阅读说明：本技术 广谱抗微生物的介孔氧化硅席夫碱银配合物纳米材料及其制备方法 (Broad-spectrum antimicrobial mesoporous silica Schiff base silver complex nano material and preparation method thereof ) 是由 陈进 毕洪凯 蔡铃 黄衍强 王建明 刘巧 于 2020-04-08 设计创作，主要内容包括：本发明涉及广谱抗微生物的介孔氧化硅席夫碱银配合物纳米材料及其制备方法。该制备方法包括：制得氨基化介孔氧化硅,制得醛基化介孔氧化硅,制得介孔氧化硅席夫碱银配合物纳米材料成品。该纳米材料对多种细菌真菌具有杀灭作用,能达到广谱、高效、持续杀菌的效果,且在抗菌的同时能防止产生耐药菌株。(The invention relates to a broad-spectrum antimicrobial mesoporous silica Schiff base silver complex nano material and a preparation method thereof. The preparation method comprises the following steps: preparing aminated mesoporous silica, preparing aldehydized mesoporous silica, and preparing the finished product of the mesoporous silica Schiff base silver complex nano material. The nanometer material has the function of killing various bacteria and fungi, can achieve the effects of broad spectrum, high efficiency and continuous sterilization, and can prevent the generation of drug-resistant strains while resisting bacteria.)

1. A preparation method of a broad-spectrum antimicrobial mesoporous silica Schiff base silver complex nano material is characterized by comprising the following steps:

firstly, dispersing mesoporous silicon oxide in toluene, adding 3-aminopropyltriethoxysilane, and reacting under reaction conditions; after the reaction, centrifuging and collecting solid matters; washing and drying the solid to obtain aminated mesoporous silica;

secondly, dispersing the aminated mesoporous silica in deionized water, adding glyoxylic acid, and reacting under reaction conditions; after the reaction, centrifuging and collecting solid matters; washing and drying the solid to obtain aldehyde mesoporous silica;

dispersing polylysine in absolute ethyl alcohol to form a mixed solution, and adjusting the pH value of the mixed solution to be alkalescent by using potassium hydroxide, wherein the pH value is 8.0 +/-0.5; adding aldehyde mesoporous silicon oxide to react under reaction conditions; after the reaction, adding soluble silver salt into the mixed solution, and then continuing the reaction; after the reaction is finished, centrifuging and collecting solid matters; and washing and drying the solid to obtain the polylysine modified mesoporous silica loaded with the silver nanoparticles, namely the finished product of the mesoporous silica Schiff base silver complex nano material.

2. The method according to claim 1, wherein in the first step, the mass-to-volume ratio of the mesoporous silica to toluene is 0.6 ± 0.01 g: 80 plus or minus 5 ml; the volume ratio of the 3-aminopropyltriethoxysilane to the toluene is 0.0025 +/-0.001: 1; adding 3-aminopropyltriethoxysilane drop by drop; the reaction conditions of the first step are as follows: the reaction temperature is 70 +/-5 ℃, the reaction time is at least 12 hours, and the stirring is continued in the reaction process; the centrifugation conditions were: the centrifugal speed is 5000 plus or minus 500rpm, and the centrifugal time is at least 5 minutes; the washing conditions were: washing with ethanol and deionized water for at least 3 times; the drying temperature was 60 ℃. + -. 5 ℃.

3. The preparation method of claim 1, wherein in the second step, the mass-to-volume ratio of the aminated mesoporous silica to the deionized water is 0.5 ± 0.01 g: 100 plus or minus 10 ml; the molar ratio of the glyoxylic acid to the 3-aminopropyltriethoxysilane of the first step is greater than 1.

4. The process according to claim 3, wherein the reaction conditions in the second step are as follows: the reaction temperature is 40 +/-5 ℃, the reaction time is at least 6 hours, and the stirring is continued in the reaction process; the centrifugation conditions were: the centrifugal speed is 5000 plus or minus 500rpm, and the centrifugal time is at least 5 minutes; the washing conditions were: washing with deionized water for at least 3 times; the drying temperature was 60 ℃. + -. 5 ℃.

5. The method according to claim 1, wherein in the third step, the mass-to-volume ratio of polylysine to absolute ethanol is 120 ± 20 mg: 60 plus or minus 10ml, and the molecular weight of the polylysine is 3000 plus or minus 500; the mass ratio of the aldehyde mesoporous silicon oxide to polylysine is 0.5-2: 1; the soluble silver salt is silver nitrate, and the mass ratio of the silver nitrate to the aldehyde mesoporous silicon oxide is 1.4 +/-0.2: 1.

6. the method according to claim 5, wherein the reaction conditions in the third step are as follows: the reaction temperature is 80 +/-5 ℃, the reaction time is at least 12 hours, and condensation reflux is carried out in the reaction process; the reaction conditions for the further reaction are: the reaction temperature is 80 ℃ plus or minus 5 ℃, the reaction time is at least 30 minutes, and the condensation reflux is carried out in the reaction process; the centrifugation conditions were: the centrifugal speed is 5000 plus or minus 500rpm, and the centrifugal time is at least 5 minutes; the washing conditions were: washing with anhydrous ethanol and deionized water for at least 3 times; the drying temperature was 60 ℃. + -. 5 ℃.

7. The method according to claim 1, wherein the mesoporous silica is SBA-15 and is prepared by the following steps:

s1, adding P123 into deionized water, and stirring until the mixture is clear; adding hydrochloric acid solution and mixing uniformly; adding tetraethoxysilane and stirring for reaction;

s2, transferring the obtained mixture to a high-temperature reaction kettle for reaction, then aging the mixture in a drying oven, and washing and drying the obtained solid matter;

and S3, grinding the solid matter into powder and calcining to obtain the SBA-15.

8. The mesoporous silica Schiff base silver complex nano-material prepared by the preparation method of any one of claims 1 to 7.

9. Use of the mesoporous silica schiff base silver complex nanomaterial of claim 8, wherein the use is for preparing an antimicrobial agent.

10. The use according to claim 9, wherein the antimicrobial agent is directed against a microorganism comprising candida albicans, candida tropicalis, candida glabrata, candida vitis, candida parapsilosis, candida luxata, escherichia coli, pseudomonas aeruginosa, salmonella enterica subspecies, klebsiella pneumoniae, morganella morganii, stenotrophomonas maltophilia, proteus mirabilis, acinetobacter baumannii, staphylococcus aureus, enterococcus faecalis, enterococcus faecium, bacillus subtilis, bacillus cereus, moraxella catarrhalis, streptococcus pneumoniae, actinobacillus and mycobacterium tuberculosis.

Technical Field

The invention relates to a broad-spectrum antimicrobial mesoporous silica Schiff base silver complex nano material and a preparation method thereof, belonging to the technical field of antimicrobial materials.

Background

According to the knowledge of the inventor, the existing antibacterial material is complex in process during synthesis, and needs to consume a large amount of manpower, material resources and financial resources, so that the cost is high, and the market popularization is not facilitated. Meanwhile, the existing antibacterial material has limited sterilization objects and usually has a sterilization effect only on certain bacteria; the sterilization duration is short, and the long-time continuous sterilization is difficult; after a large amount of the composition is used, drug-resistant strains are easy to generate, and the health of human beings is threatened. In addition, some silver-based antibacterial materials are harmful to organisms due to high silver content, and cannot directly act on animals or human beings. Accordingly, there is a need to develop antimicrobial materials that overcome the above disadvantages.

The inventor of the invention has filed a Chinese invention patent named nanoparticle composite material, a synthetic method and application thereof on 2018, 03.01.03. the composite material SBA-15/PDA/Ag recorded in the Chinese invention patent has an antibacterial effect. After that, as a result of further research, the inventors have obtained a new research result that can overcome the above-mentioned drawbacks of the conventional materials, and have applied for the present invention.

Disclosure of Invention

The invention aims to: the problems in the prior art are solved, the preparation method of the broad-spectrum antimicrobial mesoporous silica Schiff base silver complex nano material is provided, the synthesis process is green, simple and rapid, the obtained material has a killing effect on various bacterial fungi, and broad-spectrum, efficient and continuous sterilization is realized. Meanwhile, the nano material prepared by the preparation method and the application of the nano material are also provided.

The technical scheme for solving the technical problems of the invention is as follows:

a preparation method of a broad-spectrum antimicrobial mesoporous silica Schiff base silver complex nano material is characterized by comprising the following steps:

firstly, dispersing mesoporous silicon oxide in toluene, adding 3-aminopropyltriethoxysilane, and reacting under reaction conditions; after the reaction, centrifuging and collecting solid matters; washing and drying the solid to obtain aminated mesoporous silica;

secondly, dispersing the aminated mesoporous silica in deionized water, adding glyoxylic acid, and reacting under reaction conditions; after the reaction, centrifuging and collecting solid matters; washing and drying the solid to obtain aldehyde mesoporous silica;

dispersing polylysine in absolute ethyl alcohol to form a mixed solution, and adjusting the pH value of the mixed solution to be alkalescent by using potassium hydroxide, wherein the pH value is 8.0 +/-0.5; adding aldehyde mesoporous silicon oxide to react under reaction conditions; after the reaction, adding soluble silver salt into the mixed solution, and then continuing the reaction; after the reaction is finished, centrifuging and collecting solid matters; and washing and drying the solid to obtain the polylysine modified mesoporous silica loaded with the silver nanoparticles, namely the finished product of the mesoporous silica Schiff base silver complex nano material.

The method has the advantages of green, simple and quick synthesis process, less silver required to be added, and low silver content in the prepared nano material. The nanometer material prepared by the method has a killing effect on various bacteria and fungi, can achieve broad-spectrum, high-efficiency and continuous sterilization effects, and can prevent the generation of drug-resistant strains while resisting bacteria. Compared with the composite material SBA-15/PDA/Ag invented by the prior subject group, the nano material prepared by the invention has more obvious effect of killing mycobacterium tuberculosis.

The technical scheme of the invention is further perfected as follows:

preferably, in the first step, the mass-to-volume ratio of the mesoporous silica to the toluene is 0.6 ± 0.01 g: 80 plus or minus 5 ml; the volume ratio of the 3-aminopropyltriethoxysilane to the toluene is 0.0025 +/-0.001: 1; adding 3-aminopropyltriethoxysilane drop by drop; the reaction conditions of the first step are as follows: the reaction temperature is 70 +/-5 ℃, the reaction time is at least 12 hours, and the stirring is continued in the reaction process; the centrifugation conditions were: the centrifugal speed is 5000 plus or minus 500rpm, and the centrifugal time is at least 5 minutes; the washing conditions were: washing with ethanol and deionized water for at least 3 times; the drying temperature was 60 ℃. + -. 5 ℃.

By adopting the preferable scheme, the material proportion and specific conditions in the first step can be further optimized. Wherein 3-aminopropyltriethoxysilane is APTES.

Preferably, in the second step, the mass-to-volume ratio of the aminated mesoporous silica to the deionized water is 0.5 ± 0.01 g: 100 plus or minus 10 ml; the molar ratio of the glyoxylic acid to the 3-aminopropyltriethoxysilane of the first step is greater than 1.

With this preferred embodiment, the proportions of the individual components in the second step can be further optimized. Wherein, the molar ratio of the glyoxylic acid to the 3-aminopropyltriethoxysilane in the first step is more than 1, so that the excess glyoxylic acid can be ensured to realize better reaction effect.

Preferably, the reaction conditions of the second step are: the reaction temperature is 40 +/-5 ℃, the reaction time is at least 6 hours, and the stirring is continued in the reaction process; the centrifugation conditions were: the centrifugal speed is 5000 plus or minus 500rpm, and the centrifugal time is at least 5 minutes; the washing conditions were: washing with deionized water for at least 3 times; the drying temperature was 60 ℃. + -. 5 ℃.

With this preferred embodiment, each specific condition in the second step can be further optimized.

Preferably, in the third step, the mass-volume ratio of the polylysine to the absolute ethyl alcohol is 120 +/-20 mg: 60 plus or minus 10ml, and the molecular weight of the polylysine is 3000 plus or minus 500; the mass ratio of the aldehyde mesoporous silicon oxide to polylysine is 0.5-2: 1; the soluble silver salt is silver nitrate, and the mass ratio of the silver nitrate to the aldehyde mesoporous silicon oxide is 1.4 +/-0.2: 1.

by adopting the preferred scheme, the material proportion in the third step can be further optimized. The input amount of the soluble silver salt is obviously less than that of SBA-15/PDA/Ag, so that the silver content of the nano material prepared by the method is lower.

Preferably, the reaction conditions of the third step are: the reaction temperature is 80 +/-5 ℃, the reaction time is at least 12 hours, and condensation reflux is carried out in the reaction process; the reaction conditions for the further reaction are: the reaction temperature is 80 ℃ plus or minus 5 ℃, the reaction time is at least 30 minutes, and the condensation reflux is carried out in the reaction process; the centrifugation conditions were: the centrifugal speed is 5000 plus or minus 500rpm, and the centrifugal time is at least 5 minutes; the washing conditions were: washing with anhydrous ethanol and deionized water for at least 3 times; the drying temperature was 60 ℃. + -. 5 ℃.

With this preferred embodiment, each specific condition in the third step can be further optimized.

Preferably, in the first step, the mesoporous silica is SBA-15, and the preparation process comprises:

s1, adding P123 into deionized water, and stirring until the mixture is clear; adding hydrochloric acid solution and mixing uniformly; adding tetraethoxysilane and stirring for reaction;

s2, transferring the obtained mixture to a high-temperature reaction kettle for reaction, then aging the mixture in a drying oven, and washing and drying the obtained solid matter;

and S3, grinding the solid matter into powder and calcining to obtain the SBA-15.

By adopting the preferred scheme, the specific preparation process of the mesoporous silicon oxide can be further defined.

The invention also proposes:

the mesoporous silica Schiff base silver complex nano material prepared by the preparation method is adopted.

The nanometer material has the function of killing various bacteria and fungi, can achieve the effects of broad spectrum, high efficiency and continuous sterilization, and can prevent the generation of drug-resistant strains while resisting bacteria.

The invention also proposes:

the application of the mesoporous silica Schiff base silver complex nano material is characterized in that the application is used for preparing an antimicrobial agent.

The use is that the nanomaterial described hereinbefore is suitable for antimicrobial function.

Preferably, the antimicrobial agent is directed against a microorganism including Candida albicans, Candida tropicalis, Candida glabrata, Candida vitis, Candida parapsilosis, Candida ruxoides, Escherichia coli, Pseudomonas aeruginosa, Salmonella enterica subspecies, Klebsiella pneumoniae, Morganella morganii, stenotrophomonas maltophilia, Proteus mirabilis, Acinetobacter baumannii, Staphylococcus aureus, enterococcus faecalis, enterococcus faecium, Bacillus subtilis, Bacillus cereus, Moraxella catarrhalis, Streptococcus pneumoniae, Actinobacillus actinobacillus and Mycobacterium tuberculosis.

With this preferred embodiment, the kind of microorganism to be targeted can be further specified.

Compared with the prior art, the invention has the following beneficial effects:

the preparation method is green, simple and quick, and the silver content in the prepared nano material is lower due to less silver required to be input. The nano material has a killing effect on various bacteria and fungi, can achieve the effects of broad spectrum, high efficiency and continuous sterilization, and can prevent the generation of drug-resistant strains while resisting bacteria.

Drawings

FIG. 1 shows scanning electron micrographs (A: SBA-15, B: CLA-1) and transmission electron micrographs (C: SBA-15, D: CLA-1) of example 4 of the present invention.

FIG. 2 is a graph showing the energy dispersion spectrum of CLA-1 in example 4 of the present invention.

FIG. 3 is a Fourier infrared spectrum of CLA-1 and each control group in example 4 of the present invention.

FIG. 4 shows the results of example 4 of the present invention¹³C solid nuclear magnetic resonance spectrum.

FIG. 5 is a graph showing the results of evaluating the growth effects of Escherichia coli and Staphylococcus aureus (after 72 hours of co-culture) in example 5 of the present invention.

FIG. 6 is a graph showing the results of evaluating the growth effect of Mycobacterium tuberculosis in example 5 of the present invention (after 42 days of co-culture).

Fig. 7 is a corresponding schematic diagram of embodiment 6 of the present invention.

FIG. 8 is a graph showing the results of example 7 of the present invention.

FIG. 9 is a graph showing the development results of resistance to CLA-1 and Fluconazole (FLC) by Candida albicans SC5314 of example 8 of the present invention.

FIG. 10 is a diagram of the main embodiment of the present invention.

Detailed Description

The invention is described in further detail below with reference to embodiments and with reference to the drawings. The invention is not limited to the examples given.