CN112625277B - A kind of preparation method of metal organic framework@polydopamine film - Google Patents
A kind of preparation method of metal organic framework@polydopamine film Download PDFInfo
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- CN112625277B CN112625277B CN202011390113.9A CN202011390113A CN112625277B CN 112625277 B CN112625277 B CN 112625277B CN 202011390113 A CN202011390113 A CN 202011390113A CN 112625277 B CN112625277 B CN 112625277B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/02—Polyamines
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- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明的目的在于研究一种快速、高效且可以广泛应用的方法制备金属有机框架@聚多巴胺薄膜，并应用于抗菌领域，属于无机‑聚合物杂化材料及生物医用领域。本发明的基本步骤如下：可见光照射下，将金属有机框架纳米粒子与多巴胺(DA)混合，并将所需基底置于该体系中，一定反应时间后，经过干燥，得到金属有机框架@聚多巴胺薄膜。将光敏剂载至该多孔膜上，即可得到所述金属有机框架@聚多巴胺抗菌薄膜。该方法的优点是易于操作，反应条件温和，成本低廉，得到的金属有机框架@聚多巴胺膜可以在所需基底上稳定、均匀存在，且对革兰氏阴性菌与革兰氏阳性菌均具有突出的抗菌效果。The purpose of the present invention is to study a fast, efficient and widely applicable method to prepare metal-organic framework@polydopamine thin film, and apply it to the field of antibacterial, which belongs to the fields of inorganic-polymer hybrid materials and biomedicine. The basic steps of the present invention are as follows: under the irradiation of visible light, the metal organic framework nanoparticles are mixed with dopamine (DA), and the required substrate is placed in the system, and after a certain reaction time, after drying, the metal organic framework@polydopamine is obtained film. The metal organic framework@polydopamine antibacterial film can be obtained by loading the photosensitizer on the porous film. The advantages of this method are easy operation, mild reaction conditions and low cost, the obtained metal-organic framework@polydopamine membrane can be stably and uniformly existing on the desired substrate, and has good resistance to both Gram-negative and Gram-positive bacteria. Outstanding antibacterial effect.
Description
Technical Field
The invention relates to a preparation technology of a metal organic framework film, belonging to the technical field of surface antibiosis of inorganic polymer hybrid materials and biomedical materials.
Background
A Metal Organic Framework (MOF) is a novel nano porous crystal material and is formed by constructing inorganic nodes and organic ligands. The metal organic framework has a great application prospect in the aspects of gas storage, separation science, catalytic reaction, electronic devices and drug delivery due to the high surface area, adjustable pore size and abundant physicochemical properties. Currently, most MOF materials exist in bulk or powder solid state and are applied, however, for such crystalline MOF materials, further processing is required if application in the fields of membrane science, surface engineering and sensors is required. Therefore, the assembly of MOF materials to desired material surfaces is of far-reaching value for extending the advanced applications of such crystalline materials.
At present, many MOF thin film assembling methods are available, including Langmuir-Blodgett layer-layer deposition method, liquid phase epitaxy growth method (LPE), direct solvothermal synthesis method, secondary growth method and electrochemical deposition method. In the above "bottom-up" assembly methods, it is common to grow the MOF material in situ on the surface of a pre-modified substrate material to form a crystal layer. However, in most cases, the assembly process requires a long reaction time, severe reaction conditions (high temperature), or a complicated reaction process. Therefore, the assembly of already prepared MOF materials directly to the substrate surface is another strategy than the "bottom-up" (bottom-up) approach described above. This "top-down" approach has potential applications in assembling MOFs of different sizes and morphologies to substrate materials. However, the assembly of MOF nanoparticles directly to substrate materials still presents difficulties and challenges, and the need for advanced pre-modification of the substrate materials remains. Furthermore, even if successfully assembled to a substrate surface, MOF nanoparticles tend to aggregate into clumps on the surface, fail to stably adhere to the substrate surface, and tend to fall off. Therefore, how to assemble the existing MOF nanocrystalline materials to the desired substrate material by a simple method is an urgent problem to be solved for forming uniform and stable MOF films.
In recent years, the surface chemistry inspired by mussels has become a research hotspot in the field of material science. Dopamine (DA) is a well-known neurotransmitter in the human body, and is known to self-polymerize in oxygen-containing alkaline solutions to form Polydopamine (PDA) and to form surface coatings on various material surfaces at ambient temperatures. DA is very similar in molecular structure to the dihydroxyphenylalanine in mussel foot protein, which is associated with the strong adhesion of mussels on marine substrates. Similarly, PDAs can be adhered to almost all types of substrates by similar principles, including some low surface energy substrate materials. The adhesion mechanism of PDA is caused by several different interactions, including hydrogen bonding interactions, chelation, electrostatic and hydrophobic interactions. PDA can be used as a multifunctional platform to modify the surfaces of different types of materials, and is also widely applied to the fixation of nano particles on the surface of a substrate due to the superior adhesion property of PDA. However, the DA polymerization process needs to be performed under alkaline conditions, and is not suitable for some base materials that are unstable under alkaline conditions. In addition, DA usually has a reaction time of more than 24 hours, and the use efficiency is greatly reduced due to the overlong reaction time. Therefore, the use of PDA as an intermediate medium to achieve (neutral) fast MOF nanoparticle assembly under mild conditions remains to be addressed.
Disclosure of Invention
The invention aims to provide a preparation method of a metal organic framework @ polydopamine film, which can realize the rapid preparation of a required composite film under mild conditions and is suitable for the surfaces of different substrate materials. The method solves the problems of long reaction time, complex reaction steps and uneven dispersion of MOF particles in the film in the traditional method, and the prepared film has excellent stability and can be firmly combined with a substrate material in water and an organic solvent.
In order to achieve the purpose, the preparation method of the metal organic framework @ polydopamine film specifically comprises the following steps: ultrasonically dispersing a metal organic framework and Dopamine (DA) in a trihydroxymethyl aminomethane-hydrogen chloride (Tris-HCl) buffer solution with the pH value of 7, adding a substrate material, and carrying out oscillation reaction in a shaking table at 30 ℃ for 1-4 h under the irradiation of light to obtain a metal organic framework @ polydopamine film on the surface of the substrate material;
in the method, the metal organic framework generates active oxygen under the irradiation of light, the active oxygen can promote dopamine to react to obtain Polydopamine (PDA), the aggregation caused by excessive polydopamine is avoided, and the moderately polymerized polydopamine further promotes the UiO-66 to form a uniform and stable UiO-66@ PDA composite film on the substrate material.
The above active oxygen generating metal organic framework includes, but is not limited to, UiO-66, which can generate active oxygen under visible light.
In certain embodiments, the Dopamine (DA) is present in a Tris-HCl buffer solution at a concentration of 2mg/mL and the metal-organic framework is present at a concentration of 2-4 mg/mL.
Suitable substrate materials for use herein include, but are not limited to, filter paper fiber films, polyethylene films (PE), silicon wafers.
In some preferred embodiments, the method further comprises the step of ultrasonically cleaning the metal organic framework @ polydopamine (UiO-66@ PDA) film obtained after shaking table oscillation reaction in water and ethanol, so as to remove unreacted or reaction-unstable DA and UiO-66, and obtain a composite film with uniform and stable UiO-66 nanoparticle assembly.
The metal organic framework @ polydopamine film prepared by the method has a porous property, can be loaded with a photosensitizer, and has an outstanding antibacterial effect on both gram-negative bacteria and gram-positive bacteria under the irradiation of visible light.
Therefore, as a second aspect of the present invention, the present invention provides a preparation method of a metal organic framework @ polydopamine antibacterial film, specifically:
adding a photosensitizer and the metal organic framework @ polydopamine film prepared by the method into an RB aqueous solution, adsorbing for 4-24 h at room temperature, washing and vacuum drying the obtained sample, and thus obtaining the metal organic framework @ polydopamine antibacterial film.
Compared with the prior art, the invention has the following advantages:
(1) in the invention, visible light-mediated and dopamine-assisted metal-organic frameworks are assembled on substrates of different materials to form films. The metal-organic framework nanoparticles to be assembled can generate a proper amount of active oxygen under visible light irradiation to promote polymerization of dopamine, and the Polymerized Dopamine (PDA) can promote assembly of the nanoparticles on a substrate in turn. The metal organic framework, the visible light and the dopamine act synergistically in the system to obtain the metal organic framework @ polydopamine film.
(2) According to the invention, the limitation that the traditional method needs reaction in an alkaline solution is overcome, and the assembly of the metal organic framework @ polydopamine film can be completed in a neutral environment. A film preparation mechanism based on a 'dopamine sensitization effect' is provided, dopamine is used as an electron transfer medium to transfer photogenerated electrons into a conduction band of a metal organic framework, oxygen on the surface is reduced to obtain active oxygen (ROS), and the generated active oxygen is used as an oxidizing agent to initiate dopamine polymerization in a neutral environment with the pH value of 7, so that the assembly of the metal organic framework on a substrate is promoted. The neutral environment can prevent dopamine from polymerizing rapidly under the irradiation of light, avoid excessive poly-dopamine particles from forming and aggregating in a liquid phase, and ensure that enough dopamine is used as a binder to connect the metal organic framework and the substrate. Therefore, the invention provides a new scheme for preparing the film for materials which are sensitive to pH (substrates which are easily damaged under alkaline conditions).
(3) Under the synergistic action of visible light, dopamine and a metal organic framework, the rapid assembly of the metal organic framework @ polydopamine film can be realized, and the problem of assembling the metal organic framework on the surface of an unmodified substrate material is solved. In addition, according to the invention, the substrate of the material to be reacted is not required to be modified in advance, so that the defect of long reaction time of dopamine is greatly shortened, and the film preparation can be completed within 4 hours. Therefore, the technology shortens the reaction time, optimizes the reaction conditions and simplifies the reaction steps.
(4) Under the synergistic effect of visible light, dopamine and a metal organic framework, the obtained metal organic framework @ polydopamine film is uniform and compact and has excellent stability. The appropriate amount of active oxygen generated by visible light irradiation can ensure that only a certain amount of dopamine is polymerized, and the phenomenon of massive poly-dopamine aggregation and integration can not occur, so that the metal organic framework nano particles can be uniformly distributed on the substrate and are approximately dispersed in a single layer to form a very compact film. The prepared metal organic framework @ polydopamine film can be firmly combined with a substrate, is stable in structure, is washed by deionized water, and can still maintain the film structure after ultrasonic cleaning in ethanol.
(5) The metal organic framework @ polydopamine film has excellent adsorption performance and is the combination of a photosensitizer on the filmA platform is provided. The photosensitizer is an important component in photodynamic sterilization, and can generate active oxygen (singlet oxygen) under illumination1O2) Thereby promoting bacterial inactivation. Compared with the traditional bactericide, the active oxygen has strong reactivity and small non-specificity to bacteria, so that the bacteria can be prevented from generating drug resistance, and the risk of formation of super bacteria is reduced. Through the combination of the photosensitizer and the composite film, the metal organic framework @ polydopamine antibacterial film prepared by the technology shows excellent bactericidal activity. Under visible light, the sterilization rate of the antibacterial agent for the two test bacteria, namely staphylococcus aureus and escherichia coli, can reach 99.9 percent in only 5 minutes.
Drawings
FIG. 1 is a schematic diagram of the assembly of a metal organic framework @ polydopamine film;
FIG. 2 is a schematic diagram of an antibacterial mechanism of the metal organic framework @ polydopamine antibacterial film;
FIG. 3 is a schematic diagram of the mechanism of "dopamine sensitization effect";
FIG. 4 is a comparison graph of the effects of a metal organic framework @ polydopamine film before and after the assembly on the surface of a material: (a) a raw filter paper fiber membrane; (b) a metal organic framework @ polydopamine film; (c) a partially enlarged view;
FIG. 5 is a graph showing the antibacterial property test (Staphylococcus aureus and Escherichia coli as test strains);
FIG. 6 is a graph showing the effect of a metal-organic framework @ polydopamine film after assembly on the surface of a material when the concentration of metal-organic framework nanoparticles is changed;
FIG. 7 is a graph of the effect of a metal organic framework @ polydopamine film after assembly on the surface of a material when the time of a light reaction is shortened;
FIG. 8 is a graph of the effect of a metal organic framework @ polydopamine film after assembly on the surface of a material when the light reaction is prolonged;
FIG. 9 is a graph comparing the effect of stability of a metal organic framework @ polydopamine film on the surface of a material: (a) ultrasonically cleaning the metal organic framework film; (b) and (3) carrying out ultrasonic cleaning on the metal organic framework @ polydopamine film.
Detailed Description
In the following examples, the metal-organic framework nanoparticles UiO-66 were prepared as follows:
the required metal salt is zirconium tetrachloride, the ligand is terephthalic acid, and the reaction solvent is N, N-dimethylformamide. 53mg of zirconium tetrachloride and 34mg of terephthalic acid were dispersed in a solvent by ultrasound, and a small amount of glacial acetic acid was added. Injecting the solution into a reaction kettle, reacting at 120 ℃ for 24 hours, and naturally cooling at room temperature. High-speed centrifugation to obtain a solid product, repeating the process for 3 times by using a solvent N, N-dimethylformamide, and then placing the solid product in a vacuum drying oven at 80 ℃ for drying overnight.
Example 1 preparation of a Metal organic framework @ Polydopamine film
Preparing a Tris (hydroxymethyl) aminomethane-hydrogen chloride (Tris-HCl) buffer solution with the concentration of 2mg/mL, and adjusting the pH value to 7 by using a hydrochloric acid solvent. Ultrasonically dispersing a metal organic framework UiO-66 and Dopamine (DA) in a solvent, wherein the concentration of the UiO-66 is 2mg/mL, and the concentration of the Dopamine (DA) is 2 mg/mL. The silicon chip used in the reaction is firstly cleaned in deionized water by ultrasonic for 15min, and then is added into the reaction system after cleaning, and the metal is reacted for 1h under the irradiation of a visible light source. Taking out a sample after reaction, washing with deionized water, performing ultrasonic treatment in ethanol for 20min, and performing vacuum drying at room temperature to obtain a uniformly and densely distributed metal organic framework @ polydopamine (UiO-66@ PDA) film, wherein as shown in FIG. 4, the film has extremely high stability, and the film structure cannot be damaged by high-strength ultrasonic treatment.
Example 2 preparation of a Metal organic framework @ Polydopamine film
Preparing a Tris (hydroxymethyl) aminomethane-hydrogen chloride (Tris-HCl) buffer solution with the concentration of 2mg/mL, and adjusting the pH value to 7 by using a hydrochloric acid solvent. Ultrasonically dispersing a metal organic framework UiO-66 and Dopamine (DA) in a solvent, wherein the concentration of the UiO-66 is 4mg/mL, and the concentration of the Dopamine (DA) is 2 mg/mL. The filter paper fiber membrane used in the reaction is firstly ultrasonically cleaned in deionized water for 15min, and then is added into the reaction system after being cleaned, and the metal is reacted for 4h under the irradiation of a visible light source. And taking out a sample after reaction, washing with deionized water, performing ultrasonic treatment in ethanol for 20min, and performing vacuum drying at room temperature to obtain a uniformly and densely distributed metal organic framework @ polydopamine (UiO-66@ PDA) film, as shown in FIG. 6.
Example 3 preparation of a Metal organic framework @ Polydopamine film
Preparing a Tris (hydroxymethyl) aminomethane-hydrogen chloride (Tris-HCl) buffer solution with the concentration of 2mg/mL, and adjusting the pH value to 7 by using a hydrochloric acid solvent. Ultrasonically dispersing a metal organic framework UiO-66 and Dopamine (DA) in a solvent, wherein the concentration of the UiO-66 is 2mg/mL, and the concentration of the Dopamine (DA) is 2 mg/mL. The polyethylene film (PE) used in the reaction is firstly ultrasonically cleaned in deionized water for 15min, and then is added into the reaction system after being cleaned, and the metal is reacted for 2h under the irradiation of a visible light source. And taking out a reacted sample, washing the sample by deionized water, then carrying out ultrasonic treatment in ethanol, and carrying out vacuum drying at room temperature to obtain a small amount of uniformly dispersed metal organic framework @ polydopamine (UiO-66@ PDA) film, wherein the film is shown in figure 7.
Example 4 preparation of a Metal organic framework @ Polydopamine film
Preparing a Tris (hydroxymethyl) aminomethane-hydrogen chloride (Tris-HCl) buffer solution with the concentration of 2mg/mL, and adjusting the pH value to 7 by using a hydrochloric acid solvent. Ultrasonically dispersing a metal organic framework UiO-66 and Dopamine (DA) in a solvent, wherein the concentration of the UiO-66 is 2mg/mL, and the concentration of the Dopamine (DA) is 2 mg/mL. The polyethylene film (PE) used in the reaction is firstly ultrasonically cleaned in deionized water for 15min, and then is added into the reaction system after being cleaned, and the metal is reacted for 6h under the irradiation of a visible light source. And taking out a sample after reaction, washing with deionized water, performing ultrasonic treatment in ethanol for 20min, and performing vacuum drying at room temperature to obtain a uniformly distributed metal organic framework @ polydopamine (UiO-66@ PDA) film, as shown in FIG. 8.
Example 5
1) Preparation of Metal organic framework films
Preparing a Tris (hydroxymethyl) aminomethane-hydrogen chloride (Tris-HCl) buffer solution with the concentration of 2mg/mL, and adjusting the pH value to 7 by using a hydrochloric acid solvent. The metal organic framework UiO-66 is dispersed in the solvent by ultrasonic, and the concentration of the UiO-66 is 2 mg/mL. The silicon chip used in the reaction is firstly cleaned in deionized water by ultrasonic for 15min, and then is added into the reaction system after being cleaned, and the metal is reacted for 6h under the irradiation of a visible light source. Taking out the reacted sample, washing with deionized water, performing ultrasonic treatment in ethanol for 10min, and performing vacuum drying at room temperature to obtain a substrate material with only a small amount of agglomerated and accumulated metal-organic framework particles, as shown in fig. 9 (a);
2) preparation of Metal organic framework @ Polydopamine film
Preparing a Tris (hydroxymethyl) aminomethane-hydrogen chloride (Tris-HCl) buffer solution with the concentration of 2mg/mL, and adjusting the pH value to 7 by using a hydrochloric acid solvent. Ultrasonically dispersing a metal organic framework UiO-66 and Dopamine (DA) in a solvent, wherein the concentration of the UiO-66 is 2mg/mL, and the concentration of the Dopamine (DA) is 2 mg/mL. The silicon chip used in the reaction is firstly cleaned in deionized water by ultrasonic for 15min, and then is added into the reaction system after being cleaned, and the metal is reacted for 6h under the irradiation of a visible light source. And (3) taking out a sample after reaction, washing with deionized water, performing ultrasonic treatment in ethanol for 10min, and performing vacuum drying at room temperature, wherein the surface of the substrate material still retains a metal organic framework @ polydopamine (UiO-66@ PDA) film which is excellent in stability and uniform in distribution, as shown in fig. 9 (b).
Example 6 preparation of a Metal organic framework @ Polydopamine antibacterial film
1) Selecting Bengal (RB), which can stably generate a large amount of active oxygen under visible light, as a photosensitizer, a metal organic framework @ polydopamine (UiO-66@ PDA) film (2 x 1.5cm in size) prepared in example 2 was used2) Adding the solution into 10mL of RB aqueous solution with the concentration of 4mg/mL, adsorbing for 4-24 h at room temperature, washing the obtained sample with deionized water, and drying in vacuum to obtain the uniformly distributed metal organic framework @ polydopamine antibacterial film (UiO-66@ PDA @ RB).
2) Test for antibacterial effect of metal organic framework @ polydopamine antibacterial film
Staphylococcus aureus and Escherichia coli were selected as typical test bacteria. The bacterial strains were grown in liquid medium at 37 ℃ for 12 h. The bacteria were then collected by centrifugation (3000rpm, 6 minutes) and washed three times with phosphate buffered saline. Re-dispersing the obtained bacteria in phosphate buffer salt solution, and adjusting the concentration of the bacteria by a microplate reader to obtain a bacteria solution for testing the antibacterial effect, wherein the concentration of the bacteria solution is about 106CFU/mL-1。
All samples (target samples) were tested prior to testingAnd control samples) were sterilized. The size of the sample is 2 multiplied by 1.5cm2The metal organic framework @ poly dopamine antibacterial film (UiO-66@ PDA @ RB) is placed in a 6-well culture plate, and then a bacterial solution (10) is added6CFU/mL-1Staphylococcus aureus and escherichia coli, 100 μ L) were dropped directly onto the sample. After 5min of LED visible light irradiation, 5mL phosphate buffer solution was added to the culture plate and sonicated for 3 min. And (3) adding 500 mu L of ultrasonic liquid into a sterilization tube, and adding 4.5mL of phosphate buffer saline solution for dilution to obtain the bacterial dispersion liquid required by plating culture.
200 mu L of the bacterial liquid is placed on a solid culture medium, incubated at 37 ℃ for 16 hours, photographed and recorded, and the bacterial colony number is counted. Similarly, experiments under dark conditions were performed under the same conditions. Taking the substrate material as an original filter paper fiber membrane as an example, different sample control groups, such as a metal organic framework @ polydopamine film (UiO-66@ PDA), also maintain the same experimental conditions, and are subjected to comparative tests. As shown in fig. 5, the results showed that the metal organic framework @ polydopamine antibacterial film (UiO-66@ PDA @ RB) had excellent antibacterial effects.
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