CN114479105B - Metal organic framework material for antibacterial therapy and preparation method and application thereof - Google Patents
Metal organic framework material for antibacterial therapy and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a metal organic framework material for antibacterial therapy, a preparation method and application thereof, and the scheme skillfully adopts a solvothermal method to successfully introduce TCPP into UiO-66- (SH) 2 In the framework, the prepared antibacterial material has a nano-scale size, the particle size is about 90nm, the antibacterial material can effectively contact and enter bacteria to play an antibacterial role, the antibacterial material has remarkable antibacterial performance on gram-positive bacteria, gram-negative bacteria and antibiotic-resistant bacteria, the antibacterial material of the scheme is a zirconium-based metal organic framework, and compared with other metal organic frameworks, the antibacterial material has good biocompatibility.
Description
Technical Field
The invention relates to the technical field of medical materials, in particular to a metal organic framework material for antibacterial therapy and a preparation method and application thereof.
Background
Bacteria are closely related to the life of people, and bring various conveniences to people and a series of disasters, wherein the most serious is bacterial infection. In order to treat bacterial infection, a large amount of antibiotics is put into clinical treatment, however, the use of a large amount of antibiotics causes drug resistance of bacteria, thereby causing the appearance of superbacteria. In recent years, the incidence of multi-drug resistant bacteria and wide-drug resistant bacteria is increasing, and the discovery of novel antibiotics is at a low level. Therefore, it is very necessary to develop a new material having high antibacterial properties while avoiding the generation of resistance.
Disclosure of Invention
In view of the above, the present invention aims to provide a metal organic framework material for antimicrobial therapy, which is reliable in implementation, convenient in preparation, simple and efficient in antimicrobial, and a preparation method and an application thereof.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a metal-organic frame material for antibacterial therapy is prepared from UiO-66- (SH) with Zr as metal node 2 TCPP and Ag NPs are doped to prepare the metal organic framework material UiO-66- (SH) 2 @ TCPP @ AgNP; wherein, the Ag NPs and the Zr are UiO-66- (SH) of a metal node 2 The mercapto group in (A) forms an S-Ag bond.
The invention also provides a preparation method of the metal organic framework material for antibacterial therapy, which comprises the following steps:
(1) Preparing zirconium chloride, 2,5-dimercaptoterephthalic acid and TCPP into mixed solution according to preset stoichiometric ratio
(2) Putting the mixed solution into a container with a plug, and heating to generate a precipitate;
(3) Washing the precipitate generated in the step (2), and then drying in vacuum to obtain apricot solid powder;
(4) Mixing the powder prepared in the step (3) with a silver nitrate solution, then placing the mixture under a xenon lamp to stir violently for reaction, washing and drying the product to prepare UiO-66- (SH) 2 @ TCPP @ AgNPs material.
As a preferred implementation option, in the step (1), the mixing mass ratio of the zirconium chloride, 2,5-dimercaptoterephthalic acid and TCPP is preferably 1.4: 2: 0.5-1.
As a preferable implementation option, in the step (2), the temperature of the heating treatment is preferably 130 ℃, and the treatment time is preferably 10 to 14 hours.
As a preferred implementation option, in the step (3), the precipitate generated in the step (2) is preferably washed by DMF and ethanol, and the temperature of the vacuum drying treatment is 70-100 ℃ and the time is 12-14 h.
As a better implementation choice, preferably, in the step (4), the concentration of the silver nitrate is 5-20 mg/mL, the reaction time is 1h, and the washing solvent is water and ethanol.
The metal organic framework material prepared by the preparation method is applied to the antibiosis of gram-positive bacteria, gram-negative bacteria and antibiotic-resistant bacteria.
By adopting the technical scheme, compared with the prior art, the invention has the beneficial effects that: the scheme ingeniously adopts a solvothermal method to successfully introduce TCPP into UiO-66- (SH) 2 In the framework, the prepared antibacterial material has a nano-scale size, the particle size is about 90nm, the antibacterial material can effectively contact and enter bacteria to play an antibacterial role, the antibacterial material has remarkable antibacterial performance on gram-positive bacteria, gram-negative bacteria and antibiotic-resistant bacteria, the antibacterial material is a zirconium-based metal organic framework and has good biocompatibility compared with other metal-based metal organic frameworks, in addition, ag NPs in the antibacterial material are connected with sulfydryl through S-Ag bonds, the cytotoxicity caused by leakage of the Ag NPs is reduced while the yield of active oxygen of the material is enhanced, meanwhile, the antibacterial material can promote cell proliferation under the irradiation of visible light, and has the potential of promoting wound healing.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows UiO-66- (SH) according to the invention 2 The structure of @ TCPP @ AgNPs is schematically shown;
FIG. 2 is a solid ultraviolet diffuse reflectance spectrum of the antibacterial material of the present invention, the abscissa represents wavelength and the ordinate represents absorbance;
FIG. 3 is a transient photocurrent response spectrum of the antibacterial material of the present invention, with the abscissa representing time and the ordinate representing photocurrent intensity;
FIG. 4 is a UV spectrum of the active oxygen yield of the antibacterial material under visible light, the active oxygen detecting probe is diphenyl isobenzofuran, the abscissa is time, and the ordinate represents the UV absorption ratio (I/I) 0 )；
FIG. 5 is a confocal microscope (2 μm scale) of the antibacterial material of the present invention after co-incubation with bacteria;
FIG. 6 is a scanning electron microscope image of the antibacterial material of the present invention before and after treating bacteria;
fig. 7 is a graph showing cytotoxicity of the antibacterial material according to the present invention, the abscissa represents the concentration of the antibacterial material, and the ordinate represents the cell survival rate.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples. It is to be noted that the following examples are only illustrative of the present invention, and do not limit the scope of the present invention. Likewise, the following examples are only some examples, not all examples, and all other examples obtained by those skilled in the art without any inventive work are within the scope of the present invention.
Example 1
The embodiment of the invention relates to a preparation method of a metal organic framework material for antibacterial therapy, which comprises the following steps:
(1)UiO-66-(SH) 2 preparation of @ TCPP:
zirconium chloride (30mg, 0.13mmol)) and 2,5-dimercaptoterephthalic acid (41.6mg, 0.18mmol) were dissolved in 2mL of DMF and sonicated for 10 minutes to dissolve the solution. TCPP (20.8mg, 0.03mmol) and benzoic acid (600mg, 4.91mmol) were then added and the solution sonicated for 10min. The solution was placed in a 10mL graduated tube with a stopper and reacted at 130 ℃ for 12 hours. After the reaction, the reaction mixture was centrifuged (10000 rpm,5 minutes) the precipitate was collected. The supernatant was washed colorless with DMF and then 3 times with ethanol. Collecting precipitate, vacuum drying at 70 deg.C for 14h, grinding to obtain UiO-66- (SH) 2 @ TCPP solid powder.
(2)UiO-66-(SH) 2 Preparation of @ TCPP @ AgNPs:
20mg of UiO-66- (SH) 2 @ TCPP 2mL of ultrapure water and 3mL of ethanol were added, and 200. Mu.L of AgNO was added under stirring 3 Aqueous solution (20 mg/mL). Argon gas was blown into the solution to ensure that the air in the solution was evacuated. Stir vigorously and irradiate for 1 hour using a xenon lamp. After the reaction was completed, the precipitate was collected by centrifugation (10000rpm, 5 minutes). The precipitate was washed 3 times with ultrapure water and then twice with ethanol. Collecting precipitate, vacuum drying at 70 deg.C for 14h, grinding to obtain UiO-66- (SH) 2 The solid powder of @ TCPP @ AgNPs has a schematic structure shown in FIG. 1.
Characterization test
For UiO-66- (SH) prepared in this example 2 The solid powders of @ TCPP @ AgNPs were characterized to obtain the results shown in FIGS. 2-4, in which:
FIG. 2 is a solid ultraviolet diffuse reflectance spectrum of the antibacterial material of the present invention, the abscissa represents wavelength and the ordinate represents absorbance;
FIG. 3 is a transient photocurrent response spectrum of the antibacterial material of the present invention, with the abscissa representing time and the ordinate representing photocurrent intensity;
FIG. 4 is a UV spectrum of the active oxygen yield of the antibacterial material under visible light, the active oxygen detecting probe is diphenyl isobenzofuran, the abscissa is time, and the ordinate represents the UV absorption ratio (I/I) 0 )。
Antibacterial testing
The UiO-66- (SH) produced in this example 2 The @ TCPP @ AgNPs solid powder was subjected to an antibacterial property test to obtain the structures shown in FIGS. 5 to 7, wherein,
FIG. 5 is a confocal microscope (2 μm scale) of the antibacterial material of the present invention after co-incubation with bacteria;
FIG. 6 is a scanning electron microscope image of the antibacterial material of the present invention before and after treating bacteria;
fig. 7 is a graph showing cytotoxicity of the antibacterial material according to the present invention, the abscissa represents the concentration of the antibacterial material, and the ordinate represents the cell survival rate.
Example 2
This example is an application of the metal organic frame material prepared in example 1 in antibacterial aspect, and includes:
preparing an antibacterial material into 40mg/mL suspension, adding 100 mu L of LB culture medium into each hole of a 96-hole plate, then preparing 100 mu L of the antibacterial material suspension into a first row of holes, preparing the antibacterial material into a series of concentration gradients by using a two-fold dilution method, then respectively adding 100 mu L of bacterial liquid of different bacteria into each hole, culturing at 37 ℃ for 24 hours, culturing in a dark group in a dark place, and culturing in a light group in a visible light place. After the culture is finished, taking out the bacterial liquid, coating the bacterial liquid on a solid culture medium, culturing the bacterial liquid at 37 ℃ for 24 hours, observing the growth condition of bacterial colonies, and carrying out three groups of parallel experiments on each group. The experimental result shows that the minimum antibacterial concentration of the antibacterial material to gram-positive bacteria (staphylococcus aureus), gram-negative bacteria (escherichia coli) and antibiotic-resistant bacteria (methicillin-resistant staphylococcus aureus) under illumination is 39 ppm, 19.5ppm and 19.5ppm respectively. Therefore, the antibacterial material has important value for various antibacterial applications.
For reference, the scheme also uses UiO-66- (SH) 2 、UiO-66-(SH) 2 @AgNPs、UiO-66-(SH) 2 The @ TCPP material was used as a control group to perform a minimum antimicrobial concentration test of gram-positive bacteria (staphylococcus aureus), negative bacteria (escherichia coli) and antibiotic-resistant bacteria (methicillin-resistant staphylococcus aureus), and the following results were obtained as shown in table 1 below, specifically:
TABLE 1 control experiment for minimum antimicrobial concentration
The above description is only a part of the embodiments of the present invention, and not intended to limit the scope of the present invention, and all equivalent devices or equivalent processes performed by the contents of the present specification and the attached drawings, or directly or indirectly applied to other related technical fields, are all included in the scope of the present invention.
Claims (2)
1. A preparation method of a metal organic framework material for antibacterial therapy is characterized in that the metal organic framework material is UiO-66- (SH) taking Zr as a metal node 2 TCPP and Ag NPs are doped to prepare the metal organic framework material UiO-66- (SH) 2 @ TCPP @ AgNPs; in the metal organic framework material, ag NPs and Zr are UiO-66- (SH) of metal nodes 2 The sulfydryl in the compound forms an S-Ag bond;
the preparation method comprises the following steps:
(1) Preparing zirconium chloride, 2,5-dimercaptoterephthalic acid and TCPP into mixed solution according to a preset stoichiometric ratio
(2) Putting the mixed solution into a container with a plug, and heating to generate a precipitate;
(3) Washing the precipitate generated in the step (2), and then drying in vacuum to obtain apricot solid powder;
(4) Mixing the powder prepared in the step (3) with a silver nitrate solution, then placing the mixture under a xenon lamp to stir violently for reaction, washing and drying the product to prepare UiO-66- (SH) 2 @ TCPP @ AgNPs material;
wherein in the step (1), the mixing mass ratio of the zirconium chloride, 2,5-dimercaptoterephthalic acid and TCPP is 1.4: 2: 0.5-1;
in addition, in the step (2), the temperature of the heating treatment is 130 ℃, and the treatment time is 10-14 h;
in the step (3), washing the precipitate generated in the step (2) by DMF and ethanol, wherein the temperature of vacuum drying treatment is 70-100 ℃, and the time is 12-14 h;
in the step (4), the concentration of the silver nitrate is 5-20 mg/mL, the reaction time is 1h, and the washing solvents are water and ethanol.
2. The metal organic framework material prepared by the preparation method of claim 1 has antibacterial application in gram-positive bacteria, gram-negative bacteria and antibiotic-resistant bacteria.
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