CN106693908A - Preparation method and application of nano composite material capable of simultaneously recognizing and efficient degrading tetracycline - Google Patents

Preparation method and application of nano composite material capable of simultaneously recognizing and efficient degrading tetracycline Download PDF

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CN106693908A
CN106693908A CN201710030405.3A CN201710030405A CN106693908A CN 106693908 A CN106693908 A CN 106693908A CN 201710030405 A CN201710030405 A CN 201710030405A CN 106693908 A CN106693908 A CN 106693908A
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kaolin
tetracycline
preparation
composite material
nano composite
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CN106693908B (en
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贾磊
徐君
陈泽华
别红彦
徐周庆
周涛
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Henan University of Technology
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Abstract

The invention particularly relates to a preparation method and application of a nano composite material capable of simultaneously recognizing and efficient degrading tetracycline and belongs to the technical field of nano composite materials. The preparation method of the composite material comprises the following steps of preparation of kaolin @ Ag, preparation of the kaolin @ Ag @ APTES, preparation of kaolin @ Ag @ citric acid, kaolin @ preparation of the Ag @ citric acid-Eu. The nano composite material prepared by adopting the preparation method can achieve ultrasensitive rapid detection of tetracycline in a water phase, and the standard exceeding situation of the tetracycline in the environment can be monitored through a fluorescence spectrophotometer in real time. The prepared nano composite material can achieve tetracycline degradation under sunlight exposure, can thoroughly remove the tetracycline exceeding the standard in the environment, is simple in preparation process, easy to popularize and has a certain application prospect.

Description

Can recognize simultaneously and efficient degradation tetracycline nano composite material preparation method and Using
Technical field
The invention belongs to nano composite material technical field simultaneously, and in particular to one kind can be recognized and efficient degradation tetracycline Nano composite material preparation method and application.
Background technology
Antibiotic is naturally organic by the small molecule that can suppress other growth of microorganism at low concentrations of microorganism generation Compound, its species has many kinds, common such as tetracycline, terramycin, fortimicin.Wherein tetracycline is current clinic One of most popular wide spectrum class antibiotic, is widely used in human and animal's prevention and treatment of diseases and as domestic animal Raise the growth promoter raised.China is antibiotics production and uses big country, and abuse condition is serious.In recent years, it is effective Prevention and treatment livestock and poultry, the disease of fish, some lawless persons often abuse this kind of medicine, cause in animal for economic benefit Largely remained in property food, be not only detrimental to health, and more seriously, by various metabolic pathways and Transport And Transformation Approach, tetracycline antibiotics the surrounding mediums such as soil, surface water, underground water detect, and such material have it is chronic The harm such as toxicity and savings toxicity, brings grave danger to human body and the ecosystem, such as causes drug tolerant bacteria or virus Generation.Therefore, easy, sensitive and high selectivity detection technique or method are developed for Tetracyclines antibiosis in monitors environment Element pollution etc. is significant.Therefore, the use of tetracycline is controlled, implements the letter to tetracycline in animal products and environment Just the detection and analysis of, sensitive and high selectivity is particularly significant.
Additionally, carrying out effective degraded to it after detecting that TCs is exceeded also seems most important.Mesh Before, the minimizing technology of tetracycline mainly has bioanalysis, physisorphtion and chemical degradation method etc..Bioanalysis degraded tetracycline Influence factor and degradation condition are relatively complicated, and higher concentration residual tetracycline can to microorganism produce inhibitory action and Killing action.So, the residual tetracycline for processing high concentration relies primarily on physisorphtion or chemical degradation method.However, building Although stand in the physisorphtion on the basis of nano material has very big absorption ratio to tetracycline, but the method fails fundamentally Realize the degraded of tetracycline.Degraded thus to tetracycline is current using or based on chemical method.
The content of the invention
The invention aims to solve the deficiencies in the prior art, and one kind is provided can be while recognizing and efficient degradation four There is the preparation method and application of the nano composite material of ring element, the composite high sensitivity to recognize and efficiently drop to tetracycline Xie Xing, and its preparation process is simple, it is easy to promote, with certain application prospect.
The present invention is adopted the following technical scheme that:
The preparation method of the simultaneously nano composite material of efficient degradation tetracycline can be simultaneously recognized, is comprised the following steps:
Step one, the preparation of kaolin@Ag:By kaolin ultrasonic disperse in water, 75-85 DEG C is heated to, added while stirring Sodium hydroxide solution regulation solution ph be 10.6-12.1, first be added dropwise silver nitrate the aqueous solution stirring 1-2h after add ethanol after Continuous stirring 1-2h, adds the aqueous solution and trisodium citrate the stirring 2-4h of silver nitrate, product is collected by centrifugation, respectively with water, second Alcohol is washed to supernatant water white transparency, and vacuum drying obtains kaolin Ag;
Step 2, the preparation of kaolin@Ag@APTES:By kaolin@Ag and APTES obtained in step one(The ethoxy of aminopropyl three Base silane)Ultrasonic disperse is dissolved in 1 toluene, in 16-24h is stirred at 80-100 DEG C, product is collected by centrifugation, and is washed with ethanol, very Sky is dried, and obtains kaolin@Ag@APTES;
Step 3, the preparation of kaolin@Ag@citric acids:Citric acid is dissolved in the mixed solution of DMF and water, under ultrasonic disperse Each 10mg of NHS, EDC, DDC is sequentially added, after stirring at normal temperature 4-6h, kaolin@Ag@APTES obtained in step 2 is added, continued Stirring at normal temperature 16-24 h, are collected by centrifugation product, and after DMF, distillation water washing are used successively, vacuum drying obtains kaolin Ag lemons Acid;
Step 4, the preparation of kaolin@Ag@citric acids-Eu:
Kaolin@Ag@APTES@citric acids obtained in step 3 are dissolved in ultrasonic disperse in ethanol, are added to and are contained six hydration nitre In the ethanol solution of sour europium, 5-8 h are stirred at 60-70 DEG C, product is collected by centrifugation, after ethanol, distillation water washing are used successively, vacuum Dry, obtain final product the kaolin@Ag@citric acids-Eu.
Further, the concentration of sodium hydroxide solution described in step one is 0.2-0.26mol/L, described in step one Mixing speed is 1200-1800r/min.
Further, the silver nitrate for being added in step one is 3.26 ~ 6.52 with kaolinic mass ratio:400 ~ 800, first The silver nitrate of dropwise addition is 1.6 ~ 2.56 with the mol ratio of the silver nitrate for adding:1, the concentration of the silver nitrate of addition is 0.12- The mol ratio of 0.15mol/L, the silver nitrate for adding and the trisodium citrate for adding is 1.2 ~ 1.5:2.3.
Further, the mass ratio of the Ag of kaolin@described in step 2 and APTES is 2.01:1.
Further, in the mixed solution of DMF described in step 3 and water, the volume ratio of DMF and water is 1:1, add Citric acid, NHS, EDC, DDC and kaolin@Ag@APTES mass ratio be 5:1:1:1:20.
Further, the kaolin@Ag@APTES@citric acids and the matter of six nitric hydrate europiums for being added described in step 4 Amount is than being 5.6:1.
As it is above-mentioned can recognize simultaneously and efficient degradation tetracycline nano composite material preparation method obtained in can be same When identification and efficient degradation tetracycline nano composite material detect and degrade tetracycline in application.
The present invention also provides the nano composite material that can simultaneously recognize simultaneously efficient degradation tetracycline at detection and Fourth Ring of degrading Application in element, it is specific as follows:
The Tris-HCl that kaolin@Ag@citric acids-Eu is added(pH=7.1)In cushioning liquid, colorimetric is placed in after ultrasonic disperse In ware, initial fluorescence figure is measured, configure tetracycline, above-mentioned kaolin@Ag@lemons are added sequentially to the concentration gradient of 50nM In lemon acid-Eu systems, its fluorogram is surveyed respectively, draw kaolin@Ag@citric acid-Eu to tetracycline after being fitted by data Test limit, taking-up have detected the kaolin@Ag@citric acid-Eu after tetracycline, obtain kaolin@Ag@citric acids-Eu-TC;
Above-mentioned kaolin@Ag@citric acid-Eu-TC are carried out into light degradation test under the conditions of the irradiation of simulated solar irradiation, at interval of 5min tests its UV absorption spectrogram and fluorogram, until can't detect tetracycline on UV absorption spectrogram and fluorogram Original excite or emission peak.
Further, the concentration of the tetracycline is 0.0001M.
Compared with prior art, beneficial effects of the present invention:
First:Nano composite material prepared by the present invention can realize the hypersensitive quick detection of tetracycline in water phase, by glimmering Photothermal spectroscopic analyzer can be with the exceeded situation of tetracycline in real-time monitoring environment;
Second:Nano composite material prepared by the present invention can also realize the degraded of tetracycline under sunlight, by environment Thoroughly removal is clean for exceeded tetracycline;
3rd:The preparation process is simple of nano composite material of the invention, it is easy to promote, with certain application prospect.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture or scanning transmission electron microscope figure of each intermediate product obtained in the present invention and final product, its Middle a is kaolinic transmission electron microscope picture, and b is the transmission electron microscope picture of kaolin@Ag, and c is the transmission of kaolin@Ag@citric acids-Eu Electron microscope, d is the scanning transmission electron microscope figure of kaolin@Ag@citric acids-Eu;
Fig. 2 is the powder diagram of kaolin@Ag prepared by kaolin and the present invention;
Fig. 3 is the fluorescence spectra that kaolin@Ag@citric acid-Eu prepared by the present invention are recognized to tetracycline;
Fig. 4 is degraded ultraviolet spectras of the kaolin Ag citric acid-Eu-TC of present invention preparation under simulated solar radiant Figure;
Fig. 5 is degraded fluorograms of the kaolin Ag citric acid-Eu-TC of present invention preparation under simulated solar radiant.
Specific embodiment
With reference to embodiment, the present invention is described in further detail.
It will be understood to those of skill in the art that the following example is merely to illustrate the present invention, and should not be regarded as limiting this hair Bright scope.
Embodiment 1
Load silver nano material in step one, kaolin pipe(Kaolin@Ag)Preparation:
By kaolin(400mg)In 50-100mL water, oil bath heating adds the hydrogen-oxygen of 0.2mol/L to ultrasonic disperse to 85 DEG C It is 12.1 to change sodium water solution regulation pH value(Strong agitation during regulation pH), it is slowly added dropwise 0.160mL silver nitrate aqueous solutions (0.12mol/L), add 25mL ethanol to continue to stir 1h after stirring 1h, add 0.1 mL silver nitrate aqueous solutions(0.12mol/ L)With the trisodium citrate aqueous solution of 0.1mL(0.23mol/L)Stirring 1h, product is collected by centrifugation, washed with water, ethanol respectively to Supernatant water white transparency, vacuum drying chamber dry it is stand-by after 3h, wherein, mixing speed described in the step is 1200r/min.Its Pattern is as shown in figure 1, kaolin nanotube is the hollow tubular thing of the ran of internal diameter 30, length in hundreds of nanometer ranges. Under citric acid effect, Ag ions can be introduced by kaolin nanotube by the consumption for regulating and controlling silver nitrate and kaolin nanotube Internal cavities at and be slowly reduced into silver nanoparticle ion.The kaolin@Ag that as can be seen from Figure 1 prepared by the present invention receive Mitron has good pattern and dispersiveness.From powder diffraction data(As shown in Figure 2)It can be seen that having loaded Nano silver grain After, the characteristic diffraction peak of Nano silver grain is occurred in that on XRD spectra(111,200,220 crystal faces), it was demonstrated that in the present invention Kaolin@Ag nanotubes are successfully prepared.
Step 2, the preparation of kaolin@Ag@APTES:Take 400mg kaolin@Ag and 0.85mL APTES(Aminopropyl three Ethoxysilane)Ultrasonic disperse is dissolved in 125mL toluene, and 90 DEG C of oil bath heatings stir 24h, and product centrifugation washs 3 with ethanol Secondary, vacuum drying chamber dries stand-by after 3h.
Step 3, the preparation of kaolin@Ag@citric acids:
Take citric acid 50mg and be dissolved in DMF:Water=1:In 1 25mL mixed solutions, ultrasonic disperse adds NHS, EDC, DDC successively Each 10mg, after stirring at normal temperature 4h, adds 200mg kaolin@Ag@APTES, continues stirring at normal temperature 24h, and product is collected by centrifugation, according to Secondary use DMF, distillation water washing for several times after, vacuum drying chamber dries stand-by after 3h.
Step 4, the preparation of kaolin@Ag@citric acids-Eu:
Take 0.085g kaolin@Ag@APTES@citric acids and be dissolved in ultrasonic disperse in 15mL ethanol, be added to and contain the water of 0.015g six Close in the 10mL ethanol solutions of europium nitrate, 60 DEG C of oil bath heatings stir 5h, and product is collected by centrifugation, successively with ethanol, distillation washing After washing for several times, vacuum drying chamber dries stand-by after 6h.
Tetracycline is detected with obtained kaolin@Ag@citric acid-Eu:
1mg kaolin@Ag@citric acid-Eu are taken in the Tris-HCl of 2mL(pH=7.1)In cushioning liquid, it is placed in after ultrasonic disperse In cuvette, initial fluorescence figure is measured.Configuration concentration is the tetracycline of 0.0001M, is added successively with the concentration gradient of 50nM Enter in above-mentioned kaolin@Ag@citric acid-Eu systems, their fluorogram is measured respectively, this is drawn after being fitted by data Test limit of the material to tetracycline.Be can be seen that when occurring the Fourth Ring of denier in system by the fluorescence spectra shown in Fig. 3 Element(50nM)When, because tetracycline and europium ion are coordinated, cause the enhancing of system fluorescence intensity, and with tetracycline in system Content increase, its fluorescence intensity also constantly strengthens.Follow-up data fitting draws the nano material of institute's example of the present invention to Fourth Ring The test limit of element is 6.61nM, realizes the super sensitivity detection of tetracycline.
Tetracycline is degraded with kaolin@Ag@citric acid-Eu:
Realize the material after the detection of tetracycline(Kaolin@Ag@citric acids-Eu-TC)Itself has just adsorbed a certain amount of four Ring element.By kaolin@Ag@citric acid-Eu-TC solution by photocatalysis instrument, carried out under the conditions of the irradiation of simulated solar irradiation Light degradation is tested.Light irradiation surveys once its UV absorption spectrogram and fluorogram at interval of 5min, until ultraviolet and fluorogram On all can't detect the original of tetracycline and excite or emission peak.After Fig. 4 and Fig. 5 can be seen that one h of illumination, this hair The nano material of bright institute's example can be realized to the degradable of tetracycline, realize the fast degradation to tetracycline.
Embodiment 2
Load silver nano material in step one, kaolin pipe(Kaolin@Ag)Preparation:
By kaolin(400mg)In 50-100mL water, oil bath heating adds the hydrogen-oxygen of 0.25mol/L to ultrasonic disperse to 85 DEG C It is 10.6 to change sodium water solution regulation pH value(Strong agitation during regulation pH), it is slowly added dropwise 0.256mL silver nitrate aqueous solutions (0.15mol/L), add 25mL ethanol to continue to stir 2h after stirring 2h, add 0.1 mL silver nitrate aqueous solutions(0.15mol/ L)With the trisodium citrate aqueous solution of 0.1mL(0.23mol/L)Stirring 2h, product is collected by centrifugation, washed with water, ethanol respectively to Supernatant water white transparency, vacuum drying chamber dry it is stand-by after 3h, wherein, mixing speed described in the step is 1800r/min.
Step 2, the preparation of kaolin@Ag@APTES:
Take 400mg kaolin@Ag and 0.85mL APTES(Aminopropyl triethoxysilane)Ultrasonic disperse is dissolved in 125mL toluene In, 80 DEG C of oil bath heatings stir 24h, and product centrifugation is washed 3 times with ethanol, and vacuum drying chamber dries stand-by after 3h.
Step 3, the preparation of kaolin@Ag@citric acids:
Take citric acid 50mg and be dissolved in DMF:Water=1:In 1 25mL mixed solutions, ultrasonic disperse adds NHS, EDC, DDC successively Each 10mg, after stirring at normal temperature 5h, adds 200mg kaolin@Ag@APTES, continues stirring at normal temperature 20h, and product is collected by centrifugation, according to Secondary use DMF, distillation water washing for several times after, vacuum drying chamber dries stand-by after 3h.
Step 4, the preparation of kaolin@Ag@citric acids-Eu:
Take 0.085g kaolin@Ag@APTES@citric acids and be dissolved in ultrasonic disperse in 15mL ethanol, be added to and contain 0.015g six In the 10mL ethanol solutions of nitric hydrate europium, 70 DEG C of oil bath heatings stir 5h, product are collected by centrifugation, successively with ethanol, distilled water After washing for several times, vacuum drying chamber dries stand-by after 6h.
Embodiment 3
Load silver nano material in step one, kaolin pipe(Kaolin@Ag)Preparation:
By kaolin(400mg)In 50-100mL water, oil bath heating adds the hydrogen-oxygen of 0.26mol/L to ultrasonic disperse to 85 DEG C It is 11 to change sodium water solution regulation pH value(Strong agitation during regulation pH), it is slowly added dropwise 0.160mL silver nitrate aqueous solutions(0.12mol/ L), add 25mL ethanol to continue to stir 2h after stirring 2h, add 0.1 mL silver nitrate aqueous solutions(0.12mol/L)And 0.1mL Trisodium citrate aqueous solution(0.23mol/L)Stirring 4h, product is collected by centrifugation, washed with water, ethanol respectively to supernatant without Color is transparent, vacuum drying chamber dry it is stand-by after 3h, wherein, mixing speed described in the step is 1500r/min.
Step 2, the preparation of kaolin@Ag@APTES:
Take 400mg kaolin@Ag and 0.85mL APTES(Aminopropyl triethoxysilane)Ultrasonic disperse is dissolved in 125mL toluene In, 100 DEG C of oil bath heatings stir 16h, and product centrifugation is washed 3 times with ethanol, and vacuum drying chamber dries stand-by after 3h.
Step 3, the preparation of kaolin@Ag@citric acids:
Take citric acid 50mg and be dissolved in DMF:Water=1:In 1 25mL mixed solutions, ultrasonic disperse adds NHS, EDC, DDC successively Each 10mg, after stirring at normal temperature 6h, adds 200mg kaolin@Ag@APTES, continues stirring at normal temperature 16h, and product is collected by centrifugation, according to Secondary use DMF, distillation water washing for several times after, vacuum drying chamber dries stand-by after 3h.
Step 4, the preparation of kaolin@Ag@citric acids-Eu:
Take 0.085g kaolin@Ag@APTES@citric acids and be dissolved in ultrasonic disperse in 15mL ethanol, be added to and contain 0.015g six In the 10mL ethanol solutions of nitric hydrate europium, 60 DEG C of oil bath heatings stir 8h, product are collected by centrifugation, successively with ethanol, distilled water After washing for several times, vacuum drying chamber dries stand-by after 6h.
It should be understood by those skilled in the art that, the present invention is not limited to the above embodiments, above-described embodiment and explanation Merely illustrating the principles of the invention described in book, without departing from the spirit and scope of the present invention, the present invention also has Various changes and modifications, these changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention By appending claims and its equivalent thereof.

Claims (9)

1. the preparation method of the simultaneously nano composite material of efficient degradation tetracycline can be recognized simultaneously, it is characterised in that including as follows Step:
Step one, the preparation of kaolin@Ag:By kaolin ultrasonic disperse in water, 75-85 DEG C is heated to, added while stirring Sodium hydroxide solution regulation solution ph be 10.6-12.1, first be added dropwise silver nitrate the aqueous solution stirring 1-2h after add ethanol after Continuous stirring 1-2h, adds the aqueous solution and trisodium citrate aqueous solution the stirring 1-4h of silver nitrate, and product is collected by centrifugation, and uses respectively Water, ethanol are washed to supernatant water white transparency, and vacuum drying obtains kaolin Ag;
Step 2, the preparation of kaolin@Ag@APTES:By kaolin@Ag and APTES obtained in step one(The ethoxy of aminopropyl three Base silane)Ultrasonic disperse is dissolved in toluene, in 16-24h is stirred at 80-100 DEG C, product is collected by centrifugation, and is washed with ethanol, vacuum Dry, obtain kaolin@Ag@APTES;
Step 3, the preparation of kaolin@Ag@citric acids:Citric acid is dissolved in the mixed solution of DMF and water, under ultrasonic disperse NHS, EDC, DDC are sequentially added, after stirring at normal temperature 4-6h, kaolin@Ag@APTES obtained in step 2 is added, is continued normal temperature and is stirred 16-24 h are mixed, product is collected by centrifugation, after DMF, distillation water washing are used successively, vacuum drying obtains kaolin Ag citric acids;
Step 4, the preparation of kaolin@Ag@citric acids-Eu:
Kaolin@Ag@APTES@citric acids obtained in step 3 are dissolved in ultrasonic disperse in ethanol, are added to and are contained six hydration nitre In the ethanol solution of sour europium, 5-8 h are stirred at 60-70 DEG C, product is collected by centrifugation, after ethanol, distillation water washing are used successively, vacuum Dry, obtain final product the kaolin@Ag@citric acids-Eu.
2. according to claim 1 can recognize simultaneously and efficient degradation tetracycline nano composite material preparation method, Characterized in that, the concentration of sodium hydroxide solution described in step one is 0.2-0.26mol/L, mixing speed described in step one It is 1200-1800r/min.
3. according to claim 1 can recognize simultaneously and efficient degradation tetracycline nano composite material preparation method, Characterized in that, the silver nitrate added in step one is 3.26 ~ 6.52 with kaolinic mass ratio:400 ~ 800, the nitre being first added dropwise Sour silver is 1.6 ~ 2.56 with the mol ratio of the silver nitrate for adding:1, the concentration of the silver nitrate of addition is 0.12-0.15mol/L, The silver nitrate and the mol ratio of the trisodium citrate for adding for adding are 1.2 ~ 1.5:2.3.
4. according to claim 1 can recognize simultaneously and efficient degradation tetracycline nano composite material preparation method, Characterized in that, the mass ratio of the Ag of kaolin@described in step 2 and APTES is 2.01:1.
5. according to claim 1 can recognize simultaneously and efficient degradation tetracycline nano composite material preparation method, Characterized in that, in the mixed solution of DMF described in step 3 and water, the volume ratio of DMF and water is 1:1, the citric acid of addition, The mass ratio of NHS, EDC, DDC and kaolin@Ag@APTES is 5:1:1:1:20.
6. according to claim 1 can recognize simultaneously and efficient degradation tetracycline nano composite material preparation method, Characterized in that, the kaolin@Ag@APTES@citric acids added described in step 4 are with the mass ratio of six nitric hydrate europiums 5.6:1。
7. as described in any one of claim 1 to 6 can recognize simultaneously and efficient degradation tetracycline nano composite material system Nano composite material the answering in detection and tetracycline of degrading of simultaneously efficient degradation tetracycline can be simultaneously recognized obtained in Preparation Method With.
8. according to claim 7 by the preparation that can simultaneously recognize the simultaneously nano composite material of efficient degradation tetracycline Application of the nano composite material of simultaneously efficient degradation tetracycline in detection and tetracycline of degrading can be simultaneously recognized obtained in method, Characterized in that, specific as follows:
The Tris-HCl that kaolin@Ag@citric acids-Eu is added(pH=7.1)In cushioning liquid, colorimetric is placed in after ultrasonic disperse In ware, initial fluorescence figure is measured, configure tetracycline, above-mentioned kaolin@Ag@lemons are added sequentially to the concentration gradient of 50nM In lemon acid-Eu systems, its fluorogram is surveyed respectively, draw kaolin@Ag@citric acid-Eu to tetracycline after being fitted by data Test limit, taking-up have detected the kaolin@Ag@citric acid-Eu after tetracycline, obtain kaolin@Ag@citric acids-Eu-TC;
Above-mentioned kaolin@Ag@citric acid-Eu-TC are carried out into light degradation test under the conditions of the irradiation of simulated solar irradiation, at interval of 5min tests its UV absorption spectrogram and fluorogram, until can't detect tetracycline on UV absorption spectrogram and fluorogram Original excite or emission peak.
9. according to claim 8 by the preparation that can simultaneously recognize the simultaneously nano composite material of efficient degradation tetracycline Application of the nano composite material of simultaneously efficient degradation tetracycline in detection and tetracycline of degrading can be simultaneously recognized obtained in method, Characterized in that, the concentration of the tetracycline is 0.0001M.
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