CN112705195B

CN112705195B - Functional material for degrading and determining tetracycline, preparation method and application

Info

Publication number: CN112705195B
Application number: CN202011476079.7A
Authority: CN
Inventors: 陈扬; 王莉
Original assignee: Southeast University
Current assignee: Southeast University
Priority date: 2020-11-25
Filing date: 2020-12-15
Publication date: 2022-03-08
Anticipated expiration: 2040-12-15
Also published as: CN112705195A

Abstract

The invention discloses a functional material, which is a nano material formed by terbium ions, 3-hydroxy-2-picolinic acid and silver nano particles through a solvothermal reaction. The functional material can degrade tetracycline and emit light to indicate the content of the tetracycline, and has dual functions of degradation and light emission. The invention discloses a synthetic method of the functional material, which is simple and is easy and convenient to operate. The functional material of the invention has high tetracycline degradation activity, high tetracycline determination sensitivity and high tetracycline determination speed, and can be used for degradation and monitoring of tetracycline in biological samples and environmental samples.

Description

Functional material for degrading and determining tetracycline, preparation method and application

Technical Field

The invention relates to a functional material for simultaneously degrading and determining tetracycline, a preparation method and application, and belongs to the technical field of environmental protection and luminescence detection.

Background

Tetracycline antibiotics (TCs) are antibiotics with tetraacene as a parent nucleus, and tetracycline, aureomycin, oxytetracycline and the like are widely used in the past decades as anti-inflammatory drugs, veterinary drugs and feed additives for livestock breeding due to broad-spectrum antibacterial effect and low price, and are the most widely used and used antibiotics in the world. The large amount of tetracycline antibiotics is used to cause residues in livestock and poultry bodies, cow milk and the like, and the food with tetracycline residues after long-term intake can damage lungs, intestines, stomachs, kidneys, skins and bones of people, particularly teeth and bones of children, and has the greatest development harm. The tetracycline antibiotics used in large quantities are not fully absorbed by the organisms, and many are released into surface water, ground water, soil through animal or human excreta, resulting in serious ecological damage and environmental pollution. The residual quantity of tetracycline and oxytetracycline regulated in China in milk is less than 100 mug/L, and the residual quantity in muscles, livers and kidneys is less than 100, 300 and 600 mug/kg. The FDA of the United states stipulates that the residual quantity of tetracycline and oxytetracycline in milk is respectively less than 80 mug/L and 30 mug/L. Therefore, simple, rapid and accurate detection of tetracycline pollution in environment and food is of great importance to environmental protection and health safety.

At present, methods for removing tetracycline mainly comprise ozone oxidation, photocatalytic degradation, biodegradation, ultrafiltration, reverse osmosis membrane treatment and the like. Chinese patent publication No. CN 109985647A, 2019, Zenghongyan, and the like, a preparation method of a silver phosphate/metal oxide composite photocatalyst for efficiently degrading tetracycline, and discloses a method for degrading tetracycline under simulated sunlight by using the silver phosphate/metal oxide composite photocatalyst; chinese patent publication No. CN 109926064A, 2019, discloses a narrow-band photocatalytic material for degrading tetracycline by visible light and a preparation method thereof, and discloses a photocatalytic material for degrading tetracycline by visible light; chinese patent publication No. CN 105478454A, 2016, Mayulong, etc., a method for removing residual high-concentration tetracycline in pharmaceutical mushroom dregs, and discloses a method for oxidizing high-concentration tetracycline by using metal ions to catalyze ozone; chinese patent publication No. CN 111205477A, 2020 Liuxiang and the like, a preparation method of a ZIF-67 catalyst and application thereof in degrading antibiotics such as tetracycline and the like, and discloses a method for degrading tetracycline by generating hydroxyl radicals by the ZIF-67 catalyst under the oxidation condition of hydrogen peroxide; chinese patent publication No. CN 107159094 a, 2017, chen anwei, etc., discloses a method for removing tetracycline from wastewater by using a magnetic magnesium hydroxide adsorbent, and discloses a method for removing tetracycline by using a magnetic magnesium hydroxide adsorbent; liweiying et al reported a method for removing tetracycline from water by using a nanofiltration membrane and a reverse osmosis membrane (university of Tongji academic (Nature science edition), 2013, 41, 735-741); chinese patent publication No. CN 107988095A, 2018, Anzhuiqing and the like, a microbial agent for efficiently degrading tetracycline antibiotics and application thereof, and discloses a method for screening Enterococcus Faecium (Enterococcus Faecium) and degrading the tetracycline antibiotics together with other Enterococcus; chinese patent publication No. CN 110295128A, 2019, Zhengyi and the like, a tetracycline antibiotic-degrading strain and application thereof, and discloses a tetracycline antibiotic-degrading strain HNS2-5-2 strain and a method for degrading tetracycline antibiotics by using the strain. As the tetracycline assay, an immunoassay, a colorimetric assay, a high performance liquid chromatography and the like have been reported. Chenli et al reported simultaneous determination of tetracycline antibiotics and their degradation products in soil by ultra performance liquid chromatography-electrospray tandem mass spectrometry (geology front, 2019, 6, 1-6); chinese patent publication No. CN 101290306A, 2008, Yan Ning Ring, etc., a method for detecting the residual quantity of tetracycline antibiotics in milk and dairy products, and discloses a method for determining the tetracycline antibiotics by using an ultra-high performance liquid chromatography-electrospray tandem triple quadrupole mass spectrometer; chinese patent publication No. CN 110726836A, 2004, Liu Zhi hong, etc., an enzyme-linked immunoassay paper box for detecting tetracycline drugs, and discloses a method for measuring tetracycline antibiotics by using an enzyme-labeled antibody absorbance method. Chinese patent publication No. CN 100338467A, 2020, Wangjie, etc., a time-resolved fluoroimmunoassay test strip for quantitatively determining tetracycline and norfloxacin, and discloses a method for determining tetracycline by using the time-resolved fluoroimmunoassay test strip.

The reported methods are long in time consumption, and require complicated equipment, so that it is necessary to develop a simple, rapid and sensitive method for measuring tetracycline antibiotics.

Disclosure of Invention

The purpose of the invention is as follows: the first purpose of the invention is to provide a material capable of degrading tetracycline and detecting tetracycline by luminescence, the second purpose of the invention is to provide a preparation method of the material, and the third purpose is to provide an application method of the material for degrading and detecting tetracycline.

The invention content is as follows: in order to achieve the first object, the invention adopts the technical scheme that: one functional material is a material comprising terbium ion (Tb)³⁺) 3-hydroxy-2-picolinic acid (HPA) and silver nanoparticles (AgNP) are prepared by solvothermal reaction.

The functional material is in a porous network-wrapped nano particle shape, the nano particles are silver nano particles, and the particle size of the silver nano particles is 50-200 nm.

The functional material takes silver nanoparticles as a catalytic center and terbium ions as a luminescent center, and utilizes the reaction of catalytic degradation of tetracycline to sensitize the luminescence of the terbium ions.

The functional material can be used for degrading tetracycline by catalyzing oxygen and/or hydrogen peroxide to generate active oxygen free radicals through the silver nanoparticles.

The functional material enhances the luminescence of terbium ions to measure tetracycline through the excimer resonance effect of the silver nanoparticles.

The functional material has a luminescence indicating function, can indicate the content of tetracycline through the luminescence intensity of terbium ions, has the luminescence intensity in direct proportion to the degradation rate, and can also indicate the degradation rate of the tetracycline in the degradation process by luminescence.

In order to achieve the second object, the invention also provides a preparation method of the functional material, which comprises the steps of preparing silver nanoparticles in the first step, mixing a silver nitrate aqueous solution and a polyvinylpyrrolidone aqueous solution, adding the mixture into ethylene glycol, transferring the mixed solution into a stainless steel reaction kettle with a tetrafluoroethylene lining, reacting for 5-24 hours at 180-200 ℃, cooling to room temperature, centrifugally separating precipitates, washing the precipitates, and drying at 60-80 ℃ to obtain the silver nanoparticles. And secondly, preparing a functional material, namely adding a terbium nitrate aqueous solution into an N, N-dimethylformamide solution of 3-hydroxy-2-picolinic acid, magnetically stirring the solution for 10 minutes for mixing, adding silver nanoparticles dispersed in ethanol ultrasonically into the mixed solution, stirring the solution for 20 minutes, sealing the mixture in a tetrafluoroethylene-lined reaction kettle, reacting for 3-6 hours at the temperature of 130-150 ℃, cooling to room temperature, centrifugally separating and precipitating, washing the precipitate with absolute ethyl alcohol and pure water, and drying the precipitate at the temperature of 60 ℃ to obtain the functional material.

Wherein terbium ions in the mixed solution are: 3-hydroxy-2-pyridinecarboxylic acid: the molar ratio of the silver nanoparticles is 1: 1: 1-5.

In order to achieve the third purpose, the invention provides the application of the functional material in degrading tetracycline and/or determining the content of tetracycline.

Specifically, the method for degrading tetracycline comprises the following steps: adding the functional material into a sample solution containing tetracycline, preferably adding the functional material and a hydrogen peroxide solution into the sample solution containing tetracycline, uniformly mixing, degrading the tetracycline in the sample solution under the action of the functional material, wherein the degradation degree is in direct proportion to the absorbance of the solution, measuring the absorbance value of the solution to obtain the degradation rate, or measuring the luminescence intensity of the solution to obtain the degradation rate of the tetracycline according to the direct proportion of the degradation degree to the luminescence intensity of the solution.

Specifically, the method for determining tetracycline:

1) firstly, respectively adding a certain amount of functional material solution into a series of standard tetracycline solutions with known concentration, uniformly mixing, standing for 30 minutes, measuring the fluorescence intensity of terbium ions under the wavelength of 545nm, and drawing a working curve of the fluorescence intensity and the tetracycline concentration;

2) then adding a certain amount of functional material solution into a sample solution containing tetracycline, uniformly mixing, standing for 30 minutes, observing the luminescent color of the sample solution under an ultraviolet lamp, comparing the luminescent color with the luminescent color of a standard tetracycline solution with a known concentration, and measuring the content of tetracycline by visual colorimetry; or measuring the 545nm fluorescence intensity by a fluorescence spectrophotometer, and obtaining the tetracycline concentration according to the working curve of the fluorescence intensity and the standard tetracycline concentration and the measured fluorescence intensity of the sample.

Has the advantages that: compared with the prior art, the functional material has the following advantages:

1) the functional material of the invention can degrade tetracycline and emit light to indicate the content of the tetracycline at the same time, and has dual functions of degradation and light emission.

2) The functional material disclosed by the invention enhances the luminescence of terbium ions by utilizing the excimer resonance effect and the degradation reaction of silver nanoparticles, so that the determination sensitivity is improved.

3) The functional material of the invention utilizes the luminescence of the rare earth ions to detect the tetracycline, the long fluorescence life of the rare earth ions allows the interference of various non-specific fluorescence to be eliminated by a time-resolved fluorescence technology, the signal-to-noise ratio is high, the interference of common background fluorescence in a sample solution is avoided, and the determination of the tetracycline in a biological sample has advantages.

4) The preparation method of the functional material is simple and does not need complex organic synthesis.

Drawings

FIG. 1 is a scanning electron microscope image of AgNPs and a functional material AgNP-HPA-Tb for degrading and determining tetracycline;

FIG. 2 is a graph showing the ultraviolet-visible spectrum of the functional material AgNP-HPA-Tb for degrading and measuring tetracycline;

FIG. 3 degradation and determination of tetracycline degradation curve of functional material AgNP-HPA-Tb for tetracycline degradation;

FIG. 4 degradation and determination of tetracycline functional material AgNP-HPA-Tb degradation tetracycline luminous intensity change;

FIG. 5 degradation and determination of tetracycline functional material AgNP-HPA-Tb luminescence detection of tetracycline.

Detailed Description

The technical solution of the present invention will be described in detail below with reference to the accompanying drawings and examples.

Example 1 preparation of functional Material AgNP-HPA-Tb for degradation and determination of Tetracycline

Preparing silver nano particles: to 4 mL of ethylene glycol, 1 mL of 0.1M AgNO was added₃Stirring the aqueous solution and 4 mL of an aqueous solution containing 0.04 g of polyvinylpyrrolidone for 20 minutes, transferring the solution to a stainless steel reaction kettle lined with tetrafluoroethylene, heating the solution at 180 ℃ for 5 hours, cooling the solution to room temperature, centrifuging the solution to separate a precipitate, and using anhydrous ethyl acetate to separate the precipitateWashing with alcohol for 6 times, and drying at 80 deg.C for 1 hr to obtain silver nanoparticles with particle diameter of about 50-200 nm as shown in FIG. 1A.

Preparation of AgNP-HPA-Tb: to 5 mL of N, N-Dimethylformamide (DMF), 1 mL of a 30 mM DMF solution of 3-hydroxy-2-pyridinecarboxylic acid, 1 mL of 20 mM Tb (NO) were added₃)₃And (2) after stirring and mixing the aqueous solution, adding 2 mL of ethanol solution containing 0.01 g of the prepared silver nanoparticles, and uniformly stirring by magnetic force to obtain a mixed solution, wherein terbium ions in the mixed solution are as follows: 3-hydroxy-2-pyridinecarboxylic acid: the molar ratio of the silver nanoparticles is 1: 1: 1, stirring for 10 minutes, transferring the mixed solution into a stainless steel reaction kettle, reacting for 5 hours at 130 ℃, cooling to room temperature, centrifugally separating and precipitating, washing the precipitate for 3 times by using ethanol and pure water, and drying in a drying oven at 60 ℃ for later use. FIG. 1B is the scanning electron microscope image of AgNP-HPA-Tb prepared, the AgNP-HPA-Tb material is in the form of network-coated nano particles with the size of about 0.5-2 microns.

Example 2 preparation of AgNP-HPA-Tb material as functional material for degradation and determination of tetracycline

To 5 mL of N, N-Dimethylformamide (DMF), 1 mL of a 30 mM DMF solution of 3-hydroxy-2-pyridinecarboxylic acid, 1 mL of 20 mM Tb (NO) were added₃)₃After the aqueous solution was mixed with stirring, 2 mL of an ethanol solution containing 0.05 g of the silver nanoparticles prepared in example 1 was added, and the mixture was stirred by magnetic force until terbium ion: 3-hydroxy-2-pyridinecarboxylic acid: the molar ratio of the silver nanoparticles is 1: 1: 5, stirring for 10 minutes, transferring the mixed solution into a stainless steel reaction kettle, reacting for 5 hours at 140 ℃, cooling to room temperature, centrifugally separating and precipitating, washing the precipitate for 3 times by using ethanol and pure water, and drying in a drying oven at 60 ℃ for later use. FIG. 1C is a scanning electron microscope image of the prepared AgNP-HP-Tb, and the AgNP-HPA-Tb material is in a network wrapping nano particle shape and is about 1-2 microns in size.

Example 3 application of functional material AgNP-HPA-Tb in tetracycline degradation

mu.L of 0.01M tetracycline hydrochloride aqueous solution and 10. mu.L of the AgNP-HPA-Tb suspension prepared in example 2 (0.3 mg/mL) were added to 970. mu.L of HEPES (N-2-hydroxyethylpiperazine-N' -2-ethanesulfonic acid) buffer solution (10 mM, pH 7), and 10. mu.L of 10 mM peroxygen was addedAnd (3) mixing the hydrogen hydride solution uniformly, reacting for 20 minutes, and measuring the ultraviolet visible absorption spectrum of the tetracycline solution at intervals of several minutes. FIG. 2 is a graph of the UV-VIS absorption spectrum of tetracycline under the action of AgNP-HPA-Tb, and absorption peaks of tetracycline at 275 nm and 358 nm disappear, which shows that the tetracycline is completely degraded. FIG. 3 is a tetracycline degradation curve showing that the absorbance of tetracycline decreases as the reaction proceeds, and in the absence of hydrogen peroxide, the AgNP-HPA-Tb preparations of examples 1 and 2 degraded tetracycline by about 40% and 50%, respectively, after 120 minutes (FIG. 3A), and in the presence of hydrogen peroxide, the AgNP-HPA-Tb preparations of examples 1 and 2 degraded tetracycline by about 55% and 80%, respectively, after 120 minutes (FIG. 3B). Tb as the reaction proceeds³⁺The fluorescence intensity (at 545 nm) of (A) was increased continuously and was proportional to the degree of degradation (degradation rate) (FIG. 4).

Example 4 application of AgNP-HPA-Tb luminescent detection tetracycline as functional material

mu.L of the AgNP-HPA-Tb suspension (0.3 mg/mL) prepared in example 2 and 10. mu.L of 10 mM hydrogen peroxide solution were added to 970. mu.L of HEPES buffer solution (10 mM, pH 7), 10. mu.L of tetracycline hydrochloride aqueous solutions of different concentrations were sequentially added to the HEPES buffer solution to prepare standard tetracycline solutions containing tetracycline 0, 0.05, 0.5, 1, 2, 3.5, 5 and 10. mu.M, and after mixing and reacting uniformly for 30 minutes, the fluorescence intensity at 545nm was measured under 278 nm excitation. FIG. 5 is Tb³⁺Linear dependence of fluorescence intensity on tetracycline concentration, Tb³⁺The fluorescence intensity is directly proportional to the tetracycline concentration, with a detection limit of 0.01. mu.M. Because the degradation reaction has an enhancement effect on terbium ion luminescence, other substances have no interference on the determination, and the determination of tetracycline has good selectivity. And (3) measuring the fluorescence intensity of an unknown tetracycline sample, and obtaining the content of the tetracycline sample by using a linear relation graph.

Claims

1. The functional material is characterized by being prepared by the following steps of: adding a terbium nitrate aqueous solution into an N, N-dimethylformamide solution of 3-hydroxy-2-picolinic acid, stirring and mixing, adding silver nanoparticles dispersed in ethanol to obtain a mixed solution, stirring and mixing, transferring the mixed solution into a stainless steel reaction kettle, reacting at the temperature of 130-150 ℃ for 3-6 hours, cooling to room temperature, centrifugally separating and precipitating, washing the precipitate with ethanol and pure water, and drying to obtain the functional material.

2. The functional material of claim 1, wherein the functional material is in the form of a porous network-encapsulated nanoparticle.

3. The method for preparing a functional material according to claim 1 or 2, comprising the following synthetic steps: adding a terbium nitrate aqueous solution into an N, N-dimethylformamide solution of 3-hydroxy-2-picolinic acid, stirring and mixing, adding silver nanoparticles dispersed in ethanol to obtain a mixed solution, stirring and mixing, transferring the mixed solution into a stainless steel reaction kettle, reacting at the temperature of 130-150 ℃ for 3-6 hours, cooling to room temperature, centrifugally separating and precipitating, washing the precipitate with ethanol and pure water, and drying to obtain the functional material.

4. The method for preparing a functional material according to claim 3, wherein the ratio of terbium ion in the mixed solution: 3-hydroxy-2-pyridinecarboxylic acid: the molar ratio of the silver nanoparticles is 1: 1: 1-5.

5. The method for preparing the functional material according to claim 3 or 4, wherein the silver nanoparticles are prepared by mixing a silver nitrate aqueous solution and a polyvinylpyrrolidone aqueous solution, adding the mixture into ethylene glycol, transferring the mixed solution into a stainless steel reaction kettle lined with tetrafluoroethylene, reacting for 5-24 hours at 180-200 ℃, cooling to room temperature, centrifugally separating and precipitating, washing the precipitate, and drying to obtain the silver nanoparticles.

6. Use of the functional material of claim 1 or 2 for degradation and/or determination of tetracycline.

7. The use according to claim 6, wherein the tetracycline is degraded by adding a solution containing a functional material and hydrogen peroxide or a solution containing a functional material to a sample solution containing tetracycline, mixing uniformly, measuring the UV-visible absorbance or fluorescence intensity of the solution at intervals of 20 minutes, and measuring the degradation rate of tetracycline based on the absorbance or fluorescence intensity.

8. The use according to claim 6, wherein the method for measuring tetracycline comprises the steps of adding solutions containing the functional material and hydrogen peroxide into a series of tetracycline solutions with known concentrations, mixing uniformly, standing for 30 minutes, measuring the luminous intensity of terbium ions at 545nm, drawing a working curve of the tetracycline concentration and the luminous intensity, measuring the luminous intensity of the sample solution under the same conditions, and obtaining the tetracycline content in the sample solution according to the working curve and the luminous intensity of the sample solution.