CN117143597A - Aggregation-induced emission carbon dot, preparation method and application thereof - Google Patents
Aggregation-induced emission carbon dot, preparation method and application thereof Download PDFInfo
- Publication number
- CN117143597A CN117143597A CN202311115221.9A CN202311115221A CN117143597A CN 117143597 A CN117143597 A CN 117143597A CN 202311115221 A CN202311115221 A CN 202311115221A CN 117143597 A CN117143597 A CN 117143597A
- Authority
- CN
- China
- Prior art keywords
- aggregation
- induced emission
- carbon dots
- emission carbon
- ultrasonic treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004220 aggregation Methods 0.000 title claims abstract description 34
- 230000002776 aggregation Effects 0.000 title claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 45
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 21
- 238000003384 imaging method Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000012265 solid product Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229960000583 acetic acid Drugs 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 241000252212 Danio rerio Species 0.000 abstract description 21
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 9
- 229910052691 Erbium Inorganic materials 0.000 abstract description 3
- 210000002249 digestive system Anatomy 0.000 abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 abstract description 2
- 210000000695 crystalline len Anatomy 0.000 abstract description 2
- 235000013601 eggs Nutrition 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 210000001161 mammalian embryo Anatomy 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 210000002257 embryonic structure Anatomy 0.000 description 7
- 230000005284 excitation Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- FWBHETKCLVMNFS-UHFFFAOYSA-N 4',6-Diamino-2-phenylindol Chemical compound C1=CC(C(=N)N)=CC=C1C1=CC2=CC=C(C(N)=N)C=C2N1 FWBHETKCLVMNFS-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 241000251468 Actinopterygii Species 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000012984 biological imaging Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000001218 confocal laser scanning microscopy Methods 0.000 description 3
- 210000003712 lysosome Anatomy 0.000 description 3
- 230000001868 lysosomic effect Effects 0.000 description 3
- 210000001325 yolk sac Anatomy 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001255 X-ray photoelectron diffraction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000001418 larval effect Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 238000000116 DAPI staining Methods 0.000 description 1
- 241000283070 Equus zebra Species 0.000 description 1
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 241000251539 Vertebrata <Metazoa> Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 210000001136 chorion Anatomy 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002073 fluorescence micrograph Methods 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011503 in vivo imaging Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000012758 nuclear staining Methods 0.000 description 1
- 210000003463 organelle Anatomy 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000037384 skin absorption Effects 0.000 description 1
- 231100000274 skin absorption Toxicity 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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
- A61K49/0063—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres
- A61K49/0065—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres the luminescent/fluorescent agent having itself a special physical form, e.g. gold nanoparticle
- A61K49/0067—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres the luminescent/fluorescent agent having itself a special physical form, e.g. gold nanoparticle quantum dots, fluorescent nanocrystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/645—Specially adapted constructive features of fluorimeters
- G01N21/6456—Spatial resolved fluorescence measurements; Imaging
- G01N21/6458—Fluorescence microscopy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Biochemistry (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Biophysics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Biomedical Technology (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses an aggregation-induced emission carbon dot, a preparation method and application thereof, wherein the method comprises the following steps: 1) TPE, er (NO) 3 ) 3 And Yb (NO) 3 ) 3 Dissolving in glacial acetic acid, and performing ultrasonic treatment to obtain a mixture; 2) Transferring the mixture into a reaction kettle for hydrothermal reaction; 3) Cooling to room temperature after the reaction is finished, and adding deionized water to form suspension; 4) Carrying out ultrasonic treatment on the suspension, centrifuging, and collecting a solid product; repeating the ultrasonic and centrifugal stepsAnd (5) drying the obtained solid product in vacuum to obtain the aggregation-induced emission carbon dots. The invention provides a method for synthesizing AIE carbon dots doped with rare earth elements Yb and Er, which has aggregation-induced emission characteristics, can be well applied to cell imaging, proves the biological safety of the AIE carbon dots in long-term imaging of zebra fish and zebra fish eggs, and has the characteristic of selective imaging of the crystalline lens and digestive system of the zebra fish.
Description
Technical Field
The invention relates to the field of nano materials, in particular to an aggregation-induced emission carbon dot, a preparation method and application thereof.
Background
Photoluminescent materials have gained increasing attention in recent years due to their wide application in the fields of chemical probes, sensors, information storage, and bioimaging. However, such materials widely exhibit an aggregation fluorescence quenching (ACQ) effect, i.e., the fluorescence thereof is significantly reduced or even lost in the aggregated state or solid state, which places a great limitation on the development and use of photoluminescence. In contrast to the ACQ material phenomenon, tang Benzhong was equal to the aggregation-induced emission (AIE) effect demonstrated in 2001, and bright fluorescence could be observed in the aggregated state. The discovery breaks the constraint of the traditional concept and opens up a new way for the design and functional development of luminescent materials.
The molecular structure of a luminescent material with AIE effect at low concentrations contains several free-rotating aromatic groups. Thus, in a high concentration or solid state, non-radiative decay is blocked due to intramolecular spin (RIR) limitations caused by intermolecular pi-pi stacking. Thus, as AIE phosphors are more aggregated, they exhibit stronger fluorescence intensity, overcoming all ACQ effects.
Successful implementation of biological imaging requires fluorescent probes with good photostability, high definition, good dispersibility in water, and biocompatibility. Carbon Dots (CDs) are important members of the carbon material family because of their unique optical properties and simple synthetic methods. The carbon dots have no toxicity problem caused by leakage of heavy metal ions of the inorganic quantum dots, and have better biocompatibility. There is still the ACQ problem described above, which can result in a loss of sufficient sensitivity in biological imaging to monitor minor changes. However, the AIE carbon dots emit bright fluorescence even in the aggregate state, in addition to the common advantage of having ordinary carbon dots. Thus, AIE carbon dots are a good substitute for bioimaging fluorescent markers.
Among many luminescent materials, rare Earth (RE) complexes generally have higher emission efficiency in the aggregated state and in the solid state, which luminescent properties are very similar to AIE luminophores. Except that rare earth luminescence is a sensitization process in which energy is transferred from the excited triplet state of the ligand to the excited state of the rare earth ion (T1-RE). On the other hand, rare earth ions have unique luminescence characteristics, high-intensity emission signals, long fluorescence lifetime, high quantum efficiency and the like. However, rare earth doped AIE carbon dots have been recently reported, and the combination of rare earth elements and AIE carbon dots is hopeful to bring new prospects for biological imaging applications. But now no reliable solution is disclosed.
Disclosure of Invention
The invention aims to solve the technical problem of providing an aggregation-induced emission carbon dot, a preparation method and application thereof aiming at the defects in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of aggregation-induced emission carbon dots comprises the following steps:
1) TPE, er (NO) 3 ) 3 And Yb (NO) 3 ) 3 Dissolving in glacial acetic acid, and performing ultrasonic treatment to obtain a mixture;
2) Transferring the mixture obtained in the step 1) into a reaction kettle, and carrying out hydrothermal reaction under heating;
3) Cooling to room temperature after the reaction is finished, and adding deionized water into the obtained product to form suspension;
4) Carrying out ultrasonic treatment on the suspension, centrifuging, and collecting a solid product; repeating the steps of ultrasonic treatment and centrifugation, and vacuum drying the obtained solid product to obtain the aggregation-induced emission carbon dots.
Preferably, the step 1) specifically comprises: 166-664mg TPE, 11.6-42.6mg Er (NO) 3 ) 3 And 65-260mg Yb (NO) 3 ) 3 Dissolving in 20-40mL glacial acetic acid, and performing ultrasonic treatment for 15-60 min to obtain a mixture.
Preferably, the step 1) specifically comprises: 332mg TPE, 21.3mg Er (NO 3 ) 3 And 129.2mg Yb (NO) 3 ) 3 Dissolved in 40mL glacial acetic acid and sonicated for 30 minutes to give a mixture.
Preferably, the step 2) specifically comprises: transferring the mixture obtained in the step 1) into a reaction kettle, and reacting for 8-24 hours at 170-200 ℃.
Preferably, the step 2) specifically comprises: the mixture obtained in step 1) was transferred to an 80mL autoclave lined with polytetrafluoroethylene and reacted at 180℃for 16 hours.
Preferably, the step 3) specifically comprises: after the completion of the reaction, the reaction mixture was cooled to room temperature, and 200mL of deionized water was added to the obtained product to form a suspension.
Preferably, the step 4) specifically comprises: carrying out ultrasonic treatment on the suspension for 2-10 minutes, centrifuging at a speed of 5000-20000 rpm for 5-20 minutes, and collecting a solid product; repeating the ultrasonic treatment and the centrifugation step for 2-5 times, and vacuum drying the obtained solid product at 50-70 ℃ to obtain the aggregation-induced emission carbon dots.
Preferably, the step 4) specifically comprises: after the suspension is subjected to ultrasonic treatment for 5 minutes, centrifuging at a speed of 10000 revolutions per minute for 10 minutes, and collecting a solid product; repeating the steps of ultrasonic treatment and centrifugation for three times, and vacuum drying the obtained solid product at 60 ℃ to obtain the aggregation-induced emission carbon dots.
The invention also provides an aggregation-induced emission carbon dot, which is prepared by the method.
The invention also provides an application of the aggregation-induced emission carbon dots prepared by the method in cell imaging.
The beneficial effects of the invention are as follows:
the invention provides a method for synthesizing AIE carbon dots doped with rare earth elements Yb and Er, which has aggregation-induced emission characteristics, can overcome the problem of aggregation fluorescence quenching (ACQ) effect of the traditional carbon dot material, has high emission signal intensity, long fluorescence lifetime and high quantum efficiency, can be well applied to cell imaging, proves the biological safety of zebra fish and zebra fish eggs in long-term imaging, and has the characteristic of selective imaging of the crystalline lens and digestive system of the zebra fish.
Drawings
FIG. 1 is a graph showing the effect of dispersing carbon dots prepared in example 1 in a solvent;
FIG. 2 is a transmission electron micrograph of the carbon dots prepared in example 1;
FIG. 3 is an X-ray diffraction spectrum (a), a Raman spectrum (b) and a Fourier infrared spectrum (c) of the carbon spot prepared in example 1;
FIG. 4 is an X-ray photoelectron diffraction (XPS) spectrum of a carbon spot prepared in example 1;
FIG. 5 is a fluorescence spectrum of the carbon dots prepared in example 1 at different excitation wavelengths;
FIG. 6 is an image of the carbon dots prepared in example 1 versus the nucleus;
FIG. 7 is a graph showing the results of imaging zebra fish embryos (Embruso) and young fish (Larval zebranfish) with carbon dots prepared in example 1.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The test methods used in the following examples are conventional methods unless otherwise specified. The material reagents and the like used in the following examples are commercially available unless otherwise specified. The following examples were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
An aggregation-induced emission carbon dot, the preparation method thereof comprising the steps of:
1) 332mg TPE, 21.3mg Er (NO 3 ) 3 And 129.2mg Yb (NO) 3 ) 3 Dissolving in 40mL glacial acetic acid, and performing ultrasonic treatment for 30 minutes to obtain a mixture;
2) Transferring the mixture obtained in the step 1) into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 80mL, and reacting for 16 hours at 180 ℃;
3) Cooling to room temperature after the reaction is finished, and adding 200mL of deionized water into the obtained product to form suspension;
4) After the suspension is subjected to ultrasonic treatment for 5 minutes, centrifuging at a speed of 10000 revolutions per minute for 10 minutes, and collecting a solid product; the steps of ultrasonic treatment and centrifugation are repeated three times, and the obtained solid product is dried in vacuum at 60 ℃ to obtain yellow aggregation-induced emission carbon dots AIE-CDs (hereinafter referred to as carbon dots).
Since the carbon dot powder is poor in dispersibility in water, it is difficult to conduct experiments. To solve this problem, carbon dot powder was dissolved in DMSO to a concentration of 1mg/mL, again at a volume ratio of 1:1, after deionized water is added, the solution still becomes turbid liquid, but precipitated solid powder is uniformly dispersed in the deionized water, and the fluorescence still is bright yellow; reference is made to fig. 1.
Performance testing
Referring to fig. 2, which is a transmission electron micrograph of carbon dots prepared in example 1, wherein a is a TEM photograph of carbon dots obtained by using acetic acid as a solvent, it can be seen that the carbon dots are uniformly distributed in a spherical shape, and the diameter of individual particles is about 5 nm; panel b shows TEM images of carbon dots obtained with DMSO as solvent, and it can be seen that the carbon dots are spherical and have a particle size of about 5nm, similar to that in acetic acid. And c and d correspond to the high resolution transmission electron microscope (HR-TEM) images of a and b respectively, and it can be seen that when the solvent is acetic acid and DMSO respectively, the fine lattice spacing of the carbon dots is 0.208nm, and no obvious difference exists.
Referring to fig. 3, an X-ray diffraction spectrum (a), a raman spectrum (b) and a fourier infrared spectrum (c) of the carbon spot prepared in example 1; the X-ray diffraction (XRD) analysis result shows that a significant peak at about 20 degrees corresponds to the interplanar spacing shown in HR-TEM, and the structural Raman spectrum of the graphene-like material in AIE-CDs shows two peaks at 1340 and 1590cm respectively -1 They represent the D peak and the G peak, respectively, describing the lattice defect of carbon atoms and the sp of carbon atoms 2 Hybrid in-plane stretching vibration; by calculation to obtain I D /I G 0.821, indicating sp in AIE-CDs 2 The content of carbon atoms of the graphite being relatively higher than the disordered sp 3 Carbon sourceContent of seeds. Fourier transform infrared spectroscopy (FT-IR) confirmed the presence of functional groups or chemical bonds, including hydroxyl groups (3440 cm) -1 ) Amino (3100 cm) -1 ) Aminocarbonyl (1682 cm) -1 )、C-N(1589cm -1 ) And c=c (1462 cm -1 ) Etc., it was confirmed that the AIE-CDs prepared contained nitrogen-containing functional groups.
Referring to FIG. 4, the X-ray photoelectron diffraction (XPS) spectrum of the carbon spot prepared in example 1, the peaks at 533.08, 284.8, 406.11, 200.1 and 164.35eV belonging to O1s, C1 s, N1 s, yb 4d and Er 4d, respectively; the contents of elements C, O, N, yb and Er in AIE-CDs were 95.65%, 3.82%, 0.39%, 0.1% and 0.04%, respectively.
Referring to FIG. 5, in order to obtain fluorescence spectra of carbon dots prepared in example 1 at different excitation wavelengths, AIE-CDs showed almost no signal when in a solution dispersion state, and yellow fluorescence when in a powder aggregation state. The fluorescence signal is gradually enhanced as the excitation wavelength increases when the excitation wavelength is between 300-440nm, and the AIE-CDs aggregate state images the best emission at 525 when the excitation wavelength is 440 nm; when the excitation wavelength increases again, the fluorescence index drops greatly.
Referring to FIG. 6, to study the distribution of AIE-CDs in Hela cells, cells were stained with the organelle commercial dye DAPI (a fluorescent dye that binds strongly to DNA, specifically for nuclear staining) and the commercial lysosome-specific dye Lyso-Tracker Green together with AIE-CDs for the purpose of imaging the nuclei of the carbon dots prepared in example 1. As shown in fig. 6, a, b, c are sequentially the stained fluorescence images of AIE-CDs, DAPI and Lyso-Tracker Green, with DAPI staining the Hela nuclei blue, lyso-Tracker Green staining the lysosomes Green, and AIE-CDs distributed on the nuclei as well, which stain the nuclei yellow. And d, the image obtained by superposing AIE-CDs, DAPI and Lyso-Tracker Green fluorescent images has better and obvious observation effect.
Cell imaging method: heLa cells were incubated in 2mL of medium containing 10. Mu.g/mL AIE-CDs solution for 30 min, then washed 3 times with PBS, then further incubated with commercial lysosome specific probes (Lyso-Tracker Green,100 nM) for 30 min, counterstained with 4% paraformaldehyde solution for 15 min, nuclei stained with DAPI, and cell fluorescence observed under Confocal Laser Scanning Microscopy (CLSM) fields.
Referring to fig. 7, the results of imaging zebra fish embryos (Embruso) and young fish (Larval zebranfish) with carbon dots prepared in example 1 are shown.
To verify the applicability of AIE-CDs for in vivo imaging, zebra fish embryos and young fish were used as vertebrate models because their embryos developed rapidly and the embryos also had imaging optical transparency.
The zebra fish embryo imaging method comprises the following steps: 5 zebra fish or 5 zebra fish embryos are pipetted into a 6-well cell culture plate, 2mL embryo culture medium containing 10. Mu.g/mL AIE-CDs solution is added and incubated at 28℃for 30 minutes in the absence of light. After the incubation, the zebra fish or zebra fish embryos were rinsed 3 times with PBS and then transferred in. Heating the fixing liquid in a metal bath pot at 85 ℃ until the fixing liquid is dissolved, slightly cooling (the cooling time is about 20 seconds, otherwise, the temperature is increased, embryo shrinkage is caused, the viscosity is too high when the temperature is low, and the adjustment of embryo body position is not facilitated), taking 500 mu L of the fixing liquid into a confocal culture dish, transferring the zebra fish or the zebra fish embryo into the confocal culture dish, adjusting the zebra fish to a proper position under a split microscope by using a blunt needle, and observing the fluorescence condition of the zebra fish or the zebra embryo under the view of a Confocal Laser Scanning Microscope (CLSM) after the fixing liquid is solidified.
Referring to the imaging results of FIG. 7, it can be seen in panel c that fluorescence occurs inside the embryo and the yolk sac portion is not fluorescent. AIE-CDs can enter the embryo through the chorion, and the difference in fluorescence intensity between the yolk sac and the inner region of the embryo suggests that AIE-CDs have different degrees of affinity for different tissues of the embryo. In the f graph, the accumulation of AIE-CDs in the digestive system and yolk sac of the young zebra fish is obvious, which indicates that the AIE-CDs enter the young zebra fish through ingestion and skin absorption and have tissue affinity to the young zebra fish.
Example 2
This example provides the use of aggregation-induced emission carbon dots prepared in example 1 in cell imaging.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (10)
1. The preparation method of the aggregation-induced emission carbon dot is characterized by comprising the following steps of:
1) TPE, er (NO) 3 ) 3 And Yb (NO) 3 ) 3 Dissolving in glacial acetic acid, and performing ultrasonic treatment to obtain a mixture;
2) Transferring the mixture obtained in the step 1) into a reaction kettle, and carrying out hydrothermal reaction under heating;
3) Cooling to room temperature after the reaction is finished, and adding deionized water into the obtained product to form suspension;
4) Carrying out ultrasonic treatment on the suspension, centrifuging, and collecting a solid product; repeating the steps of ultrasonic treatment and centrifugation, and vacuum drying the obtained solid product to obtain the aggregation-induced emission carbon dots.
2. The method for preparing aggregation-induced emission carbon dots according to claim 1, wherein step 1) specifically comprises: 166-664mg TPE, 11.6-42.6mg Er (NO) 3 ) 3 And 65-260mg Yb (NO) 3 ) 3 Dissolving in 20-40mL glacial acetic acid, and performing ultrasonic treatment for 15-60 min to obtain a mixture.
3. The method for preparing aggregation-induced emission carbon dots according to claim 2, wherein step 1) specifically comprises: 332mg TPE, 21.3mg Er (NO 3 ) 3 And 129.2mg Yb (NO) 3 ) 3 Dissolved in 40mL glacial acetic acid and sonicated for 30 minutes to give a mixture.
4. The method for preparing aggregation-induced emission carbon dots according to claim 1, wherein step 2) specifically comprises: transferring the mixture obtained in the step 1) into a reaction kettle, and reacting for 8-24 hours at 170-200 ℃.
5. The method for preparing aggregation-induced emission carbon dots according to claim 4, wherein step 2) specifically comprises: the mixture obtained in step 1) was transferred to an 80mL autoclave lined with polytetrafluoroethylene and reacted at 180℃for 16 hours.
6. The method for preparing aggregation-induced emission carbon dots according to claim 1, wherein step 3) specifically comprises: after the completion of the reaction, the reaction mixture was cooled to room temperature, and 200mL of deionized water was added to the obtained product to form a suspension.
7. The method for preparing aggregation-induced emission carbon dots according to claim 1, wherein step 4) specifically comprises: carrying out ultrasonic treatment on the suspension for 2-10 minutes, centrifuging at a speed of 5000-20000 rpm for 5-20 minutes, and collecting a solid product; repeating the ultrasonic treatment and the centrifugation step for 2-5 times, and vacuum drying the obtained solid product at 50-70 ℃ to obtain the aggregation-induced emission carbon dots.
8. The method for preparing aggregation-induced emission carbon dots according to claim 7, wherein step 4) specifically comprises: after the suspension is subjected to ultrasonic treatment for 5 minutes, centrifuging at a speed of 10000 revolutions per minute for 10 minutes, and collecting a solid product; repeating the steps of ultrasonic treatment and centrifugation for three times, and vacuum drying the obtained solid product at 60 ℃ to obtain the aggregation-induced emission carbon dots.
9. Aggregation-induced emission carbon dot, characterized in that it is produced by the method according to any one of claims 1 to 8.
10. Use of aggregation-induced emission carbon dots prepared according to the method of any one of claims 1 to 8 in cell imaging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311115221.9A CN117143597A (en) | 2023-08-31 | 2023-08-31 | Aggregation-induced emission carbon dot, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311115221.9A CN117143597A (en) | 2023-08-31 | 2023-08-31 | Aggregation-induced emission carbon dot, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117143597A true CN117143597A (en) | 2023-12-01 |
Family
ID=88905607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311115221.9A Pending CN117143597A (en) | 2023-08-31 | 2023-08-31 | Aggregation-induced emission carbon dot, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117143597A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105349139A (en) * | 2015-12-11 | 2016-02-24 | 哈尔滨工业大学 | Carboxyl-containing carbon quantum dot solution emitting green fluorescence and preparation method thereof |
| CN113402398A (en) * | 2021-06-18 | 2021-09-17 | 湖北大学 | Carbon dot precursor based on aggregation-induced emission effect, carbon dot, and preparation method and application thereof |
-
2023
- 2023-08-31 CN CN202311115221.9A patent/CN117143597A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105349139A (en) * | 2015-12-11 | 2016-02-24 | 哈尔滨工业大学 | Carboxyl-containing carbon quantum dot solution emitting green fluorescence and preparation method thereof |
| CN113402398A (en) * | 2021-06-18 | 2021-09-17 | 湖北大学 | Carbon dot precursor based on aggregation-induced emission effect, carbon dot, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Integration of IR‐808 sensitized upconversion nanostructure and MoS2 nanosheet for 808 nm NIR light triggered phototherapy and bioimaging | |
| CN108192602B (en) | Metal-free polymer carbon dot with room-temperature phosphorescence property, and preparation method and application thereof | |
| Sheng et al. | Graphene oxide based fluorescent nanocomposites for cellular imaging | |
| Hui et al. | Fluoridated HAp: Ln 3+(Ln= Eu or Tb) nanoparticles for cell-imaging | |
| Feng et al. | Design of multi-functional AIEgens: tunable emission, circularly polarized luminescence and self-assembly by dark through-bond energy transfer | |
| Ge et al. | New nanoplatforms based on UCNPs linking with polyhedral oligomeric silsesquioxane (POSS) for multimodal bioimaging | |
| Bogdan et al. | Carbohydrate-coated lanthanide-doped upconverting nanoparticles for lectin recognition | |
| US20120178099A1 (en) | Highly fluorescent carbon nanoparticles and methods of preparing the same | |
| Chen et al. | Mesoporous silica as nanoreactors to prepare Gd‐encapsulated carbon dots of controllable sizes and magnetic properties | |
| Li et al. | Multifunctional carbon dots for highly luminescent orange-emissive cellulose based composite phosphor construction and plant tissue imaging | |
| Meng et al. | One-pot synthesis of highly cross-linked fluorescent polyphosphazene nanoparticles for cell imaging | |
| He et al. | Optimization of upconversion luminescence of Nd 3+-sensitized BaGdF 5-based nanostructures and their application in dual-modality imaging and drug delivery | |
| EP3063091B1 (en) | Biocompatible graphene quantum dots for drug delivery and bioimaging applications | |
| Kačenka et al. | Dual imaging probes for magnetic resonance imaging and fluorescence microscopy based on perovskite manganite nanoparticles | |
| CN109456762B (en) | Multi-red light emission tuning panchromatic carbon dot and preparation method and application thereof | |
| CN113881429A (en) | Red fluorescent carbon dot for nucleolus imaging and preparation method and application thereof | |
| CN110367209B (en) | Preparation method of fluorescent mulberry silk under near-infrared illumination and product | |
| Zhao et al. | A novel strategy for the aqueous synthesis of down-/up-conversion nanocomposites for dual-modal cell imaging and drug delivery | |
| CN110713829A (en) | Preparation of orange carbon dots and p-Fe thereof3+Detection of (2) | |
| US20090226724A1 (en) | Multifunctional nanostructure and method | |
| CN117143597A (en) | Aggregation-induced emission carbon dot, preparation method and application thereof | |
| Chu et al. | Fluorescent silkworm silk prepared via incorporation of green, yellow, red, and near-infrared fluorescent quantum dots | |
| Fernandes et al. | Non-traditional intrinsic luminescence from non-conjugated polymer dots: designing a hybrid biomaterial | |
| Zhu et al. | Optical encoding of microbeads based on silica particle encapsulated quantum dots and its applications | |
| Yan et al. | Multifunctional polymer nanoparticles: ultra bright near-infrared fluorescence and strong magnetization and their biological applications |
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 |