CN115025243A - Preparation method and application of silver nanoparticle loaded on two-dimensional sheet metal organic framework modified by mercaptophenylboronic acid - Google Patents
Preparation method and application of silver nanoparticle loaded on two-dimensional sheet metal organic framework modified by mercaptophenylboronic acid Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 64
- RADLTTWFPYPHIV-UHFFFAOYSA-N (2-sulfanylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1S RADLTTWFPYPHIV-UHFFFAOYSA-N 0.000 title claims abstract description 55
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 46
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- XDFNWJDGWJVGGN-UHFFFAOYSA-N 2-(2,7-dichloro-3,6-dihydroxy-9h-xanthen-9-yl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1C2=CC(Cl)=C(O)C=C2OC2=CC(O)=C(Cl)C=C21 XDFNWJDGWJVGGN-UHFFFAOYSA-N 0.000 description 1
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- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/24—Heavy metals; Compounds thereof
- A61K33/38—Silver; Compounds thereof
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- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
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- A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
- A61K47/51—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent
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Abstract
The invention discloses a preparation method and application of silver nanoparticles loaded on a two-dimensional sheet metal organic framework modified by mercaptophenylboronic acid, wherein the preparation method comprises the following steps: adding copper nitrate, polyvinylpyrrolidone and trifluoroacetic acid into a solvent, mixing, adding tetracarboxyphenol porphyrin for reaction to obtain a two-dimensional sheet metal organic framework, and adding AgNO 3 And NaBH 4 Reacting to obtain two-dimensional flaky metal organic framework loaded silver nanoparticles; dispersing the silver nanoparticle into pure water, adding the mercaptophenylboronic acid, mixing and reacting to obtain the mercaptophenylboronic acid modified two-dimensional sheet metal organic framework loaded silver nanoparticles. The invention has simple preparation process, easily obtained raw materials, low cost and easy large-scale production. The nano composite material prepared by the invention has the characteristics of high selectivity and low biological toxicity, can effectively inhibit the growth of gram-positive bacteria and the formation of a biological membrane, has low antibacterial concentration, and has good application potential for controlling the drug resistance of pathogenic bacteria caused by antibiotic abuse.
Description
Technical Field
The invention belongs to biological medicine, and particularly relates to a preparation method and application of a mercapto phenylboronic acid modified two-dimensional sheet metal-nanosheet silver-loaded nanoparticle.
Background
The generation of pathogenic bacteria is caused by the abuse of antibiotics, and is a big pain point in the world health field. It is estimated that diseases caused by drug-resistant bacteria cause a great amount of human deaths each year, and silver nanoparticles have been widely used as a nano material which is definitely proved to have bacteriostatic effects, but the nano material has higher bacteriostatic concentration and no targeting property, resulting in non-negligible in vivo toxicity. In recent years, photodynamic therapy plays an increasingly important role in the fields of wound healing, disease treatment and the like due to non-invasiveness and deep tissue permeability, but the high-efficiency bacteriostatic ability is limited by the inherent short life and limited diffusion distance of active oxygen species. In addition, most of the traditional antibacterial materials are concentrated on one antibacterial mechanism, so that the antibacterial effect is generally poor. Thus, the synergy of multiple bacteriostatic mechanisms and the targeted clearance of bacteria are undoubtedly the key to the intelligent design of bacteriostatic materials. Therefore, a bacteriostatic material which is more efficient, low in bacteriostatic concentration, good in biocompatibility and has a targeting effect is sought to be used as a substitute of antibiotics, so that the risk of drug-resistant bacteria can be reduced undoubtedly, and the bacteriostatic material has an important significance on the management and control and treatment of diseases related to pathogenic bacteria infection.
Disclosure of Invention
The invention aims to: aiming at the problems in the prior art, the invention provides a preparation method of silver nanoparticles loaded on a two-dimensional sheet metal organic framework modified by mercaptophenylboronic acid.
The invention also provides silver-loaded nanoparticles of the two-dimensional sheet metal organic framework modified by the mercaptophenylboronic acid and application of the silver-loaded nanoparticles.
The technical scheme is as follows: in order to achieve the purpose, the preparation method of the silver nanoparticle loaded on the two-dimensional sheet metal organic framework modified by the mercaptophenylboronic acid comprises the following steps:
(1) copper nitrate Cu (NO) 3 ) 2 .3H 2 Adding O, polyvinylpyrrolidone and trifluoroacetic acid into a solvent, mixing, adding N, N-Dimethylformamide (DMF) solvent containing tetracarboxyphenol porphyrin (TCPP) for reaction, washing after the reaction, and drying in vacuum to obtain a two-dimensional sheet metal organic framework (CuTCPP);
(2) dispersing the two-dimensional sheet metal organic framework obtained in the step (1) in a solvent, and then adding AgNO 3 And NaBH 4 After the reaction product is washed, the product is frozen, dried and collected to obtain the silver-loaded nano-particles of the two-dimensional metal organic framework;
(3) dispersing the two-dimensional flaky metal organic framework silver-loaded nanoparticles obtained in the step (2) in pure water, adding mercaptophenylboronic acid, mixing, incubating the mixture, and centrifuging to obtain a precipitate, namely the mercaptophenylboronic acid-modified two-dimensional flaky metal organic framework silver-loaded nanoparticles.
Wherein, Cu (NO) in the step (1) 3 ) 2 .3H 2 The molar ratio of O, TCPP and PVP is 75: 30: 1.14-75: 20: 1.14.
preferably, the two-dimensional sheet metal organic framework prepared in the step (1)Middle Cu (NO) 3 ) 2 .3H 2 The molar ratio of O, TCPP and PVP is 75: 25: 1.14.
wherein the solvent in the step (1) is a mixed solvent of N, N-Dimethylformamide (DMF) and ethanol.
Preferably, the volume ratio of DMF to ethanol in the mixed solvent is 3: 1.
Wherein the reaction in the step (1) is carried out for 2-3 hours at the temperature of 80-100 ℃.
Preferably, the reaction in step (1) is carried out at 80 ℃ for 3 hours.
And (2) washing the copper-based metal organic framework obtained after the reaction in the step (1) by using ethanol and DMF (dimethyl formamide), and drying in vacuum to obtain powder which is a two-dimensional sheet metal organic framework.
And (3) dispersing the two-dimensional sheet metal organic framework in ethanol under the oscillating ultrasound, reducing silver nitrate in situ by sodium borohydride for half an hour, and centrifugally washing, freezing and drying the obtained solution to obtain the two-dimensional sheet metal organic framework loaded silver nanoparticles for later use.
Wherein, AgNO in the step (2) 3 And NaBH 4 The mol ratio of CuTCPP to AgNO is 2:5-1.5:5.5 3 The mass ratio is 4: 3-4: 4.
Preferably, AgNO is added in the preparation of the silver-loaded nano-particles of the two-dimensional sheet metal organic framework in the step (2) 3 And NaBH 4 The molar ratio of CuTCPP to AgNO is 2:5 3 The mass ratio is 4: 3.
Preferably, the concentration of the two-dimensional flaky metal nanosheets in step (2) is 2.5 mg/mL.
And (3) dispersing the two-dimensional metal nanosheet-loaded silver nanoparticles in pure water, adding mercaptoboric acid, mixing, and stirring the mixture at room temperature in a dark place for 12-15 h.
Preferably, in step (3), the mixture is stirred at room temperature for 12h in the absence of light.
Wherein in the step (3) of preparing the silver-loaded nanoparticles of the two-dimensional sheet metal organic framework modified by the mercaptophenylboronic acid, the mass ratio of CuTCPP @ AgNPs to the mercaptophenylboronic acid is 50000:6-50000: 10.
Preferably, the mass ratio of CuTCPP @ AgNPs to mercaptophenylboronic acid in step (3) is 50000: 7.7.
The invention relates to a method for preparing a silver nanoparticle loaded on a mercapto phenylboronic acid modified two-dimensional sheet metal-nanosheet.
The invention relates to application of silver nanoparticles loaded on a two-dimensional sheet metal organic framework modified by mercaptophenylboronic acid in clearing gram-positive bacteria and inhibiting biofilm formation.
The invention relates to application of a mercapto phenylboronic acid modified two-dimensional flaky metal-nanosheet silver-loaded nanoparticle in preparation of a reagent for removing gram-positive bacteria and inhibiting biofilm formation of gram-positive bacteria.
Wherein the gram-positive pathogenic bacteria are staphylococcus aureus, pneumococcus, streptococcus, anthrax and the like.
In the invention, copper nitrate, polyvinylpyrrolidone such as PVP (K30) and trifluoroacetic acid are reacted in a DMF-ethanol solution to obtain a two-dimensional sheet metal organic framework; reducing silver nitrate and the two-dimensional sheet metal organic framework in situ by sodium borohydride to form silver-loaded nanoparticles of the two-dimensional sheet metal organic framework; the silver nanoparticle loaded on the two-dimensional sheet metal organic framework modified by the mercaptophenylboronic acid is obtained by modifying the mercaptophenylboronic acid on the surface of the silver nanoparticle through Ag-S bonds.
The two-dimensional flaky metal-nanosheet loaded silver nanoparticle modified by the mercaptophenylboronic acid, prepared by the invention, realizes efficient and low-concentration use and removal of staphylococcus aureus in gram-positive pathogenic bacteria such as staphylococcus aureus. Silver nanoparticles have been widely used for inhibiting the growth of bacteria, but the bacteriostatic mechanism is single, and the release of excessive silver ions can bring adverse effects on body tissues. In order to overcome the defect that the life of ROS is short and the diffusion distance is insufficient, so that the efficiency of the justice is poor, the method uses the mercaptophenylboronic acid as the targeting group of the staphylococcus aureus to reduce the diffusion distance between the material and the bacteria and improve the accessibility of the nano-drug, and the synergistic effect of the release of the metal ions of the silver nano-particles and the metal nano-sheets and the photodynamic therapy is favorable for further improving the bacteriostatic effect of the material. The result shows that the composite material prepared by the invention has good bacteriostatic efficiency at 25 mu g/mL and simultaneously shows enhanced in-vitro bacteriostatic and biofilm formation capabilities. The results of an in vitro flat plate growth experiment, live and dead bacteria staining, a bacteria morphology scanning electron microscope test, a biofilm removal experiment and a cytotoxicity experiment effectively show that the silver nanoparticle loaded by the nanosheet modified by the mercaptophenylboronic acid has enhanced bacteria removal capability and good biocompatibility, and meanwhile, the fluorescent probe disclosed by the invention is easy to obtain raw materials, simple in process, low in cost and easy for large-scale production.
The invention discloses a silver nanoparticle-loaded two-dimensional metal nanosheet composite material modified by mercaptophenylboronic acid for efficiently and specifically inhibiting staphylococcus aureus, which is high in inhibition efficiency, and has the characteristics of high selectivity and low biological toxicity. The composite nanomaterial for efficiently removing staphylococcus aureus, which is prepared by the invention, can efficiently inhibit the growth of staphylococcus aureus and the formation of a biological membrane, has low bacteriostatic concentration and good biocompatibility, and has good application potential for controlling the drug resistance of pathogenic bacteria caused by antibiotic abuse.
The invention adopts the mercaptophenylboronic acid as a targeting element of gram-positive bacteria, and enhances the antibacterial efficiency by cooperating with metal ion release and photodynamic therapy. The two-dimensional sheet structure can be used as a carrier for in-situ reduction of silver nitrate, so that the synthesized silver nanoparticles have the characteristic of uniform dispersion; meanwhile, the two-dimensional sheet structure can provide abundant specific surface area, increase the contact of the two-dimensional sheet structure with target bacteria and improve the inhibition effect. The material prepared by the invention and the targeted synergistic antibacterial strategy can avoid the increase of the drug resistance of gram-positive pathogenic bacteria caused by the abuse of antibiotics, delay the treatment effect of diseases and improve the treatment deficiency of the antibiotics. In addition, the material prepared by the invention effectively overcomes the defects of high biotoxicity and no targeting property caused by high bacteriostatic concentration of common silver nanoparticles, and has strong bacteriostatic ability.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. the invention provides a brand-new silver-loaded nanoparticle with a two-dimensional flaky metal organic framework modified by mercaptophenylboronic acid and used for removing gram-positive bacteria, and the silver-loaded nanoparticle is simple in preparation process, easy in obtaining of raw materials, low in cost and easy for large-scale production.
2. The two-dimensional sheet metal organic framework loaded silver nanoparticles modified by the mercaptophenylboronic acid for clearing staphylococcus aureus, which are prepared by the invention, have the advantages of high bacteriostasis efficiency, low concentration required by bacteriostasis, good biocompatibility and high-efficiency in-vitro bacteriostasis and biofilm removal capability.
3. The silver-loaded nanoparticles of the mercaptophenylboronic acid-modified two-dimensional sheet metal organic framework for removing gram-positive bacteria, which are prepared by the method, can effectively remove staphylococcus aureus and inhibit the formation of a biofilm, are more convenient, efficient, high in sensitivity and cost-saving, and have important significance for controlling the abuse of antibiotics and protecting the health of human bodies.
Drawings
FIG. 1 is a transmission electron microscope and ultraviolet fluorescence chart test chart of silver nanoparticles loaded on a two-dimensional sheet metal organic framework modified by mercaptophenylboronic acid; wherein (A) a Scanning Electron Microscope (SEM) image of a two-dimensional sheet copper-based metal organic framework (CuTCPP nanosheet); (B) a Transmission Electron Microscope (TEM) image of a two-dimensional sheet copper-based metal organic framework (CuTCPP @ AgNPs) loaded with silver nanoparticles, and (C) a high-resolution TEM image of a two-dimensional sheet copper-based metal organic framework loaded with silver nanoparticles (CuTCPP @ AgNPs @ MBA) modified by mercaptophenylboronic acid; (D) ultraviolet-visible absorption spectra of various materials; (E) fluorescence spectra of various materials;
FIG. 2 is an infrared, X-ray diffraction pattern (XRD), thermogravimetry, X-ray electron spectrum (XPS) diagram of the mercaptophenylboronic acid modified two-dimensional sheet metal organic framework supported silver nanoparticles of the present invention; (A) infrared spectra of each material; (B) XRD patterns of the materials; (C) thermogravimetric maps of each material; (D) XPS spectra of CuTCPP @ AgNPs @ MBA; (E) a Cu2p map of CuTCPP @ AgNPs @ MBA, (F) an Ag3d map of CuTCPP @ AgNPs @ MBA;
FIG. 3 is a bacteriostatic mechanism diagram of silver nanoparticles loaded on a two-dimensional sheet metal organic framework modified by mercaptophenylboronic acid according to the invention; wherein (A) the active oxygen generating capability of each material is tested, and 2, 7-Dichlorodihydrofluorescein (DCF) is used as a fluorescence indicator; (B) the release of Ag ions under the condition of the existence of near infrared irradiation;
FIG. 4 is a graph of a flat panel experiment biofilm removal experiment of silver nanoparticles loaded on a mercaptophenylboronic acid-modified two-dimensional sheet metal organic framework for removal of gram-positive bacteria Staphylococcus aureus according to the present invention; wherein (A) different materials are used for bacterial flat-plate chart under the condition of near infrared light treatment or not; (B) bacterial plate count plots under treatment of different materials; (C) bacterial panels treated with different concentrations of CuTCPP @ AgNPs @ MBA; (D) counting graphs of bacterial plates treated by CuTCPP @ AgNPs @ MBA at different concentrations;
FIG. 5 is a schematic representation of a biofilm removal experiment of silver nanoparticles loaded on a mercaptophenylboronic acid-modified two-dimensional platelet metal-organic framework for gram-positive bacteria, Staphylococcus aureus, according to the present invention; wherein, (A) different materials process the bacterial biomembrane crystal violet staining pattern; (B) a graph of the change in mass of biofilms under different material treatment bacteria;
FIG. 6 is a scanning electron microscope image of bacteria loaded with silver nanoparticles of the two-dimensional sheet metal organic framework modified with mercaptophenylboronic acid for the removal of gram-positive bacteria Staphylococcus aureus according to the present invention; wherein, (a) SEM image of PBS treated bacteria; (B) SEM images of CuTCPP treated bacteria; (C) SEM picture of CuTCPP @ AgNPs treated bacteria; (D) SEM image of CuTCPP @ AgNPs @ MBA treated bacteria;
FIG. 7 is a fluorescent image of viable and dead bacteria staining of silver nanoparticles loaded onto a two-dimensional sheet metal organic framework modified with mercaptophenylboronic acid for the removal of gram-positive bacteria Staphylococcus aureus in accordance with the present invention; wherein, A and E are Calcein (Calcein) -AM and Propidium Iodide (PI) staining patterns, respectively, of PBS-treated bacteria; b and F are respectively a Calcein-AM staining graph and a PI staining graph of the CuTCPP processing bacteria; c and G are respectively a CuTCPP @ AgNPs treatment bacterium Calcein-AM staining graph and a PI staining graph; d and H are respectively CuTCPP @ AgNPs @ MBA treatment bacteria Calcein-AM staining and PI staining graphs;
FIG. 8 is a cytotoxicity plot of cleared mercaptophenylboronic acid-modified two-dimensional platelet metal organic framework-loaded silver nanoparticles of the present invention for gram-positive bacteria Staphylococcus aureus.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
The experimental methods described in the examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
The preparation method of the silver-loaded nanoparticles of the two-dimensional sheet metal organic framework modified by the mercaptophenylboronic acid comprises the following steps:
(1) preparation of two-dimensional sheet metal organic framework: adding Cu (NO) 3 ) 2 . 3H 2 O (18mg,0.075mmol), trifluoroacetic acid (50. mu.L, 1.0moL/L) and PVP (K30) (50.0mg, molecular weight 44000-54000) were added to a 100mL capped vial containing 60mL of a mixture of DMF and ethanol (v: v ═ 3: 1). Then, 20mL of a mixed solution of N, N-Dimethylformamide (DMF) and ethanol (v: v,3:1) containing tetrakis- (4-carboxyphenyl) porphyrin (TCPP) (20mg,0.025mmol) was added dropwise with stirring. Then, the solution is subjected to ultrasonic treatment for 10 minutes, and finally, the solution is heated to 80 ℃ and kept for 3 hours; washing the red nanosheet with ethanol twice after centrifugation, and drying in vacuum to obtain CuTCPP for later use.
(2) Preparing silver nanoparticles loaded on a two-dimensional sheet metal organic framework: dispersing the CuTCPP nanosheets (20mg) synthesized in step (1) in 8mL of ethanol, followed by AgNO 3 (1mL,100mmol/L in EtOH) was added to the above solution and stirred for 1 hour, then 2.5mL NaBH was added under vigorous stirring 4 (100mmol/L in ice water) for 30 minutes. Then washing the precipitate for 3 to 5 times by water, centrifuging the precipitate, freeze-drying the precipitate and collecting a product to obtain CuTCPP @ AgNPs;
(3) preparing silver-loaded nanoparticles of a two-dimensional sheet metal organic framework modified by mercaptophenylboronic acid: the resulting CuTCPP @ AgNPs (2.5mg/mL pure water solution) and an aqueous solution (50. mu.M) of mercaptophenylboronic acid (MBA) were mixed at a volume ratio of 20: 1. Then, the mixture is stirred and reacted for 12 hours at room temperature in the dark, and is centrifuged for 15 minutes at 12000rpm to remove unreacted chemical substances, and precipitate, namely silver-loaded nanoparticles of the mercaptophenylboronic acid-modified two-dimensional sheet metal organic framework (CuTCPP @ AgNPs @ MBA), is obtained.
Example 2
The silver nanoparticles loaded on the two-dimensional flaky metal organic framework modified by mercaptophenylboronic acid prepared in example 1 are subjected to transmission electron microscopy and ultraviolet fluorescence tests, and the results show that the synthesized copper-based metal organic framework is a two-dimensional flaky material (fig. 1A), silver nanoparticles are uniformly distributed on the nanosheets (fig. 1B), the average particle size is about 17nm, and the lattice spacing of gold nanoparticles is 0.245nm (fig. 1C); the ultraviolet absorption spectrum result shows that CuTCPP @ AgNPs has an ultraviolet absorption peak at the wavelength of 420nm and is a characteristic peak of Ag NPs, the successful loading of gold nanoparticles is proved to have a corresponding characteristic absorption peak (figure 1D), and after the mercaptophenylboronic acid is grafted, the spectrum absorption peak of CuTCPP @ AgNPs @ MBA is reduced, and the successful grafting of MBA is proved; the fluorescence spectrum result (figure 1E) shows that the CuTCPP two-dimensional nanosheet has a strong emission peak at 400nm, and after Ag NPs are grafted, the absorption peak at the wavelength of 440nm of a new emission peak is increased, so that the successful loading of the silver nanoparticles is proved; when MBA is grafted, a new emission peak is reduced at 440nm, and the success of the grafting of the MBA is proved.
Example 3
The solid powders of CuTCPP, CuTCPP @ AgNPs and CuTCPP @ AgNPs @ MBA obtained during the silver nanoparticle loading process of the mercaptophenylboronic acid-modified two-dimensional flake metal-nanosheet prepared in example 1 were tested for infrared spectroscopy, XRD and XPS, respectively. FIG. 2A shows an IR spectrum at 1669cm -1 The C ═ O stretching vibration peak proves that PVP and TCPP exist in CuTCPP, 1000cm- 1 The Cu-N stretching vibration peak proves that Cu is successfully modified in the nanosheet framework; in XRD of FIG. 2B, the existence of characteristic peaks of 8 degrees, 9.5 degrees, 12.5 degrees and 20.5 degrees proves the successful synthesis of CuTCPP nano-sheets; 38.1 DEG and 44.3 DEG corresponding to Ag NPs (111) and (200) crystalsAnd finally, successfully loading Ag NPs on the surface of the CuTCPP nanosheet; the thermogravimetric test result of fig. 2C shows that the loading of the silver nanoparticles is about 30%, and the modification of the mercaptophenylboronic acid is about 0.5%. The XPS spectrum (FIG. 2D) results show that CuTCPP @ AgNPs @ MBA has C, N, O, B, S, Ag and Cu elements. The adsorption energies at 934.6eV and 954.5eV (FIG. 2E) belong to Cu2p respectively 1/2 And Cu2p 3/2 . The characteristic peaks at 374.3eV and 368.3eV (FIG. 2F) belong to Ag3d 3/2 and Ag3d 5/2 . The results prove that the silver nanoparticles are grafted on the surface of the CuTCPP nanosheet.
Example 4
The cuscpp, cuscpp @ AgNPs and cuscpp @ AgNPs @ MBA obtained in the process of loading silver nanoparticles onto the two-dimensional sheet metal-nanosheets modified by the mercaptophenylboronic acid prepared in embodiment 1 are used for detecting the generation capability of active oxygen of different materials under near-infrared irradiation through 2, 7-dichlorofluorescein diacetate (DCFH-DA) (the addition amount is about 6 times of the mass of each material) and detecting the silver ion release change of the cuscpp @ AgNPs @ MBA under the near-infrared irradiation through an inductively coupled plasma emission spectrometer (ICP-OES) to verify the antibacterial mechanism, and the results show that the modification of the mercaptophenylboronic acid can effectively improve the generation capability of the active oxygen (fig. 3A), the release of the silver ions can be accelerated under the near-infrared irradiation (fig. 3B), and the antibacterial potential is remarkably superior.
Example 5
Test for inhibition experiment of silver-loaded nanoparticles of mercaptophenylboronic acid-modified two-dimensional sheet metal organic framework prepared in example 1 and gram-positive bacterium staphylococcus aureus: the bacteria obtained from the culture were centrifuged, washed and diluted to 10 7 CFU/mL. Incubating the prepared bacterial suspension with PBS buffer solution (pH 7.4,10mmol/L as a control), CuTCPP nano-sheets (50 mu g/mL), CuTCPP @ AgNPs (75 mu g/mL) and CuTCPP @ AgNPs @ MBA (75 mu g/mL) at 37 ℃ for 2 hours (the concentrations of the above materials are calculated according to the amount of tetracarboxyphenylporphyrin and thermogravimetric data in a standardized manner, and the concentrations converted for calculating the ROS generation capacity of the material under illumination are calculated according to the final concentration of the added bacterial liquid), and then illuminating with or without near infrared light for 20 minutes (660nm,30mW/cm and 30 mW/cm) 2 ). 100 μ L of the diluted suspension was spread on LB agar platesThen, the cells were incubated at 37 ℃ overnight. Colonies were photographed and counted. Biofilm inhibition experiments were evaluated by crystal violet staining. After the incubation, bacterial pellets were collected and fixed with 2.5% glutaraldehyde at 4 ℃ for 2 hours, and then dehydrated successively for 15 minutes using 30, 50, 70, 90 and 100% ethanol. The samples were then dried in a vacuum oven at 25 ℃ and analyzed by scanning electron microscopy and X-ray elemental spectroscopy. Meanwhile, the effect of live and dead bacteria treated by different materials is evaluated by adopting a Calein-PI double staining method and taking a picture under a fluorescence microscope; cytotoxicity of the material was assessed using a mouse melanoma cell, B16F10, in an MTT assay.
The in-vitro plate experiment of bacteria is shown in figure 4, and the experiment result shows that the two-dimensional sheet metal organic framework silver nanoparticles modified by the mercaptophenylboronic acid have enhanced bacteria clearing capacity, show near-infrared light enhancement and concentration dependence behaviors, can realize a remarkable antibacterial effect at a lower concentration, have high sensitivity, and can obtain a superior antibacterial effect under the condition of ensuring lower toxicity. The result of the biomembrane removing capability test is shown in figure 5, the result shows that the silver-loaded nanoparticles of the two-dimensional sheet metal organic framework modified by the mercaptophenylboronic acid show enhanced biomembrane removing capability, CuTCPP @ AgNPs @ MBA is obviously superior to CuTCPP and CuTCPP @ AgNPs, and the fluorescence imaging (figure 6) and the morphological test (figure 7) of the live and dead bacteria of the bacteria treated by the material are consistent with the results of in vitro bacteriostasis experiments and biomembrane removing capability tests, which indicates that the composite material prepared by the invention has excellent staphylococcus aureus removing capability, and meanwhile, the composite material is used for efficiently and specifically inhibiting gram-positive bacteria staphylococcus aureus and can effectively identify the gram-positive bacteria.
Example 6
Biocompatibility analysis of silver nanoparticles loaded on the mercaptophenylboronic acid-modified two-dimensional sheet metal-organic framework prepared in example 1.
Silver nanoparticles are loaded on the two-dimensional flaky metal organic framework modified by the mercaptophenylboronic acid prepared in the example 1, and the cytotoxicity test is as follows: mouse melanoma cells B16F10 in DMEM containing 10% fetal bovine serum and 25mM glucose in 96-well platesAt 5% CO 2 And culturing at 37 ℃ for 24 h. Next, PBS buffer (pH 7.4,10mmol/L, as a control), CuTCPP nanoplatelets (10,50, 100. mu.g/mL), CuTCPP @ AgNPs (10,50, 100. mu.g/mL), and CuTCPP @ AgNPs @ MBA (10,50, 100. mu.g/mL) were added and incubation continued at 37 ℃ for 24 hours. Then 20. mu.L of MTT37 ℃ was added per well and incubated for 4 h. Finally, the supernatant was removed and replaced with DMSO to dissolve the azomethine. And cell viability was assessed by measuring the ratio of absorbance at 570nm between the experimental and control groups.
The cytotoxicity test obtained is shown in FIG. 8. The above results show that: the nanocomposite prepared in example 1 has low cytotoxicity, and also has a survival rate of about 60% at a concentration of 100. mu.g/mL, indicating good biocompatibility of the material.
Example 7
Example 7 was prepared identically to example 1, except that: cu (NO) in step (1) 3 ) 2 .3H 2 The molar ratio of O, TCPP and PVP is 75: 30: 1.14; the reaction in step (1) was carried out at 100 ℃ for 2 hours. AgNO in step (2) 3 And NaBH 4 The molar ratio of CuTCPP to AgNO is 2:5 3 The mass ratio is 4: 3.
Example 8
Example 8 was prepared in the same manner as example 1, except that: cu (NO) in step (1) 3 ) 2 .3H 2 The molar ratio of O, TCPP and PVP is 75: 20: 1.14; the reaction in step (1) was carried out at 90 ℃ for 2.5 hours. AgNO in step (2) 3 And NaBH 4 A molar ratio of 1.5:5.5, CuTCPP and AgNO 3 The mass ratio is 4: 4.
Claims (10)
1. A preparation method of silver nanoparticles loaded on a two-dimensional sheet metal organic framework modified by mercaptophenylboronic acid is characterized by comprising the following steps:
(1) copper nitrate Cu (NO) 3 ) 2 .3H 2 Adding O, polyvinylpyrrolidone and trifluoroacetic acid into a solvent, mixing, adding N, N-Dimethylformamide (DMF) containing tetracarboxyphenol porphyrin (TCPP) into the solvent for reaction, washing the reaction product after the reaction, and drying the reaction product in vacuum to obtain a two-dimensional sheet metal organic framework (CuTCPP);
(2) dispersing the two-dimensional sheet metal organic framework obtained in the step (1) in a solvent, and then adding AgNO 3 And NaBH 4 After the reaction product is washed, the product is frozen, dried and collected to obtain the silver-loaded nano-particles of the two-dimensional metal organic framework;
(3) and (3) dispersing the two-dimensional flaky metal organic framework loaded silver nanoparticles obtained in the step (2) in pure water, adding mercaptophenylboronic acid into the pure water for mixing, incubating the mixture, and centrifuging to obtain a precipitate, namely the mercaptophenylboronic acid modified two-dimensional flaky metal organic framework loaded silver nanoparticles.
2. The method for preparing silver nanoparticles loaded on two-dimensional flaky metal organic framework modified by mercaptophenylboronic acid according to claim 1, wherein in the step (1), Cu (NO) is added 3 ) 2 .3H 2 The molar ratio of O, TCPP and PVP is 75: 30: 1.14-75: 20: 1.14.
3. the method for preparing silver nanoparticles loaded on a two-dimensional flaky metal organic framework modified by mercaptophenylboronic acid according to claim 1, wherein the solvent in the step (1) is preferably a mixed solvent of N, N-dimethylformamide and ethanol.
4. The preparation method of the silver nanoparticle loaded on the mercaptophenylboronic acid-modified two-dimensional sheet metal organic framework according to claim 1, wherein the reaction in step (1) is carried out at 80-100 ℃ for 2-3 hours, the copper-based metal organic framework obtained after the reaction is washed with ethanol and DMF, and the powder obtained after vacuum drying is a two-dimensional sheet metal nanosheet.
5. The preparation method of the mercaptophenylboronic acid-modified two-dimensional sheet metal-nanosheet silver-loaded nanoparticle as claimed in claim 1, wherein the two-dimensional sheet metal-organic framework in step (2) is dispersed in an ethanol solution under oscillatory ultrasound, silver nitrate is reduced in situ by sodium borohydride for half an hour, and the obtained solution is centrifugally washed and freeze-dried to obtain the two-dimensional sheet metal-organic framework silver-loaded nanoparticle for later use.
6. The method for preparing silver nanoparticles loaded on the mercaptophenylboronic acid-modified two-dimensional sheet metal-organic framework according to claim 1, wherein AgNO in the step (2) 3 And NaBH 4 The mol ratio of CuTCPP to AgNO is 2:5-1.5:5.5 3 The mass ratio is 4: 3-4: 4.
7. The method for preparing silver nanoparticles loaded on two-dimensional flaky metal-nanosheets modified by mercaptophenylboronic acid according to claim 1, wherein the silver nanoparticles loaded on two-dimensional metal nanosheets in step (3) are dispersed in pure water, mercaptoboronic acid is added and mixed, and then the mixture is stirred at room temperature in the dark for 12-15 h.
8. The method for preparing silver nanoparticles loaded on the two-dimensional flaky metal-organic framework modified by mercaptophenylboronic acid according to claim 1, wherein the mass ratio of the silver nanoparticles loaded on the two-dimensional flaky metal-organic framework to the mercaptophenylboronic acid in step (3) is 50000:6-50000: 10.
9. the silver nanoparticle loaded on the mercaptophenylboronic acid-modified two-dimensional sheet metal-organic framework, which is prepared by the method for preparing silver nanoparticles loaded on the mercaptophenylboronic acid-modified two-dimensional sheet metal-organic framework according to claim 1.
10. The application of the mercaptophenylboronic acid modified two-dimensional sheet metal organic framework loaded silver nanoparticles as claimed in claim 9 in clearing gram-positive bacteria and inhibiting biofilm formation.
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