CN112126428A - Orange fluorescent carbon dot and preparation method and application thereof - Google Patents
Orange fluorescent carbon dot and preparation method and application thereof Download PDFInfo
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- CN112126428A CN112126428A CN202011076508.1A CN202011076508A CN112126428A CN 112126428 A CN112126428 A CN 112126428A CN 202011076508 A CN202011076508 A CN 202011076508A CN 112126428 A CN112126428 A CN 112126428A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 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 30
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- KBOPZPXVLCULAV-UHFFFAOYSA-N mesalamine Chemical compound NC1=CC=C(O)C(C(O)=O)=C1 KBOPZPXVLCULAV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229960004963 mesalazine Drugs 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 238000001514 detection method Methods 0.000 claims description 12
- 238000000502 dialysis Methods 0.000 claims description 11
- 239000007850 fluorescent dye Substances 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000003384 imaging method Methods 0.000 abstract description 7
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 230000009977 dual effect Effects 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract 1
- 230000005284 excitation Effects 0.000 description 10
- 238000002189 fluorescence spectrum Methods 0.000 description 10
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 5
- 239000000872 buffer Substances 0.000 description 4
- 238000004737 colorimetric analysis Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001139 pH measurement Methods 0.000 description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- 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
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- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/645—Specially adapted constructive features of fluorimeters
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Abstract
The invention provides an orange fluorescent carbon dot and a preparation method and application thereof, belonging to the field of preparation of fluorescent nano materials. The preparation method comprises the following steps: adding 5-aminosalicylic acid and citric acid into deionized water, and uniformly stirring to obtain a mixed solution; transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction; the obtained product is centrifuged to remove insoluble substances, and dialyzed to remove impurities, so as to obtain an orange fluorescent carbon dot solution. The invention has simple process and low requirement on preparation conditions; and the orange color obtainedThe fluorescent carbon dots have low toxicity and good biocompatibility. The prepared orange fluorescent carbon dots can be used for detecting Cu in a fluorescent/colorimetric dual mode2+And pH and cell imaging.
Description
Technical Field
The invention relates to a fluorescent nano material, in particular to an orange fluorescent carbon dot and a preparation method thereof, and the orange fluorescent carbon dot is used for a fluorescent/colorimetric dual-mode Cu2+And pH sensing and cell imaging.
Background
Carbon dots have received much attention as a novel carbon nanomaterial since they were discovered in 2004. At present, there are many methods for synthesizing carbon dots, which can be classified into two major types, chemical methods and physical methods. Chemical methods include electrochemical synthesis, combustion/pyrolysis/hydrothermal/acid oxidation, template synthesis, microwave/ultrasonic methods, other chemical methods, and the like. Physical methods include arc discharge, laser ablation/passivation, plasma treatment, and the like.
The carbon dot has the advantages of excellent photoluminescence performance, good light stability, excellent water solubility, low toxicity and the like. These properties make them promising for imaging, drug delivery, medical diagnostics, fingerprint detection and fluorescent inks. In particular, carbon dots have been widely used as chemical sensors and biosensors. However, most of these sensors can measure only one target. To further enrich their detection function, many efforts have been made to construct multifunctional sensors based on carbon dots. Currently, most synthetic multifunctional carbon dots emit blue fluorescence under ultraviolet excitation. In the bio-related field, blue fluorescent carbon dots are not attractive as optical probes because the autofluorescence of organisms is generally blue, which can interfere with detection; in addition, ultraviolet light excitation can cause damage to organisms. Therefore, the development of multifunctional carbon dot-based fluorescent probes with long wavelength emission is of great significance.
Colorimetric methods are also important detection methods, and the content of a component to be detected can be determined by comparing or measuring the color depth of a colored substance solution. The dual fluorescence/colorimetric analysis has been widely studied because it can provide a highly sensitive fluorescence detection method and can visualize a target with the naked eye. However, the research of fluorescent and colorimetric dual-mode sensors based on carbon dots is still in an early stage, and has a great research space.
Disclosure of Invention
The invention aims to provide an orange fluorescent carbon dot and a preparation method thereof, the preparation method has simple process and low requirement on preparation conditions, and the prepared orange fluorescent carbon dot has excellent light stability and biocompatibility and can be used for a fluorescent/colorimetric dual-mode Cu2+And pH sensing and cell imaging.
The technical scheme provided by the invention for realizing the aim is as follows:
a preparation method of an orange fluorescent carbon dot comprises the following steps:
(1) according to the mass 1: 1-2: 70-170 adding citric acid and 5-aminosalicylic acid into deionized water to prepare a mixed solution;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal reaction kettle for hydrothermal reaction;
(3) centrifuging the product obtained in the step (2) to remove insoluble substances to obtain a clear brown solution, and dialyzing by using a dialysis bag to remove impurities to obtain an orange fluorescent carbon dot solution;
(4) and (4) freeze-drying the orange fluorescent carbon dot solution obtained in the step (3) to obtain the target orange fluorescent carbon dot.
In the step (1), the mass ratio of citric acid to 5-aminosalicylic acid to deionized water is 1: 1-1.5: 80-170.
The temperature of the hydrothermal reaction in the step (2) is 180-220 ℃, and the time is 1-5 h.
And (4) dialyzing for 12-24 hours by using a dialysis bag with the molecular weight cutoff of 500-1000 Da in the dialysis in the step (3).
The orange fluorescent carbon dots prepared by the method can be used for Cu in a fluorescent/colorimetric dual-mode2+And pH detection and cell imaging.
Compared with the prior art, the invention has the advantages that:
(1) the prepared orange fluorescent carbon dot has good orange luminescence property, and can avoid interference of biological autofluorescence when being used for biological labeling and cell imaging.
(2) The prepared orange fluorescent carbon dots have strong stability, small toxic and side effects and good water solubility.
(3) The prepared orange fluorescent carbon dot can be used as fluorescent/colorimetric dual-mode Cu2+And pH detection and cell imaging.
Drawings
FIG. 1 is a photograph of the orange fluorescent carbon dot solution prepared in example 1 under excitation of a fluorescent lamp and a wavelength of 560nm, respectively
FIG. 2 is a transmission electron micrograph and a size distribution of orange fluorescent carbon dots prepared in example 1
FIG. 3 is an infrared spectrum of orange fluorescent carbon dots prepared in example 1
FIG. 4 is an X-ray photoelectron spectrum of an orange fluorescent carbon dot prepared in example 1
FIG. 5 shows the UV absorption spectrum and fluorescence emission spectrum of the orange fluorescent carbon dot prepared in example 1
FIG. 6 is a fluorescence emission spectrum of the orange fluorescent carbon dot prepared in example 1 at different excitation wavelengths
FIG. 7 shows orange fluorescent carbon dots vs. Cu prepared in example 12+Graph of selectivity (fluorescence method)
FIG. 8 shows orange fluorescent carbon dots vs. Cu prepared in example 12+Graph of selectivity (colorimetry)
FIG. 9 is a Cu-in-orange fluorescent carbon dot solution prepared in example 12+Fluorescence emission spectrum of concentration change
FIG. 10 is a Cu-in-orange fluorescent carbon dot solution prepared in example 12+Photograph of concentration change under fluorescent lamp
FIG. 11 is a fluorescence emission spectrum of the orange fluorescent carbon dot solution prepared in example 1 with pH variation
FIG. 12 is a photograph of the orange fluorescent carbon dot solution prepared in example 1 under fluorescent light as a function of pH
FIG. 13 shows the addition of Cu to orange fluorescent carbon dot-labeled HeLa cells prepared in example 12+Front and rear laser confocal images
FIG. 14 is a confocal laser mapping of orange fluorescent carbon dot-labeled HeLa cells prepared in example 1 with pH variation
Detailed Description
The following examples further illustrate the invention, but the invention is not limited to these examples.
Example 1
Preparation of orange fluorescent carbon dots:
(1) adding 0.24g of citric acid and 0.30g of 5-aminosalicylic acid into 20mL of deionized water to prepare a mixed solution;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 3h at 200 ℃;
(3) centrifuging the product obtained in the step (2) by a centrifuge at the rotating speed of 4000r/min for 20min to remove insoluble substances to obtain a clear brown solution, and dialyzing the clear brown solution by a dialysis bag with the molecular weight cutoff of 500-1000 Da for 24h to obtain an orange fluorescent carbon dot solution;
(4) and (4) freeze-drying the orange fluorescent carbon dot solution obtained in the step (3) to obtain the orange fluorescent carbon dot, wherein the fluorescence quantum yield (based on rhodamine 6G) of the orange fluorescent carbon dot is 14.0%.
The photos of the prepared orange fluorescent carbon dot solution under the excitation of a fluorescent lamp and the wavelength of 560nm are respectively shown in figure 1, wherein the left picture is a picture under the excitation of the wavelength of 560nm, the color is orange, the right picture is a picture of the orange fluorescent carbon dot solution under the irradiation of the fluorescent lamp, and the color is brown.
The transmission electron micrograph and size distribution of the prepared orange fluorescent carbon dots are shown in FIG. 2.
The infrared spectrum of the prepared orange fluorescent carbon dot is shown in FIG. 3.
The X-ray photoelectron spectrum of the prepared orange fluorescent carbon dot is shown in FIG. 4.
The ultraviolet absorption spectrum and the fluorescence emission spectrum of the prepared orange fluorescent carbon dot are shown in figure 5.
The fluorescence emission spectrograms of the prepared orange fluorescent carbon dots under different excitation wavelengths are shown in figure 6, wherein 1-8 are fluorescence spectrograms under the excitation of wavelengths of 500nm, 510nm, 520nm, 530nm, 540nm, 550nm, 560nm and 570nm respectively.
Example 2
Preparation of orange fluorescent carbon dots:
(1) adding 0.24g of citric acid and 0.30g of 5-aminosalicylic acid into 25mL of deionized water to prepare a mixed solution;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 3h at 180 ℃;
(3) centrifuging the product obtained in the step (2) by a centrifuge at the rotating speed of 4000r/min for 20min to remove insoluble substances to obtain a clear brown solution, and dialyzing the clear brown solution by a dialysis bag with the molecular weight cutoff of 500-1000 Da for 24h to obtain an orange fluorescent carbon dot solution;
example 3
Preparation of orange fluorescent carbon dots:
(1) adding 0.24g of citric acid and 0.30g of 5-aminosalicylic acid into 30mL of deionized water to prepare a mixed solution;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 3h at 220 ℃;
(3) and (3) centrifuging the product obtained in the step (2) by using a centrifugal machine at the rotating speed of 4000r/min for 20min to remove insoluble substances to obtain a clear brown solution, and dialyzing the clear brown solution by using a dialysis bag with the molecular weight cutoff of 500-1000 Da for 24h to obtain an orange fluorescent carbon dot solution.
Example 4
Preparation of orange fluorescent carbon dots:
(1) adding 0.24g of citric acid and 0.30g of 5-aminosalicylic acid into 35mL of deionized water to prepare a mixed solution;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 2h at 200 ℃;
(3) and (3) centrifuging the product obtained in the step (2) by using a centrifugal machine at the rotating speed of 4000r/min for 20min to remove insoluble substances to obtain a clear brown solution, and dialyzing the clear brown solution by using a dialysis bag with the molecular weight cutoff of 500-1000 Da for 24h to obtain an orange fluorescent carbon dot solution.
Example 5
Preparation of orange fluorescent carbon dots:
(1) adding 0.24g of citric acid and 0.30g of 5-aminosalicylic acid into 40mL of deionized water to prepare a mixed solution;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 4 hours at the temperature of 200 ℃;
(3) and (3) centrifuging the product obtained in the step (2) by using a centrifugal machine at the rotating speed of 4000r/min for 20min to remove insoluble substances to obtain a clear brown solution, and dialyzing the clear brown solution by using a dialysis bag with the molecular weight cutoff of 500-1000 Da for 24h to obtain an orange fluorescent carbon dot solution.
Example 6
Orange fluorescent carbon dot pair Cu prepared in example 12+Selective experiments of (2):
using 0.01 mol.L at pH 7.2-1Tris-HCl buffer and CuCl2、BiCl3、CaCl2、CdCl2、FeCl3、HgCl2、KCl、AlCl3、BaCl2、MgCl2、MnCl2、NaCl、PbCl2、ZnCl2Respectively preparing the metal ions with the concentration of 262 mu mol.L-10.44mg of the orange fluorescent carbon dot prepared in example 1 was dissolved in 1mL of the above solution containing different metal ions, the excitation wavelength was fixed at 550nm, and fluorescence spectrum detection was performed at 20 ℃ according to (F/F)0) To further achieve the aim of Cu2+And (4) selective detection. According to the color of the solution under sunlight, the aim of treating Cu is further achieved2+And (4) selective colorimetric detection.
Orange fluorescent carbon dot pair Cu2+The graph of selectivity (fluorescence) is shown in FIG. 7: orange fluorescent carbon dot pair Cu2+There is a maximum response.
Orange fluorescent carbon dot pair Cu2+The graph of selectivity (colorimetry) is shown in FIG. 8: when Cu is added into the carbon dot solution2+After which it is dark brown and after addition of other ions it is light yellow or light brown. Orange fluorescent carbon dot pair Cu2+And (4) selectivity is realized.
Example 7
Orange fluorescent carbon dots prepared in example 1 as Cu2+Sensitivity test of the probe:
using 0.01 mol.L at pH 7.2-1Tris-HCl buffer and CuCl2Separately preparing Cu2+The concentration was 0.05. mu. mol. L-1、0.1μmol·L-1、0.25μmol·L-1、0.5μmol·L-1、0.75μmol·L-1、1μmol·L-1、2.5μmol·L-1、5μmol·L-1、7.5μmol·L-1、10μmol·L-1、25μmol·L-1、50μmol·L-1、75μmol·L-1、100μmol·L-1、125μmol·L-1、150μmol·L-1、175μmol·L-1、200μmol·L-1、225μmol·L-1、250μmol·L-1、275μmol·L-1、300μmol·L-1、325μmol·L-1、350μmol·L-1、375μmol·L-1And 400. mu. mol. L-10.44mg of the orange fluorescent carbon dot prepared in example 1 was dissolved in 1mL of the aqueous solution containing Cu at different concentrations2+In an aqueous solution of (2), immobilization ofThe fluorescence spectrum detection is carried out at 20 ℃ with the emission wavelength of 550 nm.
Orange fluorescent carbon dot solution with Cu2+The fluorescence emission spectrum with concentration variation is shown in FIG. 9, wherein 1-27 are Cu2 +The concentration is 0 mu mol.L-1、0.05μmol·L-1、0.1μmol·L-1、0.25μmol·L-1、0.5μmol·L-1、0.75μmol·L-1、1μmol·L-1、2.5μmol·L-1、5μmol·L-1、7.5μmol·L-1、10μmol·L-1、25μmol·L-1、50μmol·L-1、75μmol·L-1、100μmol·L-1、125μmol·L-1、150μmol·L-1、175μmol·L-1、200μmol·L-1、225μmol·L-1、250μmol·L-1、275μmol·L-1、300μmol·L-1、325μmol·L-1、350μmol·L-1、375μmol·L-1And 400. mu. mol. L-1The fluorescence emission spectrogram of the Tris-HCl buffer solution dissolved with the orange fluorescent carbon dots; it can be seen from the figure that with Cu2+The intensity of the fluorescence peak at 595nm gradually decreases with increasing concentration.
Orange fluorescent carbon dot solution with Cu2+The photograph of the concentration change under the fluorescent lamp is shown in FIG. 10, and Cu is sequentially arranged from left to right in the FIG. 102+The concentration is 0 mu mol.L-1、0.05μmol·L-1、0.1μmol·L-1、0.25μmol·L-1、0.5μmol·L-1、0.75μmol·L-1、1μmol·L-1、2.5μmol·L-1、5μmol·L-1、7.5μmol·L-1、10μmol·L-1、25μmol·L-1、50μmol·L-1、75μmol·L-1、100μmol·L-1、125μmol·L-1、150μmol·L-1、175μmol·L-1、200μmol·L-1、225μmol·L-1、250μmol·L-1、275μmol·L-1、300μmol·L-1、325μmol·L-1、350μmol·L-1、375μmol·L-1And 400. mu. mol. L-1Dissolved orange fluorescent carbon dotsA photograph of the Tris-HCl buffer solution under a fluorescent lamp; it can be seen from the figure that with Cu2+The solution gradually changed in color from light yellow to dark brown as the concentration increased.
Example 8
Experiment for detecting pH of orange fluorescent carbon dots prepared in example 1:
0.44mg of the orange fluorescent carbon dot prepared in example 1 was dissolved in 1mL of Tris-HCl buffer solutions with different pH values, the excitation wavelength was fixed at 550nm, fluorescence spectrum detection was performed at 20 ℃, and the pH value was detected according to the change in fluorescence intensity.
The fluorescence emission spectrum of the orange fluorescent carbon dot as a function of pH is shown in FIG. 11, wherein: 1 to 17 are fluorescence emission spectrograms at pH values of 7.0, 7.2, 7.4, 7.6, 7.8, 8.0, 8.2, 8.4, 8.6, 8.8, 9.0, 9.2, 9.4, 9.6, 9.8, 10.0 and 10.2, respectively. It can be seen from the figure that the fluorescence intensity decreases with increasing pH.
The photo of the orange fluorescent carbon dot under the fluorescent lamp as a function of pH is shown in FIG. 12, and the photo of the fluorescent lamp under the fluorescent lamp.
Example 9
Orange fluorescent carbon dots prepared in example 1 vs Cu in live cells2+Sensing experiments:
the orange fluorescent carbon dots prepared in example 1 were added to Tris-HCl buffer at pH 7.2 (the concentration of the carbon dots was 1.32mg/mL) for incubating HeLa cells for 30 min.
HeLa cells marked by orange fluorescent carbon dots after adding Cu2+The front and rear confocal laser images are shown in fig. 13, in which: a is a laser confocal image of carbon spot-labeled HeLa cells (showing orange fluorescence); b adding Cu into HeLa cells marked by carbon points2+(768μmol·L-1) Confocal laser mapping (orange fluorescence quenching).
Example 10
Experiment of orange fluorescent carbon dots prepared in example 1 on pH sensing in living cells:
the orange fluorescent carbon dots prepared in example 1 were added to Tris-HCl buffers of different pH values (the concentration of the carbon dots was 1.32mg/mL) respectively for incubating HeLa cells for 30 min.
The confocal laser mapping of orange fluorescent carbon dot-labeled HeLa cells as a function of pH is shown in fig. 14. In the figure: a is laser confocal mapping of carbon dot labeled HeLa cells at pH 7.2; b is a laser confocal map of HeLa cells marked by carbon points at pH 8.2; c is the confocal laser map of carbon-point labeled HeLa cells at pH 9.2. It can be seen from the figure that the fluorescence intensity of the cells gradually decreases with increasing pH.
Claims (9)
1. The preparation method of the orange fluorescent carbon dot is characterized by comprising the following steps:
(1) according to the mass ratio of 1: 1-2: 70-170 adding citric acid and 5-aminosalicylic acid into deionized water to prepare a mixed solution;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal reaction kettle for hydrothermal reaction;
(3) centrifuging the product obtained in the step (2) to remove insoluble substances to obtain a clear brown solution, and dialyzing by using a dialysis bag to remove impurities to obtain an orange fluorescent carbon dot solution;
(4) and (4) freeze-drying the orange fluorescent carbon dot solution obtained in the step (3) to obtain the target orange fluorescent carbon dot.
2. The method for preparing an orange fluorescent carbon dot according to claim 1, wherein the mass ratio of the citric acid, the 5-aminosalicylic acid and the deionized water in the step (1) is 1: 1-1.5: 80-170.
3. The method for preparing an orange fluorescent carbon dot according to claim 1, wherein the temperature of the hydrothermal reaction in the step (2) is 180-220 ℃ and the time is 1-5 hours.
4. The method for preparing orange fluorescent carbon dots according to claim 1, wherein the dialysis in the step (3) is carried out for 12-24 h by using a dialysis bag with a molecular weight cutoff of 500-1000 Da.
5. An orange fluorescent carbon dot prepared by the method of any one of claims 1 to 4.
6. The method for detecting Cu by using the orange fluorescent carbon dot as a fluorescent probe as claimed in claim 52+The use of (1).
7. The method of claim 5, wherein the orange fluorescent carbon dot detects Cu colorimetrically2+The use of (1).
8. Use of the orange fluorescent carbon dot of claim 5 as a fluorescent probe for detecting pH.
9. Use of the orange fluorescent carbon dot of claim 5 for colorimetric detection of pH.
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