CN115557489B - Preparation method of near infrared light thermal fluorescent probe based on carbon quantum dots - Google Patents
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 18
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000502 dialysis Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- 238000002189 fluorescence spectrum Methods 0.000 description 12
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000007626 photothermal therapy Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- MOFVSTNWEDAEEK-UHFFFAOYSA-M indocyanine green Chemical compound [Na+].[O-]S(=O)(=O)CCCCN1C2=CC=C3C=CC=CC3=C2C(C)(C)C1=CC=CC=CC=CC1=[N+](CCCCS([O-])(=O)=O)C2=CC=C(C=CC=C3)C3=C2C1(C)C MOFVSTNWEDAEEK-UHFFFAOYSA-M 0.000 description 3
- 229960004657 indocyanine green Drugs 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011503 in vivo imaging Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
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- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011275 oncology therapy Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 239000012221 photothermal agent Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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Abstract
The invention discloses a preparation method of a near infrared light thermal fluorescent probe based on carbon quantum dots. According to the method, 1, 5-naphthalene diamine and p-phenylenediamine are used as raw materials, citric acid is added in the reaction process, and the NIR carbon point with fluorescence emission in a near infrared region and photo-thermal effect is prepared through hydrothermal reaction. The preparation method is simple and convenient, the synthesis cost is low, the emission peak of the prepared NIR carbon point is 800nm and far higher than that of the existing near infrared CDs, and the preparation method has higher ultraviolet absorption in the infrared region, has good photo-thermal effect and photo-thermal stability, and can be used as photo-thermal nano materials to be applied to the field of photo-thermal treatment.
Description
Technical Field
The invention belongs to the field of nano material preparation, and relates to a preparation method of a near infrared light thermal fluorescent probe based on carbon quantum dots.
Background
Carbon Dots (CDs) are a type of nanoparticle found in 2004, and are also called carbon quantum dots, graphene quantum dots, and carbon nanodots. Typically, CDs have diameters of about 2-8nm. However, there are some reports that CDs can reach a particle size of about 20 nm. CDs have the advantages of unique fluorescence characteristics, adjustable emission wavelength, biocompatibility, low environmental influence, photobleaching resistance and the like, and have potential application prospects in the fields of biological imaging, biological sensing, photodynamic therapy (PDT), photothermal therapy (PTT) and the like. However, the shorter wavelength of the emitted light limits the application of blue and green fluorescent carbon dots in vivo imaging. Therefore, near infrared-emitting CDs are receiving attention because of their small harm to living beings and their ability to prevent interference of autofluorescence. The synthesis of near infrared emission CDs is generally carried out by using o-phenylenediamine (LIP, XUE S, SUN L, et al formation and fluorescent mechanism of red emissive carbon dots from o-phenylenediamine and catechol system [ J ]. Light: science & Applications,2022,11 (1): 298), or by synthesizing citric acid and urea as precursors (TIANZ, ZHANG X, LID, et al full-Color Inorganic Carbon Dot Phosphors for White-Light-emission Diodes [ J ]. Advanced Optical Materials,2017,5 (19): 1700416), and in addition, covalent modification of commercial dyes on the CDs surface (HUANG X, ZHANG F, ZHU L, et al effect of Injection Routes on the Biodistribution, clearence, and Tumor Uptake of Carbon Dots [ J ]. ACS Nano,2013,7 (7): 5684-93). However, the CDs produced by these methods have emission peaks below 700nm, or CDs produced by surface modification have poor anti-light quenching effect, which limits further development.
Photothermal therapy has become one of the most potential methods in cancer therapy at present, so the development of nanomaterials with photothermal effect is of great significance. The most studied organic dyes are currently used as photothermal agents, such as indocyanine green (ICG), which however rapidly changes with the irradiation of light, resulting in a rapid decrease in photothermal effects. Accordingly, scientists are working on modifying ICG to obtain better stability. Therefore, development of a material having a good photothermal effect and good photothermal stability is essential for development of photothermal therapy.
Disclosure of Invention
The invention aims to provide a preparation method of a near infrared photo-thermal fluorescent probe based on carbon quantum dots.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the near infrared light thermal fluorescent probe based on the carbon quantum dots comprises the following steps:
step 1, the mass ratio of 1, 5-naphthalene diamine to p-phenylenediamine is 0.8-1.2: 1, ultrasonically dissolving 1, 5-naphthalene diamine and p-phenylenediamine in N, N-dimethylformamide to form a precursor solution, placing the precursor solution in a reaction kettle, performing hydrothermal reaction for 10-12 h at 180-200 ℃, and cooling to room temperature;
step 2, adding aqueous solution of citric acid into the solution after the reaction in the step 1, and continuously carrying out hydrothermal reaction for 1-2 h at 180-200 ℃ to obtain near infrared luminous carbon dot solution;
and 3, placing the near infrared luminous carbon dot solution into a dialysate for dialysis, changing the dialysate every 4 hours, continuously dialyzing for 24 hours to remove solvents and impurities, and then freeze-drying to obtain the near infrared luminous carbon dot, wherein the dialysate comprises the following components in percentage by volume: 1 and water.
Preferably, in the step 1, the mass ratio of the 1, 5-naphthalene diamine to the p-phenylenediamine is 1:1.
preferably, in step 2, the concentration of citric acid in the aqueous solution of citric acid is 10mg/mL.
Preferably, in step 3, the dialysis bag has a molecular weight of 1000Da.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, 1, 5-naphthalene diamine and p-phenylenediamine are used as raw materials, citric acid is added in the reaction process, and the NIR carbon point with fluorescence emission in a near infrared region and photo-thermal effect is prepared through hydrothermal reaction.
(2) The NIR carbon point prepared by the invention has larger sp 2 The conjugated region, therefore the fluorescence emission region red shifted to near infrared region, and its emission peak was at 800nm, far higher than the existing near infrared CDs. Meanwhile, the NIR carbon point prepared by the method has high ultraviolet absorption in an infrared region, has good photo-thermal effect, and further tests show that the NIR carbon point has good photo-thermal stability, and has stable temperature rise and no attenuation in four laser irradiation cycles.
Drawings
FIG. 1 is a transmission electron microscope image of NIR carbon dots synthesized in example 1.
FIG. 2 is an ultraviolet absorption spectrum of NIR carbon dots synthesized in example 1.
FIG. 3 is a fluorescence spectrum of NIR carbon dots synthesized in example 1.
FIG. 4 is an infrared spectrum of NIR carbon points synthesized in example 1.
Figure 5 is an X-ray photoelectron spectrum of the NIR carbon point synthesized in example 1.
FIG. 6 is a graph of photo-thermal effect measurements of NIR carbon dots synthesized in example 1 at different concentrations.
Fig. 7 is a graph of temperature change of NIR carbon point synthesized in example 1 versus irradiation with different power 808 lasers.
FIG. 8 is the photo-thermal stability of NIR carbon dots synthesized in example 1.
FIG. 9 is a fluorescence spectrum of CDs synthesized in comparative example 1 without 1, 5-naphthalene diamine.
FIG. 10 is a fluorescence spectrum of CDs synthesized without the addition of p-phenylenediamine in comparative example 2.
FIG. 11 is a graph showing the comparison of fluorescence spectra of CDs synthesized without adding citric acid in example 1 and comparative example 3.
FIG. 12 is a fluorescence spectrum of CDs synthesized in comparative example 4 using o-phenylenediamine instead of p-phenylenediamine.
FIG. 13 is a fluorescence spectrum of CDs synthesized in comparative example 5 using meta-phenylenediamine instead of para-phenylenediamine.
Detailed Description
The invention will be described in further detail with reference to specific embodiments and drawings.
Example 1
100mg of 1, 5-naphthalenediamine and 100mg of p-phenylenediamine were dissolved in 20mL of N, N-dimethylformamide. The precursor was dissolved in the solvent to clarify by sonication for 10 minutes. Subsequently, the mixed solution was transferred to a 50ml polystyrene liner and a stainless steel autoclave. Then the electrothermal blowing dry box is set to 180 ℃ and kept for 6 hours. When the autoclave was cooled to room temperature, 5mL of an aqueous solution containing 50mg of citric acid was added, and the reaction was continued at 180℃for 1 hour. When the reaction was completed, a dark brown liquid was obtained and the NIR carbon spot was purified by dialysis. The ratio of ethanol to water was 1 using a dialysis bag with a molecular weight of 1000 daltons as follows: 1, the dialyzate is changed every 4 hours, and the dialyzate is continuously dialyzed for 24 hours to remove the solvent and the impurities. The NIR carbon point was then dried using a freeze dryer and stored in the dark at 4 ℃ for characterization and use.
Comparative example 1
This comparative example is essentially the same as example 1, except that no 1, 5-naphthalene diamine is added.
Comparative example 2
This comparative example is essentially the same as example 1, except that no para-phenylenediamine is added.
Comparative example 3
This comparative example is essentially the same as example 1, except that no citric acid is added.
Comparative example 4
This comparative example is essentially the same as example 1, except that o-phenylenediamine is used instead of p-phenylenediamine.
Comparative example 5
This comparative example is essentially the same as example 1, except that m-phenylenediamine is used in place of p-phenylenediamine.
Fig. 1 is a Transmission Electron Microscope (TEM) photograph and a High Resolution Transmission Electron Microscope (HRTEM) photograph of the prepared NIR carbon point, and it can be seen from fig. 1 that the NIR carbon point is spherical and has excellent dispersibility in ethanol. As can be seen from FIG. 2, the NIR carbon dots are relatively uniform in particle size, about 7-8nm in size.
Fig. 2 is a graph of the ultraviolet-visible absorption spectrum of the NIR carbon point, from which it can be seen that the NIR carbon point has a distinct absorption band at 316nm and a broad absorption peak caused by n-pi transitions at 400-600 nm. FIG. 3 is a fluorescence spectrum of NIR carbon dots, and it can be seen from the figure that the fluorescence emission peaks of NIR carbon dots are located at 610nm and at 790nm, and the emission peak at 790nm corresponds to an optimal excitation wavelength of 680nm. The NIR carbon dots are proved to have stronger near infrared fluorescence emission, so that interference caused by biological background fluorescence can be well avoided.
FIG. 4 is an infrared spectrum of NIR carbon dots, and analysis of transmission peak intensity shows that the surface of the NIR carbon dots is rich in amino groups, carbonyl groups and the like. Located at 3344, 3224, 2920 and 2850cm -1 The left and right characteristic absorption bands are due to the stretching vibration of the N-H and C-H groups. At 1618cm -1 The absorption peak of (2) is due to c=o bond stretching vibration. At 1608cm -1 And 1514cm -1 The peaks of (C) are due to the stretching vibration of c=n and c=c, respectively. At 1288cm -1 Is considered to belong to the stretching vibration of the c—o bond. The result of Fourier transform infrared spectrum confirms that amino groups, carbonyl groups and the like exist on the surface of the NIR carbon point, and confirms the synthesis of the NIR carbon point.
Fig. 5 is an X-ray photoelectron spectrum of an NIR carbon point, which is known to consist essentially of three elements, carbon, oxygen, and nitrogen, in proportions of 69.82%, 14.19%, and 11.19%, respectively.
Fig. 6 is a graph of photo-thermal effect measurements at different concentrations of NIR carbon point. By 808 laser (1.2W/cm) 2 ) Different concentrations of NIR carbon point were irradiated and tested for temperature change over ten minutes. As shown, NIR carbon spots (0.1,0.2,0.5,0.8 and 1.0 mg/mL) at different concentrations at a power of 1.2W/cm 2 Under 808 laser irradiation, the temperature was raised to 7.2, 11.3, 19.5, 26.2 and 32.0 ℃ in ten minutes, respectively. In contrast, 1.2W/cm was used 2 The 808 laser of (c) irradiated the deionized water solution, and the ten minutes temperature was raised by only 0.9 ℃. Indicating that the NIR carbon point has good photo-thermal effect.
FIG. 7 is a graph showing the change in temperature of NIR carbon spot under irradiation with lasers of different powers 808, as shown, at laser powers of 0.5,0.8,1.0 and 1.2W/cm, respectively 2 Under ten minutes of irradiation, the NIR carbon spot solutions (1.0 mg/mL) were warmed to 16.0, 21.1, 28.3 and 34.5℃respectively. Indicating that the concentration of the solution at the NIR carbon point is 1.0mg/mL and the laser power is 1.2W/cm 2 When the power is applied, the photo-thermal effect of NIR carbon dots is good, and under the power, the deionized water solution only rises to 0.9 ℃ without seriously damaging cells, so that the power has potential value in the treatment of cancers.
FIG. 8 is a photo-thermal stability test of NIR carbon dots, as shown, at a power of 1.2W/cm for a solution of NIR carbon dots in four cycles (natural cooling down) 2 The temperature increases of 34.0, 33.7, 34.6 and 34.4 ℃ under the irradiation of the laser respectively, which shows that the photo-thermal effect of the NIR carbon point is stable and cannot be attenuated due to long-time illumination in four cycles.
FIG. 9 is a fluorescence spectrum of CDs synthesized in comparative example 1 without 1, 5-naphthalene diamine. It can be seen that the fluorescence emission peak of CDs is mainly around 600nm without adding 1, 5-naphthalene diamine.
FIG. 10 is a fluorescence spectrum of CDs synthesized without the addition of p-phenylenediamine in comparative example 2. It can be seen that without the addition of p-phenylenediamine, there is a significant decrease in the fluorescence intensity of CDs.
FIG. 11 is a graph showing the comparison of fluorescence spectra of CDs synthesized without adding citric acid in example 1 and comparative example 3. It can be seen that the emission intensity of CDs at about 800nm is significantly reduced without adding citric acid for surface modification.
FIG. 12 is a fluorescence spectrum of CDs synthesized in comparative example 4 using o-phenylenediamine instead of p-phenylenediamine. It can be seen that the emission peak at around 800nm was very weak with o-phenylenediamine instead of the synthesized CDs.
FIG. 13 is a fluorescence spectrum of CDs synthesized in comparative example 5 using meta-phenylenediamine instead of para-phenylenediamine. It can be seen that the emission peak at about 800nm was almost absent by using m-phenylenediamine instead of the synthesized CDs.
Claims (4)
1. The preparation method of the near infrared photothermal fluorescent probe based on the carbon quantum dots is characterized by comprising the following steps of:
step 1, the mass ratio of 1, 5-naphthalene diamine to p-phenylenediamine is 1:1, ultrasonically dissolving 1, 5-naphthalene diamine and p-phenylenediamine in N, N-dimethylformamide to form a precursor solution, placing the precursor solution in a reaction kettle, performing hydrothermal reaction at 180-200 ℃ for 10-12 hours, and cooling to room temperature;
step 2, adding an aqueous solution of citric acid into the solution obtained after the reaction in the step 1, and continuously carrying out hydrothermal reaction at 180-200 ℃ for 1-2 hours to obtain a near infrared luminous carbon dot solution;
and 3, placing the near infrared luminous carbon dot solution into a dialysate for dialysis, changing the dialysate every 4 hours, continuously dialyzing for 24 hours to remove solvents and impurities, and then freeze-drying to obtain the near infrared luminous carbon dot, wherein the dialysate comprises the following components in percentage by volume: 1 and water.
2. The method according to claim 1, wherein in step 2, the concentration of citric acid in the aqueous solution of citric acid is 10mg/mL.
3. The method according to claim 1, wherein in step 3, the dialysis bag has a molecular weight of 1000Da.
4. A near infrared photothermal fluorescent probe based on carbon quantum dots prepared by the preparation method according to any one of claims 1 to 3.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756675A (en) * | 2014-01-17 | 2014-04-30 | 西安亚博生物技术有限公司 | Nitrogen doped carbon quantum dot as well as preparation method and application thereof |
| KR20160014188A (en) * | 2014-07-28 | 2016-02-11 | 건양대학교산학협력단 | Method to prepare highly photoluminescence carbon quantum dots by hydrothermal reaction |
| CN109324027A (en) * | 2018-11-18 | 2019-02-12 | 湖南科技大学 | A method of fluorescent carbon point is prepared as carbon source using p-phenylenediamine and acetic acid and detects aureomycin |
| CN110982517A (en) * | 2019-11-02 | 2020-04-10 | 上海大学 | Method for preparing full-spectrum fluorescent carbon dots by one-pot method |
| CN114609107A (en) * | 2022-03-14 | 2022-06-10 | 吉林大学 | Fluorescent probe based on red light carbon quantum dots and application of fluorescent probe in detection of ethanol concentration in ethanol-water system |
| CN114887060A (en) * | 2022-05-24 | 2022-08-12 | 南京师范大学 | Near-infrared carbon dot/molybdenum disulfide composite material and application thereof |
| CN114921245A (en) * | 2022-04-28 | 2022-08-19 | 澳门大学 | Near-infrared carbon dots and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756675A (en) * | 2014-01-17 | 2014-04-30 | 西安亚博生物技术有限公司 | Nitrogen doped carbon quantum dot as well as preparation method and application thereof |
| KR20160014188A (en) * | 2014-07-28 | 2016-02-11 | 건양대학교산학협력단 | Method to prepare highly photoluminescence carbon quantum dots by hydrothermal reaction |
| CN109324027A (en) * | 2018-11-18 | 2019-02-12 | 湖南科技大学 | A method of fluorescent carbon point is prepared as carbon source using p-phenylenediamine and acetic acid and detects aureomycin |
| CN110982517A (en) * | 2019-11-02 | 2020-04-10 | 上海大学 | Method for preparing full-spectrum fluorescent carbon dots by one-pot method |
| CN114609107A (en) * | 2022-03-14 | 2022-06-10 | 吉林大学 | Fluorescent probe based on red light carbon quantum dots and application of fluorescent probe in detection of ethanol concentration in ethanol-water system |
| CN114921245A (en) * | 2022-04-28 | 2022-08-19 | 澳门大学 | Near-infrared carbon dots and preparation method and application thereof |
| CN114887060A (en) * | 2022-05-24 | 2022-08-12 | 南京师范大学 | Near-infrared carbon dot/molybdenum disulfide composite material and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| Bright Multicolor Bandgap Fluorescent Carbon Quantum Dots for Electroluminescent Light-Emitting Diodes;Fanglong Yuan等;Adv. Mater.;第第29卷卷;第1604436（1-6）页 * |
| Multicolor emissive carbon dot with solvatochromic behavior across the entire visible spectrum;Aniruddha Kundu;Carbon(第第156期期);第110-111页 * |
| 水热法一步合成N/P-掺杂碳点及其荧光性能研究;杨凤;廖彩云;王美娜;郑保战;肖丹;吴莉;郭勇;;化学研究与应用(第03期);全文 * |
| 红色荧光碳点的制备与发光性能研究;汪亦凡;陈建彬;随磊;王伟;;安徽化工(第01期);全文 * |
| 荧光碳点的制备及其肿瘤诊断和治疗中的应用研究进展;吕春祥;李利平;;新型炭材料(第01期);全文 * |
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