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 PDFInfo
- Publication number
- 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
- Authority
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- China
- Prior art keywords
- kaolin
- tetracycline
- preparation
- composite material
- nano composite
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004098 Tetracycline Substances 0.000 title claims abstract description 67
- 235000019364 tetracycline Nutrition 0.000 title claims abstract description 67
- 150000003522 tetracyclines Chemical class 0.000 title claims abstract description 67
- 229960002180 tetracycline Drugs 0.000 title claims abstract description 66
- 229930101283 tetracycline Natural products 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 28
- 230000000593 degrading effect Effects 0.000 title claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000015556 catabolic process Effects 0.000 claims abstract description 25
- 238000006731 degradation reaction Methods 0.000 claims abstract description 25
- 238000001514 detection method Methods 0.000 claims abstract description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 88
- 239000005995 Aluminium silicate Substances 0.000 claims description 76
- 235000012211 aluminium silicate Nutrition 0.000 claims description 76
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 59
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 21
- 238000005119 centrifugation Methods 0.000 claims description 20
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 20
- 238000001291 vacuum drying Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 9
- 235000015165 citric acid Nutrition 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 7
- 229940038773 trisodium citrate Drugs 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- -1 aminopropyl Chemical group 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 3
- 235000005979 Citrus limon Nutrition 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- 244000248349 Citrus limon Species 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 241001465754 Metazoa Species 0.000 description 4
- 239000002071 nanotube Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000011953 bioanalysis Methods 0.000 description 2
- 238000002144 chemical decomposition reaction Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NQYDFSLFJNXWJE-UHFFFAOYSA-N europium;hydrate Chemical compound O.[Eu] NQYDFSLFJNXWJE-UHFFFAOYSA-N 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 229930195503 Fortimicin Natural products 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- BIDUPMYXGFNAEJ-APGVDKLISA-N astromicin Chemical compound O[C@@H]1[C@H](N(C)C(=O)CN)[C@@H](OC)[C@@H](O)[C@H](N)[C@H]1O[C@@H]1[C@H](N)CC[C@@H]([C@H](C)N)O1 BIDUPMYXGFNAEJ-APGVDKLISA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000037353 metabolic pathway Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 229940063650 terramycin Drugs 0.000 description 1
- 229940072172 tetracycline antibiotic Drugs 0.000 description 1
- 229940040944 tetracyclines Drugs 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0296—Nitrates of compounds other than those provided for in B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Biochemistry (AREA)
- Engineering & Computer Science (AREA)
- Pathology (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Hydrology & Water Resources (AREA)
- Immunology (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Toxicology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Cosmetics (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
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
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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