阅读说明：本技术 一种Phe@CuNCs复合材料的制备方法及应用 (Preparation method and application of Phe @ CuNCs composite material ) 是由 庆伟霞 王勇 于 2019-09-18 设计创作，主要内容包括：本发明属于纳米材料科学领域,具体涉及一种Phe@CuNCs复合材料的制备方法及应用。本申请将硫酸铜、苯丙氨酸和水合肼混合,在碱性条件下反应,经过滤、冷冻干燥,即得Phe@CuNCs复合材料。本发明制备条件温和简单,成本低廉；所制备的纳米复合材料具有降解染料作用和抗菌性质,用于刚果红的降解和大肠杆菌及金黄色葡萄球菌的抑制。(The invention belongs to the field of nano material science, and particularly relates to a preparation method and application of a Phe @ CuNCs composite material. The preparation method comprises the steps of mixing copper sulfate, phenylalanine and hydrazine hydrate, reacting under an alkaline condition, filtering, and freeze-drying to obtain the Phe @ CuNCs composite material. The preparation method has mild and simple preparation conditions and low cost; the prepared nano composite material has the functions of degrading dye and resisting bacteria, and is used for degrading Congo red and inhibiting escherichia coli and staphylococcus aureus.)

1. A preparation method of a Phe @ CuNCs composite material is characterized by comprising the following steps: mixing copper sulfate, phenylalanine and hydrazine hydrate, reacting under an alkaline condition, filtering, and freeze-drying to obtain the Phe @ CuNCs composite material.

2. The method of making a Phe @ CuNCs composite material according to claim 1, comprising the steps of:

(1) Mixing a copper source and a phenylalanine solution in proportion, and stirring and reacting at 20-60 ℃ for 20-50min to obtain a mixed solution I;

(2) Adding hydrazine hydrate into the mixed solution I, mixing, and stirring and reacting at 20-60 ℃ for 20-50min to obtain a mixed solution II;

(3) And (3) continuously adding a sodium hydroxide solution into the mixed solution II to adjust the pH value to 10-14, stirring and reacting at the temperature of 20-60 ℃ for 20-30min, filtering, and freeze-drying to obtain yellow Phe @ CuNCs.

3. the method of making a Phe @ CuNCs composite material of claim 2, wherein: the copper source in the step (1) is any one of a copper sulfate solution, a copper nitrate solution, a copper chloride solution or a copper acetate solution; the molar concentration of the copper source is 5-8 mmoL/L, and the molar concentration of the phenylalanine solution is 40-70 mmoL/L.

4. The method of making a Phe @ CuNCs composite material of claim 3, wherein: the reaction volume ratio of the copper source, the phenylalanine solution and the hydrazine hydrate is 1:3 (0.1-0.2).

5. The method of making a Phe @ CuNCs composite material of claim 2, wherein: the concentration range of the sodium hydroxide solution in the step (3) is 0.5-5 moL/L.

6. The Phe @ CuNCs composite prepared as described in any one of claims 1-5, for use as a catalyst for rapid recyclable congo red degradation and as a gram-inhibiting bacteriostatic.

7. the use according to claim 6, wherein said Phe @ CuNCs composite material is rapidly recyclable Congo red by: degrading a Phe @ CuNCs composite material at 20-60 ℃ according to the mass ratio of the Phe @ CuNCs composite material to Congo red being 3: 1; the highest degradation rate of the Phe @ CuNCs composite material can reach 94% within 70 min, and the highest degradation rate can reach 58% after the Phe @ CuNCs composite material is recycled for 14 times.

8. Use according to claim 6, characterized in that: the minimum concentration of the Phe @ CuNCs composite material used for inhibiting gram bacteria is 0.3 mmoL/L.

Technical Field

The invention belongs to the field of nano material science, relates to a nano copper cluster composite material wrapped by phenylalanine, and particularly relates to a preparation method and application of a Phe @ CuNCs composite material.

Background

With the widespread use of organic dyes, the treatment of dye wastewater has become a global problem. Congo red is a typical benzidine direct azo dye, has a complex and stable structure, has high loss rate in the production and use processes, is easy to enter water, and has great harm to the environment. If the traditional biochemical treatment method (such as an activated sludge method) is adopted to treat the sewage, the effect is not ideal. Congo red produces more toxic aromatic amines if anaerobic conditions are used. Therefore, there is an urgent need to develop a fast, efficient, low-cost, safe method for removing congo red. Patent CN201610213298.3 discloses a preparation method and application of a nano zinc oxide photocatalyst. The preparation method comprises the steps of preparing polyvinyl alcohol (PVA) and zinc nitrate hexahydrate [ Zn (NO)₃)₂·6H₂O]Firstly, preparing a polyvinyl alcohol-zinc nitrate mixture aqueous solution; and then water in the mixture water solution is removed by adopting a vacuum freeze drying technology, the nano zinc oxide photocatalyst prepared by the method shows good photocatalytic activity for both dyes, but the specification shows that the preparation method of the patent is complex, high-temperature calcination is required, energy consumption is serious, the degradation rate in a short time is low, the patent needs photocatalysis, and the application patent does not need photocatalysis.

Generally, pyococcus species belong to gram-positive bacteria, which produce exotoxins to cause diseases in humans, while enterobacteria belong to gram-negative bacteria, which produce endotoxins to cause diseases in humans by means of endotoxins. Currently, the indiscriminate use of antibiotics causes antibiotic resistance and secondary infection clinically. Patent CN201510651518.6 discloses a preparation method of copper-doped nano titanium dioxide with photocatalytic bacteriostatic property, which mainly aims at improving the photocatalytic bacteriostatic effect of titanium dioxide and adopts nano TiO as raw material₂The metal is doped on the particle surface, so that the property of the particle surface is changed, and the particle has antibacterial and catalytic properties, but the material is mainly applied to the field of photoelectric materials and cannot be applied to preparation of medicines for available use. Therefore, the development of new antibacterial materials is imminent.

Disclosure of Invention

In order to solve the technical problems, the invention provides a preparation method and application of a Phe @ CuNCs composite material. The preparation method has mild and simple preparation conditions and low cost; the prepared nano composite material has the functions of degrading dye and resisting bacteria, and is used for degrading Congo red and inhibiting escherichia coli and staphylococcus aureus.

the technical scheme of the invention is realized as follows:

A preparation method of Phe @ CuNCs composite material comprises the steps of mixing a copper source, a phenylalanine solution and hydrazine hydrate, reacting under an alkaline condition, filtering, and freeze-drying to obtain the Phe @ CuNCs composite material.

The preparation method of the Phe @ CuNCs composite material comprises the following steps:

(1) Mixing a copper source and a phenylalanine solution in proportion, and stirring and reacting at 20-60 ℃ for 20-50min to obtain a mixed solution I;

(2) adding hydrazine hydrate into the mixed solution I, mixing, and stirring and reacting at 20-60 ℃ for 20-50min to obtain a mixed solution II;

(3) And (3) continuously adding a sodium hydroxide solution into the mixed solution II until the pH value is 10-14, stirring and reacting at the temperature of 20-60 ℃ for 20-30min, filtering, and freeze-drying to obtain yellow Phe @ CuNCs.

The copper source in the step (1) is any one of a copper sulfate solution, a copper nitrate solution, a copper chloride solution or a copper acetate solution; the molar concentration of the copper source is 5-8 mmoL/L, and the molar concentration of the phenylalanine solution is 40-70 mmoL/L.

the reaction volume ratio of the copper source, the phenylalanine solution and the hydrazine hydrate is 1:3 (0.1-0.2).

the concentration range of the sodium hydroxide solution in the step (3) is 0.5-5 moL/L.

The prepared Phe @ CuNCs composite material is applied as a catalyst for rapidly and circularly degrading Congo red and a bacteriostatic agent for inhibiting gram bacteria, wherein the gram bacteria comprise staphylococcus aureus and escherichia coli.

The method for rapidly and circularly degrading Congo red by the Phe @ CuNCs composite material comprises the following steps: degrading a Phe @ CuNCs composite material at 20-60 ℃ according to the mass ratio of the Phe @ CuNCs composite material to Congo red being 3: 1; the highest degradation rate of the Phe @ CuNCs composite material can reach 94% within 70 min, and the highest degradation rate can reach 58% after the Phe @ CuNCs composite material is recycled for 14 times.

The minimum concentration of the Phe @ CuNCs composite material used for inhibiting gram bacteria is 0.3 mmoL/L.

the invention has the following beneficial effects:

1. The Phe @ CuNCs prepared by the method has potential application value in the aspects of dye degradation and antibiosis, can be used for rapidly and efficiently degrading Congo red dye, is environment-friendly and pollution-free in the degradation process, can be repeatedly used for at least 14 times, is highly sensitive to escherichia coli and staphylococcus aureus, and has the advantages of mild and simple preparation conditions and low cost.

2. The bacteriostasis mechanism of the Phe @ CuNCs composite material is obviously shown in figures 8 and 9, and after the Phe @ CuNCs composite material is added, the surface of bacteria is collapsed and perforated, so that the cell wall is damaged, and the bacteria are killed.

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 is a UV-graphic representation of Phe @ CuNCs prepared in example 1.

FIG. 2 is an infrared image of Phe @ CuNCs prepared in example 1.

FIG. 3 is an XPS plot of Phe @ CuNCs prepared in example 1.

FIG. 4 is a TEM and DLS (inset) image of Phe @ CuNCs prepared in example 1.

FIG. 5 is a UV-Vis spectrum of an aqueous solution of Phe @ CuNCs catalyzed Congo red degradation prepared in example 1.

FIG. 6 is a review of the number of cycles in which Phe @ CuNCs prepared in example 1 catalyzed degradation of Congo red.

FIG. 7 is a plot of the inhibition zones for Phe @ CuNCs prepared in example 1 against Staphylococcus aureus and Escherichia coli.

FIG. 8 is an SEM image of Staphylococcus aureus before and after Phe @ CuNCs bacteriostasis.

FIG. 9 is an SEM image of E.coli before and after Phe @ CuNCs bacteriostasis.

FIG. 10 is a graph showing the effect of Phe @ CuNCs usage on Congo red.

FIG. 11 is a graph of the effect of temperature on Phe @ CuNCs degradation of Congo red.

FIG. 12 is a graph of the effect of time on Phe @ CuNCs degradation of Congo red.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.