CN113740256B - Detection method and detection kit for tetracycline - Google Patents
Detection method and detection kit for tetracycline Download PDFInfo
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- CN113740256B CN113740256B CN202110866597.8A CN202110866597A CN113740256B CN 113740256 B CN113740256 B CN 113740256B CN 202110866597 A CN202110866597 A CN 202110866597A CN 113740256 B CN113740256 B CN 113740256B
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- 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 65
- 229960002180 tetracycline Drugs 0.000 title claims abstract description 58
- 229930101283 tetracycline Natural products 0.000 title claims abstract description 58
- 238000001514 detection method Methods 0.000 title claims abstract description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 325
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 160
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 130
- 239000002131 composite material Substances 0.000 claims abstract description 69
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000007853 buffer solution Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003607 modifier Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 7
- 125000002091 cationic group Chemical group 0.000 claims description 7
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 description 14
- 230000004048 modification Effects 0.000 description 12
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- 239000011148 porous material Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 229940040944 tetracyclines Drugs 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000006862 quantum yield reaction Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
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- 239000006171 Britton–Robinson buffer Substances 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 3
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
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- 229930186147 Cephalosporin Natural products 0.000 description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 2
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 2
- 229930182555 Penicillin Natural products 0.000 description 2
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229930003268 Vitamin C Natural products 0.000 description 2
- 229940124587 cephalosporin Drugs 0.000 description 2
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- 238000000605 extraction Methods 0.000 description 2
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- 229940049954 penicillin Drugs 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 2
- 235000019154 vitamin C Nutrition 0.000 description 2
- 239000011718 vitamin C Substances 0.000 description 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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- 238000004108 freeze drying Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
-
- 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
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
-
- 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
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- 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
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pathology (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The application discloses a method for detecting tetracycline, which comprises the following steps: s11: providing a buffer solution and carbon quantum dot composite central radial silicon dioxide sphere, wherein the carbon quantum dot composite central radial silicon dioxide sphere comprises a silicon dioxide sphere and carbon quantum dots, the silicon dioxide sphere is in a central radial shape, and the surface of the silicon dioxide sphere is provided with an amino modified group; the carbon quantum dots are loaded in the silicon dioxide spheres; s21: mixing the carbon quantum dot composite central radial silicon dioxide spheres and an object to be tested in the buffer solution to obtain a first mixed solution; and detecting the first mixed solution by a fluorescence spectrometer. According to the method for detecting the tetracycline, disclosed by the application, the carbon quantum dot composite central radial silicon dioxide ball is simply mixed with the object to be detected in the buffer solution, so that the high-sensitivity detection of the tetracycline can be realized, the detection range is 0.5-60 mu M, the detection process can be completed at room temperature, and the method is simple and efficient and has a good application prospect.
Description
Technical Field
The application relates to the field of chemical substance detection, in particular to a detection method and a detection kit for tetracycline.
Background
Tetracycline (TET) is widely used as one of antibiotics because of its ease of preparation, high antibacterial property, and the like. However, in many countries and regions, in addition to being used for treatment, tetracyclines are used as animal growth promoters and the like in the cultivation of animals such as domestic animals, poultry, aquatic products and the like, tetracyclines remained in animal-derived foods such as meat, eggs, milk and the like pose a great threat to human health, on the other hand, tetracycline residues remained in foods can cause drug-resistant pathogenic bacteria to be transmitted through food chains, and adverse effects on natural environment and ecology can be caused, so how to cope with the residues of tetracyclines in various products is a problem to be solved urgently, and detection and management of tetracyclines are of great importance.
The existing detection method for tetracycline comprises the following steps: high performance liquid chromatography, thin layer chromatography, capillary electrophoresis, etc. These conventional detection methods often require complicated equipment or complicated processing procedures for the analyte, and have room for improvement in both detection sensitivity and detection efficiency for tetracycline.
Disclosure of Invention
Based on the above, the application provides a method for detecting tetracycline, which comprises the following steps:
s11: providing a buffer solution and carbon quantum dot composite central radial silicon dioxide sphere, wherein the carbon quantum dot composite central radial silicon dioxide sphere comprises a silicon dioxide sphere and carbon quantum dots, the silicon dioxide sphere is in a central radial shape, and the surface of the silicon dioxide sphere is provided with an amino modified group; the carbon quantum dots are loaded in the silicon dioxide spheres;
s21: mixing the carbon quantum dot composite central radial silicon dioxide spheres and an object to be tested in the buffer solution to obtain a first mixed solution; and detecting the first mixed solution by a fluorescence spectrometer.
According to the method for detecting the tetracycline, the carbon quantum dot composite central radial silica sphere is simply mixed with the object to be detected in the buffer solution, so that the high-sensitivity detection of the tetracycline can be realized, the detection limit is low, the detection process can be completed at room temperature, simplicity and high efficiency are realized, the carbon quantum dot composite central radial silica sphere used in the detection process is used as a support carrier of a composite material, the carrier has a large three-dimensional pore canal and a highly accessible inner surface, modification grafting is easy to realize, in addition, the amino modification groups on the surface of the central radial silica sphere enable the carbon quantum dot to be inserted in the three-dimensional network pore canal of the carbon quantum dot through electrostatic adsorption, thereby avoiding fluorescence self-quenching caused by aggregation of the carbon quantum dot, realizing fluorescence emission of the carbon quantum dot in a solid state, greatly improving fluorescence quantum yield and stability, realizing the detection range of the tetracycline to be 0.5-60 mu M based on the special structure and property of the composite material, and the detection method is simple and high-efficient and has a high application prospect.
In one embodiment, the silica spheres have three-dimensional network pores with an average diameter of 10nm to 20nm, and the carbon quantum dots have an average particle diameter of 1nm to 10nm.
In one embodiment, the carbon quantum dot composite central radial silica sphere in the detection method is prepared by the following method:
s1: providing silica spheres, wherein the silica spheres are in a central radial shape;
s2: providing an amino modifier, mixing the amino modifier with the silica spheres, and reacting to obtain a second mixed solution;
s3: and providing a carbon quantum dot precursor mixed solution, mixing the carbon quantum dot precursor mixed solution with the second mixed solution, and performing a hydrothermal reaction to obtain the carbon quantum dot composite central radial silica spheres.
In one embodiment, the step S1 includes:
and S101, providing a catalyst and a first solvent, dissolving the catalyst in the first solvent to obtain a first solution, adding a template agent into the first solution, fully mixing, adding a silicon source, and reacting to obtain the silicon dioxide spheres.
In one embodiment, the catalyst is triethanolamine, the first solvent is at least one of water and ethanol, and the concentration of the first solution is 20mg/mL to 30mg/mL.
In one embodiment, the templating agent comprises an anionic templating agent and a cationic templating agent, the molar ratio of the anionic templating agent to the cationic templating agent being 0.2:1 to 2:1.
In one embodiment, the silicon source is ethyl orthosilicate and the mass ratio of the catalyst to the silicon source is 1:93-1:62.
In one embodiment, the amino modifier in the step S2 is a mixed solution of at least one of 3-oxypropyl triethoxysilane and 3-aminopropyl trimethoxysilane dissolved in an alcohol substance and ammonia water, and the concentration of the silica spheres after the silica spheres are mixed with the amino modifier is 0.02g/mL to 0.1g/mL.
In one embodiment, the carbon quantum dot precursor in the step S3 includes a carbon source and a nitrogen source, the molar ratio of the carbon source to the nitrogen source is 1:1-1:3, the carbon source includes at least one of citric acid monohydrate and acetic acid, and the nitrogen source includes at least one of diethylenetriamine, ethylenediamine and triethylenetetramine.
On the other hand, the application also provides a kit for tetracycline detection, which at least comprises a carbon quantum dot composite central radial silicon dioxide sphere, wherein the carbon quantum dot composite central radial silicon dioxide sphere comprises a silicon dioxide sphere and carbon quantum dots, the silicon dioxide sphere is in a central radial shape, and the surface of the silicon dioxide sphere is provided with an amino modified group; the carbon quantum dots are loaded in the silicon dioxide spheres; the kit is used for detecting the tetracycline by the detection method.
The kit has the advantages of low cost, high detection sensitivity, high efficiency, high specificity, convenient use method, high-efficiency detection of tetracycline by combining a fluorescence spectrometer at room temperature, and good application prospect.
Drawings
The following describes the embodiments of the present application in further detail with reference to the accompanying drawings:
FIG. 1 is a diagram of steps for detecting tetracycline in an embodiment of the application;
fig. 2 is a flowchart of a method for preparing a carbon quantum dot composite central radial silica sphere according to an embodiment of the present application;
FIG. 3 is a fluorescence spectrum diagram of carbon quantum dot composite central radial silica sphere material for detecting tetracyclines with different concentrations in the embodiment of the application;
FIG. 4 is a graph showing the relative fluorescence intensity of carbon quantum dot composite central radial silica sphere material for detecting tetracyclines with different concentrations in an embodiment of the present application;
FIG. 5 is a graph showing the relative fluorescence intensity of carbon quantum dot composite central radial silica sphere material in the present application for detecting tetracycline in the presence of different interfering substances;
FIG. 6 is a scanning electron microscope photograph of a central radial silica sphere in the process of the preparation method of the carbon quantum dot composite central radial silica sphere provided by the embodiment of the application;
fig. 7 is a transmission electron microscope photograph of a central radial silica sphere in the process of the preparation method of the carbon quantum dot composite central radial silica sphere provided by the embodiment of the application;
FIG. 8 is a Zeta potential diagram of carbon quantum dots, central radial silica spheres and amino-modified central radial silica spheres in an embodiment of the present application;
FIG. 9 is a transmission electron micrograph of a carbon quantum dot composite center radial silica sphere in an embodiment of the application;
FIG. 10 is a scanning diagram of a transmission electron microscope element of a carbon quantum dot composite center radial silica sphere in an embodiment of the application;
FIG. 11 is a fluorescence spectrum of a carbon quantum dot composite center radial silica sphere according to an embodiment of the present application;
FIG. 12 is a graph showing fluorescence intensity data of a carbon quantum dot composite center radial silica sphere in a 50-day process of being dispersed and stored in water in an embodiment of the present application;
FIG. 13 is a graph showing fluorescence intensity data of carbon quantum dot composite central radial silica spheres at different sodium chloride concentrations in an embodiment of the present application;
FIG. 14 is a photograph of solid phase sample of carbon quantum dot composite center radial silica spheres under fluorescent and ultraviolet lamps in an embodiment of the present application;
FIG. 15 is fluorescence quantum yield data for carbon quantum dots and carbon quantum dot composite central radial silica spheres;
FIG. 16 is a graph showing the change in fluorescence intensity of the carbon quantum dot composite center radial silica sphere material of example 6 with the molar ratio of diethylenetriamine to citric acid monohydrate and the hydrothermal reaction time;
FIG. 17 is a fluorescence spectrum of the sample of example 1 and comparative example 1.
Detailed Description
In order to clarify the application in more detail, a further explanation of the technical solution of the application will be provided below in connection with a preferred embodiment and a drawing.
Referring to fig. 1, the application provides a method for detecting tetracycline, which comprises the following steps:
s11: providing a buffer solution and carbon quantum dot composite central radial silicon dioxide sphere, wherein the carbon quantum dot composite central radial silicon dioxide sphere comprises a silicon dioxide sphere and carbon quantum dots, the silicon dioxide sphere is in a central radial shape, and the surface of the silicon dioxide sphere is provided with an amino modified group; the carbon quantum dots are loaded in the silicon dioxide spheres; s21: mixing the carbon quantum dot composite central radial silicon dioxide spheres and an object to be tested in the buffer solution to obtain a first mixed solution; and detecting the first mixed solution by a fluorescence spectrometer.
According to the method for detecting the tetracycline, the carbon quantum dot composite central radial silica sphere is simply mixed with the object to be detected in the buffer solution, so that the high-sensitivity detection of the tetracycline can be realized, the detection limit is low, the detection process can be completed at room temperature, simplicity and high efficiency are realized, the carbon quantum dot composite central radial silica sphere used in the detection process is used as a support carrier of a composite material, the carrier has a large three-dimensional pore canal and a highly accessible inner surface, modification grafting is easy to realize, in addition, the amino modification groups on the surface of the central radial silica sphere enable the carbon quantum dot to be inserted in the three-dimensional network pore canal of the carbon quantum dot through electrostatic adsorption, thereby avoiding fluorescence self-quenching caused by aggregation of the carbon quantum dot, realizing fluorescence emission of the carbon quantum dot in a solid state, greatly improving fluorescence quantum yield and stability, realizing the detection range of the tetracycline to be 0.5-60 mu M based on the special structure and property of the composite material, and the detection method is simple and high-efficient and has a high application prospect.
Referring to fig. 2, in some preferred embodiments, the preparation method of the carbon quantum dot composite central radial silica sphere includes the following steps:
s1: providing silica spheres, wherein the silica spheres are in a central radial shape;
s2: providing an amino modifier, mixing the amino modifier with the silica spheres, and reacting to obtain a second mixed solution;
s3: and providing a carbon quantum dot precursor mixed solution, mixing the carbon quantum dot precursor mixed solution with the second mixed solution, and performing a hydrothermal reaction to obtain the carbon quantum dot composite central radial silica spheres.
The preparation method is simple, short in preparation period and easy to operate, and the carbon quantum dot composite central radial silicon dioxide ball prepared by the method comprises a silicon dioxide ball and carbon quantum dots, wherein the silicon dioxide ball is in a central radial shape, and the surface of the silicon dioxide ball is provided with an amino modified group; the carbon quantum dots are supported in the silica spheres. The carbon quantum dot composite central radial silicon dioxide sphere material takes the central radial silicon dioxide sphere as a support carrier of the composite material, and the carrier has a large three-dimensional pore canal, a high accessible inner surface and easy modification grafting.
In some preferred embodiments, the silica spheres in the obtained carbon quantum dot composite central radial silica spheres have three-dimensional network pore channels, wherein the average diameter of the three-dimensional network pore channels is 10nm-20nm, and the average particle size of the carbon quantum dots is 1nm-10nm; further preferably, the average diameter of the three-dimensional network pore canal is 15nm-18nm, and the average particle diameter of the carbon quantum dots is 3nm-7nm.
In the preparation process, preferably, the step S1 at least comprises the step S101 of dissolving a catalyst in a first solvent to obtain a first solution, adding a template agent into the first solution, fully mixing, adding a silicon source, and reacting to obtain the silica spheres. In particular, the catalyst may be triethanolamine; the first solvent may be at least one of water and ethanol, and preferably, the concentration of the catalyst in the first solution is 20mg/mL to 30mg/mL, and the silicon source may be ethyl orthosilicate.
In some embodiments, the templating agent added to the first solution comprises an anionic templating agent and a cationic templating agent, and the preferred molar ratio of anionic templating agent to cationic templating agent is 0.2:1-2:1. The use of a combination of templating agents allows for better intercalation of anions into the hydrophobic region of the micelle to form a central radial structure. In the present application, sodium salicylate is preferably used as the anionic template and cetyltrimethylammonium bromide is preferably used as the cationic template.
In some embodiments, the process of adding the silicon source in step S1 is a uniform rate, and the process of adding the silicon source may be manually dropping a quantitative silicon source at intervals, for example: 1mL of silicon is added every 2 minutes, and the silicon source can also be added by an instrument such as a syringe pump, for example: the injection rate of the syringe pump was set to 0.5 mL/min. Further preferably, after the silicon source is added, the mass ratio of the catalyst to the silicon source in the reaction liquid is 1:93-1:62. Step S1 may further include step S102: and (3) carrying out post-treatment on the obtained silica spheres. Specifically, the method comprises the steps of alternately washing the silica spheres obtained in the step S101 for at least 2 times by using ethanol and deionized water, removing catalyst impurities in the silica sphere product, dispersing the silica spheres in a mixed solution of hydrochloric acid and ethanol in a mass ratio of 0.5:1, extracting for at least 2 times, purifying the silica spheres, and then washing the product for multiple times by using ethanol and deionized water respectively to remove a small amount of extract residues in the product. Preferably, the extraction is carried out at a temperature of 50-70 ℃, and the stirring time for a single extraction is at least 2 hours, more preferably 4 hours.
Further, step S1 may further include step S103: and (3) drying the product obtained in the step S102, wherein the drying mode can be natural air drying, freeze drying or drying by a rotary steaming instrument. Preferably, in the present application, the product is dried using a rotary evaporator at 60-80 ℃ to give a white powder of silica spheres as a central radial. Preferably, the white powder is stored in a low temperature environment below 10 ℃, in embodiments of the application, the silica microspheres are stored in a refrigerator at 4 ℃ for use.
In some embodiments, in step S2, the amino modifier is a mixed solution of ammonia water after at least one of 3-oxypropyl triethoxysilane and 3-aminopropyl trimethoxysilane is dissolved in an alcohol substance, and the concentration of the silica spheres after the silica spheres are mixed with the amino modifier is 0.02g/mL to 0.1g/mL.
Before amino modification, the central radial silicon dioxide sphere prepared in the step S1 is negatively charged, and is positively charged after amino modification, and meanwhile, the central radial silicon dioxide sphere is provided with three-dimensional holes, so that the carbon quantum dots with negative charge have excellent adsorption performance, and the carbon quantum dots obtained in the subsequent step S2 can be uniformly and stably present in the central radial silicon dioxide sphere. Based on the stable structure, the carbon quantum dots in the central radial silicon dioxide sphere avoid fluorescence quenching caused by aggregation, and can realize fluorescence emission in a solid state, so that the stability is greatly improved, and on the other hand, the fluorescence quantum yield of the carbon quantum dots is also greatly improved.
In some embodiments, the carbon quantum dot precursor in step S3 comprises a carbon source comprising at least one of citric acid monohydrate, acetic acid, and a nitrogen source comprising at least one of diethylenetriamine, ethylenediamine, and triethylenetetramine in a molar ratio of 1:1-1:3 to the carbon source. Under the condition, the prepared carbon quantum dot is doped with nitrogen, and the carbon quantum dot doped with nitrogen further improves the stability of the carbon quantum dot because the strength of the carbon-nitrogen bond is larger than that of the carbon-carbon bond.
The technical scheme of the application is further described below by referring to examples:
example 1
Embodiment 1 is a preparation method and application of a carbon quantum dot composite central radial silicon dioxide sphere, comprising the following steps:
s1a: 60mg of triethanolamine was dissolved in 20ml of pure water, sonicated for 10 minutes, and continuously stirred at 70℃for 30 minutes, 0.16g of sodium salicylate anionic template and 0.38g of cetyltrimethylammonium bromide cationic template were added, and stirring was continued for 2 hours. 1ml of ethyl orthosilicate was added every 2 minutes, a total of 4ml of ethyl orthosilicate was added and stirring was continued slightly for a further 6 hours. And after the ethanol and the deionized water are alternately washed for a plurality of times, dispersing the mixture into a mixed solution of hydrochloric acid and ethanol with the mass ratio of 0.5:1, stirring the mixture for 4 hours at the temperature of 60 ℃, repeatedly extracting the mixture for three times, respectively alternately washing the mixture with the ethanol and the deionized water, drying the mixture by a rotary evaporator to obtain white powder, namely the central radial silica spheres, and storing the white powder in a refrigerator at the temperature of 4 ℃.
S2a: 0.5g of the central radial silica sphere powder prepared in the step S1a was dissolved in 6.25ml of a 10% mixed solution of 3-oxypropyl triethoxysilane and ethanol, 400ul of ammonia water was added thereto, and after 2 minutes of sonication, the mixture was subjected to shaking reaction at 25℃for 12 hours. After washing with ethanol and deionized water alternately, the precipitate was dissolved in 50ml deionized water. To obtain a dispersion of amino-modified central radial silica microspheres.
S3a: 5g of citric acid monohydrate and 10ml of diethylenetriamine are weighed as carbon quantum dot precursors, after ultrasonic mixing for 10 minutes, the dispersion liquid of the central radial silicon dioxide ball after amino modification is added, after ultrasonic mixing is continued for 30 minutes, the mixture is fully mixed, the mixture is transferred into a stainless steel high-pressure reaction kettle with tetrafluoroethylene internal memory, hydrothermal reaction is carried out for 6 hours at 200 ℃, the mixture is naturally cooled to room temperature after the reaction is finished, ethanol and deionized water are respectively used for alternately and thoroughly washing until the supernatant liquid does not have fluorescence, and the mixture is put into an oven for drying, thus obtaining the carbon quantum dot composite central radial silicon dioxide ball.
Britton-Robinson buffer with pH=7.0 was used as a solvent to prepare a tetracycline stock solution with a final concentration of 50mM, which was then further diluted to a tetracycline solution with a different concentration. Dispersing the prepared carbon quantum dot composite central radial silicon dioxide sphere material in a certain amount of Britton-Robinson buffer solution with pH value of 7.0 to obtain a plurality of groups of mixtures, and then adding the tetracycline solutions with different concentrations respectively to ensure that the final concentration of the tetracycline in each group of mixtures is in the range of 0-1000 mu M and the concentrations are different. The mixtures of each set of added tetracycline solutions were then transferred to quartz cuvettes and each examined with a fluorescence spectrometer within 30 seconds. FIG. 14 is a fluorescence spectrum of the carbon quantum dot composite center radial silica sphere material for detecting tetracycline with different concentrations, and in combination with FIG. 15, it can be known that the linear detection range of the carbon quantum dot composite center radial silica sphere material for detecting tetracycline is 0.5-60 μm.
Example 2, with reference to the procedure of example 1, the tetracycline in milk was detected as follows:
the carbon quantum dot composite central radial silica sphere powder prepared in example 1 was dissolved in Britton-Robinson buffer solution at ph=7.0, and the prepared carbon quantum dot composite central radial silica sphere solution was 0.5mg/mL; dissolving tetracycline in the pretreated milk, and preparing tetracycline solutions with concentrations of 500 μm,1000 μm and 2500 μm (to obtain ph=7.0); taking 490 mu L of carbon quantum dot composite central radial silicon dioxide sphere solution in three cuvettes respectively, adding 10 mu L of tetracycline solution with the concentration of 500 mu M,1000 mu M and 2500 mu M into the three cuvettes respectively, uniformly mixing, placing the mixed solution in a fluorescence spectrometer, respectively measuring fluorescence intensity values of the three under the excitation of the wavelength of 360nm, and calculating the concentration of the tetracycline. This set of experiments was repeated three times and the test results are shown in the following table:
according to the table, the detection recovery rate of the tetracycline in the milk is in the range of 91.9% -104.7%, and the relative standard deviation is smaller than 6.6, so that the result shows that the tetracycline sensing detection method provided by the application has higher accuracy in detection of a real sample.
The sensing detection platform is required to truly realize detection of a real sample, and not only needs to have higher sensitivity, but also needs to have higher selectivity. To evaluate the feasibility of the detection method proposed by us in practical application, we aimed at some interfering substances that may exist in the real scene: penicillin (PNC), cephalosporin (CPS), glucose (Glu), sucrose (SUC), vitamin C (VC), citric Acid (CA), cysteine (Cys), tyrosine (Tyr), glycine (Gly), al 3+ 、Ca 2+ 、K + 、Mg 2+ 、Na + And Zn 2+ And the like, wherein the concentrations of the interfering substances are 50 times the concentrations of the tetracyclines (TET) to be detected (1 mM for tetracyclines and 50mM for other interfering substances), and the other detection conditions are the same as those of the tetracyclines detected in the milk. FIG. 17 shows a bar graph of relative fluorescence intensity at 446nm in the presence and absence of tetracycline after addition of various interfering substances, as evident in the dry stateWhen a large amount of interference exists, the tetracycline still can cause the carbon quantum dot composite central radial silicon dioxide sphere to generate obvious quenching effect, and the interference substance has no obvious influence on the quenching effect, thereby proving the specificity of the carbon quantum dot composite central radial silicon dioxide sphere to tetracycline detection.
Example 3
Example 3 differs from example 1 only in that the amount of triethanolamine is 40mg, cetyltrimethylammonium bromide is 0.24g and sodium salicylate is 0.1g.
Example 4
Example 4 differs from example 1 only in that the amount of triethanolamine is 50mg, the amount of cetyltrimethylammonium bromide is 0.325mg, and the amount of sodium salicylate is 0.15g.
Example 5
Example 5 differs from example 1 only in that the molar ratio of hydrochloric acid to ethanol mixture in step S1a is 1:1.
Example 6
The present embodiment differs from embodiment 1 in that: the molar ratio of diethylenetriamine to citric acid monohydrate is 1:1, 2:1 and 3:1, and the hydrothermal reaction time is 4 hours, 5 hours and 6 hours respectively. Other reaction conditions were the same as in example 1. .
Comparative example 1
Comparative example 1 differs from example 1 only in that step S2a is not performed.
The samples obtained in the respective examples and comparative examples were characterized and tested.
Referring to fig. 6 and 7, the scanning electron microscope test was performed on the central radial silica spheres obtained in step S1a of example 1, and it was found that the silica spheres obtained in step S1a were uniform in size, good in dispersibility, and about 220nm in average diameter, and at the same time, the central radial silica spheres had large three-dimensional channels and highly accessible inner surfaces, and the pore diameters of the channels were about 17nm. Further, nitrogen adsorption test was performed on the central radial silica spheres to obtain the central radial silica spheres having a specific surface area of 620m 2 And/g, it is verified that the carbon quantum dot has high specific surface area, namely the carbon quantum dot isThe high density doping in the interior lays a foundation. The morphology of the central radial silica spheres prepared in the processes of example 2, example 3 and example 4 is similar to that of fig. 7, and correspondingly, the morphology of the finally prepared carbon quantum dot composite central radial silica spheres is also similar to that of fig. 9.
The potential test was performed on the carbon quantum dots synthesized individually, the central radial silica spheres obtained in step S1a, and the amino-modified central radial silica spheres prepared in step S2a, respectively, to obtain A, B and C curves in fig. 4, respectively. It can be seen that the carbon quantum dots are negatively charged, the central radial silica spheres which are not modified by the amino groups are negatively charged, and the central radial silica spheres which are modified by the amino groups are electrically charged, so that better combination can be formed with the carbon quantum dots through the action of electrostatic adsorption compared with the central radial silica spheres before modification, and the carbon quantum dots can stably exist in the pore channels of the central radial silica spheres after modification to form a stable compound.
FIG. 9 is a transmission electron micrograph of the carbon quantum dot composite center radial silica spheres obtained in example 1, showing that the silica spheres are slightly corroded in an alkaline reaction environment, and the average particle diameter is reduced to about 140 nm. In addition, the sample was subjected to nitrogen adsorption test, and the obtained specific surface area was 78m 2 And/g. Fig. 10 is a graph showing the results of scanning the carbon quantum dot composite central radial silica sphere sample obtained in example 1 by using a transmission electron microscope, and it can be seen that the sample contains four elements: carbon, nitrogen, oxygen, silicon.
FIG. 11 is a graph of fluorescence spectra of the carbon quantum dot composite central radial silica sphere sample obtained in example 1 at different excitation wavelengths, wherein the characteristic peaks of the weak carbon quantum dots are shown on a curve D, and the excitation wavelength and the emission wavelength of the sample are respectively tested by a curve E and a curve F, so that the optimal emission wavelength of the sample is 446nm. The solutions in the cuvettes in the upper right hand corner are the colour of the sample under the fluorescent lamp and the violet lamp respectively, the sample appears slightly milky under the fluorescent lamp and clearly blue under the uv lamp.
Fig. 12 is a graph showing the fluorescence intensity results of the sample tested during 50 days of the dispersion of the carbon quantum dot composite central radial silica sphere sample obtained in example 1 in water, and it can be seen that the fluorescence intensity of the sample is substantially unchanged during the dispersion, and it is noted that the same stability is exhibited when the sample is dispersed in other liquids such as ethanol, and the sample has excellent stability in the liquid. Fig. 13 is fluorescence intensity data of samples in sodium chloride aqueous solutions with different concentrations, and it can be seen that the fluorescence intensity of the carbon quantum dot composite central radial silica sphere sample of example 1 is hardly affected even in a high ion concentration environment, and also proves that the carbon quantum dot composite central radial silica sphere sample has excellent stability. Fig. 14a is a photograph of the sample under a fluorescent lamp in a solid state, and fig. 14b is a photograph of the sample under an ultraviolet lamp in a solid state, and it can be seen that the solid powder emits bright blue fluorescence under the ultraviolet lamp, thereby realizing solid state fluorescence emission of carbon dots. Fig. 15a is the quantum yield of carbon quantum dots prepared separately, and fig. 15b is the quantum yield of carbon quantum dot composite central radial silica sphere sample. The preparation method of the carbon quantum dot of fig. 15a is prepared with reference to the aforementioned step S3a, except that the central radial silica sphere modified with no amino group is added. Comparing fig. 15a and 15b, it can be seen that the fluorescence quantum yield is greatly enhanced due to the dispersion of a large number of carbon quantum dots in the network channels of the central radial silica sphere.
The fluorescence intensities of the carbon quantum dot composite central radial silica spheres prepared in example 5, example 6 and example 7 were tested, and as shown in fig. 16, the curve H, I, J is a curve with hydrothermal reaction for 4, 5 and 6 hours, respectively, and it can be seen that the samples can all show better fluorescence intensities, and when the molar ratio of diethylenetriamine to citric acid monohydrate is 2:1 and the hydrothermal reaction time is 5 hours, and the prepared sample has the highest fluorescence intensity.
As a result of fluorescence spectrum test on the carbon quantum dot composite central radial silica spheres obtained in example 1 and comparative example 1, as shown in fig. 17, it can be seen that the fluorescence intensity of the carbon quantum dot composite central radial silica sphere composite material without being modified by amino group is much weaker than that of the carbon quantum dot composite central radial silica sphere composite material without being modified by amino group, indicating that the carbon quantum dot cannot be firmly bonded in the pore canal of the central radial silica sphere without being modified by amino group.
With reference to the above, the application further provides a kit for tetracycline detection, which at least comprises a carbon quantum dot composite central radial silica sphere, wherein the carbon quantum dot composite central radial silica sphere comprises a silica sphere and carbon quantum dots, the silica sphere is in a central radial shape, and the surface of the silica sphere is provided with an amino modified group; the carbon quantum dots are loaded in the silicon dioxide spheres; the kit is used for detecting the tetracycline by the detection method.
In some preferred embodiments, the carbon quantum dot composite central radial silica sphere in the kit is the carbon quantum dot composite central radial silica sphere prepared in any one of the foregoing embodiments, and has corresponding structural characteristics.
Preferably, the kit can also comprise a buffer solution, the type of the buffer solution is not limited, and the pH of the buffer solution is ensured to be about 7.0.
The kit has the advantages of low cost, high detection sensitivity, high efficiency, high specificity, convenient use method, high-efficiency detection of tetracycline by combining a fluorescence spectrometer at room temperature, and good application prospect.
In summary, it can be known that in the detection method of tetracycline provided by the application, the carbon quantum dot composite central radial silica sphere has excellent fluorescence performance and stability, the preparation method is simple and efficient, has wide application prospects in detection of biological and chemical substances, is simple and efficient in detection process when used for detecting tetracycline, and has low cost of a detection kit, easy manufacture and wide application prospects.
Finally, it should be noted that: the foregoing examples are merely illustrative of the present application and are not intended to limit the embodiments of the present application, and it should be understood by those skilled in the art that the technical features of the foregoing embodiments may be combined in any desired manner, and other modifications and equivalent substitutions of some technical features may be made on the basis of the specific embodiments, and thus, it is not intended to be exhaustive of all embodiments, and all modifications, improvements, equivalent substitutions and the like which belong to the technical scope of the present application are included in the spirit and principle of the present application.
Claims (10)
1. A method for detecting tetracycline, comprising the steps of:
s11: providing a buffer solution and carbon quantum dot composite central radial silicon dioxide sphere, wherein the carbon quantum dot composite central radial silicon dioxide sphere comprises a silicon dioxide sphere and carbon quantum dots, the silicon dioxide sphere is in a central radial shape, and the surface of the silicon dioxide sphere is provided with an amino modified group; the carbon quantum dots are loaded in the silicon dioxide spheres;
s21: mixing the carbon quantum dot composite central radial silicon dioxide spheres and an object to be tested in the buffer solution to obtain a first mixed solution; and detecting the first mixed solution by a fluorescence spectrometer.
2. The method for detecting tetracycline according to claim 1, wherein said silica spheres have three-dimensional network channels having an average diameter of 10nm to 20nm, and said carbon quantum dots have an average particle diameter of 1nm to 10nm.
3. The method for detecting tetracycline according to claim 1 or 2, wherein the carbon quantum dot composite central radial silica sphere is prepared by the following steps:
s1: providing silica spheres, wherein the silica spheres are in a central radial shape;
s2: providing an amino modifier, mixing the amino modifier with the silica spheres, and reacting to obtain a second mixed solution;
s3: and providing a carbon quantum dot precursor mixed solution, mixing the carbon quantum dot precursor mixed solution with the second mixed solution, and performing a hydrothermal reaction to obtain the carbon quantum dot composite central radial silica spheres.
4. The method for detecting tetracycline according to claim 3, wherein said step S1 comprises:
and S101, providing a catalyst and a first solvent, dissolving the catalyst in the first solvent to obtain a first solution, adding a template agent into the first solution, fully mixing, adding a silicon source, and reacting to obtain the silicon dioxide spheres.
5. The method for detecting tetracycline according to claim 4, wherein said catalyst is triethanolamine, said first solvent is at least one of water and ethanol, and the concentration of said first solution is 20mg/mL to 30mg/mL.
6. The method for detecting tetracycline according to claim 4, wherein said templates comprise an anionic template and a cationic template, and the molar ratio of said anionic template to said cationic template is 0.2:1-2:1.
7. The method for detecting tetracycline according to claim 4, wherein said silicon source is ethyl orthosilicate, and the mass ratio of said catalyst to said silicon source is 1:93-1:62.
8. The method for detecting tetracycline according to claim 3, wherein said amino modifier in said step S2 is a mixed solution of ammonia water after at least one of 3-oxypropyl triethoxysilane and 3-aminopropyl trimethoxysilane is dissolved in an alcohol, and a concentration of said silica spheres after said silica spheres are mixed with said amino modifier is 0.02g/mL to 0.1g/mL.
9. The method for detecting tetracycline according to claim 3, wherein the carbon quantum dot precursor in step S3 comprises a carbon source and a nitrogen source, the molar ratio of the carbon source to the nitrogen source is 1:1-1:3, the carbon source comprises at least one of citric acid monohydrate and acetic acid, and the nitrogen source comprises at least one of diethylenetriamine, ethylenediamine and triethylenetetramine.
10. The kit for detecting the tetracycline is characterized by at least comprising a carbon quantum dot composite central radial silicon dioxide sphere, wherein the carbon quantum dot composite central radial silicon dioxide sphere comprises a silicon dioxide sphere and carbon quantum dots, the silicon dioxide sphere is in a central radial shape, and the surface of the silicon dioxide sphere is provided with an amino modified group; the carbon quantum dots are loaded in the silicon dioxide spheres; the kit is used for detecting tetracycline by the detection method of any one of claims 1-9.
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