CN110560160B - Preparation method and application of Phe @ CuNCs composite material - Google Patents
Preparation method and application of Phe @ CuNCs composite material Download PDFInfo
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- CN110560160B CN110560160B CN201910880020.5A CN201910880020A CN110560160B CN 110560160 B CN110560160 B CN 110560160B CN 201910880020 A CN201910880020 A CN 201910880020A CN 110560160 B CN110560160 B CN 110560160B
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- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims abstract description 28
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims abstract description 13
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 241000894006 Bacteria Species 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000000593 degrading effect Effects 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000006731 degradation reaction Methods 0.000 claims description 17
- 230000015556 catabolic process Effects 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 230000003385 bacteriostatic effect Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 241000588724 Escherichia coli Species 0.000 abstract description 10
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 6
- 229960005190 phenylalanine Drugs 0.000 description 6
- 239000000975 dye Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QDGAVODICPCDMU-UHFFFAOYSA-N 2-amino-3-[3-[bis(2-chloroethyl)amino]phenyl]propanoic acid Chemical compound OC(=O)C(N)CC1=CC=CC(N(CCCl)CCCl)=C1 QDGAVODICPCDMU-UHFFFAOYSA-N 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000002158 endotoxin Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000001044 red dye Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 208000003322 Coinfection Diseases 0.000 description 1
- 241000305071 Enterobacterales Species 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002095 exotoxin Substances 0.000 description 1
- 231100000776 exotoxin Toxicity 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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Abstract
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.
Description
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]As a raw material, firstly preparingA polyvinyl alcohol-zinc nitrate mixture aqueous solution is prepared; 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.
Example 1
A preparation method of a Phe @ CuNCs composite material comprises the following steps:
(1) 0.3 mL of 5 mmoL/L copper sulfate and 0.9 mL of 50 mmoL/L phenylalanine are uniformly mixed, then 2.1 mL of secondary water is added, and magnetic stirring is carried out for 30 minutes at room temperature;
(2) adding 60 mu L of hydrazine hydrate into the mixture obtained in the step (1), and continuously stirring the mixture at room temperature for 30 minutes;
(3) to the above (2), 100. mu.L of 1.0 moL/L sodium hydroxide was further added, and the mixture was magnetically stirred at room temperature for 30 minutes. Filtration and freeze-drying gave a yellow solid, whose characterization pattern is shown in FIGS. 1-4.
As can be seen from fig. 1 and 2, the Phe @ CuNCs composite material of the present application is clearly different from Phe;
as can be seen from fig. 3, the composite material prepared in this example contains Cu (0.11%), C (69.39%), N (8.94%), and O (21.56%).
As can be seen from FIG. 4, the Phe @ CuNCs prepared in this example had an average particle size of 0.78 nm.
Example 2
A preparation method of a Phe @ CuNCs composite material comprises the following steps:
(1) uniformly mixing 0.3 mL of 6 mmoL/L copper nitrate and 0.9 mL of 40 mmoL/L phenylalanine, adding 2.1 mL of secondary water, and magnetically stirring at room temperature for 30 minutes;
(2) adding 30 mu L of hydrazine hydrate into the mixture obtained in the step (1), and continuously stirring the mixture at room temperature for 20 minutes;
(3) 0.5 moL/L sodium hydroxide was added to the above solution (2) to adjust the pH to 10, and the mixture was magnetically stirred at room temperature for 20 minutes. Filtered and freeze-dried to give a yellow solid.
Example 3
A preparation method of a Phe @ CuNCs composite material comprises the following steps:
(1) uniformly mixing 0.3 mL of 8 mmoL/L copper acetate and 0.9 mL of 50 mmoL/L phenylalanine, adding 2.1 mL of secondary water, and magnetically stirring at room temperature for 30 minutes;
(2) adding 40 mu L of hydrazine hydrate into the mixture obtained in the step (1), and continuously stirring the mixture at room temperature for 50 minutes;
(3) 0.5 moL/L sodium hydroxide was added to the above solution (2) to adjust the pH to 14, and the mixture was magnetically stirred at room temperature for 50 minutes. Filtered and freeze-dried to give a yellow solid.
Example 4
A preparation method of a Phe @ CuNCs composite material comprises the following steps:
(1) uniformly mixing 0.3 mL of 7 mmoL/L copper chloride and 0.9 mL of 60 mmoL/L phenylalanine, adding 2.1 mL of secondary water, and magnetically stirring at room temperature for 30 minutes;
(2) adding 40 mu L of hydrazine hydrate into the mixture obtained in the step (1), and continuously stirring the mixture at room temperature for 50 minutes;
(3) 0.5 moL/L sodium hydroxide was added to the above solution (2) to adjust the pH to 14, and the mixture was magnetically stirred at room temperature for 50 minutes. Filtered and freeze-dried to give a yellow solid.
Application Effect example 1
The Phe @ CuNCs composite material prepared in the example 1 is used as a catalyst, and Congo red dye is catalytically degraded under natural light.
Influence of usage amount of composite material on Congo red
mu.L of 1.0 mM Congo red was taken in a 5mL tube, and 0, 50, 100, 200, 300, 400, 500. mu.L of 0.6 mM Phe @ CuNCs solution was added, and diluted to 3 mL with secondary water. After standing for 2 hours, taking 1 mL of the mixed solution, diluting to 3.5 mL, and detecting the ultraviolet absorption value; as can be seen from FIG. 10, Congo red was degraded most frequently by using 300. mu.L of Phe @ CuNCs.
② influence of temperature on Congo Red
Taking 100 mu L of 1.0 mM Congo red and 300 mu L of Phe @ CuNCs solution in a 5mL test tube, diluting the solution to 3 mL by using secondary water, placing the tube in a water bath kettle at different temperatures of 20 ℃, 30 ℃, 40 ℃, 50 ℃ and 60 ℃ for heating for 1h, taking 1 mL of mixed solution, diluting the mixed solution to 3.5 mL, and detecting the ultraviolet absorbance value. As can be seen from FIG. 11, Congo red has the highest degradation rate when used at 50 ℃.
Time stabilization
Taking 100 mu L of 1.0 mM Congo red and 300 mu L of Phe @ CuNCs solution in a 5mL test tube, diluting the test tube to 3 mL with secondary water, placing the test tube in a water bath kettle at 50 ℃, and detecting the ultraviolet absorption values of the test tube for 10, 20, 30, 40, 50, 60, 70 and 80 min; as can be seen from FIG. 12, Congo red was the highest in degradation rate at 70 min.
And (4) after the experimental conditions are optimized, measuring the absorbance of the solution and calculating the degradation rate of the solution. The Congo red degradation rate reaches 94 percent in 70 minutes (figure 5), and the degradation rate reaches 58 percent after the Congo red is recycled for 14 times (figure 6).
Application Effect example 2
The inhibition of E.coli and S.aureus by Phe @ CuNCs prepared in example 1 was examined by the paper method:
the bacterial culture medium is put into an incubator at 37 ℃ for overnight culture for 18 h, and the corrected bacterial concentration is 5 multiplied by 105CFU/mL. Adding 100 μ L of the bacterial solution into the surface of agar plate, coating with sterile coating rod, and standing at room temperature for 10 min. The disc was taken with sterile forceps, gently placed into a plate, and gently pressed against the agar. The Phe @ CuNCs mother liquor was diluted to 0.30, 0.40, 0.50 and 0.60 mmoL/L, respectively, at a concentration of 0.6 mmoL/L (calculated as copper sulfate). After 20 mu L of the solution is dripped on each paper sheet, the paper sheet is cultured in a constant temperature incubator at 37 ℃ for 18 h, taken out and measured by a ruler, and the diameters of inhibition zones are all larger than 12 mm (see figure 7), which indicates that Phe @ CuNCs are highly sensitive to escherichia coli and staphylococcus aureus.
The bacteriostasis mechanism of the Phe @ CuNCs composite material is observed under a scanning electron microscope, wherein the images 8A and 9A are normal staphylococcus aureus and escherichia coli, and the images 8B and 9B are the normal staphylococcus aureus and the escherichia coli after the Phe @ CuNCs is added. As is apparent from FIGS. 8B and 9B, after Phe @ CuNCs was added, the bacterial surface collapsed and perforated, breaking the cell wall and killing the bacteria.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A preparation method of a Phe @ CuNCs composite material is characterized by comprising the following steps: mixing a copper source, phenylalanine and hydrazine hydrate, reacting under an alkaline condition, filtering, and freeze-drying to obtain a Phe @ CuNCs composite material;
the method 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) adding sodium hydroxide solution into the mixed solution II continuously to adjust the pH value to 10-14, stirring and reacting at 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).
2. The method of making a Phe @ CuNCs composite material of claim 1, wherein: the concentration range of the sodium hydroxide solution in the step (3) is 0.5-5 moL/L.
3. The use of Phe @ CuNCs composite material prepared by the method of claim 1 or 2 as a catalyst for rapid recyclable congo red degradation or as a gram-bacteria-inhibiting bacteriostatic.
4. The use according to claim 3, 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.
5. Use according to claim 3, characterized in that: the minimum concentration of the Phe @ CuNCs composite material used for inhibiting gram bacteria is 0.3 mmoL/L.
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