CN116790248B - Zinc-nitrogen doped carbon dot and preparation method and application thereof - Google Patents
Zinc-nitrogen doped carbon dot and preparation method and application thereof Download PDFInfo
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- CN116790248B CN116790248B CN202310661429.4A CN202310661429A CN116790248B CN 116790248 B CN116790248 B CN 116790248B CN 202310661429 A CN202310661429 A CN 202310661429A CN 116790248 B CN116790248 B CN 116790248B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 177
- UHIJLWIHCPPKOP-UHFFFAOYSA-N [N].[Zn] Chemical compound [N].[Zn] UHIJLWIHCPPKOP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 116
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 65
- -1 polyphenol compound Chemical class 0.000 claims abstract description 61
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002243 precursor Substances 0.000 claims abstract description 46
- 229910052742 iron Inorganic materials 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 28
- 238000001514 detection method Methods 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000013305 food Nutrition 0.000 claims abstract description 24
- 150000003943 catecholamines Chemical class 0.000 claims abstract description 19
- 238000012544 monitoring process Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 238000004806 packaging method and process Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 27
- 229960003638 dopamine Drugs 0.000 claims description 21
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 16
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000007613 environmental effect Effects 0.000 claims description 6
- 239000005022 packaging material Substances 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- SGNZYJXNUURYCH-UHFFFAOYSA-N 5,6-dihydroxyindole Chemical compound C1=C(O)C(O)=CC2=C1NC=C2 SGNZYJXNUURYCH-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 238000006862 quantum yield reaction Methods 0.000 abstract description 23
- 150000008442 polyphenolic compounds Chemical class 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 229910021392 nanocarbon Inorganic materials 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 abstract 1
- 238000000502 dialysis Methods 0.000 description 56
- 239000012153 distilled water Substances 0.000 description 39
- 239000012045 crude solution Substances 0.000 description 38
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 30
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 27
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- 239000000843 powder Substances 0.000 description 26
- 239000002994 raw material Substances 0.000 description 23
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- 230000000052 comparative effect Effects 0.000 description 14
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- 238000005303 weighing Methods 0.000 description 12
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 10
- 229960001763 zinc sulfate Drugs 0.000 description 10
- 229910000368 zinc sulfate Inorganic materials 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 9
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 231100000252 nontoxic Toxicity 0.000 description 5
- 230000003000 nontoxic effect Effects 0.000 description 5
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- 239000006185 dispersion Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- 102000008857 Ferritin Human genes 0.000 description 3
- 108050000784 Ferritin Proteins 0.000 description 3
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- 235000013361 beverage Nutrition 0.000 description 3
- 229910052796 boron Inorganic materials 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
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 229940045803 cuprous chloride Drugs 0.000 description 3
- 238000003745 diagnosis Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 230000036541 health Effects 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
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- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 238000012921 fluorescence analysis Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 238000010672 photosynthesis Methods 0.000 description 2
- 230000029553 photosynthesis Effects 0.000 description 2
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- 238000006722 reduction reaction Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229960000306 zinc gluconate Drugs 0.000 description 2
- 239000011670 zinc gluconate Substances 0.000 description 2
- 235000011478 zinc gluconate Nutrition 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- GPHZPKCKVSSLIV-UHFFFAOYSA-N (3-formylphenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC(C=O)=C1 GPHZPKCKVSSLIV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DZAUWHJDUNRCTF-UHFFFAOYSA-N 3-(3,4-dihydroxyphenyl)propanoic acid Chemical compound OC(=O)CCC1=CC=C(O)C(O)=C1 DZAUWHJDUNRCTF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000001576 FEMA 2977 Substances 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- BPKGOZPBGXJDEP-UHFFFAOYSA-N [C].[Zn] Chemical compound [C].[Zn] BPKGOZPBGXJDEP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
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- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 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 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 125000002791 glucosyl group Chemical class C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001575 pathological effect Effects 0.000 description 1
- 230000007170 pathology Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229960003110 quinine sulfate Drugs 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- 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
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- 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
- C09K11/0883—Arsenides; Nitrides; Phosphides
-
- 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"
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- 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
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Molecular Biology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a zinc-nitrogen doped carbon dot, a preparation method and application thereof, and belongs to the technical field of nano carbon materials and new materials. The invention relates to a method for preparing a novel metal doped carbon dot with high fluorescence intensity, which is to mix catecholamine substances with metal salt solution to generate self-assembly metal polyphenol coordination reaction to form metal polyphenol compound precursor solution of an integrated carbon source, nitrogen source and metal source; and then preparing the novel metal doped carbon dot with high fluorescence quantum yield and luminous intensity by a hydrothermal reaction one-step method. The invention has the advantages of low cost, simple method, no pollution and few byproducts, and the prepared carbon dots are stable and have high fluorescence quantum yield (78%), can be used for detecting iron ions, and are suitable for food quality detection, environment monitoring, intelligent food packaging and other aspects.
Description
Technical Field
The invention relates to a zinc-nitrogen doped carbon dot and a preparation method and application thereof, in particular to a zinc-nitrogen doped carbon dot with high fluorescence quantum yield and a preparation method and application thereof, belonging to the technical field of nano carbon materials and new materials.
Background
Carbon dots are also known as carbon quantum dots or carbon nanodots, and in 2004 Xu et al have first discovered and reported carbon quantum dots having fluorescent properties during the preparation of single-walled carbon nanotubes. The discovery of carbon dots opens up a new development direction of fluorescent nanomaterials, and as the carbon dots are intensively studied, the carbon dots are discovered to be a zero-dimensional carbon nanomaterial with good fluorescent optical properties, and are generally composed of dispersed carbon nanoparticles with a size of less than 10 nm. Meanwhile, more researches find that the carbon dot has the advantages of fluorescence performance comparable with that of the semiconductor quantum dot, high stability, low toxicity, better biocompatibility and the like. In production, the cost of carbon dot raw materials is low, and the preparation method is simple, so that large-scale production is easy to realize. The advantages lead the carbon dots to have wide application prospect in the fields of biological marking, medical imaging, medical diagnosis, environmental monitoring, food analysis and detection, intelligent food packaging and the like. In particular, in the aspect of metal ion monitoring, for example, the exceeding of iron in drinking water or beverage easily causes the damage of the functions of various organs of the body and causes serious toxic reaction, and the exceeding of iron in soil can seriously reduce photosynthesis of plants and influence the growth and development of the plants besides the damage to human bodies, and in the medical diagnosis, the health of the human bodies can be monitored or pathological research can be carried out by monitoring the concentration of iron ions or tracking ferritin.
However, most of the prepared carbon dots have no fluorescent light emitting property or weak fluorescence for further application depending on the raw materials, and the raw materials of the carbon nanodots having strong fluorescence in part have toxicity and chemical hazards, such as meta-diphenol, hydroquinone, etc., which are strong carcinogens, which limit further wide application of the carbon dots in the fields of biology, medical treatment and food. For example, CN 105131948A discloses a metal doped carbon dot with high fluorescence quantum yield, and a preparation method and application thereof, which uses sodium citrate and cuprous chloride as raw materials, although the prepared carbon dot has strong fluorescence intensity and 70% fluorescence quantum yield and can be used for detecting iron ions, the scheme has the following problems that the used raw material cuprous chloride is a strong reducing substance, has strong corrosiveness in use, has great safety risk in use, residual copper ions after reduction are common toxic metal ions, has obvious toxicity to human bodies and environment, has larger application limit, and in addition, the patent refers to cuprous chloride and/or cupric sulfate, but does not prove to be a dominant carbon dot formed by cuprous ions or cupric ions, but obviously, the electron orbit characteristics of the outer layer of the cupric ions are not suitable for preparing the carbon dot with high fluorescence quantum yield, and the patent also finally selects cuprous ions as raw materials, so that it can be inferred that the cuprous ions are main copper sources of the patent, but the cuprous ions are extremely unstable, especially in water, are oxidized, and thus the electron orbitals of the cuprous ions are in a complex state under the preparation process such as that the oxygen is required, and the experiment condition is not required. The formed cuprous carbon dots also have obvious Yi Shidian sub-reduction reaction, which easily causes the problem of poor stability of the obtained carbon dots during use. Therefore, the luminous performance and biocompatibility of the carbon dots are improved by selecting nontoxic raw materials and carrying out reasonable structure regulation and control design, so that the method is an effective way for widening the application range of the carbon dots.
At present, in the existing method and technology, the doping of elements to carbon dots is a common method, but most of the element doping is concentrated on single doping or double doping of elements such as nitrogen, sulfur, phosphorus, boron and the like, while raw materials are sodium citrate or p-phenylenediamine as a carbon source, boric acid, sulfamide or amino acid as a boron source, a sulfur source and a nitrogen source, and the raw materials are more, so that the method has the advantages of chemical hazard, high cost and lower fluorescence quantum yield, and further application of the carbon dots is still limited. For example, in the literature of fluorescence mechanism and application research for preparing polymer carbon dots based on amino acid moleculesDiscloses a scheme for preparing nitrogen-doped carbon dots by taking serine and tryptophan as raw materials and combining a 200 ℃ hydrothermal method, wherein the fluorescence quantum yield of the prepared carbon dots is only 46.83 percent at the maximum, and the nitrogen-doped carbon dots are prepared for Fe 3+ Has selectivity, but only has a certain quenching response, and has no detailed minimum detection limit. In the literature of "preparation of fluorescent carbon dots based on element, functional group and space conformation transfer strategy and application thereof in cell imaging", a method for preparing nitrogen and boron doped carbon dots by using p-phenylenediamine, 3-formylphenylboric acid and ethanol as raw materials and hydrothermal reaction at 180 ℃ for 24 hours is disclosed, wherein the fluorescence intensity of the carbon dots is only about 55 and the carbon dots do not contain Fe 3+ The performance is detected, meanwhile, the p-phenylenediamine used as a raw material for the carbon point is listed as a cancerogenic substance, has combustibility and is a dangerous chemical; in this paper, another carbon dot material prepared by hydrothermal reaction of cysteine and citric acid as raw materials at 200℃for 60min is also disclosed, which has a fluorescence quantum yield of only 68% and does not contain Fe 3+ Performance was measured. In addition, in literature of glucose salt-based preparation of metal ion doped carbon dots, structure and performance research thereof, a method for preparing zinc gluconate from N 2 Under the atmosphere, the zinc ion doped carbon dot obtained by calcining at 160 ℃ for 1h has the fluorescence quantum yield of only 13.98 percent and the intensity of only about 450 percent, and can only detect Zn 2+ However, zinc gluconate has high cost, the preparation method of the carbon point is dangerous and complex, and N is required to be introduced 2 Stabilizing the reaction.
In other researches, dopamine is used as a carbon dot preparation raw material, for example, qu et al discloses that dopamine is taken as a raw material singly, and the dopamine-based carbon dot is prepared by hydrothermal reaction for 6 hours at 180 ℃, and although the dopamine is nontoxic, the prepared carbon dot has extremely weak fluorescence property, the fluorescence intensity is only about 650, and the size is difficult to control. In addition, kang et al disclose a carbon dot prepared from dopamine and o-phenylenediamine as raw materials by hydrothermal reaction at 180 ℃ for 6 hours, wherein the fluorescence intensity of the carbon dot is only about 3700, the fluorescence quantum yield in ethanol solution is only 28%, and the raw materials used for the carbon dot comprise o-phenylenediamine, and the risks are as described above. Compared with the invention, the disclosed carbon dots and the preparation method thereof are not ideal in terms of safety and effect.
Therefore, development of a novel carbon dot which has high fluorescence quantum yield, high luminous intensity, nontoxic raw materials and products and can be used for detecting iron ions is needed, and the novel carbon dot has important technical value and economic and social significance for widening the application field of the carbon dot, in particular in the fields of high-efficiency food hazard analysis and detection, medical precise imaging, environment monitoring, visual food intelligent packaging technology and the like.
Disclosure of Invention
[ technical problem ]
The existing carbon dots have weak fluorescence intensity, low quantum yield, multiple raw materials or large raw material danger or can not be used for detecting iron ions, so that the application of the carbon dots is limited.
Technical scheme
In order to solve at least one of the problems, the present invention utilizes a metal polyphenol compound as a carbon source, a nitrogen source and a metal source of carbon dots, and prepares a novel carbon dot with high fluorescence quantum yield and high luminous intensity by a simple one-step hydrothermal method, and particularly provides a zinc-nitrogen doped carbon dot and a preparation method thereof. The method is simple, green, pollution-free, high in reaction speed, low in raw material consumption and low in cost, and the detection limit for detecting the iron ions is relatively low. At present, no carbon dot prepared by utilizing a metal polyphenol network exists, and compared with the existing carbon dot, the zinc-nitrogen doped carbon dot prepared by the method has higher fluorescence quantum yield and luminous intensity.
A first object of the present invention is to provide a method for preparing zinc nitrogen doped carbon dots, comprising the steps of:
(1) Carbon source and nitrogen source solutions:
dissolving catecholamine substances in deionized water, and regulating the pH value to obtain a catecholamine substance carbon source and nitrogen source solution;
(2) Metal polyphenol coordination complex precursor solution:
mixing catecholamine substance solution and metal salt solution to prepare metal polyphenol compound precursor solution; the metal in the metal salt solution is zinc;
(3) And preparing zinc-nitrogen doped carbon points through hydrothermal reaction.
In one embodiment of the present invention, the catecholamine substance solution in the step (1) is obtained by dissolving a catecholamine substance in deionized water, and the concentration is 5-60mg/mL.
In one embodiment of the present invention, the ph of the catecholamine substance solution of step (1) is adjusted to 1 to 4.
In one embodiment of the present invention, the catecholamine-like substance of step (1) includes one of 3, 4-dihydroxyhydrocinnamate, 5, 6-dihydroxyindole, L-dopamine, catecholamine, dopamine hydrochloride, or dopamine. The amino structure and the phenolic hydroxyl structure existing in the dopamine play a vital role in the metal coordination effect of the invention, particularly in the carbon point synthesis process, zinc element is easily introduced into a polymer carbon point system through the coordination reaction of amino and hydroxyl and zinc ions, and fluorescent carbon points are generated in one step, so that catecholamine substances containing amino or ring-opened indole groups and hydroxyl can be theoretically used as raw materials for the carbon point synthesis.
In one embodiment of the present invention, the metal salt solution in step (2) is obtained by dissolving a metal salt in deionized water at a concentration of 1-30mg/ml.
In one embodiment of the present invention, the mass ratio of the metal salt and catecholamine substance in the step (2) is 0.1:1 to 3:1.
in one embodiment of the invention, the reaction in step (2) is carried out at 200-400rpm and 20-25℃for 1-10min.
In one embodiment, the step (3) includes: and adding the precursor solution into a hydrothermal high-pressure reaction kettle to react for a certain time, and naturally cooling to 45 ℃ to obtain a crude carbon dot dispersion liquid.
In one embodiment of the invention, the hydrothermal autoclave in the step (3) is a stainless steel flange autoclave with a polytetrafluoroethylene lining and is provided with a temperature-controlled heating furnace.
In one embodiment of the invention, the hydrothermal reaction temperature in step (3) is 115-205 ℃, the pressure is 1MPa, preferably 140-180 ℃, and the reaction time is 1.5-8 hours, preferably 4-6 hours.
In one embodiment, the method further comprises step (4) purifying the separation; alternatively, specifically: and (3) primarily separating the crude carbon dot dispersion liquid by using a microfiltration membrane to obtain a secondary carbon dot dispersion liquid, and placing the secondary carbon dot dispersion liquid in a dialysis bag for dialysis to obtain a carbon dot solution.
In one embodiment of the invention, the dialysis bag of step (4) has a molecular weight cut-off of any one or a combination of at least two of 1kDa, 2kDa, 3.5kDa, 20kDa or 50 kDa.
In one embodiment of the invention, the dialysis time of step (4) is 8-72 hours.
In one embodiment, the method further comprises the step ((5) concentrating and drying; optionally, specifically, placing the carbon dot solution in a round bottom flask for concentrating and freeze drying or high temperature drying to obtain the iron-nitrogen doped carbon dot.
In one embodiment of the present invention, the concentration temperature in step (5) is 80-100 ℃.
In one embodiment of the present invention, the freeze-drying in the step (5) is performed under vacuum, the temperature is-100 to-40 ℃, the drying time is 12-48h, the oven drying is performed under normal pressure, the temperature is 70-100 ℃, and the drying time is 12-24h.
The second object of the invention is a zinc nitrogen doped carbon dot prepared by the method of the invention.
A third object of the present invention is the use of the zinc nitrogen doped carbon dots of the present invention in the field of food detection, environmental monitoring or packaging for the detection of iron ions (or iron-containing substances such as ferritin).
Optionally, the application refers to the aspect of metal ion monitoring; for example, exceeding of iron in drinking water or beverages easily causes functional impairment of various organs of the body and causes serious toxic reactions; the iron in the soil is out of standard, so that the damage to human bodies is avoided, the photosynthesis of plants is also seriously reduced, and the growth and development of the plants are affected; in medical diagnosis, human health can be monitored or pathology can be studied by monitoring iron ion concentration or tracking ferritin.
The fourth object of the invention is to provide a food detection material which contains the zinc-nitrogen doped carbon dot. Optionally, the detection test paper containing the carbon dots is soaked in the food extracting solution or the fluid food sample solution, and after soaking, the fluorescence intensity of the test paper is detected by using a fluorescence spectrophotometer.
A fifth object of the present invention is to provide an environmental monitoring material, which contains a zinc-nitrogen doped carbon dot according to the present invention. Alternatively, the fluorescence intensity of the sample solution can be detected in an aqueous environment by adding the carbon spot to the sample aqueous solution and directly by a fluorescence spectrophotometer. Further, the iron ion concentration may be determined based on the fluorescence intensity.
A sixth object of the present invention is to provide a packaging material comprising a zinc nitrogen doped carbon dot according to the present invention. Optionally, for the packaging material of the fluid food, the label material containing the carbon dots can be compounded in the material, and if the metal ions in the food exceed the standard, the content of the iron ions can be judged by the luminous degree of the carbon dot fluorescent label on the packaging material.
[ advantageous effects ]
(1) The invention is based on self-assembled metal polyphenol coordination reaction to preferentially prepare the metal polyphenol compound carbon dot precursor of the integrated carbon source, nitrogen source and metal source, greatly improves the fluorescence quantum yield and fluorescence intensity of the dopamine carbon dot through the change of the electron orbit arrangement and energy level transition of nitrogen element and metal iron, controls the metal polyphenol network ligand structure through adjusting the pH value, can realize the quantitative regulation and control of the performance of the metal doped carbon dot, and endows the carbon dot with the beneficial effects of hydrophilicity, biocompatibility, high fluorescence intensity, innocuity and pollution-free by virtue of hydrophilic groups such as amino groups, hydroxyl groups and the like which are rich outside the metal polyphenol network (the groups can interact with protein, water molecules or solution which is rich in hydroxyl groups as well so as to improve the compatibility).
(2) The invention selects food-grade zinc sulfate, food-grade polyethylene glycol and nontoxic dopamine hydrochloride, has safe raw materials, no preparation risk, no environmental pollution risk and no human health risk. In addition, the zinc ions used in the preparation method have stability, and a more stable complex is formed by means of metal ion coordination reaction, so that high-fluorescence carbon dots can be formed stably and in one step by doping under the condition that nitrogen or other anaerobic states are not needed.
(3) The metal doped carbon dots prepared by the method are stable and nontoxic, and the quantum yield can reach 78%; can be used for detecting iron ions, so that the minimum limit of iron ion detection can reach 2.95 mu M.
(4) The invention is suitable for being applied to water pollution monitoring, food and beverage metal ion monitoring and the like, and has the potential advantage of monitoring in-vivo metal ions; the invention has wide application prospect in the aspects of food quality detection, intelligent food packaging, medical imaging and the like.
Drawings
FIG. 1 is a graph showing the comparison of fluorescence intensity of carbon dots prepared in examples 1 to 5 and comparative examples 1 to 6.
FIG. 2 is a graph showing the comparison of fluorescence quantum yields of carbon dots prepared in examples 1 to 5 and comparative examples 1 to 6.
FIG. 3 is a graph showing the emission spectra of carbon dots prepared in example 1 at different excitation wavelengths.
FIG. 4 is a graph showing the emission spectra of the carbon dots prepared in comparative example 1 at different excitation wavelengths.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for better illustration of the invention, and should not be construed as limiting the invention.
The testing method comprises the following steps:
1. fluorescence quantum yield test: and analyzing fluorescent signal parameters of the metal doped carbon point and the reference solution by adopting a fluorescence spectrometer through a reference method to calculate the fluorescence quantum yield.
The specific operation steps are as follows: preparing quinine sulfate solution with proper concentration, measuring ultraviolet absorption spectrum, recording absorbance (A2) at 350nm, and ensuring that the absorbance value is less than 0.05; then, taking 350nm as excitation wavelength, obtaining fluorescence emission spectrum within 380-620nm, and recording fluorescence integral peak area (S2); similarly, preparing a carbon dot solution with a certain concentration, repeating the steps, and recording the absorbance (A1) and the fluorescence integral peak area (S1) of the carbon dot solution; the fluorescence quantum yield of the metal-doped carbon dots was calculated as follows.
Y 1 ＝Y 2 (S 1 /S 2 )(A 2 /A 1 )(n 1 /n 2 )
2. Fluorescence intensity test: and (3) measuring the fluorescence intensity of the analysis substance by using a fluorescence spectrometer and a fluorescence analysis method.
3. Testing of iron ion detection limits: testing the gradient diluted iron ion solution by adopting a fluorescence spectrometer and a fluorescence analysis method, testing each concentration for 3-5 times to obtain a slope value sigma, testing a blank sample for 11 times to obtain a blank sample detection value standard deviation S, and calculating by using the following formula: lod=3σ/S.
Example 1: method for preparing zinc-nitrogen doped carbon dots
(1) Preparing a carbon dot precursor solution:
respectively weighing 200mg of dopamine hydrochloride and 200mg of zinc sulfate heptahydrate, dissolving in 10mL of distilled water with pH of 3 to prepare zinc sulfate and dopamine aqueous solution, mixing with 10mL of polyethylene glycol-200, uniformly mixing by ultrasonic (100W, 5 min) and reacting for 10min to obtain carbon dot precursor solution;
(2) Preparing a carbon dot crude solution by high-pressure reaction:
placing the precursor solution into a polytetrafluoroethylene tube, placing the polytetrafluoroethylene tube into a high-pressure reaction kettle, and reacting for 7 hours at 180 ℃ to obtain zinc ion doped carbon dot crude solution;
(3) Refined carbon point:
filtering the zinc ion doped carbon dot crude solution through a 0.22 micron filter membrane, adding the solution obtained after filtering into a 1000Da dialysis bag, placing the dialysis bag into distilled water with the pH value of 3 for dialysis for 48 hours, changing distilled water for dialysis every 24 hours, and performing rotary evaporation on the dialyzed carbon dot solution to obtain concentrated solution;
(4) And (3) freeze drying:
the concentrated solution is placed in a freeze dryer for 48 hours to freeze-dry, and powder is collected to obtain zinc ion doped carbon dot solid powder.
Example 2: method for preparing zinc-nitrogen doped carbon dots
(1) Preparing a carbon dot precursor solution:
respectively weighing 200mg of dopamine hydrochloride and 200mg of zinc sulfate heptahydrate, dissolving in 10mL of distilled water with pH of 3 to prepare zinc sulfate and dopamine aqueous solution, mixing with 10mL of polyethylene glycol-200, uniformly mixing by ultrasonic (100W, 5 min) and reacting for 10min to obtain carbon dot precursor solution;
(2) Preparing a carbon dot crude solution by high-pressure reaction:
placing the precursor solution into a polytetrafluoroethylene tube, placing the polytetrafluoroethylene tube into a high-pressure reaction kettle, and reacting for 6 hours at 180 ℃ to obtain zinc ion doped carbon dot crude solution;
(3) Refined carbon point:
filtering the zinc ion doped carbon dot crude solution through a 0.22 micron filter membrane, adding the solution obtained after filtering into a 1000Da dialysis bag, placing the dialysis bag into distilled water with the pH value of 3 for dialysis for 48 hours, changing distilled water for dialysis every 24 hours, and performing rotary evaporation on the dialyzed carbon dot solution to obtain concentrated solution;
(4) And (3) freeze drying:
the concentrated solution is placed in a freeze dryer for 48 hours to freeze-dry, and powder is collected to obtain zinc ion doped carbon dot solid powder.
Example 3: method for preparing zinc-nitrogen doped carbon dots
(1) Preparing a carbon dot precursor solution:
weighing 200mg of dopamine hydrochloride and 200mg of zinc sulfate heptahydrate, dissolving in 10mL of distilled water with pH of 3 to prepare zinc sulfate and dopamine aqueous solution, mixing with 10mL of polyethylene glycol-200, uniformly mixing by ultrasonic (100W, 5 min) and reacting for 10min to obtain carbon dot precursor solution;
(2) Preparing a carbon dot crude solution by high-pressure reaction:
placing the precursor solution into a polytetrafluoroethylene tube, placing the polytetrafluoroethylene tube into a high-pressure reaction kettle, and reacting for 5 hours at 180 ℃ to obtain zinc ion doped carbon dot crude solution;
(3) Refined carbon point:
filtering the zinc ion doped carbon dot crude solution through a 0.22 micron filter membrane, adding the solution obtained after filtering into a 1000Da dialysis bag, placing the dialysis bag into distilled water with the pH value of 3 for dialysis for 48 hours, changing distilled water for dialysis every 24 hours, and performing rotary evaporation on the dialyzed carbon dot solution to obtain concentrated solution;
(4) And (3) freeze drying:
the concentrated solution is placed in a freeze dryer for 48 hours to freeze-dry, and powder is collected to obtain zinc ion doped carbon dot solid powder.
Example 4: method for preparing zinc-nitrogen doped carbon dots
(1) Preparing a carbon dot precursor solution:
respectively weighing 200mg of dopamine hydrochloride and 200mg of zinc sulfate heptahydrate, dissolving in 10mL of distilled water with pH of 1 to prepare zinc sulfate and dopamine aqueous solution, mixing with 10mL of polyethylene glycol-200, uniformly mixing by ultrasonic (100W, 5 min) and reacting for 10min to obtain carbon dot precursor solution;
(2) Preparing a carbon dot crude solution by high-pressure reaction:
placing the precursor solution into a polytetrafluoroethylene tube, placing the polytetrafluoroethylene tube into a high-pressure reaction kettle, and reacting for 7 hours at 180 ℃ to obtain zinc ion doped carbon dot crude solution;
(3) Refined carbon point:
filtering the zinc ion doped carbon dot crude solution through a 0.22 micron filter membrane, adding the solution obtained after filtering into a 1000Da dialysis bag, placing the dialysis bag into distilled water with the pH value of 3 for dialysis for 48 hours, changing distilled water for dialysis every 24 hours, and performing rotary evaporation on the dialyzed carbon dot solution to obtain concentrated solution;
(4) And (3) freeze drying:
the concentrated solution is placed in a freeze dryer for 48 hours to freeze-dry, and powder is collected to obtain zinc ion doped carbon dot solid powder.
Example 5: method for preparing zinc-nitrogen doped carbon dots
(1) Preparing a carbon dot precursor solution:
respectively weighing 200mg of dopamine hydrochloride and 200mg of zinc sulfate heptahydrate, dissolving in 10mL of distilled water with pH of 4 to prepare zinc sulfate and dopamine aqueous solution, mixing with 10mL of polyethylene glycol-200, uniformly mixing by ultrasonic (100W, 5 min) and reacting for 10min to obtain carbon dot precursor solution;
(2) Preparing a carbon dot crude solution by high-pressure reaction:
placing the precursor solution into a polytetrafluoroethylene tube, placing the polytetrafluoroethylene tube into a high-pressure reaction kettle, and reacting for 7 hours at 180 ℃ to obtain zinc ion doped carbon dot crude solution;
(3) Refined carbon point:
filtering the zinc ion doped carbon dot crude solution through a 0.22 micron filter membrane, adding the solution obtained after filtering into a 1000Da dialysis bag, placing the dialysis bag into distilled water with the pH value of 3 for dialysis for 48 hours, changing distilled water for dialysis every 24 hours, and performing rotary evaporation on the dialyzed carbon dot solution to obtain concentrated solution;
(4) And (3) freeze drying:
the concentrated solution is placed in a freeze dryer for 48 hours to freeze-dry, and powder is collected to obtain zinc ion doped carbon dot solid powder.
Example 6: method for preparing zinc-nitrogen doped carbon dots
(1) Preparing a carbon dot precursor solution:
respectively weighing 200mg of dopamine hydrochloride and 300mg of zinc sulfate heptahydrate, dissolving in 10mL of distilled water with pH of 3 to prepare zinc sulfate and dopamine aqueous solution, mixing with 10mL of polyethylene glycol-200, uniformly mixing by ultrasonic (100W, 5 min) and reacting for 10min to obtain carbon dot precursor solution;
(2) Preparing a carbon dot crude solution by high-pressure reaction:
placing the precursor solution into a polytetrafluoroethylene tube, placing the polytetrafluoroethylene tube into a high-pressure reaction kettle, and reacting for 5 hours at 180 ℃ to obtain zinc ion doped carbon dot crude solution;
(3) Refined carbon point:
filtering the zinc ion doped carbon dot crude solution through a 0.22 micron filter membrane, adding the solution obtained after filtering into a 1000Da dialysis bag, placing the dialysis bag into distilled water with the pH value of 3 for dialysis for 48 hours, changing distilled water for dialysis every 24 hours, and performing rotary evaporation on the dialyzed carbon dot solution to obtain concentrated solution;
(4) And (3) freeze drying:
the concentrated solution is placed in a freeze dryer for 48 hours to freeze-dry, and powder is collected to obtain zinc ion doped carbon dot solid powder. Comparative example 1: method for preparing undoped zinc carbon dots
(1) Preparing a carbon dot precursor solution:
200mg of dopamine hydrochloride is weighed and dissolved in 10mL of distilled water, and 10mL of polyethylene glycol-200 is used for mixing to prepare a carbon dot precursor solution;
(2) Preparing a carbon dot crude solution by high-pressure reaction:
placing the precursor solution into a polytetrafluoroethylene tube, placing the polytetrafluoroethylene tube into a high-pressure reaction kettle, and reacting for 6 hours at 180 ℃ to obtain a carbon dot crude solution;
(3) Refined carbon point:
filtering the crude carbon dot solution by a 0.22 micron filter membrane, adding the filtered solution into a 1000Da dialysis bag, placing the dialysis bag into distilled water with the pH of 3 for dialysis for 48 hours, changing distilled water for dialysis every 24 hours, and performing rotary evaporation on the dialyzed carbon dot solution to obtain concentrated solution;
(4) And (3) freeze drying:
the concentrate was placed in a freeze dryer for 48 hours to freeze-dry, and the powder was collected to obtain carbon dot solid powder.
Comparative example 2: preparation method of zinc-nitrogen doped carbon dots
(1) Preparing a carbon dot precursor solution:
weighing 200mg of dopamine hydrochloride and 200mg of zinc sulfate heptahydrate, dissolving in 10mL of distilled water with pH of 7 to prepare zinc sulfate and dopamine aqueous solution, mixing with 10mL of polyethylene glycol-200, uniformly mixing by ultrasonic (100W, 5 min) and reacting for 10min to obtain carbon dot precursor solution;
(2) Preparing a carbon dot crude solution by high-pressure reaction:
placing the precursor solution into a polytetrafluoroethylene tube, placing the polytetrafluoroethylene tube into a high-pressure reaction kettle, and reacting for 7 hours at 180 ℃ to obtain zinc ion doped carbon dot crude solution;
(3) Refined carbon point:
filtering the zinc ion doped carbon dot crude solution through a 0.22 micron filter membrane, adding the solution obtained after filtering into a 1000Da dialysis bag, placing the dialysis bag into distilled water with the pH value of 3 for dialysis for 48 hours, changing distilled water for dialysis every 24 hours, and performing rotary evaporation on the dialyzed carbon dot solution to obtain concentrated solution;
(4) And (3) freeze drying:
the concentrated solution is placed in a freeze dryer for 48 hours to freeze-dry, and powder is collected to obtain zinc ion doped carbon dot solid powder. Comparative example 3: preparation method of zinc-nitrogen doped carbon dots
(1) Preparing a carbon dot precursor solution:
weighing 200mg of dopamine hydrochloride and 200mg of zinc sulfate heptahydrate, dissolving in 10mL of distilled water with pH of 9 to prepare zinc sulfate and dopamine aqueous solution, mixing with 10mL of polyethylene glycol-200, uniformly mixing by ultrasonic (100W, 5 min) and reacting for 10min to obtain carbon dot precursor solution;
(2) Preparing a carbon dot crude solution by high-pressure reaction:
placing the precursor solution into a polytetrafluoroethylene tube, placing the polytetrafluoroethylene tube into a high-pressure reaction kettle, and reacting for 7 hours at 180 ℃ to obtain zinc ion doped carbon dot crude solution;
(3) Refined carbon point:
filtering the zinc ion doped carbon dot crude solution through a 0.22 micron filter membrane, adding the solution obtained after filtering into a 1000Da dialysis bag, placing the dialysis bag into distilled water with the pH value of 3 for dialysis for 48 hours, changing distilled water for dialysis every 24 hours, and performing rotary evaporation on the dialyzed carbon dot solution to obtain concentrated solution;
(4) And (3) freeze drying:
the concentrated solution is placed in a freeze dryer for 48 hours to freeze-dry, and powder is collected to obtain zinc ion doped carbon dot solid powder. Comparative example 4: preparation method of iron-doped carbon dots
(1) Preparing a carbon dot precursor solution:
weighing 200mg of dopamine hydrochloride and 200mg of ferric trichloride hexahydrate, dissolving in 10mL of distilled water with pH of 3 to prepare ferric trichloride and dopamine aqueous solution, mixing with 10mL of polyethylene glycol-200, uniformly mixing by ultrasonic (100W, 5 min) and reacting for 10min to obtain carbon dot precursor solution;
(2) Preparing a carbon dot crude solution by high-pressure reaction:
placing the precursor solution into a polytetrafluoroethylene tube, placing the polytetrafluoroethylene tube into a high-pressure reaction kettle, and reacting for 7 hours at 180 ℃ to obtain an iron ion doped carbon dot crude solution;
(3) Refined carbon point:
filtering the iron ion doped carbon dot crude solution through a 0.22 micron filter membrane, adding the filtered solution into a 1000Da dialysis bag, placing the dialysis bag into distilled water with the pH value of 3 for dialysis for 48 hours, changing distilled water for dialysis every 24 hours, and performing rotary evaporation on the dialyzed carbon dot solution to obtain concentrated solution;
(4) And (3) freeze drying:
the concentrated solution is placed in a freeze dryer for 48 hours to freeze-dry, and powder is collected to obtain the iron ion doped carbon dot solid powder. Comparative example 5: preparation method of iron-doped carbon dots
(1) Preparing a carbon dot precursor solution:
weighing 200mg of dopamine hydrochloride and 100mg of ferric trichloride hexahydrate, dissolving in 10mL of distilled water with pH of 3 to prepare ferric trichloride and dopamine aqueous solution, mixing with 10mL of polyethylene glycol-200, uniformly mixing by ultrasonic (100W, 5 min) and reacting for 10min to obtain carbon dot precursor solution;
(2) Preparing a carbon dot crude solution by high-pressure reaction:
placing the precursor solution into a polytetrafluoroethylene tube, placing the polytetrafluoroethylene tube into a high-pressure reaction kettle, and reacting for 7 hours at 180 ℃ to obtain an iron ion doped carbon dot crude solution;
(3) Refined carbon point:
filtering the iron ion doped carbon dot crude solution through a 0.22 micron filter membrane, adding the filtered solution into a 1000Da dialysis bag, placing the dialysis bag into distilled water with the pH value of 3 for dialysis for 48 hours, changing distilled water for dialysis every 24 hours, and performing rotary evaporation on the dialyzed carbon dot solution to obtain concentrated solution;
(4) And (3) freeze drying:
the concentrated solution is placed in a freeze dryer for 48 hours to freeze-dry, and powder is collected to obtain the iron ion doped carbon dot solid powder. Comparative example 6: preparation method of iron-doped carbon dots
(1) Preparing a carbon dot precursor solution:
weighing 50mg of dopamine hydrochloride and 150mg of ferric trichloride hexahydrate, dissolving in 10mL of distilled water with pH of 3 to prepare ferric trichloride and dopamine aqueous solution, mixing with 10mL of polyethylene glycol-200, uniformly mixing by ultrasonic (100W, 5 min) and reacting for 10min to obtain carbon dot precursor solution;
(2) Preparing a carbon dot crude solution by high-pressure reaction:
placing the precursor solution into a polytetrafluoroethylene tube, placing the polytetrafluoroethylene tube into a high-pressure reaction kettle, and reacting for 7 hours at 180 ℃ to obtain an iron ion doped carbon dot crude solution;
(3) Refined carbon point:
filtering the iron ion doped carbon dot crude solution through a 0.22 micron filter membrane, adding the filtered solution into a 1000Da dialysis bag, placing the dialysis bag into distilled water with the pH value of 3 for dialysis for 48 hours, changing distilled water for dialysis every 24 hours, and performing rotary evaporation on the dialyzed carbon dot solution to obtain concentrated solution;
(4) And (3) freeze drying:
the concentrated solution is placed in a freeze dryer for 48 hours to freeze-dry, and powder is collected to obtain the iron ion doped carbon dot solid powder.
As shown in fig. 1 and table 1, the fluorescence intensities of the carbon dots obtained for each example and comparative example; as shown in fig. 2 and table 1, the fluorescence quantum yields of the carbon dots obtained for each example and comparative example; as shown in table 1, the detection limit of iron ions at the carbon points obtained in each example and comparative example was determined.
Comparative example 7: method for preparing zinc-nitrogen doped carbon dots
(1) Preparing a carbon dot precursor solution:
respectively weighing 200mg of dopamine hydrochloride and 10mg of zinc sulfate heptahydrate, dissolving in 10mL of distilled water with pH of 3 to prepare zinc sulfate and dopamine aqueous solution, mixing with 10mL of polyethylene glycol-200, uniformly mixing by ultrasonic (100W, 5 min) and reacting for 10min to obtain carbon dot precursor solution;
(2) Preparing a carbon dot crude solution by high-pressure reaction:
placing the precursor solution into a polytetrafluoroethylene tube, placing the polytetrafluoroethylene tube into a high-pressure reaction kettle, and reacting for 5 hours at 180 ℃ to obtain zinc ion doped carbon dot crude solution;
(3) Refined carbon point:
filtering the zinc ion doped carbon dot crude solution through a 0.22 micron filter membrane, adding the solution obtained after filtering into a 1000Da dialysis bag, placing the dialysis bag into distilled water with the pH value of 3 for dialysis for 48 hours, changing distilled water for dialysis every 24 hours, and performing rotary evaporation on the dialyzed carbon dot solution to obtain concentrated solution;
(4) And (3) freeze drying:
the concentrated solution is placed in a freeze dryer for 48 hours to freeze-dry, and powder is collected to obtain zinc ion doped carbon dot solid powder.
The carbon dots prepared in examples 1 to 6 and comparative examples 1 to 7 were subjected to a fluorescence quantum yield test, a fluorescence intensity test, and an iron ion detection limit measurement, and the results are shown in Table 1.
TABLE 1
Application example 1: application of zinc-nitrogen doped carbon dots in food detection
A food detection material is a detection test paper, and contains zinc nitrogen doped carbon dots as described in example 1.
When the detection is carried out, the food extract or the fluid food sample liquid is soaked by the detection test paper, and after the soaking, the fluorescence intensity of the test paper is detected by using a fluorescence spectrophotometer.
Application example 2: application of zinc-nitrogen doped carbon dots in food detection
An environmental monitoring material comprising the zinc nitrogen doped carbon dots of example 2.
In the detection process, the environment monitoring material containing the zinc-nitrogen doped carbon point described in the embodiment 2 can be added into the aqueous solution of the sample, and the fluorescence intensity of the sample solution can be directly detected by a fluorescence spectrophotometer.
Further, the iron ion concentration may be determined based on the fluorescence intensity.
Application example 3: application of zinc-nitrogen doped carbon dots in packaging material detection
A fluid food packaging material into which a label material containing zinc nitrogen-doped carbon dots as described in example 3 can be incorporated.
When the method is specifically used for monitoring, if the metal ions in the food exceed the standard, whether the food contains the iron ions can be judged through the luminous degree of the carbon dot fluorescent label on the packaging material; further, the iron ion content may be confirmed based on the fluorescence intensity.
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (12)
1. A method of preparing zinc nitrogen doped carbon dots, the method comprising the steps of:
(1) Carbon source and nitrogen source solutions:
dissolving catecholamine substances in deionized water, and regulating the pH value to obtain a catecholamine substance carbon source and nitrogen source solution; wherein the catecholamine substance comprises one of 5, 6-dihydroxyindole, L-dopamine, catecholamine, dopamine hydrochloride or dopamine;
(2) Metal polyphenol coordination complex precursor solution:
mixing catecholamine substance solution and metal salt solution to prepare metal polyphenol compound precursor solution; the metal in the metal salt solution is zinc;
(3) And preparing zinc-nitrogen doped carbon points through hydrothermal reaction.
2. The method according to claim 1, wherein the ph of the catecholamine substance solution of step (1) is adjusted to 1-4.
3. The method according to claim 1, wherein the mass ratio of the metal salt to the catecholamine substance in the step (2) is 0.1:1 to 3:1.
4. the method according to claim 1, wherein the catecholamine substance solution in step (1) is obtained by dissolving catecholamine substances in deionized water, and the concentration is 5-60mg/mL.
5. The method according to claim 1, wherein the metal salt solution in step (2) is obtained by dissolving a metal salt in deionized water at a concentration of 1-30mg/ml.
6. The method of claim 1, further comprising step (4) purification and isolation and/or step (5) concentration and drying.
7. The zinc nitrogen doped carbon dots prepared by the method of any one of claims 1-6.
8. Use of the zinc nitrogen doped carbon dot of claim 7 in the field of food detection, environmental monitoring or packaging.
9. The use according to claim 8, characterized in that the use is the detection of iron-containing substances.
10. A food detection material capable of being used for detecting an iron-containing substance, characterized in that the material contains the zinc nitrogen-doped carbon dot according to claim 7.
11. An environmental monitoring material capable of being used for detecting iron-containing substances, characterized in that the material contains zinc nitrogen doped carbon dots according to claim 7.
12. A packaging material capable of being used for detecting iron-containing substances, characterized in that the material contains zinc nitrogen doped carbon dots according to claim 7.
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