CN112322280A - Preparation method of piperazine functionalized carbon quantum dots and application of piperazine functionalized carbon quantum dots in oxytetracycline detection - Google Patents
Preparation method of piperazine functionalized carbon quantum dots and application of piperazine functionalized carbon quantum dots in oxytetracycline detection Download PDFInfo
- Publication number
- CN112322280A CN112322280A CN202011167228.1A CN202011167228A CN112322280A CN 112322280 A CN112322280 A CN 112322280A CN 202011167228 A CN202011167228 A CN 202011167228A CN 112322280 A CN112322280 A CN 112322280A
- Authority
- CN
- China
- Prior art keywords
- carbon quantum
- piperazine
- quantum dot
- functionalized carbon
- solution
- Prior art date
- 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.)
- Pending
Links
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 title claims abstract description 108
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000004100 Oxytetracycline Substances 0.000 title claims abstract description 48
- 229960000625 oxytetracycline Drugs 0.000 title claims abstract description 48
- 235000019366 oxytetracycline Nutrition 0.000 title claims abstract description 48
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[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 IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 title claims abstract description 48
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000001514 detection method Methods 0.000 title abstract description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000502 dialysis Methods 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004108 freeze drying Methods 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 44
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000007853 buffer solution Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000005284 excitation Effects 0.000 claims description 8
- 238000001917 fluorescence detection Methods 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- CWXPZXBSDSIRCS-UHFFFAOYSA-N tert-butyl piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCNCC1 CWXPZXBSDSIRCS-UHFFFAOYSA-N 0.000 claims description 6
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 5
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 8
- 239000012491 analyte Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 229920002678 cellulose Polymers 0.000 abstract description 2
- 239000001913 cellulose Substances 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 239000000706 filtrate Substances 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- 239000000872 buffer Substances 0.000 description 6
- CYDMQBQPVICBEU-UHFFFAOYSA-N chlorotetracycline Natural products C1=CC(Cl)=C2C(O)(C)C3CC4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-UHFFFAOYSA-N 0.000 description 6
- 229960004475 chlortetracycline Drugs 0.000 description 6
- 235000019365 chlortetracycline Nutrition 0.000 description 6
- CYDMQBQPVICBEU-XRNKAMNCSA-N chlortetracycline Chemical compound C1=CC(Cl)=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 CYDMQBQPVICBEU-XRNKAMNCSA-N 0.000 description 6
- 230000000007 visual effect Effects 0.000 description 6
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000007112 amidation reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000004193 piperazinyl group Chemical group 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010511 deprotection reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002866 fluorescence resonance energy transfer Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012417 linear regression Methods 0.000 description 2
- 239000008055 phosphate buffer solution Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 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
- 230000009435 amidation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229940063650 terramycin Drugs 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
- C07D295/205—Radicals derived from carbonic acid
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- 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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/11—Compounds covalently bound to a solid support
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Immunology (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Pathology (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Biophysics (AREA)
- Manufacturing & Machinery (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention provides a preparation method of piperazine functionalized carbon quantum dots and application of the piperazine functionalized carbon quantum dots in oxytetracycline detection, wherein the preparation method comprises the steps of simultaneously dissolving citric acid and urea in ethylene glycol, and stirring; heating the solution in a reaction kettle; filtering with a filter membrane, dialyzing the filtrate in a cellulose dialysis bag, and freeze-drying the obtained dialysate to obtain carbon quantum dot powder. The method changes the light-emitting state of the carbon quantum dots and the organic matter, realizes the fluorescence migration type detection of the oxytetracycline, has simple preparation of the carbon quantum dots and wide raw material sources, can realize the fast and efficient detection of the oxytetracycline in the water body and reduce the interference of other coexisting substances in the detection process by utilizing the specific combination of the carbon quantum dot surface modification molecule piperazine and the target analyte oxytetracycline, and has strong detection specificity and high sensitivity.
Description
Technical Field
The invention belongs to the technical field of carbon nano material preparation and antibiotic detection, and particularly relates to preparation of piperazine functionalized carbon quantum dots and application of the piperazine functionalized carbon quantum dots in fluorescence detection of oxytetracycline.
Background
Terramycin is widely used in animal husbandry production, and detection of substances in the environment plays an important role in understanding pollution conditions, forecasting pollution trends, evaluating treatment effects and the like. The most common detection techniques for oxytetracycline at present comprise high performance liquid chromatography, layer-by-layer chromatography, immunoassay, chemical fluorescence and the like, and the methods are often expensive in instruments, long in detection time and mostly require complicated pretreatment processes. Therefore, the development of a simple, efficient and highly selective qualitative and quantitative detection method for oxytetracycline is still necessary.
As a new member in the carbon nano family, the carbon quantum dot has various superior performances of high fluorescence stability, photobleaching resistance, wide and continuous excitation light, adjustable emitted light, good biocompatibility and the like. In the field of fluorescence detection, carbon quantum dots are mainly applied to analysis of heavy metals, transition metals and the like at present, and the fluorescence enhancement or quenching of the carbon quantum dots caused by the substances can be used as response signals for detection of pollutants in a system. When the increase and decrease of the fluorescence intensity of the carbon quantum dot is used as a detection signal, the fluorescence intensity is easily interfered by other coexisting substances, and direct visual analysis is not easily realized. And the fluorescence detection method using the deviation of the emission wavelength as a detection signal is easier to eliminate interference, and realizes simple and high-selectivity visual fluorescence detection. Although various surface functionalization approaches have been used to improve the fluorescence properties of carbon quantum dots, the main objective of most research in the field of detection and analysis is to increase the fluorescence quantum yield or improve the detection specificity of a target analyte, rather than to achieve a specific fluorescence shift for the target analyte.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a piperazine functionalized carbon quantum dot and an application of the piperazine functionalized carbon quantum dot in fluorescence detection of oxytetracycline.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of piperazine functionalized carbon quantum dots comprises the following steps:
(1) dissolving citric acid and urea in ethylene glycol, stirring, heating, filtering, dialyzing with deionized water as dialysis external liquid, and freeze-drying the dialysate to obtain carbon quantum dot powder;
(2) adding carbon quantum dot powder into a 2- (N-morpholine) ethanesulfonic acid buffer solution, performing ultrasonic dispersion, and continuously introducing nitrogen;
(3) placing the solution obtained in the step (2) in an ice bath, sequentially adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and hydroxysuccinimide, keeping the nitrogen atmosphere, and stirring;
(4) keeping the nitrogen atmosphere, adding tert-butyloxycarbonyl piperazine into the solution obtained in the step (3) under a certain temperature condition, dropwise adding a sodium hydroxide solution into the solution, and adjusting the pH value of the solution;
(5) uniformly stirring the solution obtained in the step (4) for a certain time, then adding hydrochloric acid, and continuously stirring at room temperature;
(6) adding sodium bicarbonate powder into the solution obtained in the step (5), and dialyzing by taking deionized water as dialysis external liquid after the pH value of the solution reaches a certain value;
(7) and (4) carrying out freeze drying on the solution dialyzed in the step (6) to obtain the piperazine functionalized carbon quantum dot.
Preferably, in the step (1), the molar ratio of the citric acid to the urea to the glycol is 1 (1-3) to (40-80), preferably 1 (1.5-2.5) to (50-60); the heating temperature is 120-240 ℃, and the heating time is 2-24 hours, preferably 8-16 hours; the diameter of a filter membrane used for filtering is 0.1-0.5 mu m, and the amount of dialysis external liquid deionized water used for dialysis is 800-1500 mL; the dialysis time is 2-72 h, preferably 12-48 h; the dialysis external liquid is replaced for 2-4 times every 24 hours, and the freeze drying time is 12-48 hours.
Preferably, in the step (2), the volume ratio of the mass of the carbon quantum dot powder to the 2- (N-morpholine) ethanesulfonic acid buffer solution (pH 6) is 1mg: 0.5-2.0 mL, the ultrasonic dispersion time is 5-60 min, and the nitrogen gas introduction time is 15-60 min; preferably, the pH of the 2- (N-morpholine) ethanesulfonic acid buffer is 6.
Preferably, in the step (3), the mass ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the hydroxysuccinimide to the carbon quantum dot powder used in the step (2) is (2-5): 0.2-10): 1, wherein the stirring time is 2-24 hours, preferably 8-16 hours.
Preferably, in the step (4), the mass ratio of the tert-butyloxycarbonylpiperazine to the carbon quantum dots in the step (2) is (2-5): 1, adding a sodium hydroxide solution, and adjusting the pH of the solution to 6.0-8.0, preferably 7.0-8.0; preferably, the concentration of the sodium hydroxide solution is 1M.
Preferably, in the step (5), the stirring time is 2-24 h; preferably, 8-16 h; the mass ratio of the volume of the added hydrochloric acid (1M) to the carbon quantum dots in the step (2) is (0.2-1) mL:1mg, and the stirring time at room temperature is 1-4 h.
Preferably, in the step (6), sodium bicarbonate powder is added to adjust the pH of the solution to 5-7, the amount of deionized water of the dialysis external liquid is 800-1500 mL, and the dialysis time is 2-72 h; preferably, 12-48 h; in the step (7), the freeze drying time is 12-48 h.
The invention also provides application of the piperazine functionalized carbon quantum dot prepared by the preparation method in fluorescence detection of oxytetracycline.
Preferably, the fluorescence emission of the sample is measured using a fluorescence spectrometer with an excitation wavelength of 370 nm.
Preferably, adding 0.025M sodium bicarbonate-sodium hydroxide buffer solution with the pH of 8-10 into the piperazine functionalized carbon quantum dot and a sample containing oxytetracycline, shaking uniformly, and standing for 1h at room temperature; preferably, the pH is 9.2-10.0.
When the used excitation wavelength is 365nm, the fluorescence color of the system is transited from the original blue to the green and finally is changed into the yellow-green as the oxytetracycline concentration is increased from 0 to 10 mu M, and the method can realize the quick semi-quantitative visual identification of the oxytetracycline.
Amidation of piperazine, a six-membered ring molecule, with a carboxylic acid group at the carbon quantum dot is introduced onto the surface of the carbon quantum dot with two nitrogen atoms at opposite sites, which makes it very likely to undergo hydrogen bonding and electrostatic interactions with other molecules. When the free oxytetracycline molecules in the solution are combined through the intermolecular force, the energy of the piperazine functionalized carbon quantum dots is partially transferred to the oxytetracycline molecules through the fluorescence resonance energy transfer effect, so that the fluorescence of the oxytetracycline molecules is enhanced, and the fluorescence of the carbon quantum dots is weakened. The cooperative fluorescence emission wavelength between the piperazine functionalized carbon quantum dot and the combined oxytetracycline molecules gradually shifts along with the increase of the oxytetracycline content, so that quantitative detection and visual rapid identification of the oxytetracycline can be realized.
The mechanism of the invention is as follows: the blue fluorescent carbon quantum dots with surfaces rich in hydrophilic groups are synthesized by using citric acid and urea as raw materials through a solvothermal method, piperazine groups are introduced on the surfaces of the carbon quantum dots through an amidation reaction and a protection/deprotection method to synthesize piperazine functionalized carbon quantum dots, and the piperazine groups can be combined with oxytetracycline molecules in a solution through hydrogen bonds and electrostatic interaction. Under the excitation of 370nm wavelength under the alkaline condition, fluorescence resonance energy transfer occurs between the piperazine functionalized carbon quantum dot and the oxytetracycline molecule bonded on the surface of the piperazine functionalized carbon quantum dot, and the oxytetracycline serving as an energy receptor obtains partial excitation energy from the piperazine functionalized carbon quantum dot by taking a piperazine group as a medium, so that the autofluorescence of the oxytetracycline molecule bonded on the surface of the piperazine functionalized carbon quantum dot is enhanced. Therefore, with the increase of the oxytetracycline concentration in the range of 0-10 μ M, the fluorescence emission of the system gradually shifts in red, and the fluorescence color of the system is transited from blue to yellow-green, so that the fluorescence offset type detection and the quick visual semi-quantitative identification for the oxytetracycline are realized.
Compared with the prior art, the preparation of the piperazine functionalized carbon quantum dot and the application of the piperazine functionalized carbon quantum dot in fluorescence detection of oxytetracycline have the following advantages:
(1) the blue fluorescent carbon quantum dots with the surfaces rich in hydrophilic groups are synthesized by using citric acid and urea as raw materials through a solvothermal method, and the blue fluorescent carbon quantum dots are wide in raw material source, simple in synthesis method and low in cost.
(2) The amino group at one end of piperazine molecule is protected and then loaded on the surface of carbon quantum dot through amidation reaction, and then deprotection is carried out, so that not only can effective combination of piperazine and carbon quantum dot be ensured, but also free amino at the other end can be reserved to combine with target analyte.
(3) The specific combination of the carbon quantum dot surface modification molecule piperazine and the target analyte oxytetracycline changes the luminescent state of the carbon quantum dot and an organic substance, and realizes fluorescence migration type detection and rapid visual identification for the oxytetracycline.
(4) The specific combination of the piperazine functionalized carbon quantum dot and the oxytetracycline can reduce the interference of other coexisting substances in the detection process, and the detection method has stronger specificity and higher sensitivity.
Drawings
Fig. 1 is a TEM and particle size distribution diagram of (a) carbon quantum dots and (b) piperazine-functionalized carbon quantum dots.
FIG. 2(a) is NaHCO3-normalized fluorescence emission spectra of mixed systems after oxytetracycline with different concentrations in a NaOH buffer system is added to a piperazine functionalized carbon quantum dot solution; (b) is a linear regression curve (excitation wavelength: 370nm) plotted as the maximum emission wavelength of the piperazine functionalized carbon quantum dots as a function of oxytetracycline concentration.
FIG. 3 shows NaHCO under 365nm ultraviolet lamp irradiation3Fluorescence photographs of piperazine functionalized carbon quantum dots mixed with oxytetracycline at different concentrations in NaOH buffer (from left to right oxytetracycline concentrations: 0, 1, 2, 4, 6, 8, 10. mu.M).
FIG. 4 is NaHCO3-mixed by piperazine functionalized carbon quantum dots and aureomycin with different concentrations in NaOH buffer solutionFluorescence emission spectrum.
FIG. 5 is NaHCO3Fluorescence emission spectra of piperazine functionalized carbon quantum dots in NaOH buffer mixed with tetracycline hydrochloride of different concentrations.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example one
A preparation method of piperazine functionalized carbon quantum dots comprises the following steps:
(1) preparation of carbon quantum dots
0.65g of citric acid and 0.42g of urea were simultaneously dissolved in 25mL of ethylene glycol, and after magnetically stirring for 2 hours, the solution was placed in a 50mL Teflon stainless steel reaction vessel and heated at 200 ℃ for 10 hours. After auto-cooling to room temperature, the black product in the autoclave was filtered through a 0.22 μm filter to remove larger particulate impurities. The solution was then placed in a cellulose dialysis bag (1000MWCO), dialysis was continued for 24 hours with 800mL of deionized water as dialysis external fluid, and accelerated dialysis was performed with magnetic stirring, during which the external fluid was changed 3 times every 24 hours. And after the dialysis is finished, pouring the black solution in the dialysis bag into a glass dish, and freeze-drying for about 24 hours by using a freeze dryer to finally obtain carbon quantum dot black powder.
FIG. 1(a) is a transmission electron microscope and a particle size distribution diagram of carbon quantum dots.
(2) Preparation of piperazine functionalized carbon quantum dot
30mg of carbon quantum dot powder was added to 30mL of 2- (N-morpholine) ethanesulfonic acid buffer (pH 6), ultrasonically dispersed for 30 minutes, then nitrogen gas was introduced for 30 minutes to remove dissolved oxygen in the solution, and thereafter the solution was placed in an ice bath and 150mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 75mg of hydroxysuccinimide were added in this order, and the reaction was continued under a nitrogen atmosphere and stirred at a constant speed for 12 hours using a magnetic stirrer to ensure the reaction. 0.10g of t-butoxycarbonylpiperazine was added under nitrogen atmosphere at a low temperature of 0 ℃ and a little sodium hydroxide solution (1M) was slowly added dropwise to the solution to adjust the pH of the solution to a neutral condition of about 7.2. Stirring is continued for 24 hours at a constant speed to ensure that the tert-butyloxycarbonyl piperazine is fully and covalently connected to the surface of the carbon quantum dot. 10mL of hydrochloric acid (1M) was then added to the solution and stirring was continued at room temperature for 6 hours. Then adding sodium bicarbonate powder to neutralize the excessive hydrochloric acid in the solution, and dialyzing for 24 hours by taking 800mL of deionized water as external liquid after the pH value of the solution reaches 6 so as to remove various solutes in the mixed solution. And after dialysis, obtaining the dark brown powder of the piperazine functionalized carbon quantum dots by freeze drying.
FIG. 1(b) is a transmission electron microscope and particle size distribution diagram of piperazine functionalized carbon quantum dots.
The piperazine functionalized carbon quantum dot prepared in the first embodiment is used for detecting oxytetracycline
1mL of piperazine functionalized carbon quantum dot dispersion (0.05mg/mL) and 1mL of oxytetracycline (10. mu.M, 40. mu.M, 60. mu.M, 80. mu.M, 100. mu.M) with different concentrations were added successively to different 10mL Ampere flasks, then 8mL of sodium bicarbonate-sodium hydroxide buffer was added to each of the above mixtures, the mixtures were shaken well and allowed to stand at room temperature for 1 hour, and the fluorescence emission (excitation wavelength 370nm) of each mixture was measured using a fluorescence spectrometer.
According to the change situation of the maximum emission peak wavelength value of 5 samples, a corresponding fitting curve of the maximum emission peak wavelength value (Y) changing with the oxytetracycline concentration (X) is made, and the function corresponding to the curve is as follows: Y4.44X +447.92, correlation coefficient R20.994, and the linear range is 0-10 mu M.
FIG. 2 is NaHCO3-normalized fluorescence emission spectra of mixed system after oxytetracycline with different concentrations in NaOH buffer system is added to piperazine functionalized carbon quantum dot solution and linear regression curve drawn by maximum emission wavelength of piperazine functionalized carbon quantum dot as function of oxytetracycline concentration.
FIG. 3 is NaHCO irradiated under 365nm ultraviolet lamp3-NaOH buffer solutionFluorescence photographs of piperazine functionalized carbon quantum dots mixed with oxytetracycline at different concentrations (from left to right, oxytetracycline concentrations were 0, 1, 2, 4, 6, 8, 10. mu.M).
Comparative example 1:
selecting aureomycin and tetracycline hydrochloride which are similar to the oxytetracycline in structure to investigate the selectivity of the piperazine functionalized carbon quantum dot to the oxytetracycline, adding 1mL of piperazine functionalized carbon quantum dot dispersion (0.05mg/mL) and 1mL of aureomycin (the concentrations are respectively 1, 2, 4, 6, 8 and 10 mu M) into a 10mL ampere bottle, then adding 8mL of phosphate buffer solution, shaking uniformly, standing for 1 hour at room temperature, and testing the fluorescence emission of the solution by using a fluorescence spectrometer.
FIG. 4 is NaHCO3Fluorescence emission spectra of aureomycin with different concentrations in NaOH buffer solution after piperazine functionalized carbon quantum dots and aureomycin with different concentrations are mixed.
Comparative example 2:
selecting aureomycin and tetracycline hydrochloride which are similar to the oxytetracycline in structure to investigate the selectivity of the piperazine functionalized carbon quantum dot to the oxytetracycline, adding 1mL of piperazine functionalized carbon quantum dot dispersion (0.05mg/mL) and 1mL of tetracycline hydrochloride (the concentrations are 0, 2, 4, 6, 8, 10, 20, 40, 60, 80 and 100 mu M respectively) into a 10mL amp-fold bottle, then adding 8mL of phosphate buffer solution, shaking up by oscillation, standing for 1 hour at room temperature, and testing the fluorescence emission of the solution by using a fluorescence spectrometer.
FIG. 5 is NaHCO3Fluorescence emission spectra of piperazine functionalized carbon quantum dots in NaOH buffer mixed with tetracycline hydrochloride of different concentrations.
According to the result of the selectivity test, the interference from other coexisting substances can be effectively eliminated through the shift of a fluorescence emission peak and the change of the color of a piperazine functionalized carbon quantum dot detection system, so that the selective detection of the oxytetracycline is realized.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of piperazine functionalized carbon quantum dots is characterized by comprising the following steps:
(1) dissolving citric acid and urea in ethylene glycol, stirring, heating, filtering, dialyzing with deionized water as dialysis external liquid, and freeze-drying the dialysate to obtain carbon quantum dot powder;
(2) adding carbon quantum dot powder into a 2- (N-morpholine) ethanesulfonic acid buffer solution, performing ultrasonic dispersion, and continuously introducing nitrogen;
(3) placing the solution obtained in the step (2) in an ice bath, sequentially adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and hydroxysuccinimide, keeping the nitrogen atmosphere, and stirring;
(4) keeping the nitrogen atmosphere, adding tert-butyloxycarbonyl piperazine into the solution obtained in the step (3) under a certain temperature condition, dropwise adding a sodium hydroxide solution into the solution, and adjusting the pH value of the solution;
(5) uniformly stirring the solution obtained in the step (4) for a certain time, then adding hydrochloric acid, and continuously stirring at room temperature;
(6) adding sodium bicarbonate powder into the solution obtained in the step (5), and dialyzing by taking deionized water as dialysis external liquid after the pH value of the solution reaches a certain value;
(7) and (4) carrying out freeze drying on the solution dialyzed in the step (6) to obtain the piperazine functionalized carbon quantum dot.
2. The method for preparing a piperazine-functionalized carbon quantum dot according to claim 1, wherein: in the step (1), the molar ratio of the citric acid to the urea to the ethylene glycol is 1 (1-3) to (40-80), preferably 1 (1.5-2.5) to (50-60); the heating temperature is 120-240 ℃, and the heating time is 2-24 hours, preferably 8-16 hours; the diameter of a filter membrane used for filtering is 0.1-0.5 mu m, and the amount of dialysis external liquid deionized water used for dialysis is 800-1500 mL; the dialysis time is 2-72 h, preferably 12-48 h; the dialysis external liquid is replaced for 2-4 times every 24 hours, and the freeze drying time is 12-48 hours.
3. The method for preparing a piperazine-functionalized carbon quantum dot according to claim 1, wherein: in the step (2), the volume ratio of the mass of the carbon quantum dot powder to the 2- (N-morpholine) ethanesulfonic acid buffer solution is 1mg: 0.5-2.0 mL, the ultrasonic dispersion time is 5-60 min, and the nitrogen introduction time is 15-60 min; preferably, the pH of the 2- (N-morpholine) ethanesulfonic acid buffer is 6.
4. The method for preparing a piperazine-functionalized carbon quantum dot according to claim 1, wherein: in the step (3), the mass ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the hydroxysuccinimide to the carbon quantum dot powder used in the step (2) is (2-5): 0.2-10): 1, wherein the stirring time is 2-24 hours, preferably 8-16 hours.
5. The method for preparing a piperazine-functionalized carbon quantum dot according to claim 1, wherein: in the step (4), the mass ratio of the tert-butyloxycarbonyl piperazine to the carbon quantum dots in the step (2) is (2-5): 1, adding a sodium hydroxide solution, and adjusting the pH of the solution to 6.0-8.0, preferably 7.0-8.0; preferably, the concentration of the sodium hydroxide solution is 1M.
6. The method for preparing a piperazine-functionalized carbon quantum dot according to claim 1, wherein: in the step (5), the stirring time is 2-24 h; preferably, 8-16 h; the mass ratio of the volume of the added hydrochloric acid (1M) to the carbon quantum dots in the step (2) is (0.2-1) mL:1mg, and the stirring time at room temperature is 1-4 h.
7. The method for preparing a piperazine-functionalized carbon quantum dot according to claim 1, wherein: in the step (6), sodium bicarbonate powder is added to adjust the pH of the solution to 5-7, the amount of deionized water of the dialysis external liquid is 800-1500 mL, and the dialysis time is 2-72 h; preferably, 12-48 h; in the step (7), the freeze drying time is 12-48 h.
8. The application of the piperazine functionalized carbon quantum dot prepared by the preparation method according to any one of claims 1 to 7 in fluorescence detection of oxytetracycline.
9. Use according to claim 8, characterized in that: the fluorescence emission of the samples was tested using a fluorescence spectrometer with an excitation wavelength of 370 nm.
10. Use according to claim 8, characterized in that: adding 0.025M sodium bicarbonate-sodium hydroxide buffer solution with the pH of 8-10 into a piperazine functionalized carbon quantum dot and a sample containing oxytetracycline, shaking uniformly, and standing for 1h at room temperature; preferably, the pH is 9.2-10.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011167228.1A CN112322280A (en) | 2020-10-26 | 2020-10-26 | Preparation method of piperazine functionalized carbon quantum dots and application of piperazine functionalized carbon quantum dots in oxytetracycline detection |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011167228.1A CN112322280A (en) | 2020-10-26 | 2020-10-26 | Preparation method of piperazine functionalized carbon quantum dots and application of piperazine functionalized carbon quantum dots in oxytetracycline detection |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112322280A true CN112322280A (en) | 2021-02-05 |
Family
ID=74296620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011167228.1A Pending CN112322280A (en) | 2020-10-26 | 2020-10-26 | Preparation method of piperazine functionalized carbon quantum dots and application of piperazine functionalized carbon quantum dots in oxytetracycline detection |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112322280A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292993A (en) * | 2021-05-31 | 2021-08-24 | 山西大学 | Preparation method and application of oil-soluble carbon dots |
| CN115433572A (en) * | 2022-08-23 | 2022-12-06 | 齐齐哈尔大学 | Method for preparing carbon quantum dots based on industrial hemp, carbon quantum dots and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108435002A (en) * | 2018-03-27 | 2018-08-24 | 东华大学 | A kind of preparation method for the composite nanometer filtering film that functionalized carbon is quantum-dot modified |
| CN110003887A (en) * | 2019-04-10 | 2019-07-12 | 东北林业大学 | A kind of preparation method of molecular engram ratio fluorescent probe and the method for detecting terramycin using it |
-
2020
- 2020-10-26 CN CN202011167228.1A patent/CN112322280A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108435002A (en) * | 2018-03-27 | 2018-08-24 | 东华大学 | A kind of preparation method for the composite nanometer filtering film that functionalized carbon is quantum-dot modified |
| CN110003887A (en) * | 2019-04-10 | 2019-07-12 | 东北林业大学 | A kind of preparation method of molecular engram ratio fluorescent probe and the method for detecting terramycin using it |
Non-Patent Citations (1)
| Title |
|---|
| LEI YANG: ""A target analyte induced fluorescence band shift of piperazine modified carbon quantum dots: a specific visual detection method for oxytetracycline"", 《CHEM. COMMUN》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292993A (en) * | 2021-05-31 | 2021-08-24 | 山西大学 | Preparation method and application of oil-soluble carbon dots |
| CN113292993B (en) * | 2021-05-31 | 2022-09-23 | 山西大学 | Preparation method and application of oil-soluble carbon dots |
| CN115433572A (en) * | 2022-08-23 | 2022-12-06 | 齐齐哈尔大学 | Method for preparing carbon quantum dots based on industrial hemp, carbon quantum dots and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109370565B (en) | Double-emission fluorescent molecularly imprinted polymer nano particle and preparation method and application thereof | |
| CN112322280A (en) | Preparation method of piperazine functionalized carbon quantum dots and application of piperazine functionalized carbon quantum dots in oxytetracycline detection | |
| CN111024943A (en) | Switch-on/off type composite fluorescent nano probe for rapid detection of salmonella and preparation method thereof | |
| CN110736725B (en) | Preparation method and application of molecularly imprinted fluorescent sensor for simultaneously and visually detecting two viruses | |
| Liu et al. | A novel aptamer-mediated CuInS 2 quantum dots@ graphene oxide nanocomposites-based fluorescence “turn off–on” nanosensor for highly sensitive and selective detection of kanamycin | |
| CN108504347B (en) | Enhanced dual-emission fluorescent composite material and preparation method and application thereof | |
| Amiri et al. | Application of ratiometric fluorescence sensor-based microwave-assisted synthesized CdTe quantum dots and mesoporous structured epitope-imprinted polymers for highly efficient determination of tyrosine phosphopeptide | |
| CN109781691B (en) | Method for detecting chloramphenicol based on polystyrene nano fluorescent microsphere probe | |
| CN113655039B (en) | Microcystin ratio fluorescence sensor constructed based on molecular imprinting technology | |
| CN112251218B (en) | Preparation method of ethylenediamine functionalized carbon quantum dots and application of ethylenediamine functionalized carbon quantum dots in catechol detection | |
| CN111534299A (en) | GOQDs @ PDA-ir-MIP molecularly imprinted fluorescence sensor and preparation method and application thereof | |
| CN110018146A (en) | A method of palladium ion is detected based on fluorescent carbon quantum dot | |
| Wang et al. | Facile preparation of a multifunctional fluorescent nanosensor for chemical and biological applications | |
| CN110187124B (en) | Preparation method and application of carbon quantum dots | |
| CN112300796A (en) | Yellow fluorescent carbon dot and preparation method and application thereof | |
| WO2003060037A1 (en) | Silica sphere containing fluorescent dye molecule | |
| CN115932248A (en) | Single-molecule immunoassay method based on aggregation-induced emission material | |
| CN112300335B (en) | Preparation method and application of molecular imprinting sensor based on F-PDA (Fabry-Perot digital Assistant) | |
| CN111829993A (en) | Method for detecting hydrogen peroxide and related target object based on CaS nano fluorescent probe | |
| CN109908874B (en) | Novel MoS2QDs @ MIPs molecularly imprinted polymer and preparation method thereof | |
| CN110976906B (en) | Fluorescent palladium nanocluster and synthesis method and application thereof | |
| JP4402646B2 (en) | Particle, sensor using particle, and method for producing porous structure unit | |
| CN114354574A (en) | Multielement SERS biological detection method based on analog enzyme signal amplification | |
| CN114441489A (en) | Preparation method of ratio-type fluorescent biological probe based on fluorescent microspheres and carbon dots and application of ratio-type fluorescent biological probe in concanavalin A detection | |
| CN112611868A (en) | Probe for detecting novel coronavirus by magnetic resonance analysis method and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210205 |