CN114470205A - Oxidation-resistant optical-activity nanogold-loaded COF material and preparation method and application thereof - Google Patents

Oxidation-resistant optical-activity nanogold-loaded COF material and preparation method and application thereof Download PDF

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CN114470205A
CN114470205A CN202210144737.5A CN202210144737A CN114470205A CN 114470205 A CN114470205 A CN 114470205A CN 202210144737 A CN202210144737 A CN 202210144737A CN 114470205 A CN114470205 A CN 114470205A
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cof
bdp
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刘意
万雅婷
李丹
刘勇
王静
黄柳
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Zhongshan Meiyuan Cosmetics Co ltd
Guangdong Pharmaceutical University
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Guangdong Pharmaceutical University
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Abstract

The invention provides an antioxidant optical active nano-gold-loaded COF material, a preparation method and application thereof, and is based on a covalent organic framework material COFBDP/CD‑S‑3The chloroauric acid and the sodium borohydride are prepared by the reaction of an in-situ reduction method, wherein the covalent organic framework material COFBDP/CD‑S‑3The mass ratio of the chloroauric acid to the sodium borohydride is 1.0: 19.8-79.5: 2.0-7.6. Compared with the prior art, the nano-gold-loaded COF material adopts an in-situ reduction method to realize the uniform dispersion of nano-gold in the COF material by utilizing the covalent bonding effect between gold Au and atoms of N, S, O and the like, and meanwhile, the preparation method is simple and convenient, has good antioxidant activity and higher near-infrared region photo-thermal conversionThe method has the advantages of high chemical efficiency, good photo-thermal stability and the like, and has huge potential application prospect in the fields of biomedicine, medical diagnosis and treatment, biological imaging, photo-thermal treatment, cosmetics and the like.

Description

Oxidation-resistant optical-activity nanogold-loaded COF material and preparation method and application thereof
Technical Field
The invention relates to the technical field of nano materials, in particular to an antioxidant optical activity nano gold-loaded COF material and a preparation method and application thereof.
Background
Gold nanoparticles (AuNPs) are fine particles of gold with any dimension between 1nm and 100nm, and are widely applied to the fields of biosensing, chemical analysis, cancer diagnosis and treatment, antibiosis and the like and cosmetics due to low toxicity, high biocompatibility and antioxidant activity. Reactive Oxygen Species (ROS) play an important role in promoting chemical reactions and metabolism, and if present in excess in cells and organisms, they cause oxidative stress and damage cell membranes, resulting in cell necrosis and metabolic disorders.
Covalent organic framework materials (COFs) are crystalline porous polymers and mainly comprise light elements such as C, H, O, N, B, and a covalent organic framework material (COF) is a novel porous crystal organic polymer.
The gold atom can be covalently bonded with substances containing N, S, O and other atoms to influence the catalytic activity of the gold atom, and has the capability of scavenging active oxygen, so that the damage of ROS to cells can be reduced, and the nano gold particles are easy to aggregate to increase the particle size and reduce the specific surface area of the particles. Therefore, the method adopts an in-situ reduction method, takes a covalent organic framework COF material as a carrier, utilizes covalent bonding of nano-gold and atoms of N, S, O and the like to uniformly disperse nano-gold particles, and obtains the COF material carrying the nano-gold COF materialBDP/CD-S-3-AuHas good antioxidant activity and excellent photo-thermal property, and is suitable for carrierThe research on the rice-gold material has important significance.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide an antioxidant optically active nanogold-loaded COF material, and a preparation method and a use thereof. The nano-gold-loaded COF material disclosed by the invention overcomes the problems of particle size increase, specific surface area reduction and the like caused by easy aggregation of nano-gold particles by utilizing the covalent bonding effect between gold Au and atoms such as N, S, O and the like by adopting an in-situ reduction method, integrates the optical characteristics of a covalent organic framework COF material and nano-gold, has the advantages of good antioxidant activity, higher near-infrared region photo-thermal conversion efficiency, good photo-thermal stability and the like, can realize the capability of removing active oxygen from various free radicals, and can reduce the damage of ROS to cells.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an antioxidant optical activity nanogold-loaded COF material, a preparation method and application thereof, wherein the antioxidant optical activity nanogold-loaded COF material is based on a covalent organic framework material COFBDP/CD-S-3The chloroauric acid and the sodium borohydride are prepared by the reaction of an in-situ reduction method. Which comprises the following steps:
s1: addition of covalent organic framework materials COF in methanolBDP/CD-S-3Adding chloroauric acid aqueous solution after the first light-proof ultrasonic treatment, washing with methanol and water after the second light-proof ultrasonic treatment to obtain a precipitate;
s2: dispersing the precipitate obtained in the step S1 in methanol, adding sodium borohydride methanol solution, reacting in the dark, washing with methanol to obtain black red solid, namely the COF material carrying the nanogold COF materialBDP/CD-S-3-Au；
Preferably, said covalent organic framework material COFBDP/CD-S-3The mass ratio of the chloroauric acid to the sodium borohydride is 1: 19.8-79.5: 2-7.6; preferably 1: 39.6: 3.8;
preferably, the concentration of the covalent organic framework material COFBDP/CD-S-3 in the methanol in the step S1 is 0.3-0.6 g/L.
Preferably, the first light-shielding ultrasonic time is 30min, and the second light-shielding ultrasonic 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 is 24-72 h without light.
The covalent organic framework materials COF of the inventionBDP/CD-S-3The compound is mainly prepared by the reaction of a novel BODIPY molecule BDP which is obtained by the reaction of dimethylaminobenzaldehyde, 2, 4-dimethylpyrrole, 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, triethylamine, boron trifluoride diethyl ether, N-iodosuccinimide and 4-aminobenzene boronic acid pinacol ester and a product which is obtained by the reaction of glutaraldehyde, thiophene and glycerol and contains a sulfur nano carbon point CD-S-3; sequentially adding the novel BODIPY molecule BDP and the product sulfur-containing nano carbon dot CD-S-3 into ethanol, then adding glacial acetic acid, stirring at room temperature for reacting for 20-24 h, and washing with ethanol to obtain black red solid, namely covalent organic framework material COFBDP/CD-S-3(ii) a The mass ratio of the BDP and the product of the CD-S-3 containing the sulfur nano carbon dots is 1: 2-4.5.
Preferably, the sulfur-containing nanocarbon point CD-S-3 product obtained by reacting glutaraldehyde, thiophene and glycerol specifically comprises the following steps: taking glutaraldehyde, thiophene and glycerol, carrying out ultrasonic treatment for 5-10 min, heating to 150 ℃ in a reaction kettle, reacting for 3h, adding acetone and chloroform, centrifuging to obtain an upper layer liquid, and carrying out vacuum drying to obtain a brown oily product, namely the sulfur-containing nano carbon dot CD-S-3; the volume ratio of the glutaraldehyde to the thiophene to the glycerol is 1: 2: 0.05-0.2, preferably 1: 2: 0.1.
The novel BODIPY molecule, namely BDP, is prepared by the following steps:
s11: adding p-dimethylaminobenzaldehyde into 250mL of anhydrous dichloromethane, sequentially adding 2, 4-dimethylpyrrole and a drop of trifluoroacetic acid under the protection of argon, stirring and reacting at the dark room temperature for 18-36 h, then adding 2, 3-dichloro-5, 6-dicyan p-benzoquinone, continuing to stir and react at the dark room temperature for 3-6 h, cooling to 0 ℃, sequentially adding triethylamine and boron trifluoride diethyl etherate, continuing to stir and react at the dark room temperature for 6-12 h, washing the obtained reaction solution with water, drying anhydrous magnesium sulfate, then distilling under reduced pressure to remove the solvent, and separating by using a 300-400-mesh silica gel column chromatography to obtain an orange solid product BODIPY-0;
s12: taking 50mL of anhydrous dichloromethane, sequentially adding the product BODIPY-0 and N-iodosuccinimide of the step S11, stirring for 4.5-5.5 h at room temperature in a dark place, removing the solvent by reduced pressure distillation, and carrying out chromatographic separation on a 300-400-mesh silica gel column to obtain a red solid product BODIPY-I;
s13: and (2) taking 30mL of 1, 4-dioxane, sequentially adding the product BODIPY-I of the step S12, 4-aminophenylboronic acid pinacol ester, 4-triphenylphosphine palladium and 1mol/L of potassium carbonate aqueous solution, uniformly stirring, heating to 110 ℃ under the protection of argon, carrying out reflux reaction for 6-18 h, carrying out reduced pressure distillation to remove the solvent, and carrying out chromatographic separation on a 300-400-mesh silica gel column to obtain a purple solid product, namely a novel BODIPY molecule BDP.
Preferably, the mass ratio of p-dimethylaminobenzaldehyde, 2, 4-dimethylpyrrole, 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, triethylamine and boron trifluoride diethyl etherate in the step S11 is 1: 0.8-1.2: 6.5-6.6: 10, preferably 1: 0.9: 1.2: 6.6: 10; the concentration of the p-dimethylaminobenzaldehyde in the anhydrous dichloromethane is 2.4-9.6 g/L.
Preferably, the mass ratio of the product BODIPY-0 and N-iodosuccinimide in the step S12 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.
Preferably, the mass ratio of the product BODIPY-I, the 4-aminophenylboronic acid pinacol ester, the 4-triphenylphosphine palladium and the potassium carbonate in the step S13 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.
The invention provides an antioxidant optical activity nanogold-loaded COF material which is prepared by adopting the preparation method of the antioxidant optical activity nanogold-loaded COF material.
The invention provides an application of an oxidation-resistant optical activity nanogold-loaded COF material, and the oxidation-resistant optical activity nanogold-loaded COF material is used for biomedical photothermal therapy.
Compared with the prior art, the invention has the following beneficial effects:
(1) the nano-gold-loaded COF material adopts an in-situ reduction method to utilize the covalent bonding effect between gold Au and atoms of N, S, O and the like in the COFBDP/CD-S-3COF (chip on film) material with nanogold loaded thereon to obtain nanogold-loaded COF materialBDP/CD-S-3-AuThe method realizes the uniform dispersion of the nano-gold in the COF material, simultaneously has simple and convenient preparation method, and overcomes the problems of particle size increase, specific surface area reduction and the like caused by easy aggregation of nano-gold particles.
(2) In the present invention, the nanogold-carrying COF material (COF)BDP/CD-S-3-Au) The optical characteristics of the covalent organic framework COF material and the nanogold are integrated, the optical material has the advantages of good antioxidant activity, higher near-infrared region photo-thermal conversion efficiency, good photo-thermal stability and the like, the capacity of removing active oxygen from various free radicals can be realized due to the good antioxidant performance of the optical material, the damage of ROS to cells can be reduced, and the optical material has a huge potential application prospect in the fields of biomedicine, medical diagnosis and treatment, biological imaging, photo-thermal treatment, cosmetics and the like.
Drawings
FIG. 1 is the COF of example 1BDP/CD-S-3-AuScanning electron microscope images of;
FIG. 2 is the COFB of example 1DP/CD-S-3-AuTransmission electron microscopy images of;
FIG. 3 COF of example 1BDP/CD-S-3-AuA graph of the temperature of (a) and the time of laser irradiation at 808 nm;
FIG. 4 COF of example 2BDP/CD-S-3-Au-3Graph of DPPH radical scavenging rate versus concentration.
FIG. 5 COF of example 1BDP/CD-S-3-AuXRD pattern of (a).
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments are described in detail. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention in any way, since various changes and modifications may be made to the invention herein disclosed by those skilled in the art, which fall within the scope of the invention as claimed.
Example 1
The embodiment provides an antioxidant optical active nano-gold-loaded COF material, a preparation method and application thereof, and the nano-gold-loaded COF material COFBDP/CD-S-3-AuThe preparation method comprises the following steps:
1) synthesis of novel BODIPY molecule BDP
S11, adding 1.0g of dimethylaminobenzaldehyde into 250mL of anhydrous dichloromethane, introducing argon for protection, sequentially adding 2mL of 2, 4-dimethylpyrrole and one drop of trifluoroacetic acid, introducing argon for stirring and reacting at a dark room temperature for 24 hours, adding 2.4g of 2, 3-dichloro-5, 6-dicyan-p-benzoquinone into a reaction system, stirring and reacting at a room temperature for 4 hours, cooling to 0 ℃, sequentially adding 18mL of triethylamine and 18mL of boron trifluoride diethyl etherate, stirring and reacting at a room temperature for 8 hours, washing the reaction liquid with water for 3 times, drying with anhydrous magnesium sulfate, distilling under reduced pressure to remove a solvent, and separating by column chromatography to obtain an orange solid product, namely BODIPY-0 for later use.
S12, taking 50mL of anhydrous dichloromethane, adding 0.2g of BODIPY-0 product, then adding 0.26g of N-iodosuccinimide, stirring for 5h at room temperature in the dark, removing the solvent by reduced pressure distillation, and performing column chromatography separation to obtain a red solid product, namely BODIPY-I, for later use.
S13, taking 30mL of 1, 4-dioxane, adding 0.2g of product BODIPY-I, then adding 0.27g of 4-aminobenzene boronic acid pinacol ester, 0.089g of 4-triphenylphosphine palladium and 3mL of 1mol/L potassium carbonate aqueous solution, uniformly stirring, heating to 110 ℃ under the protection of argon, carrying out reflux reaction for 12 hours, carrying out reduced pressure distillation to remove the solvent, and carrying out column chromatography separation to obtain a purple solid product, namely the novel BODIPY molecular BDP.
2) Synthesis of sulfur-containing nano carbon dot CD-S-3
Firstly, taking 300uL 50% glutaraldehyde, 600uL thiophene and 30uL glycerol, carrying out ultrasonic treatment for 5min, heating to 150 ℃ in a stainless steel reaction kettle, reacting for 3h, then adding acetone and chloroform, centrifuging for 3 times respectively, taking upper-layer liquid, and carrying out vacuum drying to obtain a brown oily product, namely the sulfur-containing nanocarbon point CD-S-3.
3) Covalent organic framework materials COFBDP/CD-S-3Synthesis of (2)
Firstly, taking 18mL of ethanol, sequentially adding 8g of novel BODIPY molecule BDP and 20g of sulfur-containing nano carbon dot CD-S-3, then adding 50uL of glacial acetic acid, stirring for 24h at room temperature, and washing with ethanol for three times to obtain a black-red solid product, namely a covalent organic framework material COFBDP/CD-S-3。
4) COF material carrying nano goldBDP/CD-S-3-AuPreparation of
First, 10mL of methanol was taken and 10mg of COF was addedBDP/CD-S-3Carrying out light-shielding ultrasonic treatment for 30min, adding 5mL of 200mM chloroauric acid aqueous solution, carrying out light-shielding ultrasonic treatment for 1h, washing with methanol and water for 2 times, dispersing the obtained precipitate in 10mL of methanol, adding 5mL of 200mM sodium borohydride methanol solution, carrying out light-shielding reaction for 48h, and washing with methanol for 3 times to obtain a black-red solid product, namely the COF (chip on film) material carrying the nano-gold COF (chip on film)BDP/CD-S-3-Au. Is described as COFBDP/CD-S-3-Au-1。
The COF material carrying nanogold obtained in the embodiment is subjected to a scanning electron microscopeBDP/CD-S-3-AuPerforming characterization, wherein the scanning electron microscope image obtained by the characterization result is shown in FIG. 1;
COF (chip on film) of the COF material carrying nanogold obtained in the embodiment by using a transmission electron microscopeBDP/CD-S-3-AuAnd (5) performing characterization, wherein the transmission electron micrograph obtained is shown in FIG. 2.
The obtained COF material carrying nanogold obtained in the embodimentBDP/CD-S-3-AuThe photothermal properties of (A):
a COFBDP/CD-S-3-AuUniformly dispersed in N, N-dimethylformamide to give 0.5-1mg/mL COFBDP/CD-S-3-AuThe dispersion was irradiated with a laser beam at 808nm for various periods of time, and the COF was measuredBDP/CD-S-3-AuThe dispersion was heated at 0, 2, 4, 6, 8, 10, 12min to obtain COFBDP/CD-S-3-AuAs shown in FIG. 3, the relationship between the temperature of (2) and the time of laser irradiation at 808 nm.
The COF material carrying nano gold obtained in the embodimentBDP/CD-S-3-AuThe antioxidant performance is measured as follows:
a COFBDP/CD-S-3-AuUniformly dispersed in ethanol to obtain the components with the concentrations of 20, 80, 160,240. 320, 400ug/ml COFBDP/CD-S-3-AuAdding equal volume of 0.1 mmol/L1, 1-diphenyl-2-trinitrophenylhydrazine (DPPH) ethanol solution into the dispersion, and reacting at room temperature in the dark for 30min to respectively obtain COFBDP/CD-S-3-AuThe absorbance A of each sample system at 517nm is respectively measured for sample systems with the concentrations of 10, 40, 80, 120, 160 and 200iSubstituting into formula R ═ 1- (a)i-Aj)/A0]X 100%, wherein R is clearance,%; a. the0The absorbance value of DPPH solution added with equal volume of ethanol; ai is the absorbance value of each sample system; a. thejReplacing DPPH solution with ethanol, and obtaining COF (chip on film) under various concentrationsBDP/CD-S-3-AuThe DPPH radical scavenging rate of the dispersion is related to the sample concentration, as shown in FIG. 4.
COF as shown in FIG. 5BDP/CD-S-3-AuXRD pattern of (A), from which the COFBDP/CD-S-3And COFBDP/CD-S-3-AuCharacteristic peaks appeared at around 2 θ ═ 4.1 °, indicating that some degree of crystallinity possessed by COF was present in both materials.
2. Characteristic peaks of Au exist in the COFBDP/CD-S-3-Au sample at 2 theta of 38.2 degrees, 44.3 degrees, 64.6 degrees and 77.6 degrees, and corresponding crystal face indexes are respectively (111), (200), (220) and (311), which shows that the COFBDP/CD-S-3-Au is successfully loaded with the nano-gold particles on COF, and the crystal face index of the nano-gold is mainly (111).
The oxidation-resistant optical activity nanogold-loaded COF material provided by the embodiment is prepared by adopting the preparation method of the oxidation-resistant optical activity nanogold-loaded COF material; the antioxidant optical activity nano-gold-loaded COF material is used for photo-thermal treatment of biomedicine and the like.
Example 2
The present embodiment provides an oxidation-resistant optical-activity nanogold-loaded COF material, and a manufacturing method and a use thereof, which are substantially the same as those of embodiment 1, except that:
COF as in example 1BDP/CD-S-3-AuThe preparation method is characterized in that 200mM chloroauric acid aqueous solution is replaced by 100mM chloroauric acid aqueous solution and 400mM chloroauric acid aqueous solution respectively to prepare the nano-gold-loaded COF material, COFBDP/CD-S-3-Au-2And COFBDP/CD-S-3-Au-3。
Example 3
The present embodiment provides an oxidation-resistant optical-activity nanogold-loaded COF material, and a manufacturing method and a use thereof, which are substantially the same as those of embodiment 1, except that:
COF as in example 1BDP/CD-S-3-AuThe difference is that 200mM sodium borohydride methanol solution is replaced by 200mM ascorbic acid water solution to prepare the nano-gold-loaded COF material which is marked as COFBDP/CD-S-3-Au-4。
Example 4
The present embodiment provides an oxidation-resistant optical-activity nanogold-loaded COF material, and a manufacturing method and a use thereof, which are substantially the same as those of embodiment 1, except that:
COF as in example 1BDP/CD-S-3-AuExcept that 200mM aqueous chloroauric acid solution was replaced with 200mM aqueous silver nitrate solution to prepare COFBDP/CD-S-3-Ag。
Example 5
The oxidation-resistant optical-activity nanogold-loaded COF material provided by the embodiment, the preparation method and the application thereof are basically the same as those of the embodiment 1, and the same as those of the COF material in the embodiment 1BDP/CD-S-3-AuThe difference is that:
1) synthesis of novel BODIPY molecule BDP:
in the step S11, the mass ratio of p-dimethylaminobenzaldehyde, 2, 4-dimethylpyrrole, 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, triethylamine and boron trifluoride diethyl etherate is 1: 1.1: 1.2: 6.6: 10; the concentration of p-dimethylaminobenzaldehyde in anhydrous dichloromethane was 2.4 g/L.
The mass ratio of the product BODIPY-0 to the N-iodosuccinimide in the step S12 is 1: 1; the concentration of the product BODIPY-0 in anhydrous dichloromethane was 4.8 g/L.
In the step S13, the mass ratio of the product BODIPY-I, the 4-aminophenylboronic acid pinacol ester, the 4-triphenylphosphine palladium and the potassium carbonate is 1: 1.35: 0.45: 2.1; the concentration of the product BODIPY-I in 1, 4-dioxane was 2.4 g/L.
2) And (3) synthesizing sulfur-containing nano carbon dot CD-S-3: the volume ratio of the glutaraldehyde to the thiophene to the glycerol is 1: 2: 0.05.
3) Covalent organic framework materials COFBDP/CD-S-3The synthesis of (2): covalent organic framework materials COFBDP/CD-S-3Stirring and reacting for 24 hours at room temperature; the mass ratio of the BDP of the novel BODIPY molecule to the CD-S-3 of the sulfur-containing nano carbon dots is 1: 3.3.
4) COF material carrying nano goldBDP/CD-S-3-AuThe preparation of (1): the covalent organic framework material COFBDP/CD-S-3The mass ratio of the chloroauric acid to the sodium borohydride is 1: 19.8: 7.6; covalent organic framework materials COFBDP/CD-S-3The concentration in methanol was 0.3 g/L. The second light-shielding ultrasonic time is 1.5 h; the concentration of the chloroauric acid aqueous solution is 400mmol/L, and the concentration of the sodium borohydride methanol solution is 20 mmol/L; the reaction time was 72h away from light.
Example 6
The oxidation-resistant optical-activity nanogold-loaded COF material provided by the embodiment, the preparation method and the application thereof are basically the same as those of the embodiment 1, and the same as those of the COF material in the embodiment 1BDP/CD-S-3-AuThe difference is that:
2) synthesis of novel BODIPY molecule BDP:
in the step S11, the mass ratio of p-dimethylaminobenzaldehyde, 2, 4-dimethylpyrrole, 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, triethylamine and boron trifluoride diethyl etherate is 1: 0.9: 1.2: 6.5: 10; the concentration of p-dimethylaminobenzaldehyde in anhydrous dichloromethane was 9.6 g/L.
The mass ratio of the product BODIPY-0 and N-iodosuccinimide in the step S12 is 1: 2.25; the concentration of the product BODIPY-0 in anhydrous dichloromethane was 2 g/L.
In the step S13, the mass ratio of the product BODIPY-I, the 4-aminophenylboronic acid pinacol ester, the 4-triphenylphosphine palladium and the potassium carbonate is 1: 1.35: 0.45: 2.1; the concentration of the product BODIPY-I in 1, 4-dioxane was 4 g/L.
2) And (3) synthesizing sulfur-containing nano carbon dot CD-S-3: the volume ratio of the glutaraldehyde to the thiophene to the glycerol is 1: 2: 0.2.
3) Covalent organic framework materials COFBDP/CD-S-3The synthesis of (2): covalent organic framework materials COFBDP/CD-S-3Stirring and reacting for 20 hours at room temperature; the mass ratio of the BDP of the novel BODIPY molecule to the CD-S-3 of the product containing sulfur nano carbon dots is 1: 3.3.
4) COF material carrying nano goldBDP/CD-S-3-AuThe preparation of (1): the covalent organic framework material COFBDP/CD-S-3The mass ratio of the chloroauric acid to the sodium borohydride is 1: 70: 5; covalent organic framework materials COFBDP/CD-S-3The concentration in methanol was 0.6 g/L. The second light-shielding ultrasonic time is 1 h; the concentration of the chloroauric acid aqueous solution is 100mmol/L, and the concentration of the sodium borohydride methanol solution is 20 mmol/L; the reaction time was 24h under dark conditions.
Example 7
The oxidation-resistant optical-activity nanogold-loaded COF material provided by the embodiment, the preparation method and the application thereof are basically the same as those of the embodiment 1, and the same as those of the COF material in the embodiment 1BDP/CD-S-3-AuThe difference is that:
3) synthesis of novel BODIPY molecule BDP:
in the step S11, the mass ratio of p-dimethylaminobenzaldehyde, 2, 4-dimethylpyrrole, 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, triethylamine and boron trifluoride diethyl etherate is 1: 0.8: 1.2: 6.5: 10; the concentration of p-dimethylaminobenzaldehyde in anhydrous dichloromethane was 2.4 g/L.
The mass ratio of the product BODIPY-0 to the N-iodosuccinimide in the step S12 is 1: 2; the concentration of the product BODIPY-0 in anhydrous dichloromethane was 4.8 g/L.
In the step S13, the mass ratio of the product BODIPY-I, the 4-aminophenylboronic acid pinacol ester, the 4-triphenylphosphine palladium and the potassium carbonate is 1: 1.35: 0.45: 2.1; the concentration of the product BODIPY-I in 1, 4-dioxane was 8.4 g/L.
2) Synthesizing the sulfur-containing nanocarbon point CD-S-3: the volume ratio of the glutaraldehyde to the thiophene to the glycerol is 1: 2: 0.05.
3) Covalent organic framework materials COFBDP/CD-S-3The synthesis of (2): covalent organic framework materials COFBDP/CD-S-3Stirring and reacting for 24 hours at room temperature; the mass ratio of the BDP of the novel BODIPY molecule to the CD-S-3 of the sulfur-containing nano carbon dots is 1: 2.
4) COF material carrying nano goldBDP/CD-S-3-AuThe preparation of (1): the covalent organic framework material COFBDP/CD-S-3The mass ratio of the chloroauric acid to the sodium borohydride is 1: 79.5: 3; covalent organic framework materials COFBDP/CD-S-3The concentration in methanol was 0.5 g/L. The second light-shielding ultrasonic time is 1.2 h; the concentration of the chloroauric acid aqueous solution is 200mmol/L, and the concentration of the sodium borohydride methanol solution is 120 mmol/L; the reaction time was 36h under dark conditions.
Example 8
The oxidation-resistant optical-activity nanogold-loaded COF material provided by the embodiment, the preparation method and the application thereof are basically the same as those of the embodiment 1, and the same as those of the COF material in the embodiment 1BDP/CD-S-3-AuThe difference is that:
4) synthesis of novel BODIPY molecule BDP:
in the step S11, the mass ratio of p-dimethylaminobenzaldehyde, 2, 4-dimethylpyrrole, 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, triethylamine and boron trifluoride diethyl etherate is 1: 1.2: 6.6: 10; the concentration of p-dimethylaminobenzaldehyde in anhydrous dichloromethane was 7 g/L.
The mass ratio of the product BODIPY-0 to the N-iodosuccinimide in the step S12 is 1.8; the concentration of the product BODIPY-0 in anhydrous dichloromethane was 3 g/L.
In the step S13, the mass ratio of the product BODIPY-I, the 4-aminophenylboronic acid pinacol ester, the 4-triphenylphosphine palladium and the potassium carbonate is 1: 1.35: 0.45: 2.1; the concentration of the product BODIPY-I in 1, 4-dioxane was 5 g/L.
2) And (3) synthesizing sulfur-containing nano carbon dot CD-S-3: the volume ratio of the glutaraldehyde to the thiophene to the glycerol is 1: 2: 0.1.
3) Covalent organic framework materials COFBDP/CD-S-3The synthesis of (2): covalent organic framework materials COFBDP/CD-S-3Stirring and reacting for 22h at room temperature; the mass ratio of the BDP of the novel BODIPY molecule to the CD-S-3 of the sulfur-containing nano carbon dots is 1: 3.
4) COF material carrying nano goldBDP/CD-S-3-AuThe preparation of (1): the covalent organic framework material COFBDP/CD-S-3The mass ratio of the chloroauric acid to the sodium borohydride is 1: 50: 4; covalent organic frameworksMaterial COFBDP/CD-S-3The concentration in methanol was 0.4 g/L. The second light-shielding ultrasonic time is 1 h; the concentration of the chloroauric acid aqueous solution is 300mmol/L, and the concentration of the sodium borohydride methanol solution is 100 mmol/L; the reaction time was 72h away from light.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention.

Claims (10)

1. A preparation method of an oxidation-resistant optical active nano-gold-loaded COF material is characterized in that the material is based on a covalent organic framework material COFBDP/CD-S-3The gold chloride acid and the sodium borohydride are prepared by the reaction of an in-situ reduction method, and the method comprises the following steps:
s1: addition of covalent organic framework materials COF in methanolBDP/CD-S-3Adding chloroauric acid aqueous solution after the first light-proof ultrasonic treatment, washing with methanol and water after the second light-proof ultrasonic treatment to obtain a precipitate;
s2: dispersing the precipitate obtained in the step S1 in methanol, adding sodium borohydride methanol solution, reacting in the dark, washing with methanol to obtain black red solid, namely the COF material carrying the nanogold COF materialBDP/CD-S-3-Au；
The covalent organic framework material COFBDP/CD-S-3The mass ratio of the chloroauric acid to the sodium borohydride is 1: 19.8-79.5: 2-7.6;
the step S1 is performed by using a common frame material COFBDP/CD-S-3The concentration of the compound in methanol is 0.3-0.6 g/L.
2. The method for preparing the anti-oxidation optical activity nano-gold-loaded COF material according to claim 1, wherein the first light-shielding ultrasonic time is 30min, and the second light-shielding ultrasonic 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 is 24-72 h without light.
3. The method for preparing oxidation-resistant optically active nanogold-loaded COF material according to claim 1 or 2, wherein the covalent organic framework material COF isBDP/CD-S-3The compound is mainly prepared by the reaction of novel BODIPY molecules (BDP) obtained by the reaction of dimethylaminobenzaldehyde, 2, 4-dimethylpyrrole, 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, triethylamine, boron trifluoride diethyl ether, N-iodosuccinimide and 4-aminobenzene boronic acid pinacol ester and the reaction of a product (sulfur-containing nano carbon dot CD-S-3) obtained by the reaction of glutaraldehyde, thiophene and glycerol; the preparation method specifically comprises the steps of sequentially adding the novel BODIPY molecule BDP and the product of the sulfur-containing nano carbon dot CD-S-3 into ethanol, then adding glacial acetic acid, stirring at room temperature for reaction for 20-24 h, and washing with ethanol to obtain black red solid, namely covalent organic framework material COFBDP/CD-S-3(ii) a The mass ratio of the BDP of the novel BODIPY molecule to the CD-S-3 of the product sulfur-containing nano carbon dots is 1: 2-4.5.
4. The method for preparing an antioxidant optically active nanogold-loaded COF material according to claim 3, wherein the product of the reaction of glutaraldehyde, thiophene and glycerol, which is a sulfur-containing nanocarbon point CD-S-3, specifically comprises the following steps: taking glutaraldehyde, thiophene and glycerol, carrying out ultrasonic treatment for 5-10 min, heating to 150 ℃ in a reaction kettle, reacting for 3h, adding acetone and chloroform, centrifuging to obtain an upper layer liquid, and carrying out vacuum drying to obtain a brown oily product, namely the sulfur-containing nano carbon dot CD-S-3; the volume ratio of the glutaraldehyde to the thiophene to the glycerol is 1: 2: 0.05-0.2.
5. The method for preparing an antioxidant optically active nanogold-loaded COF material according to claim 3, wherein the novel BODIPY molecule (BDP) is prepared by the following steps:
s11: adding p-dimethylaminobenzaldehyde into 250mL of anhydrous dichloromethane, sequentially adding 2, 4-dimethylpyrrole and a drop of trifluoroacetic acid under the protection of argon, stirring and reacting at the dark room temperature for 18-36 h, then adding 2, 3-dichloro-5, 6-dicyan p-benzoquinone, continuing stirring and reacting at the dark room temperature for 3-6 h, cooling to 0 ℃, sequentially adding triethylamine and boron trifluoride diethyl etherate, continuing stirring and reacting at the dark room temperature for 6-12 h, washing the obtained reaction solution with water, drying anhydrous magnesium sulfate, then distilling under reduced pressure to remove the solvent, and separating by using a 300-400-mesh silica gel column chromatography to obtain an orange solid product BODIPY-O;
s12: taking 50mL of anhydrous dichloromethane, sequentially adding the product BODIPY-O and N-iodosuccinimide of the step S11, stirring for 4.5-5.5 h at room temperature in a dark place, removing the solvent by reduced pressure distillation, and carrying out chromatographic separation on a 300-400-mesh silica gel column to obtain a red solid product BODIPY-I;
s13: and (2) taking 30mL of 1, 4-dioxane, sequentially adding the product BODIPY-I of the step S12, 4-aminophenylboronic acid pinacol ester, 4-triphenylphosphine palladium and 1mol/L of potassium carbonate aqueous solution, uniformly stirring, heating to 110 ℃ under the protection of argon, carrying out reflux reaction for 6-18 h, carrying out reduced pressure distillation to remove the solvent, and carrying out chromatographic separation on a 300-400-mesh silica gel column to obtain a purple solid product, namely a novel BODIPY molecule BDP.
6. The method for preparing the oxidation-resistant optically active nanogold-loaded COF material according to claim 5, wherein the mass ratio of p-dimethylaminobenzaldehyde, 2, 4-dimethylpyrrole, 2, 3-dichloro-5, 6-dicyano-p-benzoquinone, triethylamine and boron trifluoride diethyl etherate in step S11 is 1: 0.8-1.2: 6.5-6.6: 10; the concentration of the p-dimethylaminobenzaldehyde in the anhydrous dichloromethane is 2.4-9.6 g/L.
7. The method for preparing the anti-oxidation COF material carrying nano gold with optical activity according to claim 5, wherein the mass ratio of BODIPY-O and N-iodosuccinimide in the step S12 is 1: 1-2.25; the concentration of the product BODIPY-O in anhydrous dichloromethane is 2-4.8 g/L.
8. The method for preparing an antioxidant optically active nanogold-loaded COF material according to claim 5, wherein the mass ratio of the product BODIPY-I, 4-aminophenylboronic acid pinacol ester, 4-triphenylphosphine palladium and potassium carbonate in the step S13 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.
9. An oxidation-resistant optical-activity nanogold-loaded COF material, which is prepared by adopting the preparation method of the oxidation-resistant optical-activity nanogold-loaded COF material according to any one of claims 1 to 8.
10. Use of an oxidation-resistant optically active nanogold-loaded COF material for biomedical photothermal therapy.
CN202210144737.5A 2022-02-16 2022-02-16 Oxidation-resistant optical-activity nanogold-loaded COF material and preparation method and application thereof Pending CN114470205A (en)

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CN115192708A (en) * 2022-07-07 2022-10-18 安徽医科大学 Nano composite material loaded with anti-tumor drug, nano drug-loaded system, preparation and application
CN115926189A (en) * 2023-01-12 2023-04-07 台州学院 Novel composite material HKUST-1@ PQ and preparation method thereof

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CN115192708A (en) * 2022-07-07 2022-10-18 安徽医科大学 Nano composite material loaded with anti-tumor drug, nano drug-loaded system, preparation and application
CN115192708B (en) * 2022-07-07 2024-02-27 安徽医科大学 Nanocomposite loaded with antitumor drug, nano drug-carrying system, preparation and application
CN115926189A (en) * 2023-01-12 2023-04-07 台州学院 Novel composite material HKUST-1@ PQ and preparation method thereof
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