An antioxidant optically active nano-gold-loaded COF material, its preparation method and use

Abstract

The present invention provides an antioxidant optically active nano-gold-loaded COF material, its preparation method and uses, which are prepared by an in-situ reduction method using a covalent organic framework material COF BDP / CD‑S‑3 , chloroauric acid and sodium borohydride through reaction, wherein the mass ratio of the covalent organic framework material COF BDP / CD‑S‑3 , chloroauric acid and sodium borohydride is 1.0: 19.8-79.5: 2.0-7.6. Compared with the prior art, the nano-gold-loaded COF material of the present invention uses the in-situ reduction method to utilize the covalent binding effect between gold Au and atoms such as N, S, O, etc., realizing the uniform dispersion of nano-gold in the COF material. At the same time, the preparation method is simple and convenient, and has the advantages of good antioxidant activity, high photothermal conversion efficiency in the near-infrared region, good photothermal stability, etc., and has great potential application prospects in the fields of biomedicine, medical diagnosis and treatment, bioimaging, photothermal therapy, cosmetics, etc.

Description

Technical Field

[0001] The present invention relates to the technical field of nanomaterials, and particularly relates to an antioxidant optically active gold-loaded COF material, a preparation method thereof, and uses thereof. Background Art

[0002] Gold nanoparticles (AuNPs) are fine particles of gold with any dimension between 1 nm and 100 nm. They are widely used in biological sensing, chemical analysis, cancer diagnosis and treatment, antibacterial and other fields due to their low toxicity, high biocompatibility and antioxidant activity, and also have very wide applications in the cosmetics field. Reactive oxygen species (ROS) play an important role in promoting chemical reactions and metabolism. If they are present in cells and organisms in excess, they will cause oxidative stress, damage cell membranes, resulting in cell necrosis and metabolic disorders.

[0003] Covalent organic frameworks (COFs) are a kind of crystalline porous polymers, mainly composed of light mass elements such as C, H, O, N, B, etc. As an emerging porous crystalline organic polymer, compared with traditional porous materials such as molecular sieves, metal-organic frameworks and porous polymers, COFs also have advantages such as low density, regular pore structure, good thermal stability, and controllable properties, and can be widely used in photoconductive devices, adsorption, drug delivery and other fields.

[0004] Gold atoms can covalently bind to substances containing atoms such as N, S, O, etc., affecting their catalytic activity, and at the same time having the ability to scavenge reactive oxygen species, which can reduce the damage of ROS to cells. However, gold nanoparticles are prone to aggregation, resulting in an increase in particle size and a decrease in specific surface area. Therefore, in this application, an in-situ reduction method is adopted, using a covalent organic framework COF material as a carrier, and utilizing the covalent binding of gold nanoparticles to atoms such as N, S, O, etc., to uniformly disperse the gold nanoparticles, obtaining a gold-loaded COF material COF BDP / CD-S-3-Au , which has good antioxidant activity and excellent photothermal properties, and is of great significance for the research of gold-loaded materials. Summary of the Invention

[0005] In view of the above problems existing in the prior art, the purpose of the present invention is to provide an antioxidant optically active nano-gold-loaded COF material, its preparation method and use. The nano-gold-loaded COF material of the present invention uses an in-situ reduction method to utilize the covalent binding effect between gold Au and atoms such as N, S, and O, overcoming the problems such as easy aggregation of nano-gold particles resulting in an increase in particle size and a decrease in specific surface area. It combines the optical properties of covalent organic framework COF materials and nano-gold, and has the advantages of good antioxidant activity, high photothermal conversion efficiency in the near-infrared region, good photothermal stability, etc. It can achieve the ability to scavenge active oxygen species of various free radicals and reduce the damage of ROS to cells.

[0006] To achieve the purpose of this invention, the following technical solutions are adopted:

[0007] The present invention provides an antioxidant optically active nano-gold-loaded COF material, its preparation method and use. The antioxidant optically active nano-gold-loaded COF material is based on the covalent organic framework material COF BDP / CD-S-3 , chloroauric acid, and sodium borohydride are prepared by an in-situ reduction method reaction. It includes the following steps:

[0008] S1: Add the covalent organic framework material COF BDP / CD-S-3 to methanol. After the first ultrasonic treatment in the dark, add an aqueous solution of chloroauric acid. After the second ultrasonic treatment in the dark, wash with methanol and water to obtain a precipitate;

[0009] S2: Disperse the precipitate obtained in step S1 in methanol, then add a sodium borohydride methanol solution, react in the dark, and wash with methanol to obtain a black-red solid, namely the nano-gold-loaded COF material COF BDP / CD-S-3-Au ;

[0010] Preferably, the mass ratio of the covalent organic framework material COF BDP / CD-S-3 , chloroauric acid, and sodium borohydride is 1:19.8 - 79.5:2 - 7.6; preferably 1:39.6:3.8;

[0011] Preferably, the concentration of the covalent organic framework material COFBDP / CD-S-3 in methanol in step S1 is 0.3 - 0.6 g / L.

[0012] Preferably, the first ultrasonic treatment time in the dark is 30 min, and the second ultrasonic treatment time in the dark is 1 - 1.5 h; the concentration of the aqueous solution of chloroauric acid is 100 - 400 mmol / L, and the concentration of the sodium borohydride methanol solution is 20 - 400 mmol / L; the reaction time in the dark is 24 - 72 h.

[0013] The covalent organic framework material COF described in the present invention BDP / CD-S-3It is made by reacting a novel BODIPY molecule BDP, which is mainly obtained by reacting p-dimethylaminobenzaldehyde, 2,4-dimethylpyrrole, 2,3-dichloro-5,6-dicyano-p-benzoquinone, triethylamine, boron trifluoride diethyl ether, N-iodosuccinimide, and 4-aminophenylboronic acid pinacol ester, with a sulfur-containing nanocarbodots CD-S-3 product mainly obtained by reacting glutaraldehyde, thiophene, and glycerol; specifically, it includes sequentially adding the novel BODIPY molecule BDP and the sulfur-containing nanocarbodots CD-S-3 product in ethanol, then adding glacial acetic acid, stirring at room temperature for 20 - 24 h, and washing with ethanol to obtain a black-red solid, i.e., a covalent organic framework material COF BDP / CD-S-3 The mass ratio of the novel BODIPY molecule BDP to the sulfur-containing nanocarbodots CD-S-3 product is 1∶2 - 4.5.

[0014] Preferably, the sulfur-containing nanocarbodots CD-S-3 product obtained by reacting glutaraldehyde, thiophene, and glycerol is prepared by the following steps: Take glutaraldehyde, thiophene, and glycerol, ultrasonicate for 5 - 10 min, then heat to 150 °C in a reaction kettle and react for 3 h, add acetone and chloroform, centrifuge to take the upper layer liquid, and vacuum dry to obtain a brown oily sulfur-containing nanocarbodots CD-S-3 product; the volume ratio of glutaraldehyde, thiophene, and glycerol is 1∶2∶0.05 - 0.2, preferably 1∶2∶0.1.

[0015] The novel BODIPY molecule BDP in the present invention is specifically prepared by the following steps:

[0016] S11: Take 250 mL of anhydrous dichloromethane, add p-dimethylaminobenzaldehyde, sequentially add 2,4-dimethylpyrrole and a drop of trifluoroacetic acid under argon protection, stir and react in the dark at room temperature for 18 - 36 h, then add 2,3-dichloro-5,6-dicyano-p-benzoquinone, continue to stir and react in the dark at room temperature for 3 - 6 h, cool to 0 °C, then sequentially add triethylamine and boron trifluoride diethyl ether, continue to stir and react in the dark at room temperature for 6 - 12 h, wash the obtained reaction solution with water, dry with anhydrous magnesium sulfate, then distill off the solvent under reduced pressure, and separate by silica gel column chromatography with 300 - 400 mesh to obtain an orange solid product BODIPY-0;

[0017] S12: Take 50 mL of anhydrous dichloromethane, sequentially add the product BODIPY-0 obtained in step S11 and N-iodosuccinimide, stir in the dark at room temperature for 4.5 - 5.5 h, distill off the solvent under reduced pressure, and separate by silica gel column chromatography with 300 - 400 mesh to obtain a red solid product BODIPY-I;

[0018] S13: Take 30 mL of 1,4-dioxane, and successively add the product BODIPY-I from step S12, 4-aminophenylboronic acid pinacol ester, tetrakis(triphenylphosphine)palladium(0), and an aqueous solution of potassium carbonate at 1 mol / L, and stir evenly. Heat to 110 °C under argon protection and reflux for 6 - 18 h. Distill off the solvent under reduced pressure, and separate by silica gel column chromatography with 300 - 400 mesh to obtain a purple solid product, the novel BODIPY molecule, i.e., BDP.

[0019] Preferably, in step S11, the mass ratio of p-dimethylaminobenzaldehyde, 2,4-dimethylpyrrole, 2,3-dichloro-5,6-dicyano-p-benzoquinone, triethylamine, and boron trifluoride diethyl ether is 1:0.8 - 1.2:1.2:6.5 - 6.6:10, preferably 1:0.9:1.2:6.6:10; the concentration of p-dimethylaminobenzaldehyde in anhydrous dichloromethane is 2.4 - 9.6 g / L.

[0020] Preferably, in step S12, the mass ratio of the product BODIPY-0 to N-iodosuccinimide is 1:1 - 2.25, preferably 1:1.3; the concentration of the product BODIPY-0 in anhydrous dichloromethane is 2 - 4.8 g / L.

[0021] Preferably, in step S13, the mass ratio of the product BODIPY-I, 4-aminophenylboronic acid pinacol ester, tetrakis(triphenylphosphine)palladium(0), and potassium carbonate is 1:1.35:0.45:2.1; the concentration of the product BODIPY-I in 1,4-dioxane is 2.4 - 8.4 g / L.

[0022] An antioxidant optically active nano-gold-loaded COF material provided by the present invention is prepared by using the preparation method of the aforementioned antioxidant optically active nano-gold-loaded COF material.

[0023] A use of an antioxidant optically active nano-gold-loaded COF material provided by the present invention, wherein the antioxidant optically active nano-gold-loaded COF material is used for photothermal therapy in biomedicine.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] (1) The nano-gold-loaded COF material of the present invention uses an in-situ reduction method to utilize the covalent binding between gold Au and atoms such as N, S, and O, and load nano-gold on the COF BDP / CD-S-3 to obtain the nano-gold-loaded COF material COF BDP / CD-S-3-Au , achieving uniform dispersion of nano-gold in the COF material. At the same time, the preparation method is simple and convenient, overcoming problems such as easy aggregation of nano-gold particles resulting in an increase in particle size and a decrease in specific surface area.

[0026] (2) In the present invention, the nano-gold-loaded COF material (COFBDP / CD-S-3-Au )Combining the optical properties of covalent organic framework (COF) materials and nano-gold, it has advantages such as good antioxidant activity, high photothermal conversion efficiency in the near-infrared region, and good photothermal stability. Its good antioxidant performance can achieve the ability to scavenge active oxygen species of various free radicals, reduce the damage of ROS to cells, and has great potential application prospects in the fields of biomedicine, medical diagnosis and treatment, bioimaging, photothermal therapy, cosmetics, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 Scanning electron micrograph of the COF of Example 1 BDP / CD-S-3-Au ;

[0028] Figure 2 Transmission electron micrograph of the COF B of Example 1 DP / CD-S-3-Au ;

[0029] Figure 3 Graph showing the relationship between the temperature of the COF of Example 1 BDP / CD-S-3-Au and the irradiation time of 808 nm laser;

[0030] Figure 4 Graph showing the relationship between the DPPH radical scavenging rate and the concentration of the COF of Example 2 BDP / CD-S-3-Au-3 ;

[0031] Figure 5 XRD pattern of the COF of Example 1 BDP / CD-S-3-Au ; DETAILED DESCRIPTION OF THE EMBODIMENTS

[0032] The technical solutions of the present invention will be further described below in conjunction with the drawings and through specific embodiments.

[0033] In order to make the purpose, technical solutions and advantages of the present invention clearer and more understandable, the following will be described in detail in conjunction with the embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention and are not used to limit the present invention in any way. Those skilled in the art can make various changes and modifications to the invention of the present application according to the disclosed content, and they should also fall within the scope of protection required by the present application.

[0034] Example 1

[0035] An antioxidant optically active nano-gold-loaded COF material provided in this example, its preparation method and use, the preparation of the nano-gold-loaded COF material COF BDP / CD-S-3-Au comprises the following steps:

[0036] 1) Synthesis of the novel BODIPY molecule BDP

[0037] S11. Take 250 mL of anhydrous dichloromethane, add 1.0 g of p-dimethylaminobenzaldehyde, protect it by passing argon gas, then successively add 2 mL of 2,4-dimethylpyrrole and a drop of trifluoroacetic acid, stir the reaction at room temperature in the dark under argon gas for 24 h, then add 2.4 g of 2,3-dichloro-5,6-dicyano-p-benzoquinone to the reaction system, stir the reaction at room temperature for 4 h, cool it to 0 °C, successively add 18 mL of triethylamine and 18 mL of boron trifluoride diethyl etherate, stir the reaction at room temperature for 8 h, wash the reaction solution with water 3 times, dry it with anhydrous magnesium sulfate, distill off the solvent under reduced pressure, and separate it by column chromatography to obtain an orange solid product, namely BODIPY-0, for standby.

[0038] S12. Take 50 mL of anhydrous dichloromethane, add 0.2 g of the product BODIPY-0, then add 0.26 g of N-iodosuccinimide, stir it in the dark at room temperature for 5 h, distill off the solvent under reduced pressure, and separate it by column chromatography to obtain a red solid product, namely BODIPY-I, for standby.

[0039] S13. Take 30 mL of 1,4-dioxane, add 0.2 g of the product BODIPY-I, then add 0.27 g of 4-aminophenylboronic acid pinacol ester, 0.089 g of tetrakis(triphenylphosphine)palladium(0), and 3 mL of 1 mol / L aqueous potassium carbonate solution, stir evenly, heat it to 110 °C and reflux the reaction for 12 h under argon gas protection, distill off the solvent under reduced pressure, and separate it by column chromatography to obtain a purple solid product, namely the novel BODIPY molecule BDP.

[0040] 2) Synthesis of sulfur-containing carbon nanodots CD-S-3

[0041] First, take 300 μL of 50% glutaraldehyde, 600 μL of thiophene, and 30 μL of glycerol, ultrasonicate for 5 min, heat it to 150 °C in a stainless steel autoclave and react for 3 h, then add acetone and chloroform and centrifuge 3 times to take the upper layer liquid, and dry it under vacuum to obtain a brown oily product, namely sulfur-containing carbon nanodots CD-S-3.

[0042] 3) Synthesis of covalent organic framework material COF BDP / CD-S-3

[0043] First, take 18 mL of ethanol, successively add 8 g of the novel BODIPY molecule BDP and 20 g of sulfur-containing carbon nanodots CD-S-3, then add 50 μL of glacial acetic acid, stir at room temperature for 24 h, wash it with ethanol three times to obtain a black-red solid product, namely covalent organic framework material COF BDP / CD-S-3 .

[0044] 4) Preparation of COF material loaded with gold nanoparticles BDP / CD-S-3-Au

[0045] First, take 10 mL of methanol, add 10 mg of covalent organic framework material COF BDP / CD-S-3, After ultrasonic treatment for 30 min in the dark, 5 mL of 200 mM chloroauric acid aqueous solution was added, and ultrasonic treatment was carried out for 1 h in the dark. Then, it was washed twice with methanol and water. Subsequently, the obtained precipitate was dispersed in 10 mL of methanol, and 5 mL of methanol solution of 200 mM sodium borohydride was added. The reaction was carried out in the dark for 48 h and then washed three times with methanol to obtain a black-red solid product, namely the nano-gold-loaded COF material COF BDP / CD-S-3-Au . It is denoted as COF BDP / CD-S-3-Au-1 .

[0046] The nano-gold-loaded COF material COF obtained in this example was characterized by scanning electron microscopy BDP / CD-S-3-Au . The obtained scanning electron micrograph is as shown in Figure 1 ;

[0047] The nano-gold-loaded COF material COF obtained in this example was characterized by transmission electron microscopy BDP / CD-S-3-Au . The obtained transmission electron micrograph is as shown in Figure 2 .

[0048] The nano-gold-loaded COF material COF obtained in this example BDP / CD-S-3-Au was measured for its photothermal performance

[0049] COF was uniformly dispersed in N,N-dimethylformamide to obtain a 0.5-1 mg / mL COF BDP / CD-S-3-Au dispersion. After irradiation with an 808 nm laser for different times, the temperatures of the COF BDP / CD-S-3-Au dispersion at 0, 2, 4, 6, 8, 10, and 12 min were measured respectively to obtain the relationship between the temperature of COF BDP / CD-S-3-Au and the irradiation time of the 808 nm laser, as shown in BDP / CD-S-3-Au ; Figure 3 .

[0050] The nano-gold-loaded COF material COF obtained in this example BDP / CD-S-3-Au was measured for its antioxidant performance

[0051] COF was uniformly dispersed in ethanol to obtain COF dispersions with concentrations of 20, 80, 160, 240, 320, and 400 μg / mL respectively BDP / CD-S-3-Au . Then, an equal volume of 0.1 mmol / L 1,1-diphenyl-2-picrylhydrazyl (DPPH) ethanol solution was added, and the reaction was carried out at room temperature in the dark for 30 min to obtain sample systems with COF BDP / CD-S-3-Au concentrations of 10, 40, 80, 120, 160, and 200 respectively. The absorbance A of each sample system at 517 nm was measured BDP / CD-S-3-Au . Substituting it into the formula R = [1 - (A i - A i - A j) / A0]×100%, where R is the clearance rate, %; A0 is the absorbance value of the DPPH solution plus an equal volume of ethanol; Ai is the absorbance value of each sample system; A j is the absorbance value of each sample system after replacing the DPPH solution with ethanol, and the relationship between the DPPH radical scavenging rate of the COF BDP / CD-S-3-Au dispersion liquid and the sample concentration is obtained, as Figure 4 shown.

[0052] As Figure 5 shown, the XRD pattern of COF BDP / CD-S-3-Au shows that both COF BDP / CD-S-3 and COF BDP / CD-S-3-Au have characteristic peaks at about 2θ = 4.1°, indicating that a certain degree of crystallinity of COF exists in both of these two materials.

[0053] 2. The sample COFBDP / CD-S-3-Au has characteristic peaks of Au at 2θ of 38.2°, 44.3°, 64.6°, and 77.6°, and the corresponding crystal plane indices are (111), (200), (220), and (311) respectively, indicating that nano-gold particles are successfully loaded on the COF, and the crystal plane index of the nano-gold is mainly (111).

[0054] An antioxidant optically active nano-gold-loaded COF material provided by this embodiment is prepared by using the preparation method of the aforementioned antioxidant optically active nano-gold-loaded COF material; the use of this antioxidant optically active nano-gold-loaded COF material is for photothermal therapy in biomedicine, etc.

[0055] Example 2

[0056] An antioxidant optically active nano-gold-loaded COF material, its preparation method, and its use provided by this embodiment are basically the same as those in Example 1, except that:

[0057] Same as the preparation method of COF BDP / CD-S-3-Au in Example 1, except that the 200 mM chloroauric acid aqueous solution is replaced with a 100 mM chloroauric acid aqueous solution and a 400 mM chloroauric acid aqueous solution respectively to prepare the nano-gold-loaded COF materials, denoted as COF BDP / CD-S-3-Au-2 and COF BDP / CD-S-3-Au-3 .

[0058] Example 3

[0059] An antioxidant optically active nano-gold-loaded COF material, its preparation method, and its use provided by this embodiment are basically the same as those in Example 1, except that:

[0060] Same as the preparation method of COF BDP / CD-S-3-AuThe preparation method is different in that the methanol solution of 200 mM sodium borohydride is replaced with an aqueous solution of 200 mM ascorbic acid, and the nano-gold-loaded COF material is prepared, denoted as COF BDP / CD-S-3-Au-4 。

[0061] Example 4

[0062] An antioxidant optically active nano-gold-loaded COF material provided in this example, its preparation method and use are basically the same as those in Example 1, except that:

[0063] Same as COF in Example 1 BDP / CD-S-3-Au The preparation method is different in that the aqueous solution of 200 mM chloroauric acid is replaced with an aqueous solution of 200 mM silver nitrate to obtain COF BDP / CD-S-3-Ag 。

[0064] Example 5

[0065] An antioxidant optically active nano-gold-loaded COF material provided in this example, its preparation method and use are basically the same as those in Example 1, same as COF in Example 1 BDP / CD-S-3-Au The preparation method is different in that:

[0066] 1) Synthesis of novel BODIPY molecule BDP:

[0067] In step S11, the mass ratio of p-dimethylaminobenzaldehyde, 2,4-dimethylpyrrole, 2,3-dichloro-5,6-dicyano-p-benzoquinone, triethylamine, and boron trifluoride diethyl ether is 1:1.1:1.2:6.6:10; the concentration of p-dimethylaminobenzaldehyde in anhydrous dichloromethane is 2.4 g / L.

[0068] In step S12, the mass ratio of product BODIPY-0 to N-iodosuccinimide is 1:1; the concentration of product BODIPY-0 in anhydrous dichloromethane is 4.8 g / L.

[0069] In step S13, the mass ratio of product BODIPY-I, 4-aminophenylboronic acid pinacol ester, 4-triphenylphosphine palladium, and potassium carbonate is 1:1.35:0.45:2.1; the concentration of product BODIPY-I in 1,4-dioxane is 2.4 g / L.

[0070] 2) Synthesis of sulfur-containing nanocarbons CD-S-3: The volume ratio of glutaraldehyde, thiophene, and glycerol is 1:2:0.05.

[0071] 3) Synthesis of covalent organic framework material COF BDP / CD-S-3 of covalent organic framework material COF BDP / CD-S-3 Stir and react at room temperature for 24 h; the mass ratio of the novel BODIPY molecule BDP to the product sulfur-containing nanocarbons CD-S-3 is 1:3.3.

[0072] 4) Preparation of gold nanoparticle-loaded COF material COF BDP / CD-S-3-Au The preparation of the covalent organic framework material COF BDP / CD-S-3 The mass ratio of the covalent organic framework material COF BDP / CD-S-3 , chloroauric acid, and sodium borohydride is 1:19.8:7.6; the concentration of the covalent organic framework material COF

[0073] Example 6

[0074] An antioxidant optically active gold nanoparticle-loaded COF material and its preparation method and use provided in this example are basically the same as those in Example 1. The preparation method of COF BDP / CD-S-3-Au in Example 1, the difference is that:

[0075] 2) Synthesis of novel BODIPY molecule BDP:

[0076] In step S11, the mass ratio of p-dimethylaminobenzaldehyde, 2,4-dimethylpyrrole, 2,3-dichloro-5,6-dicyano-p-benzoquinone, triethylamine, and boron trifluoride diethyl ether is 1:0.9:1.2:6.5:10; the concentration of p-dimethylaminobenzaldehyde in anhydrous dichloromethane is 9.6 g / L.

[0077] In step S12, the mass ratio of product BODIPY-0 to N-iodosuccinimide is 1:2.25; the concentration of product BODIPY-0 in anhydrous dichloromethane is 2 g / L.

[0078] In step S13, the mass ratio of product BODIPY-I, 4-aminophenylboronic acid pinacol ester, 4-triphenylphosphine palladium, and potassium carbonate is 1:1.35:0.45:2.1; the concentration of product BODIPY-I in 1,4-dioxane is 4 g / L.

[0079] 2) Synthesis of sulfur-containing carbon dots CD-S-3: The volume ratio of glutaraldehyde, thiophene, and glycerol is 1:2:0.2.

[0080] 3) Synthesis of covalent organic framework material COF BDP / CD-S-3 The synthesis of the covalent organic framework material COF BDP / CD-S-3 Stir and react at room temperature for 20 h; the mass ratio of the novel BODIPY molecule BDP and the product sulfur-containing carbon dots CD-S-3 is 1:3.3.

[0081] 4) Preparation of gold nanoparticle-loaded COF material COF BDP / CD-S-3-Au The preparation of the covalent organic framework material COFBDP / CD-S-3 The mass ratio of chloroauric acid to sodium borohydride is 1:70:5; the concentration of covalent organic framework material COF BDP / CD-S-3 in methanol is 0.6 g / L. The second ultrasonic time in the dark is 1 h; the concentration of chloroauric acid aqueous solution is 100 mmol / L, and the concentration of sodium borohydride methanol solution is 20 mmol / L; the reaction time in the dark is 24 h.

[0082] Example 7

[0083] An antioxidant optically active nano-gold-loaded COF material provided in this example, its preparation method and use are basically the same as those in Example 1, and the preparation method of COF BDP / CD-S-3-Au in Example 1, the difference is that:

[0084] 3) Synthesis of novel BODIPY molecule BDP:

[0085] In step S11, the mass ratio of p-dimethylaminobenzaldehyde, 2,4-dimethylpyrrole, 2,3-dichloro-5,6-dicyano-p-benzoquinone, triethylamine, and boron trifluoride diethyl ether is 1:0.8:1.2:6.5:10; the concentration of p-dimethylaminobenzaldehyde in anhydrous dichloromethane is 2.4 g / L.

[0086] In step S12, the mass ratio of product BODIPY-0 to N-iodosuccinimide is 1:2; the concentration of product BODIPY-0 in anhydrous dichloromethane is 4.8 g / L.

[0087] In step S13, the mass ratio of product BODIPY-I, 4-aminophenylboronic acid pinacol ester, 4-triphenylphosphine palladium, and potassium carbonate is 1:1.35:0.45:2.1; the concentration of product BODIPY-I in 1,4-dioxane is 8.4 g / L.

[0088] 2) Synthesis of sulfur-containing nanocarbon dots CD-S-3: The volume ratio of glutaraldehyde, thiophene, and glycerol is 1:2:0.05.

[0089] 3) Synthesis of covalent organic framework material COF BDP / CD-S-3 : The covalent organic framework material COF BDP / CD-S-3 is stirred at room temperature for reaction for 24 h; the mass ratio of the novel BODIPY molecule BDP and the product sulfur-containing nanocarbon dots CD-S-3 is 1:2.

[0090] 4) Preparation of nano-gold-loaded COF material COF BDP / CD-S-3-Au : The mass ratio of the covalent organic framework material COF BDP / CD-S-3 to chloroauric acid and sodium borohydride is 1:79.5:3; the covalent organic framework material COF BDP / CD-S-3The concentration in methanol is 0.5 g / L. The second time of ultrasonic treatment in the dark is 1.2 h; the concentration of chloroauric acid aqueous solution is 200 mmol / L, and the concentration of sodium borohydride methanol solution is 120 mmol / L; the reaction time in the dark is 36 h.

[0091] Example 8

[0092] An antioxidant optically active nano-gold-loaded COF material provided in this example, its preparation method and use are basically the same as those in Example 1, and the preparation method of COF BDP / CD-S-3-Au in Example 1, the difference is that:

[0093] 4) Synthesis of novel BODIPY molecule BDP:

[0094] In step S11, the mass ratio of p-dimethylaminobenzaldehyde, 2,4-dimethylpyrrole, 2,3-dichloro-5,6-dicyano-p-benzoquinone, triethylamine, and boron trifluoride diethyl ether is 1:1:1.2:6.6:10; the concentration of p-dimethylaminobenzaldehyde in anhydrous dichloromethane is 7 g / L.

[0095] In step S12, the mass ratio of product BODIPY-0 to N-iodosuccinimide is 1.8; the concentration of product BODIPY-0 in anhydrous dichloromethane is 3 g / L.

[0096] In step S13, the mass ratio of product BODIPY-I, 4-aminophenylboronic acid pinacol ester, 4-triphenylphosphine palladium, and potassium carbonate is 1:1.35:0.45:2.1; the concentration of product BODIPY-I in 1,4-dioxane is 5 g / L.

[0097] 2) Synthesis of sulfur-containing carbon nanodots CD-S-3: The volume ratio of glutaraldehyde, thiophene, and glycerol is 1:2:0.1.

[0098] 3) Synthesis of covalent organic framework material COF BDP / CD-S-3 : The covalent organic framework material COF BDP / CD-S-3 is stirred at room temperature for 22 h; the mass ratio of the novel BODIPY molecule BDP and the product sulfur-containing carbon nanodots CD-S-3 is 1:3.

[0099] 4) Preparation of nano-gold-loaded COF material COF BDP / CD-S-3-Au : The mass ratio of the covalent organic framework material COF BDP / CD-S-3 , chloroauric acid, and sodium borohydride is 1:50:4; the concentration of the covalent organic framework material COF BDP / CD-S-3 in methanol is 0.4 g / L. The second time of ultrasonic treatment in the dark is 1 h; the concentration of chloroauric acid aqueous solution is 300 mmol / L, and the concentration of sodium borohydride methanol solution is 100 mmol / L; the reaction time in the dark is 72 h.

[0100] Based on the disclosure and teachings of the above specification, those skilled in the art to which the present invention pertains can also make changes and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and changes to the invention should also fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing an antioxidant optically active nano-gold-loaded COF material, characterized in that, It is prepared by an in-situ reduction method using a covalent organic framework material, chloroauric acid, and sodium borohydride, and includes the following steps: S1: Add the covalent organic framework material to methanol. After the first ultrasonic treatment in the dark, add an aqueous solution of chloroauric acid. After the second ultrasonic treatment in the dark, wash with methanol and water to obtain a precipitate; S2: Disperse the precipitate obtained in step S1 in methanol, then add a sodium borohydride methanol solution, react in the dark, and wash with methanol to obtain a black-red solid, namely the nano-gold-loaded COF material; The mass ratio of the covalent organic framework material, chloroauric acid, and sodium borohydride is 1: 19.8 - 79.5: 2 - 7.6; In step S1, the concentration of the covalent organic framework material in methanol is 0.3 - 0.6 g / L; The covalent organic framework material is mainly made by reacting a novel BODIPY molecule BDP, which is obtained by reacting p-dimethylaminobenzaldehyde, 2,4-dimethylpyrrole, 2,3-dichloro-5,6-dicyano-p-benzoquinone, triethylamine, boron trifluoride diethyl etherate, N-iodosuccinimide, and 4-aminophenylboronic acid pinacol ester, and a sulfur-containing carbon dot CD-S-3, which is obtained by reacting glutaraldehyde, thiophene, and glycerol. Specifically, it includes adding the novel BODIPY molecule BDP and the sulfur-containing carbon dot CD-S-3 product to ethanol in sequence, then adding glacial acetic acid, and stirring at room temperature for 20 - 24 h. After washing with ethanol, a black-red solid, namely the covalent organic framework material, is obtained. The mass ratio of the novel BODIPY molecule BDP and the sulfur-containing carbon dot CD-S-3 product is 1: 2 - 4.5; The sulfur-containing carbon dot CD-S-3 product obtained by reacting glutaraldehyde, thiophene, and glycerol is specifically prepared as follows: Take glutaraldehyde, thiophene, and glycerol, ultrasonicate for 5 - 10 min, then heat to 150 °C in a reaction kettle and react for 3 h. Add acetone and chloroform, centrifuge, take the upper layer liquid, and vacuum dry to obtain a brown oily sulfur-containing carbon dot CD-S-3 product. The volume ratio of glutaraldehyde, thiophene, and glycerol is 1: 2: 0.05 - 0.2; The novel BODIPY molecule, namely BDP, is specifically prepared as follows: S11: Take 250 mL of anhydrous dichloromethane, add p-dimethylaminobenzaldehyde. Under argon protection, sequentially add 2,4-dimethylpyrrole and a drop of trifluoroacetic acid, then stir and react at room temperature in the dark for 18 - 36 h. Then add 2,3-dichloro-5,6-dicyano-p-benzoquinone, and continue to stir and react at room temperature in the dark for 3 - 6 h. After cooling to 0 °C, sequentially add triethylamine and boron trifluoride diethyl etherate, and continue to stir and react at room temperature in the dark for 6 - 12 h. The obtained reaction solution is washed with water, dried with anhydrous magnesium sulfate, then the solvent is removed by reduced pressure distillation, and separated by silica gel column chromatography with 300 - 400 mesh to obtain an orange solid product BODIPY-0; S12: Take 50 mL of anhydrous dichloromethane, and successively add the product BODIPY-0 from step S11 and N-iodosuccinimide. Stir magnetically at room temperature in the dark for 4.5 - 5.5 h. Distill off the solvent under reduced pressure, and separate by silica gel column chromatography with 300 - 400 mesh to obtain the red solid product BODIPY-I; S13: Take 30 mL of 1,4-dioxane, and successively add the product BODIPY-I from step S12, 4-aminophenylboronic acid pinacol ester, tetrakis(triphenylphosphine)palladium(0), and 1 mol / L aqueous potassium carbonate solution, and stir evenly. Heat to reflux at 110 °C for 6 - 18 h under argon protection. Distill off the solvent under reduced pressure, and separate by silica gel column chromatography with 300 - 400 mesh to obtain the purple solid product, the novel BODIPY molecule, i.e., BDP; In the said step S11, the mass ratio of p-dimethylaminobenzaldehyde, 2,4-dimethylpyrrole, 2,3-dichloro-5,6-dicyano-p-benzoquinone, triethylamine, and boron trifluoride diethyl etherate is 1:0.8 - 1.2:1.2:6.5 - 6.6:10; the concentration of p-dimethylaminobenzaldehyde in anhydrous dichloromethane is 2.4 - 9.6 g / L; In the said step S12, the mass ratio of the product BODIPY-0 to N-iodosuccinimide is 1:1 - 2.25; the concentration of the product BODIPY-0 in anhydrous dichloromethane is 2 - 4.8 g / L; In the said step S13, the mass ratio of the product BODIPY-I, 4-aminophenylboronic acid pinacol ester, tetrakis(triphenylphosphine)palladium(0), and potassium carbonate is 1:1.35:0.45:2.1; the concentration of the product BODIPY-I in 1,4-dioxane is 2.4 - 8.4 g / L.

2. The preparation method of the antioxidant optically active nano-gold-loaded COF material according to claim 1, characterized in that, The first time of ultrasonic treatment in the dark is 30 min, and the second time is 1 - 1.5 h; the concentration of the chloroauric acid aqueous solution is 100 - 400 mmol / L, and the concentration of the sodium borohydride methanol solution is 20 - 400 mmol / L; the reaction time in the dark is 24 - 72 h.

3. An antioxidant optically active nano-gold-loaded COF material, characterized in that, This oxidized optically active nano-gold-loaded COF material is prepared by the preparation method of the antioxidant optically active nano-gold-loaded COF material according to any one of claims 1 - 2.

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