CN108865124A - A kind of N, P adulterate carbon quantum dot, preparation method and application - Google Patents
A kind of N, P adulterate carbon quantum dot, preparation method and application Download PDFInfo
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- CN108865124A CN108865124A CN201810604277.3A CN201810604277A CN108865124A CN 108865124 A CN108865124 A CN 108865124A CN 201810604277 A CN201810604277 A CN 201810604277A CN 108865124 A CN108865124 A CN 108865124A
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- Prior art keywords
- quantum dot
- carbon quantum
- preparation
- adulterate
- codope
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 72
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 36
- 238000001514 detection method Methods 0.000 claims abstract description 30
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 19
- RZZPDXZPRHQOCG-OJAKKHQRSA-M CDP-choline(1-) Chemical compound O[C@@H]1[C@H](O)[C@@H](COP([O-])(=O)OP([O-])(=O)OCC[N+](C)(C)C)O[C@H]1N1C(=O)N=C(N)C=C1 RZZPDXZPRHQOCG-OJAKKHQRSA-M 0.000 claims abstract description 17
- 229960001284 citicoline Drugs 0.000 claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229930003779 Vitamin B12 Natural products 0.000 claims description 19
- 239000011715 vitamin B12 Substances 0.000 claims description 19
- 235000019163 vitamin B12 Nutrition 0.000 claims description 19
- 238000005119 centrifugation Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 claims 1
- QGZKDVFQNNGYKY-AKLPVKDBSA-N Ammonia-N17 Chemical compound [17NH3] QGZKDVFQNNGYKY-AKLPVKDBSA-N 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 50
- 230000005284 excitation Effects 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 19
- AGVAZMGAQJOSFJ-WZHZPDAFSA-M cobalt(2+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+2].N#[C-].[N-]([C@@H]1[C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP(O)(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O AGVAZMGAQJOSFJ-WZHZPDAFSA-M 0.000 description 18
- 239000000843 powder Substances 0.000 description 14
- 239000002096 quantum dot Substances 0.000 description 14
- 239000000523 sample Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 238000002835 absorbance Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000006862 quantum yield reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- AKYHKWQPZHDOBW-UHFFFAOYSA-N (5-ethenyl-1-azabicyclo[2.2.2]octan-7-yl)-(6-methoxyquinolin-4-yl)methanol Chemical compound OS(O)(=O)=O.C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 AKYHKWQPZHDOBW-UHFFFAOYSA-N 0.000 description 6
- 208000010507 Adenocarcinoma of Lung Diseases 0.000 description 6
- 239000001576 FEMA 2977 Substances 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 6
- 230000003013 cytotoxicity Effects 0.000 description 6
- 231100000135 cytotoxicity Toxicity 0.000 description 6
- 201000005249 lung adenocarcinoma Diseases 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229960003110 quinine sulfate Drugs 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000007853 buffer solution Substances 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 239000006285 cell suspension Substances 0.000 description 4
- 229960001231 choline Drugs 0.000 description 4
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000009777 vacuum freeze-drying Methods 0.000 description 4
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 3
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- 238000004113 cell culture Methods 0.000 description 3
- 230000001413 cellular effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 201000005202 lung cancer Diseases 0.000 description 3
- 208000020816 lung neoplasm Diseases 0.000 description 3
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000011895 specific detection Methods 0.000 description 3
- 230000004083 survival effect Effects 0.000 description 3
- AZKSAVLVSZKNRD-UHFFFAOYSA-M 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide Chemical compound [Br-].S1C(C)=C(C)N=C1[N+]1=NC(C=2C=CC=CC=2)=NN1C1=CC=CC=C1 AZKSAVLVSZKNRD-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229940098773 bovine serum albumin Drugs 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 2
- 235000018417 cysteine Nutrition 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000000799 fluorescence microscopy Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000013102 re-test Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 229910018089 Al Ka Inorganic materials 0.000 description 1
- 241000193738 Bacillus anthracis Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 1
- 101710088194 Dehydrogenase Proteins 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- 206010064571 Gene mutation Diseases 0.000 description 1
- 208000001953 Hypotension Diseases 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- FRLJSGOEGLARCA-UHFFFAOYSA-N cadmium sulfide Chemical class [S-2].[Cd+2] FRLJSGOEGLARCA-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- FEZWOUWWJOYMLT-DSRCUDDDSA-M cobalt;[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2,7,1 Chemical compound [Co].[N-]([C@@H]1[C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP(O)(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O FEZWOUWWJOYMLT-DSRCUDDDSA-M 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 230000034612 response to cobalamin Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- 150000003722 vitamin derivatives Chemical class 0.000 description 1
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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
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
-
- 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
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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"
-
- 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
-
- 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
Abstract
The present invention provides a kind of N, and P adulterates carbon quantum dot, preparation method and application.It is simple that the N, P adulterate carbon quantum dot preparation method, and gained N, P doping carbon quantum dot can delicately be used for cobalt ions detection.The preparation method is that citicoline carries out hydro-thermal reaction as carbon source and ethylenediamine, purification obtains the N, P adulterates carbon quantum dot, and the component that the N, P adulterate carbon quantum dot includes carbon 47%~49%, oxygen 27%~29%, nitrogen 17%~19%, phosphorus 3%~5%.Preferably, the average grain diameter that the N, P adulterate carbon quantum dot is 2.1~3.4nm, and interlamellar spacing is 0.25~0.35nm, and the mean fluorecence service life is 3.4~4.0ns.The present invention uses citicoline for carbon source, step preparation N, P codope carbon quantum dot, and preparation method is simple；The N, P codope carbon quantum dot can detect cobalt ions in solution, and detection limit can reach 53.0nM.
Description
Technical field
The present invention relates to fluorescent carbon technical field of nano material, in particular to a kind of N, P adulterate carbon quantum dot, its preparation side
Method and application.
Background technique
Carbon dots are as a member new in carbon nanomaterial family, and carbon dots have many superior photoluminescent properties, such as by changing
Become size and its controllable fluorescent emission of excitation wavelength, resistance to photobleaching, without optical flare.Carbon is weight needed for constituting organism
One of element is wanted, carbon dots being made of it bio-toxicity itself is low, has good environment friendly and biocompatibility.This
Outside, the reaction condition for preparing carbon dots is mild, and step is simple, abundant raw material and cheap.Carbon dots surface is hydrophilic rich in carboxyl, hydroxyl etc.
Group has water-soluble well.For metal quantum point, carbon quantum dot is nontoxic, small to the harm of environment, cost
It is cheaper.The sensor made of it can be used to detect the biochemical war agents such as explosive and anthrax.With good biofacies
The carbon dots of capacitive and hypotoxicity are suitable for life science.
Salinas-Castillo etc. is using citric acid as carbon source, and in the presence of polyimides (PEI), microwave cracking is prepared for
Carbon quantum dot, this carbon quantum dot also possess good upper turn other than possessing strong fluorescent emission within the scope of 450~650nm
Light is changed, to Cu2+There is the detection of specificity, therefore, carbon quantum dot is successfully applied to intracellular Cu by them2+Sensing (Chem
Commun, 2013,49,1,13-1105).Qin etc. has synthesized carbon quantum dot by carbon source of flour, which can choose
Property by Hg2+It is quenched, for detecting Hg2+Detectable limit be 0.5nM (Sensor Actuators B-ch, 2013,184,156-
162).Yazid etc. uses sago starch for carbon source, is prepared for carbon quantum dot by carbonization and surface oxidation, in aqueous solution should
Carbon quantum dot can be used as optical probe by Sn2+It is quickly quenched, and is not influenced by other metal ions, to Sn2+Detect pole
It is limited to 0.36 μM (Anal Chem, 2012,725,90-95).Wang etc. uses boron doping carbon quantum dot as optical probe, right
Fe3+Specific detection is carried out, detection is limited to 0.3 μM (Microchim acta 2016,183,273-279).
Cobalt element is one of our human essential elements, is the important component of vitamin B12.Vitamin B12 can have
Help us and play hematopoiesis function, and have certain effect to the metabolism of protein, may additionally facilitate part enzymatic synthesis, and help
It is active in enhancing its.But heavy metal cobalt ions in some water, when concentration over-standard, can also cause many serious health problems, such as
Low blood pressure, paralysis, diarrhea and osseous defect etc. also result in the gene mutation of living cells.In addition, radioactive cobalt (such as cobalt -60)
Also it is important nuclear pollutant.Therefore, a kind of method for finding effectively detection cobalt ions is just becoming more and more eager demand.
Recently, the group of Chen reports carbon quantum dot as Co2+Detection probe, detection limit is at 5 μM, and raw material
Prepare pretty troublesome (RSC Adv., 2016,6,67481-67487).The team of Li has synthesized carbon quantum dot from cysteine and has been used for
Co2+Reaction detection, the reactive group of cysteine quantum dot surface also have for cobalt ions specificity response, and detect
It is limited to 2 μM (RSC Adv., 2015,5,2285-2291).Anil H.Gore et al. has studied modified cadmiumsulfide quantum dot and visits
Needle detects cobalt ions, it is found that this inorganic-quantum-dot has good specific detection (ACS for cobalt ions
Appl.Mater.Interfaces 2012,4,5217-5226).Although these detection methods energy specific detection cobalt ions,
But all there is preparations to bother, and under-sensitive disadvantage.
In the implementation of the present invention, the inventors discovered that having at least the following problems in the prior art：It is existing can
For the carbon quantum dot of cobalt ions detection, not only preparation method is cumbersome, but also insufficient to the sensitivity of cobalt ions detection.
Summary of the invention
In consideration of it, the present invention provides a kind of N, P adulterates carbon quantum dot, preparation method and application, the N, P doped carbon
Quantum dot preparation method is simple, and gained N, and P adulterates carbon quantum dot can be very delicately for cobalt ions detection.
Specifically, including technical solution below：
According to the first aspect of the invention, the present invention provides a kind of N, P to adulterate the preparation method of carbon quantum dot, two phosphorus of born of the same parents
Choline carries out hydro-thermal reaction as carbon source and ethylenediamine, and purification obtains the N, and P adulterates carbon quantum dot,
The component of the N, P doping carbon quantum dot includes carbon 47%~49% by percentage to the quality, and oxygen 27%~
29%, nitrogen 17%~19%, phosphorus 3%~5%.
Obtaining carbon quantum dot through hydro-thermal reaction is state of the art, and actual conditions can be by those skilled in the art through trying
Test determination.
Preferably, the N, P adulterate carbon quantum dot average grain diameter be 2.1~3.4nm, interlamellar spacing be 0.25~
0.35nm, mean fluorecence service life are 3.4~4.0ns.
Specifically, the raw material of the hydro-thermal reaction includes citicoline, ethylenediamine and water, every 0.3 ± 0.015 g born of the same parents two
0.1 ± 0.005g ethylenediamine and 10~15mL water is added in phosphorus choline.
Preferably, the hydrothermal temperature be 180~220 DEG C, more preferably 180~200 DEG C, most preferably 180~
190 DEG C (such as most preferably 180 DEG C, 185 DEG C).
Preferably, the hydro-thermal reaction time is 4~8h.
General carbon quantum dot is comprised the following steps through the forming process of hydro-thermal reaction：It is initially formed various water-soluble
Polymer；Then, polymer moderate occurs at high temperature is carbonized to form the nano dot of disordered structure；Again with the increasing in reaction time
Add, the nano dot carbonization of unordered nanostructure forms the carbon quantum dot with lattice.If hydrothermal temperature it is lower or
If person's time is insufficient, carbon quantum dot can not be formed.
Specifically, the method for purification is：After the hydro-thermal reaction product is cooling, centrifugation, filtering, freeze-drying are obtained
Carbon quantum dot is adulterated to the N, P.
Further,
The cooling is to be cooled to 10~25 DEG C；
The centrifugation is 8~12min of centrifugation under conditions of 11000~13000rpm；
The temperature of the freeze-drying is -50~-45 DEG C, and pressure is 8~10Pa, and the processing time is 20~28h.
Preferably, the concrete operation step of the hydro-thermal reaction is：Citicoline and ethylenediamine are added to the water, 10
Stirring is allowed to be completely dissolved and (generally require 20~40min) under 400~600r/min speed at~25 DEG C, then carries out water
Thermal response.
According to the second aspect of the invention, the present invention provides the N that above-mentioned preparation method obtains, P to adulterate carbon quantum dot.
According to the third aspect of the invention we, the present invention provides the N, P to adulterate carbon quantum dot in detection cobalt ions
Using.
Cobalt ions is taken, the cobalt ions solution of various concentration gradient is made into, N is added, P codope carbon quantum dot passes through fluorescence
Quenching detects its concentration of cobalt ions.As concentration of cobalt ions increases, fluorescence constantly weakens.Institute book N of the present invention, P adulterate carbon amounts
Son point can detect cobalt ions in sewage, and Monitoring lower-cut can reach 53.0nM.
According to the fourth aspect of the invention, the present invention provides the N, P to adulterate carbon quantum dot dimension life in detection cell
Application in plain B12.
A small amount of vitamin B12 is taken, is made into the PBS solution of low concentration, and it is cultivated together with cell, institute of the present invention is added
N is stated, the concentration of fluorescent quenching is observed after P codope carbon quantum dot.Carbon quantum dot of the present invention has well vitamin B12
Response, as vitamin B12 concentration increases in cell, fluorescence constantly weakens.Carbon quantum dot of the present invention can be to cell
The progress of middle vitamin B12 effectively detects, it is found that its detection limit reaches 81.0nM.
N of the present invention, P doping carbon quantum dot can also be used in human lung adenocarcinoma cell fluorescence imaging.
It takes human lung adenocarcinoma cell that single cell suspension is made, is placed in 37 DEG C of CO2After incubator is inoculated with 12h, discard original
Culture solution, the N for the 0.5mg/mL that addition is prepared with bovine serum albumin (DMEM) culture solution, P codope carbon quantum dot aqueous solution,
In CO2After standing 4h in incubator, original N is discarded, P codope carbon quantum dot aqueous solution, after cleaning 3 times with PBS buffer solution,
Suitable 5% paraformaldehyde solution is added, uses laser scanning co-focusing fluorescence microscope after 4 DEG C of refrigerator overnights are fixed
Cell fluorescence state is observed under the excitation of light field, ultraviolet light, blue and green light and feux rouges, and is photographed to record.It was found that cellular morphology is good
It is good, it is seen that N of the present invention, P codope carbon quantum dot do not have cytotoxicity, can be used for tracking living cells；Meanwhile excitation wave
It grows in 488nm, cell shows green fluorescence, and for excitation wavelength in 543nm, cell is displayed in red fluorescence, shows institute of the present invention
N is stated, P codope carbon quantum dot has multicolor luminous performance.Specifically, the human lung adenocarcinoma cell is human lung cancer cell A549
Cell.
The beneficial effect of technical solution provided in an embodiment of the present invention includes at least：
1, the present invention uses citicoline for carbon source, step preparation N, P codope carbon quantum dot, and preparation method is simple.
2, N of the present invention, P codope carbon quantum dot size are small, and have good water-soluble, superior fluorescence
Can be with good biocompatibility the features such as, and quantum yield is higher.
3, N of the present invention, P codope carbon quantum dot are the sensitiveest to cobalt ions detection, as concentration of cobalt ions increases,
Fluorescence constantly weakens.N of the present invention, P codope carbon quantum dot can detect cobalt ions in sewage, find its tool
There is very low detection limit, can reach 53.0nM, (cobalt ions detection limit is 210nM in the prior art, and detection method is：Use vulcanization
Cadmium quantum dot, quantum dot colors are deepened with the increase of concentration of cobalt ions, are carried out using sepectrophotofluorometer to its fluorescence
Measurement obtains concentration of cobalt ions by calculating).
4, N of the present invention, P codope carbon quantum dot have good response to vitamin B12, give birth to tieing up in cell
Plain B12 concentration increases, and fluorescence constantly weakens.N of the present invention, P codope carbon quantum dot can be to vitamin B12s in cell
It is effectively detected, it is found that there is very low detection to limit for it, reach 81.0 nM.
5, N of the present invention, P codope carbon quantum dot realize the application of imaging cancerous by cell culture, and have
There is multicolor luminous performance.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is N prepared by the embodiment of the present invention 1, and the transmission electron microscope picture of P codope carbon quantum dot, wherein A is transmission electricity
Mirror figure, the grain size distribution of B N, P codope carbon quantum dot.
Fig. 2 is N prepared by the embodiment of the present invention 1, the X-ray diffractogram of P codope carbon quantum dot.
Fig. 3 is N prepared by the embodiment of the present invention 1, the launching light spectrogram under P codope carbon quantum dot difference excitation wavelength.
Fig. 4 is N prepared by the embodiment of the present invention 1, the XPS spectrum figure of P codope carbon quantum dot.
Fig. 5 is N prepared by the embodiment of the present invention 1, the fluorescence spectra of P codope carbon quantum dot at various ph values.
Fig. 6 is N prepared by the embodiment of the present invention 1, fluorescence spectra of the P codope carbon quantum dot under different salinity.
Fig. 7 is N prepared by the embodiment of the present invention 1, the carbon quantum dot fluorescence decay curve figure of P codope.
Fig. 8 is N prepared by the embodiment of the present invention 1, the uv absorption spectra of P codope carbon quantum dot, fluorescence excitation and
The constitutional diagram of emission spectrum.
Fig. 9 is N prepared by the embodiment of the present invention 1, the toxicity test after P codope carbon quantum dot and NIH3T3 cell culture
As a result.
Figure 10 is N prepared by the embodiment of the present invention 1, relative intensity of fluorescence of the P codope carbon quantum dot under different ions
Compare figure.
Figure 11 is N prepared by the embodiment of the present invention 1, the fluorescent emission under P codope carbon quantum dot difference concentration of cobalt ions
Spectrogram.
Figure 12 is the N of the embodiment of the present invention 1, the fluorescence emission under P codope carbon quantum dot difference vitamin B12 concentration
Spectrogram.
The N of Figure 13 embodiment of the present invention 1, P codope carbon quantum dot and the laser co-focusing after A549 cell culture are micro-
Mirror image.
Specific embodiment
To keep technical solution of the present invention and advantage clearer, below in conjunction with attached drawing to embodiment of the present invention make into
One step it is described in detail.
According to the first aspect of the invention, the present invention provides a kind of N, and P adulterates the preparation method of carbon quantum dot, with born of the same parents two
Phosphorus choline is carbon source and ethylenediamine carries out hydro-thermal reaction, and purification obtains the N, and P adulterates carbon quantum dot,
The component of the N, P doping carbon quantum dot includes carbon 47%~49% by percentage to the quality, and oxygen 27%~
29%, nitrogen 17%~19%, phosphorus 3%~5%.
Obtaining carbon quantum dot through hydro-thermal reaction is state of the art, and actual conditions can be by those skilled in the art through trying
Test determination.
Preferably, the N, P adulterate carbon quantum dot average grain diameter be 2.1~3.4nm, interlamellar spacing be 0.25~
0.35nm, mean fluorecence service life are 3.4~4.0ns.
Specifically, the raw material of the hydro-thermal reaction includes citicoline, ethylenediamine and water, every 0.3 ± 0.015 g born of the same parents two
0.1 ± 0.005g ethylenediamine and 10~15mL water is added in phosphorus choline.
Preferably, the hydrothermal temperature be 180~220 DEG C, preferably 180~200 DEG C, more preferably 180~
190 DEG C (such as most preferably 180 DEG C, 185 DEG C).
Preferably, the hydro-thermal reaction time is 4~8h.
General carbon quantum dot is comprised the following steps through the forming process of hydro-thermal reaction：It is initially formed various water-soluble
Polymer；Then, polymer moderate occurs at high temperature is carbonized to form the nano dot of disordered structure；Again with the increasing in reaction time
Add, the nano dot carbonization of unordered nanostructure forms the carbon quantum dot with lattice.If hydrothermal temperature it is lower or
If person's time is insufficient, carbon quantum dot can not be formed.
Specifically, the method for purification is：After the hydro-thermal reaction product is cooling, centrifugation, filtering, freeze-drying are obtained
Carbon quantum dot is adulterated to the N, P.
Further,
The cooling is to be cooled to 10~25 DEG C；
The centrifugation is 8~12min of centrifugation under conditions of 11000~13000rpm；
The temperature of the freeze-drying is -50~-45 DEG C, and pressure is 8~10Pa, and the processing time is 20~28h.
Preferably, the concrete operation step of the hydro-thermal reaction is：Citicoline and ethylenediamine are added to the water, 10
Under 400~600r/min speed then stirring is carried out until it is completely dissolved and (generally requires 20~40min) at~25 DEG C
Hydro-thermal reaction.
According to the second aspect of the invention, the present invention provides the N that above-mentioned preparation method obtains, P to adulterate carbon quantum dot.
According to the third aspect of the invention we, the present invention provides the N, P to adulterate carbon quantum dot in detection cobalt ions
Using.
Cobalt ions is taken, the cobalt ions solution of various concentration gradient is made into, N of the present invention, P codope carbon quantum is added
Point detects its concentration of cobalt ions by fluorescent quenching.As concentration of cobalt ions increases, fluorescence constantly weakens.It is of the present invention
N, P doping carbon quantum dot can detect cobalt ions in sewage, and Monitoring lower-cut can reach 53.0nM.
According to the fourth aspect of the invention, the present invention provides the N, P to adulterate carbon quantum dot dimension life in detection cell
Application in plain B12.
A small amount of vitamin B12 is taken, is made into the PBS solution of low concentration, and it is cultivated together with cell, institute of the present invention is added
N is stated, the concentration of fluorescent quenching is observed after P codope carbon quantum dot.Carbon quantum dot of the present invention has well vitamin B12
Response, as vitamin B12 concentration increases in cell, fluorescence constantly weakens.Carbon quantum dot of the present invention can be to cell
The progress of middle vitamin B12 effectively detects, it is found that its tool detection limit reaches 81.0nM.
N of the present invention, P doping carbon quantum dot can be also used for human lung adenocarcinoma cell fluorescence imaging.
It takes human lung adenocarcinoma cell that single cell suspension is made, is placed in 37 DEG C of CO2After incubator is inoculated with 12h, discard original
Culture solution, the N for the 0.5mg/mL that addition is prepared with bovine serum albumin DMEM culture solution, P codope carbon quantum dot aqueous solution,
CO2After standing 4h in incubator, original N is discarded, P codope carbon quantum dot aqueous solution adds after cleaning 3 times with PBS buffer solution
The paraformaldehyde solution for entering suitable 5% is existed after 4 DEG C of refrigerator overnights are fixed using laser scanning co-focusing fluorescence microscope
Light field, ultraviolet light, blue and green light and the lower observation cell fluorescence state of feux rouges excitation, and photograph to record.It was found that cellular morphology is good
It is good, it is seen that N of the present invention, P codope carbon quantum dot do not have cytotoxicity, can be used for tracking living cells；Meanwhile excitation wave
It grows in 488nm, cell shows green fluorescence, and for excitation wavelength in 543nm, cell is displayed in red fluorescence, shows institute of the present invention
N is stated, P codope carbon quantum dot has multicolor luminous performance.Specifically, the human lung adenocarcinoma cell is human lung cancer cell A549
Cell.
Agents useful for same is as follows in the embodiment of the present invention：
Citicoline：The production of Aladdin reagent (Shanghai) Co., Ltd., purity 97%；
Ethylenediamine：Sinopharm Chemical Reagent Co., Ltd.'s production, is analyzed pure；
Distilled water：Self-control, is distilled to obtain by deionized water.
Embodiment 1
The preparation of N, P codope carbon quantum dot：
Step 1, the citicoline powder for weighing 0.6g is placed in the clean beaker of 50mL, and 0.2g ethylenediamine is added,
The distilled water of 30mL is completely dissolved to obtain colorless and transparent aqueous solution.
Step 2, colourless solution is transferred in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, is placed in a vacuum drying oven, at 180 DEG C
Lower heated at constant temperature 8h.
Step 3, after reaction, product cooled to room temperature to be synthesized, will obtain yellow solution.
Step 4, obtained yellow solution is placed in a centrifuge and 10min is centrifuged with the revolving speed of 12000r/min, then used
0.22 μm of micropore filter obtains clear carbon quantum dot solution after being filtered.
Step 5, clear carbon quantum dot solution will be obtained by vacuum freeze drying, wherein temperature is -48 DEG C, and the time is
For 24 hours, pressure 8.7Pa obtains N, P codope carbon quantum dot powder.
To gained N, P codope carbon quantum dot powder carries out following detection：
5mg/mL N is taken, the aqueous solution of P codope carbon quantum dot covers on the copper mesh of carbon film, and room temperature uses Japan after drying
The H-7650 type transmission electron microscope of Hitachi company production apparently examines the pattern and dispersion of sample.As a result as shown in Figure 1.Figure
In show that N, P codope carbon quantum dot favorable dispersibility do not reunite uniformly, N, P codope carbon quantum dot average grain diameter is
2.9nm, interlamellar spacing are about 0.31nm.
XRD data are acquired by U.S.'s Brooker company X-ray diffractometer, test condition is：Copper target, tube voltage 40KV, pipe
Electric current 100mA, 2 °/min of scanning speed, test scope are 10-85 °.As a result as shown in Figure 2.N, P codope carbon are shown in figure
Quantum dot layer spacing is similar to the interlamellar spacing in Fig. 1 transmission electron microscope lattice figure in 0.304nm.
Using the Cary Eclipse sepectrophotofluorometer of VARIAN Oncology Systems's production come the excitation wave of test sample
Long, launch wavelength and fluorescence intensity.Test scope：200~800nm, exciting slit width：5nm, transmite slit：5nm.As a result
As shown in figure 3, showing N, P codope carbon quantum dot possesses excitation wavelength dependence.
X-ray photoelectron spectroscopy using the U.S. Thermal company production 250 electron spectrometer of Escalab to sample into
Row characterization.Test condition is：500 μm of hot spots, measured power 150W, monochromatic Al Ka (hv=1486.6eV), energy analyzer
Fixed penetrate can 20eV.As a result as shown in Figure 4.Show that the carbon quantum dot of N doping contains C, N, O and P in figure, wherein C contains
The content that the content that the content that amount is 58.1%, O is 21.63%, N is 17.2%, P is 3.07%.
The quantum dot solution of 5mM is prepared respectively in buffer solution at various ph values, using VARIAN Oncology Systems
The Cary Eclipse sepectrophotofluorometer of production comes the excitation wavelength, launch wavelength and fluorescence intensity of test sample.Test
Range：200~800nm, exciting slit width：5nm, transmite slit： 5nm.As a result as shown in Figure 5.Show that pH value is in figure
When 1 and 13, N, the fluorescence of the carbon quantum dot of P codope still maintains stable.
The quantum dot solution of 5mM is prepared respectively in the sodium chloride solution under various concentration, using U.S.'s Varian public affairs
The Cary Eclipse sepectrophotofluorometer of department's production carrys out the excitation wavelength, launch wavelength and fluorescence intensity of test sample.It surveys
Try range：200~800nm, exciting slit width：5nm, transmite slit： 5nm.As a result as shown in Figure 6.Show that salt is dense in figure
When degree reaches 1mol/L, N, the fluorescence of the carbon quantum dot of P codope still maintains stable.
The FM-4P-TCSPC type stable state/transient state Fluorescence Spectrometer produced using the Horiba Jobin Yvon company in the U.S.
The fluorescence lifetime of test sample, test wavelength range：200nm~850nm, fluorescence lifetime test scope：The μ of 100ps~50 s.Knot
Fruit is as shown in Figure 7.N is shown in figure, the carbon quantum dot of P codope is in the mean fluorecence service life of excitation wavelength 430nm
3.59ns。
The molecular structure of sample is analyzed using the Cary-50 type spectrometer of VARIAN Oncology Systems's production.Test condition
For：Resolution ratio 0.1nm, 200~800nm of scanning range, subband samples interval 0.5nm.As a result as shown in Figure 8.It is shown in figure
N, P codope carbon quantum dot have a strong absorption peak at 250nm, this is because caused by π-π * electron transition, it is maximum
Excitation wavelength be 360nm, maximum launch wavelength be 440nm.
Embodiment 2
The preparation of N, P codope carbon quantum dot：
Step 1, the citicoline powder for weighing 0.6g is placed in the clean beaker of 50mL, addition 0.2g ethylenediamine,
The distilled water of 30mL is completely dissolved to obtain colorless and transparent aqueous solution.
Step 2, colourless solution is transferred in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, is placed in a vacuum drying oven, at 180 DEG C
Lower heated at constant temperature 4h.
Step 3, after reaction, product cooled to room temperature to be synthesized, the yellow solution that will be obtained.
Step 4, obtained yellow solution is placed in a centrifuge and 10min is centrifuged with the revolving speed of 12000r/min, then used
0.22 μm of micropore filter obtains clear carbon quantum dot solution after being filtered.
Step 5, clear carbon quantum dot solution will be obtained by vacuum freeze drying, wherein temperature is -48 DEG C, and the time is
For 24 hours, pressure 8.7Pa obtains N, the powder of P codope carbon quantum dot.
Embodiment 3
The preparation of N, P codope carbon quantum dot：
Step 1, the citicoline powder for weighing 0.6g is placed in the clean beaker of 50mL, and 0.2g ethylenediamine is added,
The distilled water of 30mL is completely dissolved to obtain colorless and transparent aqueous solution.
Step 2, colourless solution is transferred in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, is placed in a vacuum drying oven, at 180 DEG C
Lower heated at constant temperature 6h.
Step 3, after reaction, product cooled to room temperature to be synthesized, the yellow solution that will be obtained.
Step 4, obtained yellow solution is placed in a centrifuge and 10min is centrifuged with the revolving speed of 12000r/min, then used
0.22 μm of micropore filter obtains clear carbon quantum dot solution after being filtered.
Step 5, clear carbon quantum dot solution will be obtained by vacuum freeze drying, wherein temperature is -48 DEG C, and the time is
For 24 hours, pressure 8.7Pa obtains N, the powder of P codope carbon quantum dot.
Embodiment 4
The preparation of N, P codope carbon quantum dot：
Step 1, the citicoline powder for weighing 0.6g is placed in the clean beaker of 50mL, and 0.2g ethylenediamine is added,
The distilled water of 30mL is completely dissolved to obtain colorless and transparent aqueous solution.
Step 2, colourless solution is transferred in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, is placed in a vacuum drying oven, at 180 DEG C
Lower heated at constant temperature is for 24 hours.
Step 3, after reaction, product cooled to room temperature to be synthesized, the yellow solution that will be obtained.
Step 4, obtained yellow solution is placed in a centrifuge and 10min is centrifuged with the revolving speed of 12000r/min, then used
0.22 μm of micropore filter obtains clear carbon quantum dot solution after being filtered.
Step 5, clear carbon quantum dot solution will be obtained by vacuum freeze drying, wherein temperature is -48 DEG C, and the time is
For 24 hours, pressure 8.7Pa obtains N, the powder of P codope carbon quantum dot.
Embodiment 5
Using N made from sepectrophotofluorometer detection embodiment 1,2,3 and 4, the fluorescence of P codope carbon quantum dot powder
Intensity, the results are shown in Table 1.
The influence of hydro-thermal method reaction time to quantum dot fluorescence intensity at 180 DEG C of table 1
| Reaction time/h | 4 | 6 | 8 | 24 |
| Fluorescence intensity | 520 | 610 | 650 | 550 |
Hydro-thermal method synthesizes N at 180 DEG C as known from Table 1, and the optimum reacting time of P codope carbon quantum dot is 8h.Hydro-thermal
Influence of the reaction time to fluorescence intensity, main reason is that last carbonization whether complete and surface group migration and variation.
Embodiment 6
Using quinine sulfate as reference material, its fluorescence quantum yield is 54%.Firstly, weighing suitable sulfuric acid Kui
Peaceful powder is dissolved in the sulfuric acid solution of 0.1M, and suitable 1 gained N, P codope carbon quantum dot powder of embodiment is dissolved in distilled water
In；Then, N is measured simultaneously in the case where excitation wavelength is 360nm, the absorbance value of P codope carbon quantum dot and quinine sulfate, so that
The absorbance value of the two is both less than or equal to 0.05；Meanwhile N, P codope carbon quantum dot are measured in the case where excitation wavelength is 360nm
With the fluorescence emission spectrum of quinine sulfate, the integrated fluorescence intensities of the two are calculated.Finally, the phase of N, P codope carbon quantum dot
Fluorescence intensity is calculated by formula below：
In above-mentioned formula, the fluorescent quantum of fluorescence quantum yield and quinine sulfate that middle S and Φ R respectively indicates sample is produced
Rate；FS and FR respectively indicates the integrated fluorescence intensities of sample and the integrated fluorescence intensities of quinine sulfate；AS and AR respectively indicate sample
The absorbance value of product and the absorbance value of quinine sulfate；The η of the two is 1.33.The results are shown in Table 2, and wherein A is absorbance.
Its quantum yield can be seen that 27.03% by the average value of quantum dot quantum yield, other carbon quantum dots that compare are general
The quantum yield of 20% quantum yield below, N of the present invention, P codope carbon quantum dot is higher, and preparation method is simpler
It is single.
2 N of table, fluorescence quantum yield of the P codope carbon quantum dot under different absorbances
Embodiment 7
Thiazolyl blue (MTT) colorimetric method is a kind of method for detecting cell and growth.Its principle detected is living cells line grain
Amber platinic acid dehydrogenase in body can be reduced into bluish violet formazan (Formazan) crystallization not soluble in water by MTT, be deposited on simultaneously
In living cells, and dead cell is without this function.Then formazan in cell is dissolved with dimethyl sulfoxide (DMSO), using microplate reader
Detect specific absorption wavelength absorbance value, carbon quantum dot addition before and after carry out absorbance value size comparison, can between it is reversed
Reflect the quantity of living cells in sample.As a result (ordinate is cell survival rate in Fig. 9, and abscissa is carbon quantum dot as shown in Figure 9
Various concentration).The cytotoxicity statistical data of 1 gained N, P codope carbon quantum dot of embodiment is shown in figure.By comparing
Cell survival rate for 24 hours, 85% or more, cytotoxicity is all distributed at 0 grade or 1 grade cell survival rate.This result shows that,
N of the present invention, P codope carbon quantum dot do not have apparent cytotoxicity, have good cell compatibility, can be applied to
The technical field of biological material such as cell fluorescence or cell detection.
Embodiment 8
Each metal ion species are dissolved in the solution that distilled water is configured to 0.5 μM, are then respectively adding isometric 1 institute of embodiment
In the aqueous solution of the N of preparation, P codope carbon quantum dot (10mg/mL), the case where seeing fluorescence under the irradiation of ultraviolet lamp；Finally
The fluorescence emission spectrum of the re-test various N containing metal ion, P codope carbon quantum dot aqueous solution.The results are shown in Figure 10,
It is carbon quantum dot in figure respectively in the Na of 0.5mM+, K+, Ba2+, Mg2+, Zn2+, Cd2+, Mn2+, Ni2+, Ca2+, Co2+, Ag+, Hg2+,
Pb2+, Cu2+, Fe3+And Fe2+Fluorescence response figure in solution, wherein ordinate F/F0Refer to be added carbon quantum dot after metal from
Sub- fluorescence intensity and the ratio that metal-ion fluorescent intensity size before carbon quantum dot is not added.It is recognised that fluorescence from figure
The ion that intensity occurs obviously to weaken is Co2+, about 80% fluorescence is quenched.
Embodiment 9
Cobalt ions is configured to the aqueous solution of various concentration, is then respectively adding N, P prepared by isometric embodiment 1
In the aqueous solution of codope carbon quantum dot, the last re-test various N containing cobalt ions, P codope carbon quantum dot aqueous solution
Fluorescence emission spectrum.Fluorescence intensity with the increase of the concentration of cobalt ions, N, P codope carbon quantum dot declines, and cobalt ions is dense
In 5.0mM, the fluorescence of N, P codope carbon quantum dot are quenched degree substantially, and detection limit reaches 53.0nM and (obtains formula according to Figure 11
Monitoring lower-cut Stern-Volmer equation Δ F/F0=0.00867C+0.00702 is inferred in low concentration),
As shown in figure 11, wherein ordinate Δ F/F0Refer to the drop-out value and not of the carbon quantum dot fluorescence intensity after metal ion is added
The ratio of carbon quantum dot fluorescence intensity size before addition metal ion, abscissa C are concentration of cobalt ions.
Embodiment 10
A small amount of vitamin B12 is taken, the PBS solution of low concentration is made into, N prepared by the embodiment of the present invention 1 is added, P is co-doped with
The concentration of fluorescent quenching is observed after miscellaneous carbon quantum dot (concentration of N, P codope carbon quantum dot is 0.5mg/mL).With vitamin
The increase of B12 concentration, N, the fluorescence intensity decline of P codope carbon quantum dot, in 8.0mM, N, P is co-doped with vitamin B12 concentration
The fluorescence of miscellaneous carbon quantum dot is quenched substantially, with the increase of vitamin B12 concentration, N, the fluorescence intensity of P codope carbon quantum dot
Decline, detection limit reach 81.0nM, and (wherein ordinate is that the carbon quantum dot fluorescence after vitamin B12 is added is strong as shown in figure 12
Degree；Formula Monitoring lower-cut Stem-Volmer equation, Δ F/F are obtained according to Figure 120Inspection is learnt in=0.0267C+0.00427 supposition
Limit is surveyed, wherein Δ F/F0Refer under the excitation of maximum excitation wavelength 355nm wavelength, the carbon quantum dot after vitamin B12 is added is glimmering
The drop-out value of luminous intensity and the ratio that carbon quantum dot fluorescence intensity size before vitamin B12 is not added, C are that vitamin B12 is dense
Degree) wherein the concentration of Top to Bottom be respectively 8.0 mM, 7.0mM, 6.0mM, 5.0mM, 4.0mM, 3.0mM, 2.5mM,
2.0mM, 1.5mM, 1.0mM, 0.75mM, 0.5mM, 0.25mM, 125 μM, 25 μM, 5.0 μM, 1.0 μM and 0.2 μM.
Embodiment 11
The good human lung cancer cell A549's cell of upgrowth situation is taken out, culture bottle is opened under alcolhol burner, is discarded original
Culture solution, the surface 2 times of 2ml PBS buffer solution cleaning cell is added, after discarding PBS, the tryptic digestive juice of 1ml is added
Sufficiently after digestion, draw suitable 10% fetal calf serum DMEM culture solution and terminate digestion, gently piping and druming cell repeatedly make its from
Bottle wall falls off, and forms it into uniform single cell suspension, draws the cell suspension of 1mL in Petri culture dish, is placed in 37 DEG C
CO2After incubator is inoculated with 12 h, original culture solution is discarded, the N of the 0.5mg/mL prepared with DMEM culture solution is added, P is co-doped with
Miscellaneous carbon quantum dot aqueous solution, in CO2After standing 4h in incubator, original N is discarded, P codope carbon quantum dot aqueous solution is used
After PBS buffer solution is cleaned 3 times, suitable 5% paraformaldehyde solution is added, after 4 DEG C of refrigerator overnights are fixed, uses laser
Confocal fluorescent microscopic is scanned to excite in light field, ultraviolet light (UV), blue light (Blue), green light (Green) and feux rouges (Red)
Lower observation cell fluorescence state, and photograph to record.In 488nm, the green fluorescence that cell is shown, excitation wavelength exists excitation wavelength
When 543nm, the red fluorescence that cell is shown shows that carbon quantum dot has multicolor luminous performance.N prepared by embodiment 1, P are total
Doping carbon quantum dot aqueous solution (0.5mg/mL) is for marking A549 cell, and as shown in figure 13, cellular morphology is good, it is seen that N, P
Codope carbon quantum dot does not have cytotoxicity, can be used for tracking living cells.
Embodiment 12
The preparation of N, P codope carbon quantum dot：
The citicoline powder for weighing 0.6g is placed in the clean beaker of 50mL, and the steaming of 0.2g ethylenediamine, 30mL is added
Distilled water is completely dissolved to obtain colorless and transparent aqueous solution.Colourless solution is transferred in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, is placed in
In vacuum oven, the heated at constant temperature 8h at 200 DEG C.After reaction, product cooled to room temperature to be synthesized, will obtain Huang
Color solution.Be centrifuged again, filter after obtain N, P codope carbon quantum dot solution obtains N, P is co-doped with after freeze-dried
The powder of miscellaneous carbon quantum dot.Learn that average grain diameter is in 2.1nm through characterization；N, P prepared by its constituent and embodiment 1
Compared to variation, less (content that the content that wherein content of C is 56.2%, O is 24.3%, N is codope carbon quantum dot
3.4%) content of 16.1%, P are；At various ph values and in salinity, fluorescence is able to maintain stabilization.
The above is merely for convenience of it will be understood by those skilled in the art that technical solution of the present invention, not to limit
The present invention.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in this
Within the protection scope of invention.
Claims (10)
1. the preparation method of a kind of N, P doping carbon quantum dot, which is characterized in that
Citicoline carries out hydro-thermal reaction as carbon source and ethylenediamine, and purification obtains the N, and P adulterates carbon quantum dot,
The component that the N, P adulterate carbon quantum dot includes carbon 47%~49%, oxygen 27%~29%, nitrogen by percentage to the quality
17%~19%, phosphorus 3%~5%.
2. the preparation method of N as described in claim 1, P doping carbon quantum dot, which is characterized in that the N, P adulterate carbon quantum
The average grain diameter of point is 2.1~3.4nm, and interlamellar spacing is 0.25~0.35nm, and the mean fluorecence service life is 3.4~4.0ns.
3. the preparation method of N as claimed in claim 1 or 2, P doping carbon quantum dot, which is characterized in that the hydro-thermal reaction
Raw material includes citicoline, ethylenediamine and water, every 0.3 ± 0.015g citicoline be added 0.1 ± 0.005g ethylenediamine and
10~15mL water.
4. the preparation method of N as claimed in claim 1 or 2, P doping carbon quantum dot, which is characterized in that the hydro-thermal reaction temperature
Degree is 180~200 DEG C；Reaction time is 4~8h.
5. the preparation method of N as claimed in claim 1 or 2, P doping carbon quantum dot, which is characterized in that the method for purification
For：After the hydro-thermal reaction product is cooling, centrifugation, filtering, freeze-drying obtain the N, and P adulterates carbon quantum dot.
6. the preparation method of N as claimed in claim 5, P doping carbon quantum dot, which is characterized in that
The cooling is to be cooled to 10~25 DEG C；
The centrifugation is 8~12min of centrifugation under conditions of 11000~13000rpm；
The temperature of the freeze-drying is -50~-45 DEG C, and pressure is 8~10Pa, and the processing time is 20~28h.
7. the preparation method of N as claimed in claim 1 or 2, P doping carbon quantum dot, which is characterized in that the hydro-thermal reaction
Concrete operation step is：Citicoline and ethylenediamine are added to the water, at 10~25 DEG C under 400~600r/min speed
Stirring is allowed to be completely dissolved, and then carries out hydro-thermal reaction.
8. preparation method described in any one of claim 1~7 resulting N, P adulterate carbon quantum dot.
9. N according to any one of claims 8, P adulterate application of the carbon quantum dot in detection cobalt ions.
10. N according to any one of claims 8, P adulterate application of the carbon quantum dot in detection cell in vitamin B12.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796006A (en) * | 2019-03-21 | 2019-05-24 | 河北科技大学 | A kind of ionic liquid is in the preparation method and application for preparing application and nitrogen-doped carbon quantum dot in nitrogen-doped carbon quantum dot |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143035A (en) * | 2013-02-19 | 2013-06-12 | 中国科学院理化技术研究所 | Application of heteroatoms doped aqueous carbon quantum dot in preparation of photo-sensitizers for fluorescent imaging marking and photodynamic therapy (PDT) |
| CN103143377A (en) * | 2013-02-19 | 2013-06-12 | 中国科学院理化技术研究所 | Application of heteroatoms doped aqueous carbon quantum dot in photocatalyst |
| CN106629660A (en) * | 2016-12-22 | 2017-05-10 | 南京师范大学 | Preparation method of N, P co-doping carbon quantum dots, and product and application thereof |
-
2018
- 2018-06-06 CN CN201810604277.3A patent/CN108865124B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143035A (en) * | 2013-02-19 | 2013-06-12 | 中国科学院理化技术研究所 | Application of heteroatoms doped aqueous carbon quantum dot in preparation of photo-sensitizers for fluorescent imaging marking and photodynamic therapy (PDT) |
| CN103143377A (en) * | 2013-02-19 | 2013-06-12 | 中国科学院理化技术研究所 | Application of heteroatoms doped aqueous carbon quantum dot in photocatalyst |
| CN106629660A (en) * | 2016-12-22 | 2017-05-10 | 南京师范大学 | Preparation method of N, P co-doping carbon quantum dots, and product and application thereof |
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| CN109796006B (en) * | 2019-03-21 | 2022-03-01 | 河北科技大学 | Application of ionic liquid in preparation of nitrogen-doped carbon quantum dots, and preparation method and application of nitrogen-doped carbon quantum dots |
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| US11898077B2 (en) | 2020-05-21 | 2024-02-13 | Kureha Corporation | Composition and method for producing same |
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| CN111548793A (en) * | 2020-06-10 | 2020-08-18 | 山西大学 | Nitrogen-phosphorus co-doped fluorescent carbon dot and preparation method and application thereof |
| CN113980676A (en) * | 2020-12-29 | 2022-01-28 | 兰州大学 | Preparation method of nitrogen-doped carbon quantum dots in coffee grounds and method for detecting VB12 through fluorescence |
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