtain the long-afterglow@mannose@BDP composite material; the chemical structure of the Aza-BODIPY molecule is shown in 4c. .

[0027] This invention aims to construct a multifunctional antibacterial nanocomposite material. ZGGO:Cr long afterglow nanoparticles were synthesized using a hydrothermal method, and mannose with targeting properties was grafted onto the surface. Finally, amino-substituted Aza-BODIPY molecules were connected as photothermal agents through amidation. This successfully constructed a nanocomposite material with functions of real-time monitoring of drug delivery, targeted photothermal antibacterial activity, and sustainable antibacterial activity, providing a powerful tool with great potential for novel photothermal antibacterial methods. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 This is a characterization diagram of ZGGO:Cr related to the present invention; Figure 1In the image, a is the TEM image; b is the XRD image; c is the excitation and emission curves; and d is the afterglow decay curve.

[0030] Figure 2 This is a schematic diagram illustrating the construction process of the long afterglow@mannose@BDP composite material of the present invention.

[0031] Figure 3 Characterization figures for the long afterglow@mannose@BDP composite material; Figure 3 In the figure, a is the XRD pattern of the long afterglow@mannose@BDP composite material; b is the TG curve of ZGGO:Cr and ZGGO:Cr@Man; c is the Zeta potential of each product; and d is the FTIR curve.

[0032] Figure 4 The graph shows the results of the photothermal performance analysis of ZGGO:Cr@Man@BDP in this invention. Figure 4 In the figure, a is a graph showing the photothermal comparison test results of composite materials with a mass ratio of BDP molecule: ZGGO:Cr@Man-COOH ranging from 1:10 to 9:10 under the same illumination conditions; b is a graph showing the effect of different concentrations of long afterglow@mannose@BDP composite materials on photothermal conversion efficiency; c is a graph showing the heating curves under different power irradiation; d is a graph showing the heating and cooling curves and fitting curves; e is a graph showing the photothermal stability curve; and f is an infrared thermal image taken every minute during the heating process.

[0033] Figure 5 For the present invention to E. coli Figure showing the photothermal antibacterial characterization results; Figure 5In the figures, a) shows the antibacterial images of different concentrations of long-afterglow@mannose@BDP composite material under different power light irradiations; b) shows the bacterial survival rate after treatment with different concentrations of long-afterglow@mannose@BDP composite material; c) shows the bacterial survival rate under different power light irradiations. Control 1 is the control group without light irradiation; Control 2 is the control group with light irradiation; Control 3 is the control group with 1 mg / mL composite material plus bacteria without light irradiation; Control 4 is the control group with ZGGO:Cr plus light irradiation; Control 5 is the control group with Man plus light irradiation; 0.2 mg / mL is the group with 0.2 mg / mL composite material plus 1W light irradiation; 0.4 mg / mL is the group with 0.4 mg / mL composite material plus light irradiation. The following groups were identified: 0.6 mg / mL bacteria plus 0.6 mg / mL composite material plus 1W light; 0.8 mg / mL bacteria plus 0.8 mg / mL composite material plus 1W light; 1 mg / mL bacteria plus 1 mg / mL composite material plus 1W light; 0.2W bacteria plus 1 mg / mL composite material plus 0.2W light; 0.4W bacteria plus 1 mg / mL composite material plus 0.4W light; 0.6W bacteria plus 1 mg / mL composite material plus 0.6W light; 0.8W bacteria plus 1 mg / mL composite material plus 0.8W light; 1W bacteria plus 1 mg / mL composite material plus 1W light.

[0034] Figure 6 For the present invention to PA Figure showing the results of photothermal antibacterial characterization; Figure 6 In the figures, a) shows the antibacterial images of different concentrations of long-afterglow@mannose@BDP composite material under different power light irradiations; b) shows the bacterial survival rate after treatment with different concentrations of long-afterglow@mannose@BDP composite material; c) shows the bacterial survival rate under different power light irradiations. Control 1 is the control group without light irradiation; Control 2 is the control group with light irradiation; Control 3 is the control group with 1 mg / ml composite material plus bacteria without light irradiation; Control 4 is the control group with bacteria plus ZGGO:Cr plus light irradiation; Control 5 is the control group with bacteria plus Man plus light irradiation; 0.2 mg / mL is the group with bacteria plus 0.2 mg / mL composite material plus 1W light irradiation; 0.4 mg / mL is the group with bacteria plus 0.4 mg / mL composite material. The following groups were selected for treatment: 1W light exposure group; 0.6mg / mL bacteria plus 0.6mg / mL composite material plus 1W light exposure group; 0.8mg / mL bacteria plus 0.8mg / mL composite material plus 1W light exposure group; 1mg / mL bacteria plus 1mg / mL composite material plus 1W light exposure group; 0.2W bacteria plus 1mg / mL composite material plus 0.2W light exposure group; 0.4W bacteria plus 1mg / mL composite material plus 0.4W light exposure group; 0.6W bacteria plus 1mg / mL composite material plus 0.6W light exposure group; 0.8W bacteria plus 1mg / mL composite material plus 0.8W light exposure group; 1W bacteria plus 1mg / mL composite material plus 1W light exposure group.

[0035] Figure 7 The diagram shows the results of verifying the sustained antibacterial properties of the long afterglow@mannose@BDP composite material in this invention. Figure 7 In the image, a is the antibacterial image under white light irradiation; b is the bacterial survival rate graph.

[0036] Figure 8 The figures show the results of bacterial SEM characterization and bacterial live / dead fluorescence staining experiments of this invention. Figure 8 In the middle, a is E. coli SEM images after different treatments; b is the live / dead fluorescence staining image; c is... PA SEM images after different processing. Detailed Implementation

[0037] To facilitate understanding of the present invention, a more comprehensive description is provided below, along with preferred embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the present invention.

[0038] Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used in this invention and in its specification is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0039] The inventive concept of this invention is as follows: To avoid the development of bacterial resistance, a novel antibacterial method is employed: photothermal therapy. However, the use of the organic photothermal agent BODIPY alone in photothermal therapy suffers from several drawbacks, including a lack of targeting, hindering precise treatment, and a lack of imaging platforms, making it impossible to monitor the delivery process of the photothermal agent in real time.

[0040] Based on this, the present invention develops a novel multifunctional antibacterial composite material—a long afterglow@mannose@BDP composite material (ZGGO:Cr@Man@BDP). This material uses zinc germanium gallium oxide-based long afterglow nanoparticles (ZGGO:Cr) as the core carrier, and achieves multiple functional integrations through surface modification, such as… Figure 2 As shown, long-afterglow materials possess unique persistent luminescence properties, capable of emitting light for hours to days after excitation ceases. Their near-infrared luminescence offers advantages such as deep tissue penetration and a high signal-to-noise ratio, providing real-time imaging guidance for the treatment process. Covalently linked mannose molecules on the material surface specifically recognize and bind to mannose receptors on bacterial surfaces, both blocking bacterial adhesion to host cells and achieving targeted enrichment at the infection site. The carboxyl-activated Aza-BODIPY photothermal agent generates a highly efficient photothermal effect under near-infrared light irradiation, synergistically working with the persistent luminescence properties of the long-afterglow material to achieve long-lasting antibacterial effects.

[0041] This composite material offers multiple advantages: First, the targeted modification with mannose significantly improves treatment precision and reduces impact on normal tissues; second, the real-time imaging capability of the long-afterglow material enables visual monitoring of the treatment process; and third, the synergistic effect of the photothermal agent and the long-afterglow carrier prolongs the duration of the therapeutic effect. More importantly, this physical-targeted combined action mechanism is less likely to induce bacterial resistance, providing a new solution to the increasingly serious problem of drug-resistant bacterial infections. This material has broad application prospects in clinical scenarios such as wound infections and deep tissue infections, achieving integrated diagnosis and treatment, and providing new ideas for the development of next-generation antibacterial agents.

[0042] The raw materials and instruments used in this invention are all commercially available surface-configurable products.

[0043] The beneficial effects of the present invention will be illustrated below through specific embodiments.

[0044] Example 1: Preparation method of long afterglow@mannose@BDP composite material The preparation method of the long afterglow@mannose@BDP composite material is as follows: (1) Zn 1.2 Ge 0.2 Ga 1.6 Synthesis of O4:0.5%Cr (ZGGO:Cr) long-afterglow nanoparticles: First, prepare 1M Zn(NO3)2 solution, 400mM Ga(NO3)3 solution, 10mM Cr(NO3)3 solution, and 400mM Na2GeO4 solution for later use. The molar ratio of Zn(NO3)2, Ga(NO3)3, Cr(NO3)3 to Na2GeO4 is 1.2:1.6:0.005:0.2. Add 8 mL of deionized water to the inner liner of the hydrothermal synthesis reactor. Then, slowly add 1.2 mL of Zn(NO3)2 solution, 4.0 mL of Ga(NO3)3 solution, and 0.75 mL of Cr(NO3)3 solution sequentially. While stirring continuously, add 0.5 mL of Na2GeO4 solution. Then, slowly add concentrated ammonia while stirring to adjust the pH to 8.5. After stirring for 1 hour, place the hydrothermal synthesis reactor in an oven at 220℃ for 10 hours. After the reaction is complete, collect the lower white emulsion, centrifuge three times at 8000 rpm, and wash three times with deionized water to obtain white ZGGO:Cr long-afterglow nanoparticles. Disperse the ZGGO:Cr long-afterglow nanoparticles in deionized water for later use.

[0045] (2) Synthesis of ZGGO:Cr-NH2: 100 mg of ZGGO:Cr long afterglow nanoparticles were uniformly dispersed in 40 mL of N,N-dimethylformamide (DMF) solution by ultrasonication. Under stirring, 400 μL of 3-aminopropyltriethoxysilane was slowly added dropwise to the DMF dispersion at 80 °C, and the reaction was continued for 12 h. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, washed once with DMF, and twice with DMSO to obtain ZGGO:Cr-NH2.

[0046] (3) Synthesis of ZGGO:Cr@Man: 100 mg of ZGGO:Cr-NH2 was dispersed in DMSO to prepare 50 mL of DMSO dispersion. 30 mg of mannose (Man) was added with stirring and the mixture was incubated at 70 °C for 12 h. After the reaction was completed, the mixture was centrifuged (DMSO was washed once and DMF was washed twice) to obtain light yellow particles, which were ZGGO:Cr@Man.

[0047] (4) Synthesis of ZGGO:Cr@Man-COOH: The experimental procedure for covalently attaching the carboxyl group to ZGGO:Cr@Man is as follows: 100 mg of ZGGO:Cr@Man was dispersed in 40 mL of DMF and sonicated until homogeneous. Then, 20 mL of succinic anhydride DMF solution (5 mg / mL) and 20 mL of 4-dimethylaminopyridine DMF solution (5 mg / mL) were added to the above DMF dispersion under stirring. The mixture was stirred at 25 °C for 12 h. After the reaction was completed, the reaction solution was centrifuged and washed three times with a 1:1 volume ratio ethanol / water mixture to obtain ZGGO:Cr@Man-COOH particles.

[0048] (5) Synthesis of BDP molecules: The amino-functionalized Aza-BODIPY molecule, abbreviated as BDP molecule, was obtained by organic synthesis.

[0049] Synthesis of compound 1c: 4-Aminoacetophenone (6.75 g, 50 mmol, 1 eq), thiophene-2-carboxaldehyde (6.72 g, 5.54 mL, 60 mmol, 1.2 eq), and 250 mL of methanol were added to a 500 mL round-bottom flask. The mixture was cooled to 0 °C, and 2.5 M KOH aqueous solution was added dropwise with stirring to adjust the pH to 13. The mixture was then refluxed overnight in an oil bath at 50 °C with stirring. After the reaction was complete, the system was cooled to room temperature and stirred in a 0 °C cold well. Yellow solid particles appeared. The mixture was filtered, and the filter cake was washed with petroleum ether to obtain the target product 1c, a yellow powder solid (9.88 g, yield 86.18%).

[0050] Synthesis of compound 1c-Boc: 1c (9.172 g, 40 mmol, 1 eq), potassium carbonate (22.112 g, 160 mmol, 4 eq), di-tert-butyl dicarbonate (26.192 g, 120 mmol, 3 eq), and 200 mL of ethanol were added to a 500 mL round-bottom flask. The mixture was refluxed overnight in an oil bath at 45 °C with stirring. After the reaction was complete, the mixture was quenched with saturated sodium bicarbonate aqueous solution, followed by extraction with ethyl acetate. The organic phases were combined and dried over anhydrous sodium sulfate. The mixture was filtered, the filtrate was concentrated, and purified by column chromatography (petroleum ether:ethyl acetate = 10:1~5:1) to give the target product 1c-Boc, a pale yellow flocculent solid (6.68 g, yield 50.7%).

[0051] Synthesis of compound 2c-Boc: 1c-Boc (4.94 g, 15 mmol, 1 eq), nitromethane (4.03 mL, 75 mmol, 5 eq), diethylamine (7.85 mL, 75 mmol, 5 eq), and 125 mL of methanol were added to a 300 mL round-bottom flask. The mixture was refluxed overnight in an oil bath at 75 °C with stirring. After the reaction was complete, the system was cooled to 0 °C, and 2.5 M hydrochloric acid aqueous solution was added dropwise with stirring to adjust the pH to 2-4. The reaction solution was extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated and purified by column chromatography (petroleum ether: ethyl acetate = 10:1~5:1) to obtain the target product 2c-Boc, a light white flocculent solid (3.7 g, yield 63.2%).

[0052] Synthesis of compound 3c-Boc: 2c-Boc (3.12 g, 8 mmol, 1 eq), ammonium acetate (21.6 g, 280 mmol, 35 eq) and 240 mL of anhydrous ethanol were added to a 500 mL round-bottom flask. The mixture was stirred and refluxed in an oil bath at 75 °C for 48 hours under an argon atmosphere. After the reaction was completed, the system was cooled to 0 °C, a large amount of petroleum ether was added, the mixture was filtered, the filtrate was discarded, the filter cake was dissolved with ethyl acetate and collected for concentration to obtain the target product 3c-Boc, a blackish-green powder solid (0.447 g, yield 8.08%).

[0053] Synthesis of compound 4c: 3c-Boc (0.345 g, 0.5 mmol, 1 eq) and 40 mL of ultra-dry dichloromethane were added to a Schlenk flask and stirred at 0 °C for 20 min. Then, N,N-diisopropylethylamine (0.83 mL, 5 mmol, 10 eq) was added dropwise, and stirring was continued for 40 min. Then, boron trifluoride ether (1.89 mL, 15 mmol, 30 eq) was added dropwise to the system, and the mixture was stirred at room temperature for 50 h. After the reaction was complete, the mixture was filtered, the filtrate was discarded, the filter cake was dissolved with ethyl acetate and the solution was collected and extracted with saturated brine. The organic phases were combined, dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain the target product 4c, namely BDP, a purplish-black powder solid (0.06 g, yield 22.24%).

[0054] The steps for synthesizing BDP molecules are as follows: (6) Synthesis of ZGGO:Cr@Man@BDP: The process of activating the above ZGGO:Cr@Man-COOH particles with 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) is as follows: 20 mg of ZGGO:Cr@Man-COOH particles were dissolved in 10 mL of 2-morpholinoethanesulfonic acid (MES) buffer (10 mM, pH=6.0, 150 mM NaCl). Then, 40 mg of EDC and 60 mg of NHS were dissolved in 2 mL and 3 mL of MES buffer, respectively. The MES buffer containing EDC was added to the above 10 mL buffer, and after ultrasonic dispersion, the MES buffer containing NHS was immediately added, shaken well, and placed in a shaker (200 rpm) at 37 °C for 30 min. After the reaction was completed, the activated ZGGO:Cr@Man-COOH particles were centrifuged and washed three times with MES buffer to obtain activated ZGGO:Cr@Man-COOH. The activated ZGGO:Cr@Man-COOH was dispersed in 10 mL of MES buffer for later use to obtain a ZGGO:Cr@Man-COOH buffer with a concentration of 2 mg / mL.

[0055] Next, 18 mg of BDP was dissolved in 1 mL of a 1:1 DMSO:MES mixture, and then added to 10 mL of the aforementioned ZGGO:Cr@Man-COOH buffer. After mixing, the mixture was placed on a shaker (200 rpm) and reacted at 37°C for 12 h. After the reaction, the mixture was washed once by centrifugation with MES buffer. The supernatant was observed to be purple, which should be due to unlinked BDP residue. The mixture was washed again with anhydrous ethanol until the supernatant was nearly transparent and colorless. After centrifugation, a purple solid was obtained, named the long-afterglow@mannose@BDP composite material, denoted as ZGGO:Cr@Man@BDP. The long-afterglow@mannose@BDP composite material was dispersed in MES buffer, and the solution was purple. A schematic diagram of the construction process of the long-afterglow@mannose@BDP composite material is shown below. Figure 2 As shown.

[0056] Example 2: Preparation method of long afterglow@mannose@BDP composite material The preparation method of the long afterglow@mannose@BDP composite material is as follows: (1) Zn 1.2 Ge 0.2 Ga 1.6 Synthesis of O4:0.5%Cr (ZGGO:Cr) long afterglow nanoparticles: Zn source, Ga source, Cr source and Ge source were added with water as solvent, the pH was adjusted to 8, and the reaction was carried out at 200℃ for 8 hours by hydrothermal method to obtain ZGGO:Cr long afterglow nanoparticles; wherein the molar ratio of Zn source, Ga source, Cr source and Ge source was 1.3:1.4:0.005:0.3.

[0057] (2) Synthesis of ZGGO:Cr-NH2: ZGGO:Cr-NH2 was obtained by amylating ZGGO:Cr long-afterglow nanoparticles with 3-aminopropyltriethoxysilane; the reaction temperature was 70℃ and the reaction time was 9h. The mass-to-volume ratio of ZGGO:Cr long-afterglow nanoparticles to 3-aminopropyltriethoxysilane was 100mg:300μL.

[0058] (3) Synthesis of ZGGO:Cr@Man: ZGGO:Cr-NH2 was dispersed in DMSO, mannose was added, and the reaction was carried out at 60℃ for 9 h. After centrifugation and washing, ZGGO:Cr@Man was obtained; wherein the mass ratio of ZGGO:Cr-NH2 to mannose was 100:20.

[0059] (4) Synthesis of ZGGO:Cr@Man-COOH: ZGGO:Cr@Man, succinic anhydride and 4-dimethylaminopyridine were reacted in DMF at 20°C for 9 hours to obtain ZGGO:Cr@Man-COOH; wherein the mass-volume ratio of ZGGO:Cr@Man, succinic anhydride and 4-dimethylaminopyridine was 1:0.8:0.8.

[0060] (5) Synthesis of BDP molecules: The amino-functionalized Aza-BODIPY molecule, abbreviated as BDP molecule, was obtained by organic synthesis.

[0061] Synthesis of compound 1c: 4-aminoacetophenone and thiophene-2-carboxaldehyde were subjected to an aldehyde-ketone condensation reaction in methanol as solvent, and the pH was adjusted to 12 to obtain the target product 1c; wherein the molar ratio of 4-aminoacetophenone to thiophene-2-carboxaldehyde was 1:1.

[0062] Synthesis of compound 1c-Boc: 1c and di-tert-butyl dicarbonate were subjected to an amino-protected chemical reaction in the presence of potassium carbonate using ethanol as a solvent to obtain the target product 1c-Boc; wherein the molar ratio of 1c, di-tert-butyl dicarbonate, and potassium carbonate was 1:2:3.

[0063] Synthesis of compound 2c-Boc: 1c-Boc and nitromethane were reacted with diethylamine in methanol as solvent to obtain the target product 2c-Boc; wherein the molar ratio of 1c-Boc, nitromethane and diethylamine was 1:4:4.

[0064] Synthesis of compound 3c-Boc: 2c-Boc was reacted with ammonium acetate in anhydrous ethanol as solvent via Nef reaction, Paal-Knorr reaction and electrophilic substitution reaction to obtain the target product 3c-Boc; wherein the molar ratio of 2c-Boc to ammonium acetate was 1:25.

[0065] Synthesis of compound 4c: Using ultra-dry dichloromethane as solvent, 3c-Boc and etherified boron trifluoride were subjected to coordination and bonding reactions in the presence of N,N-diisopropylethylamine to obtain the target product 4c, i.e., the BDP molecule; wherein the molar ratio of 3c-Boc, etherified boron trifluoride and N,N-diisopropylethylamine was 1:20:5.

[0066] (6) Synthesis of ZGGO:Cr@Man@BDP: ZGGO:Cr@Man-COOH was amidated with EDC and NHS to obtain activated ZGGO:Cr@Man-COOH. The activated ZGGO:Cr@Man-COOH was reacted with BDP in buffer at 37℃ for 10h. After centrifugation and washing, the long afterglow@mannose@BDP composite material was obtained. The mass ratio of ZGGO:Cr@Man-COOH, EDC and NHS was 1:1.5:2.5; the mass ratio of activated ZGGO:Cr@Man-COOH to BDP was 10:1; and the buffer was MES buffer.

[0067] Example 3: Preparation method of long afterglow@mannose@BDP composite material The preparation method of the long afterglow@mannose@BDP composite material is as follows: (1) Zn 1.2 Ge 0.2 Ga 1.6 Synthesis of O4:0.5%Cr (ZGGO:Cr) long afterglow nanoparticles: Using water as solvent, Zn source, Ga source, Cr source and Ge source were added, the pH was adjusted to 9, and the reaction was carried out at 240℃ for 12 h by hydrothermal method to obtain ZGGO:Cr long afterglow nanoparticles; wherein the molar ratio of Zn source, Ga source, Cr source and Ge source was 1.4:1.2:0.01:0.4.

[0068] (2) Synthesis of ZGGO:Cr-NH2: ZGGO:Cr-NH2 was obtained by modifying ZGGO:Cr long afterglow nanoparticles with 3-aminopropyltriethoxysilane by aminoation; the reaction temperature was 90℃ and the time was 15h; the mass-volume ratio of ZGGO:Cr long afterglow nanoparticles to 3-aminopropyltriethoxysilane was 100mg:500μL.

[0069] (3) Synthesis of ZGGO:Cr@Man: ZGGO:Cr-NH2 was dispersed in DMSO, mannose was added, and the reaction was carried out at 80℃ for 15 h. After centrifugation and washing, ZGGO:Cr@Man was obtained; wherein the mass ratio of ZGGO:Cr-NH2 to mannose was 100:50.

[0070] (4) Synthesis of ZGGO:Cr@Man-COOH: ZGGO:Cr@Man, succinic anhydride and 4-dimethylaminopyridine were reacted in DMF at 30℃ for 14h to obtain ZGGO:Cr@Man-COOH; wherein the mass-volume ratio of ZGGO:Cr@Man, succinic anhydride and 4-dimethylaminopyridine was 1:1.2:1.2.

[0071] (5) Synthesis of BDP molecules: The amino-functionalized Aza-BODIPY molecule, abbreviated as BDP molecule, was obtained by organic synthesis.

[0072] Synthesis of compound 1c: 4-aminoacetophenone and thiophene-2-carboxaldehyde were subjected to an aldehyde-ketone condensation reaction in methanol as solvent, and the pH was adjusted to 14 to obtain the target product 1c; wherein the molar ratio of 4-aminoacetophenone to thiophene-2-carboxaldehyde was 1.5.

[0073] Synthesis of compound 1c-Boc: 1c and di-tert-butyl dicarbonate were subjected to an amino-protected chemical reaction in the presence of potassium carbonate using ethanol as a solvent to obtain the target product 1c-Boc; wherein the molar ratio of 1c, di-tert-butyl dicarbonate, and potassium carbonate was 1:4:5.

[0074] Synthesis of compound 2c-Boc: 1c-Boc and nitromethane were reacted with diethylamine in methanol as solvent to obtain the target product 2c-Boc; wherein the molar ratio of 1c-Boc, nitromethane and diethylamine was 1:6:6.

[0075] Synthesis of compound 3c-Boc: 2c-Boc was reacted with ammonium acetate in anhydrous ethanol as solvent via Nef reaction, Paal-Knorr reaction and electrophilic substitution reaction to obtain the target product 3c-Boc; wherein the molar ratio of 2c-Boc to ammonium acetate was 1:50.

[0076] Synthesis of compound 4c: Using ultra-dry dichloromethane as solvent, 3c-Boc and etherified boron trifluoride were subjected to coordination and bonding reactions in the presence of N,N-diisopropylethylamine to obtain the target product 4c, i.e., the BDP molecule; wherein the molar ratio of 3c-Boc, etherified boron trifluoride and N,N-diisopropylethylamine was 1:50:20. (6) Synthesis of ZGGO:Cr@Man@BDP: ZGGO:Cr@Man-COOH was amidated with EDC and NHS to obtain activated ZGGO:Cr@Man-COOH. The activated ZGGO:Cr@Man-COOH was reacted with BDP in buffer at 37℃ for 14h. After centrifugation and washing, the long afterglow@mannose@BDP composite material was obtained. The mass ratio of ZGGO:Cr@Man-COOH, EDC and NHS was 1:2.5:3.5; the mass ratio of activated ZGGO:Cr@Man-COOH to BDP was 10:4.5; and the buffer was HEPES buffer.

[0077] Example 4: Preparation method of long afterglow@mannose@BDP composite material The preparation method of the long afterglow@mannose@BDP composite material is as follows: (1) Zn 1.2 Ge 0.2 Ga 1.6 Synthesis of O4:0.5%Cr (ZGGO:Cr) long afterglow nanoparticles: Using water as solvent, Zn source, Ga source, Cr source and Ge source were added, the pH was adjusted to 8.5, and the reaction was carried out at 220℃ for 10 h by hydrothermal method to obtain ZGGO:Cr long afterglow nanoparticles; wherein the molar ratio of Zn source, Ga source, Cr source and Ge source was 1.5:1:0.01:0.5.

[0078] (2) Synthesis of ZGGO:Cr-NH2: ZGGO:Cr-NH2 was obtained by amylating ZGGO:Cr long afterglow nanoparticles with 3-aminopropyltriethoxysilane; the reaction temperature was 80℃ and the time was 12h, wherein the mass-volume ratio of ZGGO:Cr long afterglow nanoparticles to 3-aminopropyltriethoxysilane was 100mg:400μL.

[0079] (3) Synthesis of ZGGO:Cr@Man: ZGGO:Cr-NH2 was dispersed in DMSO, mannose was added, and the reaction was carried out at 70℃ for 12 h. After centrifugation and washing, ZGGO:Cr@Man was obtained; wherein the mass ratio of ZGGO:Cr-NH2 to mannose was 100:30.

[0080] (4) Synthesis of ZGGO:Cr@Man-COOH: ZGGO:Cr@Man, succinic anhydride and 4-dimethylaminopyridine were reacted in DMF at 25℃ for 12h to obtain ZGGO:Cr@Man-COOH; wherein the mass-volume ratio of ZGGO:Cr@Man, succinic anhydride and 4-dimethylaminopyridine was 1:1:1.

[0081] (5) Synthesis of BDP molecules: The amino-functionalized Aza-BODIPY molecule, abbreviated as BDP molecule, was obtained by organic synthesis.

[0082] Synthesis of compound 1c: 4-aminoacetophenone and thiophene-2-carboxaldehyde were subjected to an aldehyde-ketone condensation reaction in methanol as solvent, and the pH was adjusted to 13 to obtain the target product 1c; wherein the molar ratio of 4-aminoacetophenone to thiophene-2-carboxaldehyde was 1:1.2.

[0083] Synthesis of compound 1c-Boc: 1c and di-tert-butyl dicarbonate were subjected to an amino-protected chemical reaction in the presence of potassium carbonate using ethanol as a solvent to obtain the target product 1c-Boc; wherein the molar ratio of 1c, di-tert-butyl dicarbonate, and potassium carbonate was 1:3:4.

[0084] Synthesis of compound 2c-Boc: 1c-Boc and nitromethane were reacted with diethylamine in methanol as solvent to obtain the target product 2c-Boc; wherein the molar ratio of 1c-Boc, nitromethane and diethylamine was 1:5:5.

[0085] Synthesis of compound 3c-Boc: 2c-Boc was reacted with ammonium acetate in anhydrous ethanol as solvent via Nef reaction, Paal-Knorr reaction and electrophilic substitution reaction to obtain the target product 3c-Boc; wherein the molar ratio of 2c-Boc to ammonium acetate was 1:35.

[0086] Synthesis of compound 4c: Using ultra-dry dichloromethane as solvent, 3c-Boc and etherified boron trifluoride were subjected to coordination and bonding reactions in the presence of N,N-diisopropylethylamine to obtain the target product 4c, i.e., the BDP molecule; wherein the molar ratio of 3c-Boc, etherified boron trifluoride and N,N-diisopropylethylamine was 1:30:10. (6) Synthesis of ZGGO:Cr@Man@BDP: ZGGO:Cr@Man-COOH was amidated with EDC and NHS to obtain activated ZGGO:Cr@Man-COOH. The activated ZGGO:Cr@Man-COOH was reacted with BDP in buffer at 37℃ for 12h. After centrifugation and washing, the long afterglow@mannose@BDP composite material was obtained. The mass ratio of ZGGO:Cr@Man-COOH, EDC and NHS was 1:2:3; the mass ratio of activated ZGGO:Cr@Man-COOH to BDP was 10:9; and the buffer was PBS buffer.

[0087] Experimental Example 1: Performance Characterization of Long Afterglow@Mannose@BDP Composite Material Taking Example 1 as an example, the following performance characterization experiments were conducted. The performance characterization results in Examples 2 to 4 are the same as those in Example 1, so they will not be described again.

[0088] The properties of the long afterglow nanoparticles ZGGO:Cr synthesized by hydrothermal method in Example 1 were characterized, and the results are as follows: Figure 1 As shown. First, the morphology of ZGGO:Cr was characterized by TEM, from... Figure 1 As can be seen from 'a', the morphology of ZGGO:Cr is spherical nanoparticles, and they are uniformly dispersed. Secondly, from... Figure 1 The XRD pattern of b in the image shows that the crystallinity of ZGGO:Cr is similar to that of the standard crystal. Next, the optical properties of ZGGO:Cr were characterized, such as... Figure 1 As shown in Figure c, the excitation spectrum (red curve) and emission spectrum (green curve) of ZGGO:Cr reflect the wavelength range of energy absorbed by the material. Figure 1 In the figure, d represents the relationship between the fluorescence decay time and intensity of ZGGO:Cr nanomaterials after three consecutive irradiations at a wavelength of 260 nm and a wavelength of 700 nm. The figure shows that the fluorescence decay characteristics of the material do not change with the increase of the number of irradiations, which illustrates the evolution law of the material's stability and luminescence lifetime under multiple irradiations.

[0089] Next, the ZGGO:Cr@Man@BDP sample from Example 1 was characterized by XRD, and the results are as follows: Figure 3As shown in Figure a, the position, intensity, and shape of the XRD diffraction peaks were obtained, and it was found that they are basically consistent with the XRD information of the ZGGO:Cr nanomaterials mentioned above. This proves that the subsequent recombination reaction does not change the crystal structure of the long-afterglow nanoparticles themselves or the defects inside the crystal, that is, the trap structure and depth of the long-afterglow nanoparticles. Next, from... Figure 3 The TG curve of b in Example 1 was used to initially determine whether the Man grafting was successful. Comparing the two curves, it was found that the curve of ZGGO:Cr@Man in Example 1 showed a significant mass loss starting from 200℃, which may be caused by the thermal decomposition of the successfully grafted Man. To further verify the success of the composite of Man and BDP with nanomaterials, Zeta potential and FTIR characterization were performed. Figure 3 As can be seen from 'c', the nanomaterial samples with different modifications have different Zeta potentials, further verifying the successful synthesis of the composite material. Meanwhile, the FTIR curves of ZGGO:Cr, ZGGO:Cr@Man, ZGGO:Cr@Man@BDP, and Man, BDP from Example 1 were compared, as shown below. Figure 3 As shown in d, the green line is found to be at 1600cm. -1 There is a distinct absorption peak at 3000 cm⁻¹, mainly related to the stretching vibration of the C=N double bond after the Man bond connection, while the peak at 3000 cm⁻¹ is also present. -1 ~3500cm -1 The regions also showed variations in peak position and intensity, mainly related to the NH stretching vibrations of amidated BDP molecules. These results reveal the successful surface modification of ZGGO:Cr nanomaterials.

[0090] Experimental Example 2: Photothermal Performance Analysis of Long Afterglow@Mannose@BDP Composite Material To analyze the photothermal properties of ZGGO:Cr@Man@BDP, a series of experiments related to the photothermal effect were conducted, such as... Figure 4 As shown, this study mainly explores the temperature changes and photothermal conversion efficiency of materials under different conditions.

[0091] First, to explore the optimal ratio of BDP molecules to ZGGO:Cr@Man-COOH nanocomposites, ZGGO:Cr@Man@BDP nanocomposites with a BDP:ZGGO:Cr@Man-COOH mass ratio ranging from 1:10 to 9:10 were synthesized and subjected to photothermal comparison tests under the same illumination conditions (808nm excitation light). Figure 4As can be seen from Figure a, the photothermal heating effect of ZGGO:Cr long afterglow nanomaterials without composite BDP molecules in water is negligible. Therefore, the photothermal performance of ZGGO:Cr@Man@BDP depends on the successful composite of BDP. It can also be seen that the photothermal curves of ZGGO:Cr@Man@BDP with different BDP ratios all show a trend of increasing temperature with time, but there are significant differences in the heating rate and the final temperature. Among them, the material with a BDP ratio of 9:10 finally reached a temperature of nearly 60℃, showing excellent photothermal effect.

[0092] Secondly, the photothermal properties of ZGGO:Cr@Man@BDP at different concentrations and under different light powers were characterized. For example... Figure 4 As shown in b, under the same illumination conditions, the heating rate and final temperature of solutions with higher concentrations (e.g., 1.5 mg / mL and 2 mg / mL) are significantly higher than those of solutions with lower concentrations (e.g., 0.5 mg / mL). This indicates that the concentration of the material has a significant impact on the photothermal conversion efficiency; the higher the concentration, the higher the photothermal conversion efficiency. However, if the concentration is too high, the maximum temperature exceeds the safe range, making it unsuitable for PTT (photothermal transfer). Furthermore, the temperature stability of the material can be demonstrated; all curves tend to stabilize after reaching a certain temperature, which may be due to the combined effect of the material's thermal conductivity and the environment's heat dissipation capacity.

[0093] Next, the effect of different power levels on the photothermal effect was tested using an optimal concentration of 1 mg / mL. Figure 4 As shown in Figure c, under different light irradiation powers (0.6W, 0.8W, 1W, 1.5W, and 2W), the temperature change curves of the material over time all show a trend of increasing temperature with increasing time, but the heating rate and final temperature differ significantly under different powers. Higher light irradiation power results in a higher heating rate and a higher final temperature. This indicates that light irradiation power has a significant impact on photothermal conversion efficiency; higher power leads to higher photothermal conversion efficiency. However, excessively high power can also cause irreversible high-temperature damage to the material due to excessively high material temperature.

[0094] In summary, using an 808nm exciter with a power of 1W, and selecting a sample with a BDP molecule to ZGGO:Cr@Man@BDP ratio of 9:10 and a concentration of 1 mg / mL, we conducted experiments to analyze the photothermal conversion efficiency and photothermal stability. Figure 4 As shown in d, the logarithmic change curve of the material's temperature over time reveals a clear linear relationship, indicating that the photothermal conversion process conforms to a first-order reaction kinetic model. The calculated photothermal conversion efficiency is 49.6%, demonstrating excellent photothermal performance and significant potential in biomedical fields such as photothermal therapy.Figure 4 As shown in e, under the above conditions, the temperature of the material changes periodically with time, indicating that the material has good photothermal conversion performance and temperature control capability under periodic illumination, which has important application value in fields such as biomedicine and environmental remediation. Figure 4 f in the image represents an infrared thermal image taken every minute during the heating process of ZGGO:Cr@Man@BDP in d, clearly showing the heating effect.

[0095] Experimental Example 3: Application of Long Afterglow@Mannose@BDP Composite Material in Photothermal Antibacterial Properties The photothermal antibacterial effect of ZGGO:Cr@Man@BDP was evaluated by in vitro antibacterial experiments in sterile PBS solution (10 mM) at pH 7.2. E. coli and PA The bacterial survival experiment yielded the following results: Figure 5 and Figure 6 As shown in Figure a, almost no bacteria died in the five control groups, indicating that light alone cannot kill bacteria. Furthermore, even when bacteria coexist with 1 mg / mL ZGGO:Cr@Man@BDP, bacterial death is negligible without 808 nm laser irradiation, demonstrating the biosafety of ZGGO:Cr@Man@BDP and its phototoxicity under near-infrared light excitation. Simultaneously, under light irradiation, ZGGO:Cr and Man, lacking photothermal properties, showed no inhibitory effect on bacteria, proving that the loading of BDP molecules provides the photothermal antibacterial ability for ZGGO:Cr@Man@BDP. Secondly, the effects of different concentrations of ZGGO:Cr@Man@BDP on bacteria under the same light conditions were verified. E. coli and PA The antibacterial effect was as follows: Figure 5 and Figure 6 As shown in b, under 808nm laser irradiation, the bacterial survival rate decreased sharply with increasing ZGGO:Cr@Man@BDP concentration. Specifically, ZGGO:Cr@Man@BDP (1mg / mL) combined with near-infrared laser irradiation (808nm, 1W) for five minutes killed [a significant number of bacteria]. E. coli and PA ( P. aeruginosa All exceeded 99%. Furthermore, from... Figure 5 and Figure 6 The value of 'c' in the equation shows that under irradiation with 808nm lasers of different powers, the same concentration of ZGGO:Cr@Man@BDP... E. coli and PA They exhibit varying degrees of antibacterial effect, with higher laser power resulting in better antibacterial effects. These results all indicate that the constructed ZGGO:Cr@Man@BDP possesses antibacterial properties. E. coli andPA Its photothermal antibacterial ability.

[0096] In addition, to verify the sustained antibacterial performance of ZGGO:Cr@Man@BDP, each bacterial sample was irradiated with 700nm white light for 1 hour using a xenon lamp. After irradiation, samples were plated after 0 min and again after 60 min of incubation. The results are as follows: Figure 7 As shown, the control group consisted of untreated bacterial samples, BDP samples were treated with BDP molecules, and ZGGO:Cr@Man@BDP samples were treated with ZGGO:Cr@Man@BDP. Comparing the control group and the control group, it was found that BDP molecules exhibit weak absorption in the visible light region, killing only a small portion of bacteria. In contrast, ZGGO:Cr@Man@BDP showed excellent antibacterial effects under white light irradiation, indicating that the material has a broad light absorption spectrum. Furthermore, it continued to kill some bacteria even after 1 hour of incubation. It is speculated that the long-afterglow material absorbs the energy of white light, and its continued luminescence after the light source is removed is absorbed by the BDP molecules, activating part of the photothermal effect.

[0097] Next, through bacterial SEM characterization and bacterial live / dead fluorescence staining experiments, it was further demonstrated that ZGGO:Cr@Man@BDP has the effect of... E. coli Its targeting ability and photothermal killing capacity for both types of bacteria, as shown in the results... Figure 8 As shown. Figure 8 The three images of 'a' in the text are unprocessed. E. coli , E. coli Processed by ZGGO:Cr@Man E. coli SEM images of bacteria treated with ZGGO:Cr@Man@BDP under 808nm irradiation clearly show that the ZGGO:Cr@Man nanoparticles are uniformly attached to the surface. E. coli On the bacterial cell surface, it was demonstrated that the introduction of Man enabled ZGGO:Cr@Man@BDP to target bacteria. Additionally, compared to the control group, the cells were plump and smooth. E. coli The bacterial cells show that, due to the photothermal properties of ZGGO:Cr@Man@BDP, E. coli The bacterial cell surface became wrinkled, the edges were no longer smooth, and the cytoplasm condensed into clumps, demonstrating that the photothermal properties of ZGGO:Cr@Man@BDP could kill a large number of bacteria under near-infrared light irradiation. Furthermore, bacterial viability and mortality fluorescence staining experiments, such as... Figure 8 As shown in b, compared to the untreated control group, it can be seen that... E. coli After treatment with ZGGO:Cr@Man@BDP and light, almost no green fluorescence was observed, and the bacterial survival rate was nearly 0%, demonstrating a significant bactericidal effect. Figure c shows the control group and experimental group, respectively. PAThe SEM images obtained without processing and after processing with ZGGO:Cr@Man@BDP under 808nm illumination are also compared. It can be seen that ZGGO:Cr@Man@BDP has a significant effect on… PA Photothermal killing effect.

[0098] The above results indicate that the photothermal effect and bacterial targeting ability of ZGGO:Cr@Man@BDP make it a promising candidate for photothermal antibacterial applications.

[0099] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0100] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the invention. Those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention should be determined by the appended claims.

Claims

1. A method for preparing a long afterglow@mannose@BDP composite material, characterized in that, Specifically, the steps include the following: ZGGO:Cr long afterglow nanoparticles were synthesized by hydrothermal method using Zn source, Ga source, Cr source and Ge source as raw materials. Amino-functionalized Aza-BODIPY molecules were obtained by organic synthesis. ZGGO:Cr-NH2 was obtained by amylating long afterglow nanoparticles with a silane coupling agent. ZGGO:Cr@Man was obtained by attaching mannose targeting molecules to the surface of ZGGO:Cr-NH2. The carboxyl group was covalently attached to ZGGO:Cr@Man to obtain ZGGO:Cr@Man-COOH; After amidation of ZGGO:Cr@Man-COOH, Aza-BODIPY molecules were linked to obtain a long afterglow@mannose@BDP composite material; The chemical structure of the Aza-BODIPY molecule is shown in 4c: 。 2. The long afterglow@mannose@BDP composite material according to claim 1, characterized in that, The Aza-BODIPY molecule is synthesized through the following steps: Using methanol as a solvent, 4-aminoacetophenone and thiophene-2-carboxaldehyde were subjected to an aldehyde-ketone condensation reaction, and the pH was adjusted to 12-14 to obtain the target product 1c; the molar ratio of 4-aminoacetophenone to thiophene-2-carboxaldehyde was 1:1-1.

5. Using ethanol as a solvent, 1c and di-tert-butyl dicarbonate were subjected to an amino-protected chemical reaction in the presence of potassium carbonate to obtain the target product 1c-Boc; the molar ratio of 1c, di-tert-butyl dicarbonate and potassium carbonate was 1:2~4:3~5. Using methanol as a solvent, 1c-Boc and nitromethane were subjected to a Henry reaction in the presence of diethylamine to obtain the target product 2c-Boc; the molar ratio of 1c-Boc, nitromethane and diethylamine was 1:4~6:4~6. Using anhydrous ethanol as a solvent, 2c-Boc was reacted with ammonium acetate via Nef reaction, Paal-Knorr reaction and electrophilic substitution reaction to obtain the target product 3c-Boc; the molar ratio of 2c-Boc to ammonium acetate was 1:25~50. Using ultra-dry dichloromethane as a solvent, 3c-Boc and etherified boron trifluoride were subjected to coordination and bonding reactions in the presence of N,N-diisopropylethylamine to obtain the target product 4c, namely the Aza-BODIPY molecule; the molar ratio of 3c-Boc, etherified boron trifluoride and N,N-diisopropylethylamine was 1:20~50:5~20. 。 3. The preparation method according to claim 1, characterized in that, The preparation method of the ZGGO:Cr long afterglow nanoparticles specifically includes the following steps: Using water as a solvent, Zn, Ga, Cr, and Ge sources were added, and the pH was adjusted to 8-9. The mixture was then reacted at 200-240℃ for 8-12 hours via a hydrothermal method to obtain ZGGO:Cr long afterglow nanoparticles. The molar ratio of the Zn, Ga, Cr, and Ge sources was 1.2-1.5:1-1.6:0.005-0.01:0.2-0.

5.

4. The preparation method according to claim 1, characterized in that, The silane coupling agent is 3-aminopropyltriethoxysilane; ZGGO:Cr-NH2 is obtained by amylating ZGGO:Cr long afterglow nanoparticles with the 3-aminopropyltriethoxysilane; the reaction temperature is 70℃~90℃, the time is 9h~15h, and the mass-volume ratio of ZGGO:Cr long afterglow nanoparticles to 3-aminopropyltriethoxysilane is 100mg:300μL~500μL.

5. The long afterglow@mannose@BDP composite material according to claim 1, characterized in that, The preparation method of ZGGO:Cr@Man specifically includes the following steps: ZGGO:Cr-NH2 was dispersed in DMSO, mannose was added, and the reaction was carried out at 60℃~80℃ for 9 to 15 hours. After centrifugation and washing, ZGGO:Cr@Man was obtained. The mass ratio of ZGGO:Cr-NH2 to mannose was 100:20~50.

6. The long afterglow@mannose@BDP composite material according to claim 1, characterized in that, The preparation method of ZGGO:Cr@Man-COOH specifically includes the following steps: ZGGO:Cr@Man, succinic anhydride, and 4-dimethylaminopyridine were reacted in DMF at room temperature for 9 to 14 hours to obtain ZGGO:Cr@Man-COOH; the mass ratio of ZGGO:Cr@Man, succinic anhydride, and 4-dimethylaminopyridine was 1:0.8~1.2:0.8~1.

2.

7. The long afterglow@mannose@BDP composite material according to claim 1, characterized in that, ZGGO:Cr@Man-COOH was amidated with 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide to obtain activated ZGGO:Cr@Man-COOH. The activated ZGGO:Cr@Man-COOH was then reacted with Aza-BODIPY in a buffer solution at 37°C for 10-14 hours. After centrifugation and washing, a long-afterglow@mannose@BDP composite material was obtained. The mass ratio of ZGGO:Cr@Man-COOH, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and N-hydroxysuccinimide was 1:1.5-2.5:2.5-3.

5. The mass ratio of activated ZGGO:Cr@Man-COOH to Aza-BODIPY was 10:1-9. The buffer solution was MES buffer, HEPES buffer, or PBS buffer.

8. A long afterglow@mannose@BDP composite material prepared by the preparation method according to any one of claims 1 to 7.

9. The application of the long afterglow@mannose@BDP composite material according to claim 8 in bacterial targeted photothermal therapy.

10. The application according to claim 9, characterized in that, The long afterglow@mannose@BDP composite material targets mannose-binding proteins on the surface of bacteria with mannose and kills bacteria through a photothermal effect generated by Aza-BODIPY under near-infrared light irradiation.

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