CN114958357B - Visible and near infrared light region double-emission fluorescent carbon dot and preparation method thereof - Google Patents
Visible and near infrared light region double-emission fluorescent carbon dot and preparation method thereof Download PDFInfo
- Publication number
- CN114958357B CN114958357B CN202110192476.XA CN202110192476A CN114958357B CN 114958357 B CN114958357 B CN 114958357B CN 202110192476 A CN202110192476 A CN 202110192476A CN 114958357 B CN114958357 B CN 114958357B
- Authority
- CN
- China
- Prior art keywords
- near infrared
- cyclodextrin
- visible
- beta
- emission
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 45
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 45
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 45
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 45
- 229960004853 betadex Drugs 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910001502 inorganic halide Chemical class 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000502 dialysis Methods 0.000 claims description 18
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 235000013024 sodium fluoride Nutrition 0.000 claims description 8
- 239000011775 sodium fluoride Substances 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 229960001031 glucose Drugs 0.000 claims description 7
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 6
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 6
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 6
- 239000008101 lactose Substances 0.000 claims description 6
- 229960001375 lactose Drugs 0.000 claims description 6
- 229960004452 methionine Drugs 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000004475 Arginine Substances 0.000 claims description 5
- FFEARJCKVFRZRR-UHFFFAOYSA-N L-Methionine Natural products CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 claims description 5
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 5
- 229930195722 L-methionine Natural products 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 5
- 229960003121 arginine Drugs 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 230000005284 excitation Effects 0.000 abstract description 10
- 241001465754 Metazoa Species 0.000 abstract description 9
- 238000003384 imaging method Methods 0.000 abstract description 9
- 238000001727 in vivo Methods 0.000 abstract description 5
- 238000003745 diagnosis Methods 0.000 abstract description 4
- 201000010099 disease Diseases 0.000 abstract description 4
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 abstract description 4
- 238000006862 quantum yield reaction Methods 0.000 abstract description 2
- 238000001917 fluorescence detection Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000002096 quantum dot Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 5
- 239000007850 fluorescent dye Substances 0.000 description 5
- 238000011503 in vivo imaging Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 208000024172 Cardiovascular disease Diseases 0.000 description 2
- 208000017667 Chronic Disease Diseases 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 241000699670 Mus sp. Species 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 241000283977 Oryctolagus Species 0.000 description 2
- 241000700159 Rattus Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000002889 endothelial cell Anatomy 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 210000005229 liver cell Anatomy 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000001575 pathological effect Effects 0.000 description 2
- 238000011897 real-time detection Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 210000004881 tumor cell Anatomy 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- 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
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
Abstract
The invention provides a double-emission fluorescent carbon dot in visible and near infrared regions, which is prepared by adopting a thermal solvent method under the action of an organic compound and inorganic halide salt by taking beta-cyclodextrin or poly beta-cyclodextrin as a carbon source. The double-emission fluorescent carbon dots in the visible and near infrared regions have high monodispersity, good stability, water solubility and higher fluorescence quantum yield; the emission wavelength is between 400 and 550nm and 600 and 800nm, and has obvious dependence on the excitation wavelength. The double-emission fluorescent carbon dots in visible and near infrared light areas can be imaged in cells and living animals, and have great application value for molecular imaging and disease diagnosis, in vivo fluorescence detection of living animals and the like. The preparation process is simple and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of material science, and particularly relates to a visible and near infrared light region double-emission fluorescent carbon dot and a preparation method thereof.
Background
In recent years, with the development of molecular imaging and disease diagnostics, research on fluorescent probes has been paid attention to by researchers; besides the common small molecule fluorescent probes, probes based on nanomaterials are becoming increasingly hot research spots due to their excellent mesoscopic effects (e.g., photoelectricity, photothermal, etc.). The carbon quantum dot is used as a novel carbon nanomaterial following carbon nanotubes and graphene, and has been widely applied to the fields of biological imaging, disease diagnosis and the like by virtue of the characteristics of excellent physical and chemical properties (surface effect, quantum size effect and the like), optical properties (adjustable fluorescence emission peak, wide excitation spectrum, photobleaching resistance and the like), small size, easiness in functional modification, low toxicity, good biocompatibility and the like. For example, in the diagnosis and treatment process of chronic diseases (such as tumor, cardiovascular diseases and the like), a fluorescence probe in a near infrared light region is utilized to realize focus positioning and real-time detection at the living body level; and then, using a fluorescent probe in a visible light region, and directly imaging the pathological section by utilizing a microscopic imaging technology.
Due to its own structure and charge transfer limitations, most of the fluorescence emitted by carbon dots currently resides mainly in the blue-green fluorescence band (lambda em Approximately 300-550 nm), it is difficult to effectively emit near infrared light fluorescence (lambda) with small biological background interference and strong tissue penetrating ability em =650-1000 nm). Most of the reported near infrared fluorescent materials have potential biotoxicity and stability problems: on the one hand, organic groups on the surface of the near infrared semiconductor quantum dot can cause cytopathy and leakage of heavy metals in the quantum dot; on the other hand, most of near infrared semiconductor quantum dots are synthesized by taking metal organic compounds as precursors in an organic phase, and organic solvents used in the synthesis process can be harmful to the environment and the physical health of human beings. There are also reports in literature that small molecular dyes are used for preparing near infrared fluorescent materials, however, small molecular organic near infrared dyes such as phenothiazine dyes can infect DNA and have cancerogenic danger to human bodies, and meanwhile, small molecular organic near infrared dyes are unstable and easy to generate photobleaching phenomenon, and have low solubility in water, so that the application of the small molecular organic near infrared dyes in biomedicine is limited.
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention aims to solve the problems in the prior art, and an object of the present invention is to provide a dual emission fluorescent carbon dot in the visible and near infrared regions, which has excellent biocompatibility and low toxicity, and is capable of dual emission in the visible and near infrared regions.
The percentages stated in the invention are mass percentages unless specified otherwise.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a visible and near infrared light region dual-emission fluorescent carbon dot, characterized in that: beta-cyclodextrin or poly beta-cyclodextrin is used as a carbon source, and a thermal solvent is adopted to prepare visible and near infrared light region double-emission fluorescent carbon points under the action of an organic compound and inorganic halogenated salt; the organic compound is selected from one or a combination of more of glucose, lactose, beta-cyclodextrin, arginine, L-methionine and glycine; the inorganic halide salt is selected from one or a combination of several of sodium chloride, sodium bromide, ammonium chloride, ammonium fluoride and sodium fluoride.
The fluorescent carbon point has the emission wavelength of 400-550 nm in the visible light region and 600-800 nm in the near infrared region.
The visible and near infrared light region double-emission fluorescent carbon dot is characterized by comprising the following preparation steps: placing a carbon source into a solvent containing an organic compound and an inorganic halide salt, reacting at 60-260 ℃ for 10 min-24 h, separating and drying the product to obtain the double-emission fluorescent carbon dots in the visible and near infrared regions; the carbon source is beta-cyclodextrin or poly beta-cyclodextrin; the organic compound is selected from one or a combination of more of glucose, lactose, beta-cyclodextrin, L-methionine and glycine; the inorganic halide salt is selected from one or a combination of several of sodium chloride, sodium bromide, ammonium chloride, ammonium fluoride and sodium fluoride.
Further, the ratio of the carbon source to the organic compound is 1:1-5 (molar ratio); the mass ratio of the carbon source to the inorganic halide salt is 1:0.2-3.
The solvent is selected from water or a mixture of water and an organic solvent, and the organic solvent is selected from one or a combination of more of ethanol, tetrahydrofuran, dimethyl sulfoxide and dimethylformamide. Further, when the solvent is a mixture of water and an organic solvent, the volume ratio of the organic solvent to the water is 1:1-5.
The invention also provides a preparation method of the visible and near infrared light region double-emission fluorescent carbon dots.
The preparation method of the double-emission fluorescent carbon dots in the visible and near infrared regions is characterized by comprising the following steps of:
(1) Selecting beta-cyclodextrin or poly beta-cyclodextrin as a carbon source;
(2) Placing the powder of the carbon source in the step (1) into a solvent containing an organic compound and an inorganic halogenated salt, and heating and reacting in a stainless steel reaction kettle;
(3) After the reaction is finished, centrifuging the reaction solution in the step (2), taking supernatant, filtering by a microporous filter membrane, and dialyzing again to remove impurities, thereby obtaining a beta-cyclodextrin-based visible and near infrared light region double-emission carbon point solution;
(4) Drying the beta-cyclodextrin-based visible and near infrared light region double-emission carbon dot solution obtained in the step (3) to obtain the visible and near infrared light region double-emission fluorescent carbon dot.
In the method, the centrifugal speed in the step (3) is 3000-10000 r/min, and the centrifugal time is 3-30 min; the aperture of the microporous filter membrane is 0.1-0.45 mu m, the cut-off molecular weight of the dialysis bag for dialysis is 600-1500 kDa, and the dialysis time is 12-36 h.
In the above method, the drying in step (4) is drying or freeze-drying, and the apparatus is a rotary evaporator, an oven, a freeze dryer, or the like.
The preparation method of the double-emission fluorescent carbon dots in the visible and near infrared light regions is characterized by comprising the following steps:
(1) Selecting beta-cyclodextrin or poly beta-cyclodextrin as a carbon source;
(2) Placing the powder of the carbon source in the step (1) into a solvent containing an organic compound and an inorganic halide salt, and heating and reacting in a stainless steel reaction kettle at 60-260 ℃ for 10 min-24 h; the organic compound is selected from one or a combination of more of glucose, lactose, beta-cyclodextrin, arginine, L-methionine and glycine; the inorganic halide salt is selected from one or a combination of more of sodium chloride, sodium bromide, ammonium chloride, ammonium fluoride and sodium fluoride;
(3) After the reaction is finished, centrifuging the reaction liquid in the step (2) at a speed of 3000-10000 r/min for 3-30 min; taking supernatant, filtering with a microporous filter membrane, and dialyzing again to remove impurities to obtain a beta-cyclodextrin-based visible and near infrared light region double-emission carbon dot solution; the aperture of the microporous filter membrane is 0.1-0.45 mu m, the cut-off molecular weight of the dialysis bag for dialysis is 600-1500 kDa, and the dialysis time is 12-36 h;
(4) Drying the carbon dot solution obtained in the step (3) to obtain the visible and near infrared light region double-emission fluorescent carbon dots; drying is oven drying or freeze drying.
The beneficial effects are that:
in the diagnosis and treatment process of chronic diseases (such as tumor, cardiovascular diseases and the like), the prior art firstly utilizes a fluorescent probe (first probe) in a near infrared light region to realize focus positioning and real-time detection at the living body level; and then using a fluorescent probe (a second probe) in the visible light region to directly image the pathological section by utilizing a microscopic imaging technology.
In order to avoid complicated operation and reduce errors as much as possible, the invention provides a double-emission fluorescent carbon dot in the visible and near infrared regions, which can be used in the visible and near infrared regions. The double-emission fluorescent carbon dots in the visible and near infrared regions have high monodispersity, good stability, water solubility and higher fluorescence quantum yield; the emission wavelength is between 400 and 550nm and 600 and 800nm, and has obvious dependence on the excitation wavelength. The double-emission fluorescent carbon dots in the visible and near-infrared light regions can emit stronger near-infrared fluorescence under 700nm (optimal excitation wavelength) except for fluorescent signals in the visible light region, and can detect the fluorescent signals in organisms, so that the double-emission fluorescent carbon dots can be imaged in cells and living animals, and have great application values for molecular imaging and disease diagnostics, in-vivo fluorescent detection of living animals in vivo and the like. The invention takes beta-cyclodextrin or poly beta-cyclodextrin as a carbon source, adopts a thermal solvent method to prepare the visible and near infrared light region double-emission fluorescent carbon dots under the action of organic compounds and inorganic halogenated salts, has simple preparation process, is green and environment-friendly, has excellent dispersibility, good water solubility and excellent biological safety, and has important and wide application prospect in biomedicine and photoelectric devices.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the present invention, and that other related drawings may be obtained from these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a fluorescence spectrum diagram of a visible light region of a fluorescent carbon quantum dot of the present invention;
FIG. 2 is a fluorescence spectrum of the fluorescent carbon quantum dots of the present invention in the near infrared region;
FIG. 3 is a TEM image of fluorescent carbon quantum dots of the present invention;
fig. 4 is a near infrared photograph of the fluorescent carbon quantum dot of the present invention under 700nm excitation.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments, wherein the described embodiments are merely some, but not all, of the embodiments of the present invention; it is noted that the following examples are only for further illustration of the invention and are not intended to limit the scope of the invention in this regard. All other embodiments, based on the embodiments of the invention, which a person skilled in the art would obtain without inventive faculty, are within the scope of the invention; furthermore, it is possible to make some insubstantial improvements and modifications of the invention in light of the above summary.
The instruments and equipment used in the following examples of the present invention are as follows:
Ultra-6600A (Rigol, china); RF-5301 fluorescence spectrophotometer (Shimadzu, japan); transmission electron microscope JEM-1200EX (JEOL, japan); small animal in vivo imager Lumina LT Series III (Perkinelme, USA).
The specific embodiments of the present invention are described in further detail as follows:
example 1:
1. the preparation method of the carbon quantum dot based on the beta-cyclodextrin by utilizing sodium bromide specifically comprises the following steps:
beta-cyclodextrin is selected as a carbon source, 1g of beta-cyclodextrin, 0.27g of sodium bromide and 0.3g of glycine are dissolved in 20mL of water solution containing N, N-dimethylformamide, and the volume ratio of the N, N-dimethylformamide to water is 1:1; after ultrasonic mixing for 10min, transferring the mixed solution into a 30mL stainless steel autoclave, reacting at 200 ℃ for 12h, and taking out; naturally cooling the reaction kettle to room temperature, taking out the mixed solution, transferring the mixed solution into a 50mL centrifuge tube, and centrifuging for 5min at a rotating speed of 5,000 rpm; taking supernatant, filtering large-size particles by using an organic microporous filter membrane with the size of 0.22 mu m, purifying for 24 hours by using a dialysis bag with the size of 1,000kDa again, and drying to obtain the carbon quantum dot product with double emission in visible and near infrared regions.
2. The properties, morphology and structure of the carbon dots are characterized as follows:
the prepared carbon dot powder can be redissolved in aqueous solution, the aqueous solution is taken for spectral characterization, and the result shows that the carbon dot powder has wider ultraviolet absorption and double-emission fluorescence in visible and near infrared light regions. As shown in fig. 1 and 2, the dependence of the fluorescence emission peak on the excitation light is large, and the position of the fluorescence peak changes with the change of the excitation light. The structure of the carbon dots was characterized by using a transmission electron microscope, as shown in fig. 3, and the prepared carbon dots were well monodisperse in an aqueous solution, spherical in shape, and about 5nm in particle diameter. The in vivo imaging capability of the carbon dots prepared by using a small animal in vivo imager is verified, as shown in fig. 4, the prepared carbon dots can emit obvious near infrared signals under the excitation of 700nm, and the result shows that the prepared carbon dots can carry out in vivo imaging on small animals (mice, rats, new zealand rabbits and the like). The imaging capability of the cells is verified by utilizing laser confocal, and after the cells are incubated for 2 hours with body cells (such as endothelial cells, tumor cells, liver cells and the like), fluorescence (lambda) emitted by carbon points can be detected inside the cells ex ＝488nm)。
Example 2:
the preparation method of the carbon quantum dot based on the poly beta-cyclodextrin by utilizing sodium bromide specifically comprises the following steps:
the preparation method comprises the steps of (1) taking poly beta-cyclodextrin as a carbon source, and dissolving 1g of poly beta-cyclodextrin, 0.27g of sodium bromide, 0.2g of glucose and 0.2g of glycine in 20mL of aqueous solution containing ethanol, wherein the volume ratio of ethanol to water is 1:1; after ultrasonic mixing for 10min, transferring the mixed solution into a 30mL stainless steel autoclave, reacting at 180 ℃ for 12h, and taking out; naturally cooling the reaction kettle to room temperature, taking out the mixed solution, transferring the mixed solution into a 50mL centrifuge tube, and centrifuging for 4min at a rotating speed of 6,000 rpm; taking supernatant, filtering large-size particles by using an organic microporous filter membrane with the size of 0.22 mu m, purifying for 24 hours by using a dialysis bag with the size of 1,000kDa again, and drying to obtain the carbon quantum dot product with double emission in visible and near infrared regions.
Example 3:
the preparation method of the carbon quantum dot based on beta-cyclodextrin by utilizing sodium fluoride specifically comprises the following steps:
beta-cyclodextrin is selected as a carbon source, and 1g of beta-cyclodextrin, 0.11 g of sodium fluoride and 0.5g of arginine are dissolved in 20mL of water solution; after ultrasonic mixing for 10min, transferring the mixed solution into a 30mL stainless steel autoclave, reacting at 220 ℃ for 8h, and taking out; naturally cooling the reaction kettle to room temperature, taking out the mixed solution, transferring the mixed solution into a 50mL centrifuge tube, and centrifuging for 20min at a rotating speed of 3,000 rpm; taking supernatant, filtering large-size particles by using an organic microporous filter membrane with the size of 0.22 mu m, purifying for 12 hours by using a dialysis bag with the size of 1,500kDa, and drying to obtain the carbon quantum dot product with double emission in visible and near infrared regions.
Example 4:
the preparation method of the carbon quantum dot based on the poly beta-cyclodextrin by utilizing sodium fluoride specifically comprises the following steps:
1g of poly beta-cyclodextrin, 0.1g of ammonium fluoride and 0.3g of methionine are dissolved in 20mL of aqueous solution containing tetrahydrofuran, and the volume ratio of the tetrahydrofuran to the water is 1:1; ultrasonic mixing for 10min, transferring the mixed solution into a 30mL stainless steel autoclave, reacting at 220 ℃ for 5h, and taking out; naturally cooling the reaction kettle to room temperature, taking out the mixed solution, transferring the mixed solution into a 50mL centrifuge tube, and centrifuging for 3min at a rotating speed of 8,000 rpm; taking supernatant, filtering large-size particles by using an organic microporous filter membrane with the size of 0.22 mu m, purifying for 36 hours by using a dialysis bag with the size of 600kDa again, and drying to obtain the carbon quantum dot product with double emission in visible and near infrared regions.
Example 5:
the preparation method of the carbon quantum dot based on beta-cyclodextrin by using ammonium fluoride specifically comprises the following steps:
beta-cyclodextrin is selected as a carbon source, 1g of beta-cyclodextrin, 0.1g of ammonium fluoride and 0.2g of glucose are dissolved in 20mL of aqueous solution containing ethanol, and the volume ratio of the ethanol to the water is 1:1; ultrasonic mixing for 10min, transferring the mixed solution into a 30mL stainless steel autoclave, reacting at 180 ℃ for 15h, and taking out; naturally cooling the reaction kettle to room temperature, taking out the mixed solution, transferring the mixed solution into a 50mL centrifuge tube, and centrifuging for 3min at a rotating speed of 10,000 rpm; taking supernatant, filtering large-size particles by using an organic microporous filter membrane with the size of 0.22 mu m, purifying for 24 hours by using a dialysis bag with the size of 1,000kDa again, and drying to obtain the carbon quantum dot product with double emission in visible and near infrared regions.
Example 6:
the preparation method of the quantum dot based on the poly beta-cyclodextrin by using ammonium fluoride specifically comprises the following steps:
1g of poly beta-cyclodextrin, 0.1g of ammonium fluoride and 0.2g of lactose are dissolved in 20mL of water solution containing dimethyl sulfoxide, and the volume ratio of the dimethyl sulfoxide to the water is 1:1; ultrasonic mixing for 10min, transferring the mixed solution into a 30mL stainless steel autoclave, reacting at the external temperature of 150 ℃ for 20h, and taking out; naturally cooling the reaction kettle to room temperature, taking out the mixed solution, transferring the mixed solution into a 50mL centrifuge tube, and centrifuging for 10min at a rotating speed of 4,000 rpm; taking supernatant, filtering large-size particles by using an organic microporous filter membrane with the size of 0.22 mu m, purifying for 24 hours by using a dialysis bag with the size of 1,000kDa again, and drying to obtain the carbon quantum dot product with double emission in visible and near infrared regions.
Characterization of properties, morphology and structure of the double-emission carbon quantum dots in the visible and near infrared regions prepared in examples 2-6 was performed. The results show that the carbon quantum dots prepared in examples 2-6 and having double emission in the visible and near infrared regions have good water solubility, can be successfully re-dissolved, and the aqueous solution is subjected to spectral characterization, so that the fluorescent light has wider ultraviolet absorption and double emission fluorescence in the visible and near infrared regions, the dependence of fluorescence emission peaks on excitation light is larger, and the positions of the fluorescence peaks change along with the change of the excitation light. The structure of the carbon dots is characterized by using a transmission electron microscope, and the result shows that the prepared carbon dots are well monodisperse and spherical in aqueous solution. The in-vivo imaging capability of the small animal living body imager is verified, and the result shows that the prepared carbon dot can emit obvious near infrared signals under the excitation of 700nm, and can carry out living body imaging on small animals (mice, rats, new Zealand rabbits and the like). The imaging capability of the cells is verified by utilizing laser confocal, and after the cells are incubated with body cells (such as endothelial cells, tumor cells, liver cells and the like), fluorescence emitted by carbon points can be detected inside the cells.
The invention takes beta-cyclodextrin as a carbon source, and realizes polymerization reaction in high-temperature aqueous solution under the action of specific organic compounds and halogenated salts to synthesize the fluorescent carbon quantum dots. The fluorescent carbon dots prepared by the invention have high monodispersity, good stability, good water solubility and excellent photoluminescence characteristics, and particularly have the emission capability of visible and near infrared fluorescence; compared with other semiconductor quantum dots, the quantum dot has the advantages of high sensitivity, good biological safety, low preparation cost and the like, can be widely applied to the fields of in-vivo imaging, detection and the like of different layers, and has good application prospect.
Claims (5)
1. A preparation method of a visible and near infrared light region double-emission fluorescent carbon dot is characterized by comprising the following steps: beta-cyclodextrin or poly beta-cyclodextrin is used as a carbon source, and a thermal solvent is adopted to prepare visible and near infrared light region double-emission fluorescent carbon points under the action of an organic compound and inorganic halogenated salt; the organic compound is selected from one or a combination of more of glucose, lactose, beta-cyclodextrin, arginine, L-methionine and glycine; the inorganic halide salt is selected from one or a combination of more of sodium chloride, sodium bromide, ammonium chloride, ammonium fluoride and sodium fluoride;
the method comprises the following steps:
(1) Selecting beta-cyclodextrin or poly beta-cyclodextrin as a carbon source; the molar ratio of the carbon source to the organic compound is 1:1-5; the mass ratio of the carbon source to the inorganic halide salt is 1:0.2-3;
(2) Placing the powder of the carbon source in the step (1) into a solvent containing an organic compound and an inorganic halogenated salt, and heating and reacting in a stainless steel reaction kettle at 150-220 ℃ for 5-20 h;
(3) After the reaction is finished, centrifuging the reaction solution in the step (2), taking supernatant, filtering by a microporous filter membrane, and dialyzing again to remove impurities, thereby obtaining a beta-cyclodextrin-based visible and near infrared light region double-emission carbon point solution;
(4) Drying the carbon dot solution obtained in the step (3) to obtain visible and near infrared light region double-emission fluorescent carbon dots;
the solvent is selected from water or a mixture of water and an organic solvent, and the organic solvent is selected from one or a combination of more of tetrahydrofuran, dimethyl sulfoxide, ethanol and dimethylformamide; when the solvent is a mixture of water and an organic solvent, the volume ratio of the organic solvent to the water is 1:1-5.
2. The method for preparing the fluorescent carbon dots according to claim 1, wherein: the fluorescent carbon dots have an emission wavelength of 400-550 nm in a visible light region and 600-800 nm in a near infrared light region.
3. The method for preparing the fluorescent carbon dots according to claim 1, wherein: the centrifugal speed in the step (3) is 3000-10000 r/min, and the centrifugal time is 3-30 min; the aperture of the microporous filter membrane is 0.1-0.45 mu m, the cut-off molecular weight of the dialysis bag for dialysis is 600-1500 kDa, and the dialysis time is 12-36 h.
4. The method for preparing the fluorescent carbon dots according to claim 1, wherein: the drying in the step (4) is drying or freeze drying.
5. The method for preparing fluorescent carbon dots according to claim 1, wherein the following steps are adopted:
(1) Selecting beta-cyclodextrin or poly beta-cyclodextrin as a carbon source;
(2) Placing the powder of the carbon source in the step (1) into a solvent containing an organic compound and an inorganic halide salt, and heating and reacting in a stainless steel reaction kettle at 150-220 ℃ for 5-20 h; the organic compound is selected from one or a combination of more of glucose, lactose, beta-cyclodextrin, arginine, L-methionine and glycine; the inorganic halide salt is selected from one or a combination of more of sodium chloride, sodium bromide, ammonium chloride, ammonium fluoride and sodium fluoride;
(3) After the reaction is finished, centrifuging the reaction liquid in the step (2) at a speed of 3000-10000 r/min for 3-30 min; taking supernatant, filtering with a microporous filter membrane, and dialyzing again to remove impurities to obtain a beta-cyclodextrin-based visible and near infrared light region double-emission carbon dot solution; the aperture of the microporous filter membrane is 0.1-0.45 mu m, the cut-off molecular weight of the dialysis bag for dialysis is 600-1500 kDa, and the dialysis time is 12-36 h;
(4) Drying the carbon dot solution obtained in the step (3) to obtain visible and near infrared light region double-emission fluorescent carbon dots; drying is oven drying or freeze drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110192476.XA CN114958357B (en) | 2021-02-20 | 2021-02-20 | Visible and near infrared light region double-emission fluorescent carbon dot and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110192476.XA CN114958357B (en) | 2021-02-20 | 2021-02-20 | Visible and near infrared light region double-emission fluorescent carbon dot and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114958357A CN114958357A (en) | 2022-08-30 |
| CN114958357B true CN114958357B (en) | 2023-04-28 |
Family
ID=82954308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110192476.XA Active CN114958357B (en) | 2021-02-20 | 2021-02-20 | Visible and near infrared light region double-emission fluorescent carbon dot and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114958357B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106995699A (en) * | 2017-05-31 | 2017-08-01 | 中国矿业大学 | Carbon quantum dot prepared by the method and this method of the adjustable fluorescent carbon point of a large amount of synthetic wavelengths |
| CN108069412A (en) * | 2016-11-14 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of preparation method of cyclodextrin nano carbon ball |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3068442A4 (en) * | 2013-11-14 | 2017-05-17 | The Royal Institution for the Advancement of Learning / McGill University | Bionanofluid for use as a contrast, imaging, disinfecting and/or therapeutic agent |
| CN106872433B (en) * | 2017-03-31 | 2019-03-08 | 中国农业大学 | Beta-cyclodextrin functionalization carbon dots material and its applied to detection testosterone method |
| CN108913132B (en) * | 2018-07-20 | 2020-08-04 | 江南大学 | Preparation method of dual-emission carbon-based nanoprobe and product thereof |
-
2021
- 2021-02-20 CN CN202110192476.XA patent/CN114958357B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108069412A (en) * | 2016-11-14 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of preparation method of cyclodextrin nano carbon ball |
| CN106995699A (en) * | 2017-05-31 | 2017-08-01 | 中国矿业大学 | Carbon quantum dot prepared by the method and this method of the adjustable fluorescent carbon point of a large amount of synthetic wavelengths |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114958357A (en) | 2022-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Singh et al. | Carbon quantum dots: Synthesis, characterization and biomedical applications | |
| Shi et al. | High-yield and high-solubility nitrogen-doped carbon dots: formation, fluorescence mechanism and imaging application | |
| CN109336909B (en) | Near-infrared two-region fluorescent compound with aggregation-induced emission property, preparation method thereof, nano-micelle and application thereof | |
| CN107551279B (en) | Ultra-small protein composite nanoparticle with near-infrared photothermal effect and multi-modal imaging function, and preparation method and application thereof | |
| CN107903893B (en) | Modified carbon nanodot with near-infrared absorption and near-infrared luminescence characteristics, and preparation method and application thereof | |
| CN112566911A (en) | Photothermal reagent | |
| CN109810698A (en) | A kind of luminous carbon quantum dot and its preparation method and application | |
| CN104587495A (en) | MRI (magnetic resonance imaging)-guided targeted photo-thermal agent and preparation method of chemotherapeutic system of MRI-guided targeted photo-thermal agent | |
| CN107936965A (en) | A kind of preparation method with carbon quantum dot with high fluorescence quantum yield and its application in cell imaging | |
| CN108440986A (en) | The fluorescent dye and its preparation method and application of near-infrared the second window excitation/emission | |
| CN109400572A (en) | The fluorescent dye and its preparation method and application of the second window of near-infrared transmitting | |
| CN105440277B (en) | Amphiphilic aggregation-induced emission molecule and its synthetic method and autofluorescence nano-micelle and application | |
| CN111662711A (en) | Preparation method and application of red fluorescent carbonized polymer dots | |
| CN112852418A (en) | Double-emission-ratio fluorescent carbon dot and preparation method and application thereof | |
| CN109504363B (en) | Preparation method and application of near-infrared two-region imaging contrast agent | |
| CN110591695B (en) | Fluorescent carbon dot nucleic acid probe based on FRET mechanism and preparation method thereof | |
| CN114455567A (en) | Preparation method and application of carbon nanoparticles | |
| CN114958357B (en) | Visible and near infrared light region double-emission fluorescent carbon dot and preparation method thereof | |
| CN105288625B (en) | A kind of porous Bi2Se3Nanosponges material, its preparation method and application | |
| CN111333819B (en) | Compound and application thereof | |
| CN110564412B (en) | Preparation method of orange fluorescent emission PEI-CDs | |
| CN107758643B (en) | Graphene quantum dot, and preparation method and application thereof | |
| CN110339356B (en) | Carbon nanodot reagent, preparation method and application thereof | |
| CN115818621A (en) | Biomass-derived carbon nanoparticles with near-infrared two-zone light emission characteristic and preparation method and application thereof | |
| CN108034283B (en) | Pegylated benzindole heptamethine cyanine dye and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |