CN111110843B

CN111110843B - Preparation method and antibacterial application of photosensitive semiconductor Zr-TCPP MOFs (zirconium-tungsten-propylene-silicon) load Ag nano particle composite material

Info

Publication number: CN111110843B
Application number: CN201911293480.4A
Authority: CN
Inventors: 邱凤仙; 毛凯丽; 朱瑶; 陈华友; 荣坚; 张涛; 杨冬亚
Original assignee: Jiangsu University
Current assignee: Jiangsu University
Priority date: 2019-12-16
Filing date: 2019-12-16
Publication date: 2022-04-26
Anticipated expiration: 2039-12-16
Also published as: CN111110843A

Abstract

The invention belongs to the technical field of nano composite material preparation, relates to a photocatalytic composite antibacterial material, and particularly relates to a preparation method of a photosensitive semiconductor Zr-TCPP MOFs structure Ag-loaded nano particle composite material ZMP-Ag, wherein ZrCl is added₄Adding benzoic acid into DMF, mixing uniformly, adding water and porphyrin, mixing uniformly to obtain a solution, transferring the solution into a reaction kettle, carrying out hydrothermal reaction at 50-200 ℃ for 1-48 h, carrying out centrifugal separation and cleaning to obtain Zr-TCPP MOFs (ZPM); then, ZPM is dissolved in 0.1-10 mM AgNO₃And transferring the solution into a reaction kettle, continuously reacting for 1-48 h at 50-200 ℃, and centrifugally separating and cleaning to obtain the ZMP-Ag. The efficient and stable photocatalytic antibacterial material ZPM-Ag is prepared by a hydrothermal method, and the preparation method is simple and has good operability; ZPM-Ag shows good stability in six-cycle operation, and is an environment-friendly antibacterial material with low toxicity. Therefore, the ZPM-Ag has wide application prospect in the aspect of antibiosis due to high visible light utilization rate and excellent sterilization performance.

Description

Preparation method and antibacterial application of photosensitive semiconductor Zr-TCPP MOFs (zirconium-tungsten-propylene-silicon) load Ag nano particle composite material

Technical Field

The invention belongs to the technical field of nano composite material preparation, relates to a photocatalytic composite antibacterial material, and particularly relates to a preparation method and antibacterial application of a photosensitive semiconductor Zr-TCPP MOFs structure Ag-loaded nano particle composite material (ZMP-Ag).

Background

Currently, cross-contamination and drug-resistant bacteria occur frequently, causing serious pollution and threatening human health. Since the 19 th century that bacteria were identified as the cause of several diseases, great efforts have been made to solve the problem of bacterial contamination, including the use of alcohol, irritant chemicals, antibiotics, and the like. Since the discovery of antibiotics, millions of lives have been saved, but their drawbacks are not negligible. Recently, the world health organization has revealed that bacterial resistance poses serious health risks to antibiotics, and worse yet, the shortage of new antibacterial drugs is posing human beings with a threat to a large number of pathogenic bacteria. Therefore, the research and development of novel and efficient sterilization materials have become one of the major problems which are concerned and urgently to be solved by researchers.

Among the novel antibacterial materials, the application of nano antibacterial materials is one of the methods for treating bacterial contamination and antibiotic resistance. Among the numerous nanoparticles, Metal Organic Frameworks (MOFs), which are composed of metals and organic frameworks, are an effective approach to address such problems. The MOFs have the characteristics of large specific surface area, good molecular structure, mild synthesis conditions and the like, wherein some MOFs can be excited by light to generate a large number of active species such as Reactive Oxygen Species (ROS) and the like, so that the MOFs have a bactericidal effect. It has been reported that MOFs with porphyrin (TCPP) as a ligand are highly efficient and environmentally friendly bactericidal materials. Wherein Zr-TCPP MOFs (ZPM) consists of Zr⁴⁺And porphyrin, and has stable crystal skeleton structure. Zr has good biocompatibility and can be connected with porphyrin ligand to form an ultra-stable MOFs structure. Porphyrin rings are known for their photosensitivity, and are the core and soul of chlorophyll, a photosynthetic pigment molecule. The porphyrin ring not only senses photons, but also transports electrons, which makes it photosynthetic not onlyIt is indispensable for all things and other life forms. Therefore, the ZPM can be used as a green and efficient antibacterial material. However, since the use of sunlight is limited and only ultraviolet rays harmful to the human body can be used, it is rarely used as an antibacterial agent. Therefore, it is important to improve ZPM to improve the utilization of visible light. It has been reported that the incorporation of noble metal nanoparticles can increase the photocatalytic activity of MOFs because noble metal nanoparticles are excellent electron acceptors that can trap photo-excited electron-hole pairs and avoid their rapid recombination, thereby increasing the generation of ROS. Therefore, the ZPM structure Ag nano particle loaded composite material prepared by the invention can enhance the utilization rate of visible light and has a bactericidal effect.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to disclose a method for preparing a green high-efficiency photocatalytic nano antibacterial material for sterilization.

Technical scheme

A preparation method of a photosensitive semiconductor Zr-TCPP MOFs structure Ag-loaded nanoparticle composite material (ZMP-Ag) comprises the following steps:

A) hydrothermal synthesis of ZPM by reacting ZrCl₄Adding benzoic acid into DMF, mixing, adding water and porphyrin (TCCP), and mixing to obtain solution containing ZrCl₄The mass-volume ratio of the benzoic acid to the DMF to the water to the porphyrin is 0.1-10 mg, 100-500 mg, 1-50 mL, 10-500 muL, 1-50 mg, preferably 10mg, 200mg, 3mL, 300 muL and 8mg, the solution is transferred into a reaction kettle, hydrothermal reaction is carried out at 50-200 ℃ for 1-48 h, preferably 150 ℃ for 24h, natural cooling is carried out to room temperature, precipitates are obtained by centrifugal separation, ethanol and water are respectively used for carrying out separation and purification for multiple times, and the Zr-TCPP MOFs (ZPM) is prepared;

B) loading silver nano particles on ZPM by a hydrothermal method, and dissolving the ZPM in 0.1-10 mM AgNO₃Mixing the solution with ZPM and AgNO₃The mass-volume ratio of the solution is 1-100 mg:10mL, preferably 20mg:10mL 2mM AgNO₃Transferring the solution into a reaction kettle, continuously reacting for 1-48 h at 50-200 ℃, preferably for 3h at 80 ℃, naturally cooling to room temperature, performing centrifugal separation to obtain precipitate, and performing multi-stage reaction by using ethanol and water respectivelyAnd separating and purifying for the second time to obtain the ZMP-Ag.

The photosensitive semiconductor MOFs structure Ag-loaded nanoparticle composite material prepared by the method is ellipsoidal in shape and about 400-600 nm in size. TEM representation results show that Ag nanoparticles are successfully loaded on the photosensitive semiconductor MOFs and are uniformly dispersed on the MOFs.

The other purpose of the invention is to apply the prepared Ag nanoparticle-loaded composite material (ZMP-Ag) with the Zr-TCPP MOFs structure of the photosensitive semiconductor to antibiosis, in particular to enhance the utilization rate of visible light for sterilization.

The antibacterial experiment steps are as follows:

activating Escherichia coli (E.coli) and Staphylococcus aureus (S.aureus), culturing in Luria-Bertani (LB) medium at 37 deg.C and 200rpm for 10 hr, and diluting with PBS buffer to bacterial concentration of 10⁶cfu·mL^-1The bacterial liquid of (4). The bacterial concentration was controlled with an ultraviolet spectrophotometer throughout the experiment. Subsequently, ZMP-Ag was dispersed in the diluted bacterial solution to 100 mg. L^-1Irradiating with visible light for 30min, spreading the mixture on solid culture medium, culturing at 37 deg.C for 10 hr, and determining the survival rate of bacteria by agar counting method.

The results show that the ZPM-Ag composite material has good antibacterial activity on escherichia coli and staphylococcus aureus.

The invention has the characteristics that:

(1) the prepared Ag nano particle loaded composite antibacterial material with the photosensitive semiconductor MOFs structure is convenient to prepare and low in price;

(2) the utilization rate of the material to visible light is improved by loading Ag nano particles on a photosensitive semiconductor MOFs, so that the antibacterial performance of the material is improved;

(3) the prepared ZPM-Ag composite material has high stability and still shows good antibacterial performance after six cycles.

Zirconium chloride (ZrCl) used in the present invention₄) Porphyrin, benzoic acid, DMF, sodium hydroxide, sodium acetate, ethanol, Trisodium Citrate (TC), Ethylene Glycol (EG), silver nitrate, ammonia, yeast extract, tryptone, phosphorusAcid buffer solution (PBS) (pH 7.4) was provided by Shanghai pharmaceutical group chemical Co., Ltd., China. All reagents used in the invention are analytical grade reagents, and deionized water is used.

Advantageous effects

The invention discloses a method for preparing a composite material for loading Ag nanoparticles on a photo-activated photosensitive semiconductor Zr-TCPP MOFs structure with an antibacterial effect, which adopts a hydrothermal method to prepare a high-efficiency and stable photocatalytic antibacterial material ZPM-Ag, and has the advantages of simple preparation method and good operability; in addition, the ZPM-Ag shows good stability in six-cycle operation, and is an antibacterial material with low toxicity and environmental friendliness. Therefore, the ZPM-Ag has wide application prospect in the aspect of antibiosis due to high visible light utilization rate and excellent sterilization performance.

Drawings

FIG. 1 TEM of ZPM prepared in example 1;

FIG. 2 TEM of ZPM-Ag prepared in example 1.

Detailed Description

The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.

Unless otherwise defined, terms (including technical and scientific terms) used herein should be construed to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art, and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

Example 1

A preparation method of a photosensitive semiconductor Zr-TCPP MOFs structure Ag-loaded nanoparticle composite material comprises the following steps:

a) ZPM is synthesized by adopting a hydrothermal method. First, 0.1mg of ZrCl was weighed₄100mg of benzoic acid are mixed homogeneously with 15ml of DMF. Then, 100. mu. L H was added₂O and 5mg of TCCP, mixed well at room temperature. Pouring the mixed solution into a reaction kettle at 200 DEG CThe reaction is carried out for 1 h. Centrifuging at 10000rpm for 5 minutes to obtain precipitate, and then separating and purifying with ethanol and water for multiple times;

b) ZPM-Ag, silver nano particles are loaded on the ZPM by adopting a hydrothermal method. First, 40mg ZPM was mixed with 10ml AgNO₃The (1mM) solution is mixed evenly and poured into a reaction kettle, the reaction is continued for 24 hours at 50 ℃, then the ZMP-Ag is collected by centrifugation at 10000rpm for 5 minutes, and the separation and purification are carried out for a plurality of times by using ethanol and water respectively.

And (3) testing antibacterial performance:

dispersing ZMP-Ag into diluted bacteria liquid to 100 mg-L^-1And irradiating with visible light for 0.5h, coating the prepared bacterial liquid and sample on a solid agar plate, culturing at 37 ℃ for 10h, and testing the sterilization effect.

The sterilization rate of the obtained sample on escherichia coli reaches 69.4%; the sterilization rate to staphylococcus aureus reaches 54.3 percent.

Example 2

a) ZPM is synthesized by adopting a hydrothermal method. First, 5mg of ZrCl was weighed₄200mg of benzoic acid are mixed homogeneously with 1ml of DMF. Then, 10. mu. L H was added₂O and 20mg of TCCP were mixed homogeneously at room temperature. The mixed solution is poured into a reaction kettle and reacts for 24 hours at the temperature of 120 ℃. Centrifuging at 10000rpm for 5min to obtain precipitate, and separating and purifying with ethanol and water for multiple times.

b) ZPM-Ag, silver nano particles are loaded on the ZPM by adopting a hydrothermal method. First, 80mg of ZPM was mixed with 10ml of AgNO₃The (0.1mM) solution is mixed evenly and poured into a reaction kettle to react continuously for 12h at 150 ℃, then ZMP-Ag is collected by centrifugation at 10000rpm for 5min and is separated and purified for a plurality of times by ethanol and water respectively.

And (3) testing antibacterial performance:

dispersing ZMP-Ag into diluted bacteria liquid to 100 mg-L^-1Irradiating with visible light for 0.5 h; and (3) coating the prepared bacterial liquid and the sample on a solid agar plate, culturing for 10 hours at 37 ℃, and testing the sterilization effect.

The sterilization rate of the obtained sample on escherichia coli reaches 43.8%; the sterilization rate to staphylococcus aureus reaches 36.2 percent.

Example 3

a) ZPM is synthesized by adopting a hydrothermal method. First, 8mg of ZrCl was weighed₄150mg of benzoic acid are mixed homogeneously with 50ml of DMF. Then, 250. mu. L H were added₂O and 50mg of TCCP were mixed homogeneously at room temperature. The mixed solution is poured into a reaction kettle and reacted for 12 hours at the temperature of 50 ℃. Centrifuging at 10000rpm for 5min to obtain precipitate, and separating and purifying with ethanol and water for multiple times.

b) ZPM-Ag, silver nano particles are loaded on the ZPM by adopting a hydrothermal method. First, 100mg ZPM was mixed with 10ml AgNO₃The (5mM) solution is mixed evenly and poured into a reaction kettle, the reaction is continued for 1h at 100 ℃, then the ZMP-Ag is collected by centrifugation for 5min at 10000rpm, and the separation and purification are carried out for a plurality of times by using ethanol and water respectively.

And (3) testing antibacterial performance:

The sterilization rate of the obtained sample on escherichia coli reaches 54.6%; the sterilization rate to staphylococcus aureus reaches 32.5 percent.

Example 4

a) ZPM is synthesized by adopting a hydrothermal method. First, 10mg of ZrCl was weighed₄200mg of benzoic acid are mixed homogeneously with 3ml of DMF. Then, 300. mu. L H was added₂O and 8mg of TCCP, mixed homogeneously at room temperature. Pouring the mixed solution into a reaction kettle, and reacting for 24 hours at 150 ℃. Centrifuging at 10000rpm for 5min to obtain precipitate, and separating and purifying with ethanol and water for multiple times.

b) ZPM-Ag, adopting hydrothermal method to make silver nano particlesThe sub-load is on the ZPM. First, 20mg ZPM was mixed with 10ml AgNO₃The (2mM) solution is mixed evenly and poured into a reaction kettle to react continuously for 3h at 80 ℃, then the ZMP-Ag is collected by centrifugation for 5min at 10000rpm and is separated and purified for a plurality of times by ethanol and water respectively.

And (3) testing antibacterial performance:

The sterilization rate of the obtained sample on escherichia coli reaches 78.8%; the sterilization rate to staphylococcus aureus reaches 64.3 percent.

Example 5

a) ZPM is synthesized by adopting a hydrothermal method. First, 3mg ZrCl was weighed₄400mg of benzoic acid are mixed homogeneously with 10ml of DMF. Then, 200. mu. L H were added₂O and 1mg of TCCP, mixed homogeneously at room temperature. The mixed solution is poured into a reaction kettle and reacted for 18 hours at the temperature of 140 ℃. Centrifuging at 10000rpm for 5min to obtain precipitate, and separating and purifying with ethanol and water for multiple times.

b) ZPM-Ag, silver nano particles are loaded on the ZPM by adopting a hydrothermal method. First, 1mg ZPM was mixed with 10ml AgNO₃The (10mM) solution is mixed evenly and poured into a reaction kettle, the reaction is continued for 18h at 200 ℃, then the ZMP-Ag is collected by centrifugation at 10000rpm for 5min, and the separation and purification are carried out for a plurality of times by using ethanol and water respectively.

And (3) testing antibacterial performance:

The sterilization rate of the obtained sample on escherichia coli reaches 43.4%; the sterilization rate to staphylococcus aureus reaches 33.2 percent.

Example 6

a) ZPM is synthesized by adopting a hydrothermal method. First, 10mg of ZrCl was weighed₄500mg of benzoic acid are mixed homogeneously with 35ml of DMF. Then, 500. mu. L H was added₂O and 30mg of TCCP were mixed homogeneously at room temperature. The mixed solution is poured into a reaction kettle and reacted for 48 hours at 90 ℃. Centrifuging at 10000rpm for 5min to obtain precipitate, and separating and purifying with ethanol and water for multiple times.

b) ZPM-Ag, silver nano particles are loaded on the ZPM by adopting a hydrothermal method. First, 10mg ZPM and 10ml AgNO were mixed₃The (8mM) solution is mixed evenly and poured into a reaction kettle, the reaction is continued for 48 hours at 60 ℃, then the ZMP-Ag is collected by centrifugation at 10000rpm for 5 minutes, and the separation and purification are carried out for a plurality of times by using ethanol and water respectively.

And (3) testing antibacterial performance:

The sterilization rate of the obtained sample on escherichia coli reaches 72.4%; the sterilization rate to staphylococcus aureus reaches 67.4 percent.

The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.

Claims

1. A preparation method of a photosensitive semiconductor Zr-TCPP MOFs structure Ag nanoparticle-loaded composite material is characterized by comprising the following steps:

A1) 0.1mg of ZrCl was weighed₄100mg benzoic acid and 15ml DMF are mixed evenly and 100 mu L H is added₂Mixing O and 5mg TCCP at room temperature, pouring the mixed solution into a reaction kettle, reacting at 200 deg.C for 1h, centrifuging at 10000rpm for 5min to obtain precipitate, and respectively usingSeparating and purifying ethanol and water for many times to obtain ZPM;

A2) 40mg of ZPM with 10ml of 1mM AgNO₃Uniformly mixing the solution, pouring the mixture into a reaction kettle, continuously reacting for 24 hours at 50 ℃, centrifuging at 10000rpm for 5min, collecting ZMP-Ag, and respectively carrying out multiple separation and purification by using ethanol and water;

or

B1) Weighing 10mg ZrCl₄200mg of benzoic acid was mixed with 3ml of DMF and 300. mu. L H was added₂Mixing O and 8mg TCCP uniformly at room temperature, pouring the mixed solution into a reaction kettle, reacting for 24h at 150 ℃, centrifuging for 5min at 10000rpm to obtain precipitate, and then respectively carrying out multiple separation and purification by using ethanol and water to obtain ZPM;

B2) 20mg of ZPM with 10ml of 2mM AgNO₃Uniformly mixing the solution, pouring the mixture into a reaction kettle, continuously reacting for 3 hours at the temperature of 80 ℃, centrifuging for 5 minutes at the rpm of 10000, collecting ZMP-Ag, and respectively carrying out multiple separation and purification by using ethanol and water;

or

C1) Weighing 10mg ZrCl₄500mg benzoic acid was mixed well with 35ml DMF and 500. mu. L H was added₂Mixing O and 30mg TCCP uniformly at room temperature, pouring the mixed solution into a reaction kettle, reacting for 48h at 90 ℃, centrifuging for 5min at 10000rpm to obtain precipitate, and then respectively carrying out multiple separation and purification by using ethanol and water to obtain ZPM;

C2) 10mg of ZPM with 10ml of 8mM AgNO₃The solution is mixed evenly and poured into a reaction kettle, the reaction lasts for 48 hours at 60 ℃, then ZMP-Ag is collected after centrifugation for 5min at 10000rpm, and the separation and purification are carried out for a plurality of times by using ethanol and water respectively.

2. The photosensitive semiconductor Zr-TCPP MOFs structure prepared by the method according to claim 1 is loaded with Ag nano particle composite ZMP-Ag.

3. The photosensitive semiconductor Zr-TCPP MOFs structure loaded Ag nanoparticle composite ZMP-Ag according to claim 2, wherein: the shape of the material is ellipsoidal, and the size of the material is 400-600 nm.

4. The application of the Ag nanoparticle-loaded composite ZMP-Ag in the photosensitive semiconductor Zr-TCPP MOFs structure according to claim 3, wherein the Ag nanoparticle-loaded composite ZMP-Ag comprises the following components in percentage by weight: it can be used for preparing antibacterial agent.