CN116925755B - Preparation method of ferric ion doped carbon point, fluorescent probe and fluorescence detection method of indium ions - Google Patents
Preparation method of ferric ion doped carbon point, fluorescent probe and fluorescence detection method of indium ions Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 106
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910001449 indium ion Inorganic materials 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000001917 fluorescence detection Methods 0.000 title claims abstract description 24
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 18
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 229910001447 ferric ion Inorganic materials 0.000 title claims abstract description 8
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 29
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
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- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 3
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- FFEARJCKVFRZRR-UHFFFAOYSA-N L-Methionine Natural products CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 claims description 2
- 229930195722 L-methionine Natural products 0.000 claims description 2
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004473 Threonine Substances 0.000 claims description 2
- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 239000004220 glutamic acid Substances 0.000 claims description 2
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 229960004452 methionine Drugs 0.000 claims description 2
- 239000012085 test solution Substances 0.000 claims 3
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims 1
- 239000000523 sample Substances 0.000 abstract description 15
- 230000035945 sensitivity Effects 0.000 abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 70
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- 239000012535 impurity Substances 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
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- 239000012498 ultrapure water Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 230000002378 acidificating effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
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- 241001465754 Metazoa Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- OIGNJSKKLXVSLS-VWUMJDOOSA-N prednisolone Chemical compound O=C1C=C[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OIGNJSKKLXVSLS-VWUMJDOOSA-N 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- 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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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- 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"
- G01N2021/6432—Quenching
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Abstract
The invention provides a preparation method of a ferric ion doped carbon point and a fluorescence detection method of a fluorescence probe and indium ions. The preparation method comprises the following steps: mixing cyclodextrin compounds, phenylenediamine and ferric salt in a mass ratio of 1:0.1:1-2:1:4 in an organic solvent to form a raw material solution, and reacting to obtain a Fe 3+ -doped carbon point; the reaction temperature is 160-240 ℃ and the reaction time is 6-20h. The invention also provides a Fe 3+ doped carbon dot which is obtained by the preparation method. The invention also provides a fluorescent probe comprising the Fe 3+ -doped carbon point and a fluorescence detection method of indium ions by using the fluorescent probe. The Fe 3+ doped carbon dot provided by the invention has good physicochemical properties, small and uniform size and good biocompatibility, and has high sensitivity and accuracy when being applied to indium ion detection.
Description
Technical Field
The invention relates to the field of construction of a fluorescent probe and detection of heavy metal ions, in particular to a preparation method of a ferric ion doped carbon point and a fluorescent probe and indium ion fluorescent detection method.
Background
As the yield of Indium Tin Oxide (ITO) thin films for liquid crystal display (lcd) electrodes of notebook computers, mobile phones and PC displays increases, the global indium consumption increases dramatically, and the number of indium production from the crust and indium recovery from the spent lcd increases year by year. Recent studies have shown that indium and its derivatives have potential toxicity to humans and animals, such as carcinogenicity, embryotoxicity and teratogenicity. In recent years, warning about toxicity of indium to aquatic ecosystems and humans has been issued, and has great significance and value for detection of indium ions in water environments and living cells.
Compared with other detection methods, the fluorescence detection has the advantages of simple operation, strong universality, high sensitivity, low cost, real-time detection and the like in the aspect of detecting indium ions. Some fluorescent probes for indium ions are reported. The novel indium ion fluorescent probe should exhibit high selectivity for indium ions and be suitable for detection of indium ions under acidic aqueous conditions, because the solubility of indium ions In aqueous solutions is high In acidic environments, whereas indium ions precipitate as In (OH) 3 In alkaline environments (pH > 8). The fluorescence detection method is divided into turn-off detection, turn-on detection and proportion detection according to response types. The use of ratio detection of two different emission bands is considered the most promising method of analyte quantification because quantification can be accomplished independent of instrument efficiency, probe concentration, and environment (temperature, solvent polarity, and pH).
In general, the fluorescence detection method is one of the most promising methods due to the advantages of high sensitivity, fast detection rate, simple operation, etc. Carbon dots are widely used for high-efficiency analysis of environmental pollutants due to their excellent biocompatibility, easy surface functionalization and good physicochemical properties. Up to now, there is no method for detecting indium ions through full spectrum carbon dots, and the invention aims to provide a fluorescence detection method for detecting indium ions based on a fluorescence probe, which has high sensitivity, high detection rate and simple operation.
Disclosure of Invention
In order to solve the above problems, the present invention aims to provide a method for preparing a carbon dot doped with ferric ion (hereinafter referred to as Fe 3+) and a fluorescence detection method for a fluorescent probe and indium ion. The Fe 3+ doped carbon dot provided by the invention has good physicochemical properties, small and uniform size and good biocompatibility, has high sensitivity and accuracy when being applied to indium ion detection, and can be used as a fluorescent probe for indium ion detection.
In order to achieve the above object, the present invention provides a method for preparing a Fe 3+ -doped carbon dot, comprising: mixing cyclodextrin compounds, phenylenediamine and ferric salt in an organic solvent to form a raw material solution, and reacting to obtain the Fe 3+ -doped carbon point; wherein the mass ratio of the cyclodextrin compound to the phenylenediamine to the ferric salt is 1:0.1:1-2:1:4; the temperature of the reaction is 160-240 ℃, and the reaction time is 6-20h.
In the preparation method, the phenylenediamine can react with hydroxyl groups in the cyclodextrin compound to dehydrate to form carbon points, and the phenylenediamine can also be used as a nitrogen source of the carbon points to realize nitrogen doping of the carbon points, so that the fluorescence intensity of the carbon points is improved. According to the method, the Fe 3+ doped carbon point can be obtained only through solvothermal reaction between raw materials without adding modifying agents such as citric acid.
Conventional carbon sites require modification of the starting materials used in the synthesis to effect a change in the color of the emitted fluorescence; at least some of the above-mentioned Fe 3+ -doped carbon dots provided by the invention can emit fluorescence of different colors by changing the excitation light conditions, and are full spectrum carbon dots.
In the above preparation method, the phenylenediamine may include one or a combination of two or more of o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, and the like.
In the preparation method, the cyclodextrin compound comprises one or more than two of beta-cyclodextrin, alpha-cyclodextrin and gamma-cyclodextrin. Wherein, the number of the surface functional groups of the beta-cyclodextrin is better than that of carbon points prepared by alpha-cyclodextrin, gamma-cyclodextrin and beta-cyclodextrin.
In the above preparation method, the ferric salt includes one or a combination of two or more of ferric chloride, ferric sulfate, ferric nitrate, and the like. The ferric salt has a catalytic effect on one hand and can promote the generation of carbon points; on the other hand, the method can be used for modifying the carbon point and promoting the protonation-deprotonation process of the carbon point in the synthesis process.
In the preparation method, the raw material solution is generally an acidic solution, and on one hand, the raw material solution can cooperate with ferric ions to promote the protonation-deprotonation process of carbon points; another aspect may provide an acidic environment for indium ion detection. In some embodiments, the pH of the feed solution may be controlled to be 4-6. Specifically, the pH of the raw material solution may be a specific value of 4, 4.5, 5, 5.5, 6, or the like, and a range having any two of the above specific values as an end point. Preferably, the pH of the stock solution is 5.5.
In the above preparation method, the organic solvent includes a first solvent and a second solvent; wherein the first solvent comprises acetic acid and the second solvent comprises N, N-dimethylformamide. The first solvent may be used to adjust the pH, and the amount of the first solvent may be adjusted according to the desired pH. Compared with other inorganic acids, the acetic acid is safer under the solvothermal condition, and can avoid severe reaction. In some embodiments, the concentration of acetic acid may be 1%.
In the above preparation method, the second solution is used for fully dissolving the reaction raw material, and the dosage of the second solvent can be adjusted correspondingly according to the dosage of the reaction raw material.
In some embodiments, the ratio of the total mass of the cyclodextrin compound, phenylenediamine, and ferric salt to the volume of the organic solvent is from 1.6 to 2.0g:7-9mL. Specifically, when the total mass of the cyclodextrin compound, phenylenediamine, and ferric salt is 1.6g, 1.7g, 1.8g, 1.9g, or 2.0g, the volume of the organic solvent may be at least one of 7.1mL, 7.5mL, 8.0mL, 8.5mL, or 9mL, or the like, respectively. It will be appreciated that the amount of organic solvent may be scaled up with the total amount of cyclodextrin compound, phenylenediamine and ferric salt.
In the above preparation method, the structure and fluorescence properties of the obtained carbon dots can be adjusted by adjusting the amount of each raw material. In some embodiments, the mass ratio of the cyclodextrin compound, the phenylenediamine, and the ferric salt may be a: b: c, wherein a may be a specific value of 1-2, e.g., 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, etc., and ranges having any two of the above specific values as endpoints; b may be 0.1 to 1, and may specifically be a specific value such as 0.1, 0.155, 0.2, 0.3, 0.31, 0.4, 0.5, 0.6, 0.62, 0.7, 0.8, 0.9, 1, and a range having any two of the specific values as endpoints; c may be 1 to 4, and may specifically be a specific value of 1, 1.5, 2, 2.5, 3, 3.5, 4, etc., and a range having any two of the above specific values as endpoints. Further, a may be 1-2, c may be 1-4, b may be greater than 0.155 and less than or equal to 1, or b may be 0.31-0.62, or b may be greater than or equal to 0.31 and less than 0.62, or b is 0.31; further, the mass ratio of the cyclodextrin compound, the phenylenediamine and the ferric salt can be 1.2:0.31:0.1.
In the above preparation method, the temperature of the reaction may be controlled to 160 to 240 ℃, specifically 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ and other specific values, and ranges having any two of the specific values as the end points. The reaction time can be controlled to be 6-20h, and specifically can be specific values such as 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h and the like, and ranges taking any two of the specific values as endpoints. In some embodiments, the temperature of the reaction is 200 ℃, and the time of the reaction is 12 hours.
The preparation method further comprises the operation of carrying out post-treatment on the reaction product after the reaction is finished, wherein the post-treatment comprises the operation of centrifugally filtering and drying the reaction product.
The invention also provides a Fe 3+ doped carbon dot which is obtained by the preparation method. The carbon dot provided by the invention has good biocompatibility, stable fluorescence, adjustable excitation wavelength, tunable emission wavelength, and can be used for biological imaging, and also used for tracking imaging and marking molecular targets in living cells, tissues and other biological systems. The carbon dots can also be used as catalysts for certain reactions, for example, the carbon dots can catalyze the dehydrogenation of water molecules to hydrogen peroxide and release hydrogen.
In some embodiments, the particle size of the Fe 3+ -doped carbon dots may be 2-2.6nm, preferably 2.5nm. Specifically, the particle diameter of the carbon dots may be a specific value of 2nm, 2.1nm, 2.2nm, 2.3nm, 2.4nm, 2.5nm, 2.6nm, or the like, and a range having any two of the above specific values as an end point.
In some embodiments, the Fe 3+ -doped carbon dots can fluoresce in the visible light band (400-700 nm). In some embodiments, the fluorescence emitted by the Fe 3+ -doped carbon dots includes one or a combination of two or more of green (wavelength 500nm-560 nm), yellow (580 nm-595 nm), blue (450-480 nm), red (605-700 nm). In some embodiments, the carbon dots doped with Fe 3+ may be full spectrum carbon dots, which can emit polychromatic fluorescence under different excitation light conditions, and can emit a combination of two or more of green, yellow, blue, and red. For example, by changing the excitation light, the above carbon dots can emit green fluorescence, yellow fluorescence, red fluorescence, and blue fluorescence.
The invention also provides a fluorescent probe which comprises the Fe 3+ -doped carbon point. In some embodiments, the above-described Fe 3+ -doped carbon dots can be used for selective detection of indium ions, i.e., the full spectrum carbon dots can specifically recognize indium ions among different ions and detect the concentration of indium ions.
In some embodiments, a green and/or yellow emitting Fe 3+ doped carbon dot may be used as a fluorescent probe. Further, compared with the Fe 3+ doped carbon point with yellow fluorescence, the indium ion detection effect of the Fe 3+ doped carbon point with green fluorescence is better. For example, in the case where green fluorescence is a probe, the fluorescence intensity of the green fluorescent carbon dots is significantly quenched, and the fluorescence intensity gradually decreases with an increase in the concentration of indium ions. The Fe 3+ -doped carbon dot has a specific recognition effect on indium ions as a fluorescent probe, has high sensitivity and accuracy, and can be used for recognizing the indium ions in environmental water samples and cells with high sensitivity.
The invention further provides a fluorescence detection method for indium ions, which comprises the step of detecting the indium ions in the solution to be detected by utilizing the fluorescent probe. In some embodiments, the solution to be tested may include indium ions, and on the basis of this, the solution to be tested may further include one or more of L-Met (L-methionine), his (histidine), glu (glutamic acid), thr (threonine), and Hf 4+、PO4 3+、Mn2+. According to the invention, the research shows that under the condition that the solution to be detected contains at least one of L-Met, his, glu, thr, hf 4+、PO4 3+、Mn2+ and indium ions, the fluorescence intensity of the Fe 3+ doped carbon point provided by the invention can be reduced along with the increase of the concentration of the indium ions. Therefore, the fluorescent probe can specifically identify the solution containing indium ions in the aqueous solution respectively containing the indium ions, L-Met, his, glu, thr, hf 4+、PO4 3+ and Mn 2+, and can also detect the indium ions in the solution simultaneously containing at least one of L-Met, his, glu, thr, hf 4+、PO4 3+ and Mn 2+ and the indium ions, which shows that the full spectrum carbon point doped by Fe 3+ has higher sensitivity and selectivity to the indium ions.
In some specific embodiments, the fluorescence detection method can perform fluorescence test on the carbon point doped with Fe 3+ by taking the fluorescence intensity of the existing indium ions as a response signal and taking the fluorescence intensity of the absent indium ions as a reference signal, so that the specific detection of the indium ions in the environmental water sample and the cells can be realized. The fluorescence detection method specifically comprises the following steps: preparing an Fe 3+ -doped aqueous solution with a full spectrum carbon point, wherein the concentration of the solution can be 0.4-0.6mg/mL, for example, specific values such as 0.4mg/mL, 0.45mg/mL, 0.5mg/mL, 0.55mg/m, 0.6mg/mL and the like, and ranges taking any two of the specific values as endpoints; adding an indium-containing solution into an aqueous solution of a carbon point doped with Fe 3+ to form a solution to be detected, measuring the fluorescence spectrum of the solution to be detected under the condition of 340nm-490nm (such as 380 nm) wavelength excitation light, wherein the linear range of the obtained linear regression curve is 0-40nmol/L, and the detection limit of indium ions can be as low as 12nmol/L (s/n=3). In some embodiments, the fluorescence intensity of the Fe 3+ doped carbon spot at 380nm wavelength is significantly reduced with increasing indium ion concentration, and the sensitivity and accuracy for indium ion detection is also higher than that of excitation light at 340nm, 490 nm. In some embodiments, the above fluorescence detection methods can be performed at room temperature.
The beneficial effects of the invention include:
1. The preparation method of the Fe 3+ doped carbon point has the advantages of simplicity, low cost and simplicity and convenience in operation. Furthermore, the preparation method provided by the invention can be used for preparing the full spectrum carbon dots, and the full spectrum carbon dots can emit fluorescence with different colors under different excitation light conditions.
2. The Fe 3+ doped carbon point provided by the invention has excellent biocompatibility, easy surface functionalization and good physical and chemical properties.
3. The Fe 3+ doped carbon point provided by the invention has the advantages of good stability, high detection rate, high sensitivity, high detection accuracy and high selective identification performance on indium ions. The Fe 3+ doped carbon point not only can detect indium ions in aqueous solution, but also can detect indium ions in cells, and has wide application prospect in the field of analysis and detection of indium ions.
Drawings
FIG. 1 is a schematic diagram of a preparation method of Fe 3+ -doped carbon dots according to the present invention.
Fig. 2 is a TEM image of carbon dots prepared in example 2.
FIG. 3 is an XPS total spectrum of carbon dots prepared in example 2.
Fig. 4A is a graph of test data showing the effect of time on the fluorescence properties of Fe 3+ doped full spectrum carbon dots of example 2.
Fig. 4B is a graph of test data showing the effect of concentration on the fluorescence properties of Fe 3+ doped full spectrum carbon dots of example 2.
Fig. 4C is a graph of data from a test of the effect of pH on the fluorescence properties of Fe 3+ doped full spectrum carbon dots of example 2.
FIG. 5 shows the change in fluorescence intensity at 380nm of the Fe 3+ -doped carbon spot of example 2 in the presence of different metal ions.
FIG. 6 is a graph showing fluorescence decay of the Fe 3+ -doped full spectrum carbon dots of example 2 in an aqueous solution containing indium ions.
FIG. 7 shows the relationship between the fluorescence intensity of the carbon dots obtained in example 2 and the concentration of indium ions under the excitation light of 380nm wavelength.
FIG. 8 is a graph of the image of cells with carbon dots prepared in example 2 under excitation light conditions of different wavelengths.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Beta-cyclodextrin used in the following examples and comparative examples was purchased from Aba Ding Shiji Co., ltd., CAS number 7585-39-9.
Example 1
The embodiment provides a preparation method of a Fe 3+ doped carbon point, the main process is shown in figure 1, and the preparation method comprises the following steps:
1.2g of beta-cyclodextrin, 0.62g of O-phenylenediamine (O-PDA) and 0.1g of ferric chloride were mixed and dissolved in 8mL of an organic solvent consisting of 7mL of DMF and 1mL of acetic acid having a concentration of 1% (pH 5.5) to form a mixed solution. Transferring the mixed solution into an autoclave chamber lined with polytetrafluoroethylene, heating for 12 hours at 200 ℃, centrifuging in a centrifuge after the solution is cooled to room temperature to remove impurities (specifically, the operation is that the supernatant after centrifugation is filtered by chemical analysis filter paper, the following examples and comparative examples are the same), obtaining red liquid, and obtaining purified Fe 3+ doped carbon dots after obtaining red solid by spin drying and freeze drying; and dissolving the carbon dots by high-purity water to obtain a carbon dot solution. The particle size of the carbon dots obtained in this example was 2 to 2.6nm. The carbon dots of this example were tested to fluoresce red, monochromatic under uv light.
Example 2
The embodiment provides a preparation method of a full spectrum carbon dot doped with Fe 3+, the main process is shown in figure 1, and the preparation method comprises the following steps:
1.2g of beta-cyclodextrin, 0.31g of O-phenylenediamine (O-PDA) and 0.1g of ferric chloride were mixed and dissolved in 8mL of an organic solvent consisting of 7mL of DMF and 1mL of acetic acid having a concentration of 1% (pH 5.5) to form a mixed solution. Transferring the mixed solution into an autoclave chamber lined with polytetrafluoroethylene, heating at 200 ℃ for 12 hours, centrifuging in a centrifuge after the solution is cooled to room temperature to remove impurities, obtaining red liquid, and obtaining purified Fe 3+ doped carbon dots after obtaining red solid through spin drying and freeze drying; and dissolving the carbon dots by high-purity water to obtain a carbon dot solution.
Fig. 2 is a TEM image of carbon dots prepared in this example, and it can be seen that the product sample of example 2 has a lattice structure of carbon dots, and the particle size of the carbon dots is about 2.5 nm.
The carbon dots obtained in this example were subjected to fluorescence test, the excitation light wavelength was 200-700nm, and the carbon dots emitted blue, green, yellow and red fluorescence, respectively, as the excitation light wavelength was varied, thereby proving that the carbon dots prepared in this example were full spectrum carbon dots.
Example 3
The embodiment provides a preparation method of a Fe 3+ doped carbon point, the main process is shown in figure 1, and the preparation method comprises the following steps:
1.2g of beta-cyclodextrin, 0.155g of O-phenylenediamine (O-PDA) and 0.1g of ferric chloride were mixed and dissolved in 8mL of an organic solvent consisting of 7mL of DMF and 1mL of acetic acid having a concentration of 1% (pH 5.5) to form a mixed solution. Transferring the mixed solution into an autoclave chamber lined with polytetrafluoroethylene, heating at 200 ℃ for 12 hours, centrifuging in a centrifuge after the solution is cooled to room temperature to remove impurities, obtaining red liquid, and obtaining purified Fe 3+ doped carbon dots after obtaining red solid through spin drying and freeze drying; and dissolving the carbon dots by high-purity water to obtain a carbon dot solution. The particle size of the carbon dots obtained in this example was 2 to 2.6nm. The carbon dots obtained in this example were subjected to fluorescence test (excitation light of 200-700 nm) which was weaker in fluorescence intensity than the carbon dots of example 2, and emitted light of a single color of weak red (nearly transparent) under ultraviolet lamp irradiation.
Comparative example 1
The comparative example provides a Zn 2+ -doped carbon dot, the preparation method of which comprises the following steps:
1.2g of beta-cyclodextrin, 0.31g of O-phenylenediamine (O-PDA) and 0.1g of zinc chloride were mixed and dissolved in 8mL of an organic solvent consisting of 7mL of DMF and 1mL of acetic acid having a concentration of 1% (pH 5.5) to form a mixed solution. Transferring the mixed solution into an autoclave chamber lined with polytetrafluoroethylene, heating at 200 ℃ for 12 hours, centrifuging in a centrifuge after the solution is cooled to room temperature to remove impurities, obtaining red liquid, and obtaining purified Zn 2+ doped carbon dots after obtaining red solid through spin drying and freeze drying; and dissolving the carbon dots by high-purity water to obtain a carbon dot solution.
Comparative example 2
The comparative example provides a Cu 2+ doped carbon dot, the preparation method of which comprises the following steps:
1.2g of beta-cyclodextrin, 0.31g of O-phenylenediamine (O-PDA) and 0.1g of copper chloride were mixed and dissolved in 8mL of an organic solvent composed of 7mL of DMF and 1mL of acetic acid having a concentration of 1% (pH 5.5) to form a mixed solution. Transferring the mixed solution into an autoclave chamber lined with polytetrafluoroethylene, heating at 200 ℃ for 12 hours, centrifuging in a centrifuge after the solution is cooled to room temperature to remove impurities, obtaining red liquid, and obtaining purified Cu 2+ doped carbon dots after obtaining red solid through spin drying and freeze drying; and dissolving the carbon dots by high-purity water to obtain a carbon dot solution.
Comparative example 3
The comparative example provides a preparation method of Fe 3+ doped carbon dots, the main process is shown in figure 1, and the preparation method comprises the following steps:
1.2g of beta-cyclodextrin, 0.31g of O-phenylenediamine (O-PDA) and 0.1g of ferric chloride were mixed and dissolved in 8mL of an organic solvent consisting of 6mL of DMF and 2mL of acetic acid having a concentration of 1% to form a mixed solution (pH 2-2.5). Transferring the mixed solution into an autoclave chamber lined with polytetrafluoroethylene, heating at 200 ℃ for 12 hours, centrifuging in a centrifuge after the solution is cooled to room temperature to remove impurities, obtaining red liquid, and obtaining purified Fe 3+ doped carbon dots after obtaining red solid through spin drying and freeze drying; the carbon dots were dissolved in high-purity water to obtain a carbon dot dispersion. The solids remained in the dispersion and the carbon dots were not completely dissolved.
Results of testing fluorescence detection performance of carbon dots prepared in the above examples and comparative examples on indium ions.
The testing method comprises the following steps: the carbon dots prepared in examples 1 to 3 and comparative examples 1 to 3 were used as samples to be measured, 100. Mu.L of the samples to be measured was taken to prepare a carbon dot solution (water as a solvent) having a concentration of 0.5mg/ml, and indium ions (0 to 90. Mu.M) having different concentrations were added to the carbon dot solution. After the reaction was sufficiently mixed at room temperature, fluorescence spectra at excitation wavelengths of 340nm, 380nm and 490nm were recorded. After measuring the fluorescence intensity on a fluorescence spectrophotometer, calculating a linear relation between a corresponding fluorescence response value delta F/F 0 and the content of indium ions, wherein:
Δf=f 0-F,F0 is the fluorescence intensity of the initial carbon dot solution in the absence of indium ions; f is the fluorescence intensity of the carbon dot solution in the state of indium ions, and DeltaF is the fluorescence intensity change of the carbon dot after the solution is added.
Analysis of the above test results revealed that the carbon dots prepared in example 2 have higher sensitivity and accuracy for recognition detection of indium ions as fluorescent probes than the carbon dots prepared in example 1, example 3 and comparative examples 1 to 3 under excitation light conditions of 380nm wavelength.
Characterization tests were performed below on the full spectrum carbon points doped with Fe 3+ prepared in example 2.
Test example 1
The present test example provides elemental composition characterization results for the carbon dots of example 2.
The testing method comprises the following steps: 100. Mu.L of the carbon dot prepared in example 2 was taken and a carbon dot solution of 0.5mg/ml concentration was prepared for testing. The results were determined by XPS at room temperature conditions and are shown in FIG. 3.
As can be seen from fig. 3, the Fe 3+ -doped full spectrum carbon point prepared in example 2 has C, N, O, fe elements.
Test example 2
This test example provides a stability test of fluorescence intensity of the carbon dots of example 2 with respect to time.
The testing method comprises the following steps: 100. Mu.L of the carbon dot prepared in example 2 was taken and a carbon dot solution of 0.5mg/ml concentration was prepared for testing. The change of fluorescence intensity of the carbon dot solution at excitation wavelengths of 340nm, 380nm and 490nm with time was observed under room temperature conditions by a fluorescence spectrophotometer, and the result is shown in FIG. 4A.
As can be seen from fig. 4A, the fluorescence intensity of the Fe 3+ doped full spectrum carbon dot prepared in example 2 remains substantially unchanged with time, which indicates that the fluorescence performance of the carbon dot provided by the present invention has good time stability.
Test example 3
This test example provides a stability test of the fluorescence intensity of the carbon dots versus the salt ion concentration of example 2.
The testing method comprises the following steps: 100. Mu.L of the carbon dots prepared in example 2 was taken, carbon dots were prepared at a concentration of 0.5mg/ml, naCl solutions (0, 10, 20, 30, 40, 50, 60 mol/L) at different concentrations were added to the carbon dot solutions at room temperature as determined by a fluorescence spectrophotometer, and the change in fluorescence intensity of the carbon dots was observed, as a result, see FIG. 4B.
As can be seen from fig. 4B, the fluorescence intensity of the Fe 3+ doped full spectrum carbon dot prepared in example 2 remains substantially unchanged with increasing salt solution concentration, which indicates that the carbon dot provided by the present invention has good light stability in environments with different salt ion concentrations.
Test example 4
This test example provides a stability test of the fluorescence intensity of the carbon dots of example 2 with respect to pH.
100. Mu.L of the carbon dot prepared in example 2 was taken and a carbon dot solution of 0.5mg/ml concentration was prepared for testing. Solutions of different pH (containing hydrochloric acid and/or sodium hydroxide, pH 1-13) were added to the carbon dot solution at room temperature as determined by fluorescence spectrophotometry, and the change in fluorescence intensity of the carbon dot was observed, as a result, see FIG. 4C.
As can be seen from fig. 4C, the fluorescence intensity of the Fe 3+ doped full spectrum carbon point remains stable in the solution at pH 3-10, comparable to the photostability of conventional carbon points.
Test example 5
This test example provides a fluorescence intensity test of the carbon dots of example 2 in solutions containing different ions.
100. Mu.L of the carbon dot prepared in example 2 was prepared for the test, 8 parts of a carbon dot solution having a concentration of 0.5mg/ml was prepared as a blank for the control. At room temperature, measuring by a fluorescence spectrophotometer, respectively and independently adding an L-Met solution, a His solution, a Glu solution, a Thr solution, a Hf 4+ solution, a PO 4 3+ solution, an In 3+ solution and a Mn 2+ solution (20 mu L for each dropwise addition) with the concentration of 0.0001g/ml into each carbon point solution, observing the change of the fluorescence intensity of the carbon points, wherein the fluorescence of the carbon points is not obviously changed after the ions to be detected are dropwise added into samples 1-6 and 8, and dropwise adding the ion solutions to be detected for 2-3 times; the fluorescence of the sample 7 after the ion to be detected is added dropwise is changed, and the ion solution to be detected is always added dropwise to a carbon point for quenching. The final concentration of each ion in the carbon dot solution (concentration at the end of the last drop) is shown in table 1, and the test results are shown in fig. 5.
TABLE 1
| Ion species to be measured | Final concentration of the ions to be measured in the carbon dot solution | |
| Sample 1 | L-Met | 6.0×10-5g/ml |
| Sample 2 | His | 6.0×10-5g/ml |
| Sample 3 | Glu | 6.0×10-5g/ml |
| Sample 4 | Thr | 6.0×10-5g/ml |
| Sample 5 | Hf4+ | 6.0×10-5g/ml |
| Sample 6 | PO4 3+ | 6.0×10-5g/ml |
| Sample 7 | In3+ | 1.6×10-4g/ml |
| Sample 8 | Mn2+ | 6.0×10-5g/ml |
As can be seen from fig. 5, after adding In 3+, the fluorescence intensity of the Fe 3+ doped full spectrum carbon dot decreases, while the addition of other amino acids or ions has no significant effect on the fluorescence intensity of the carbon dot. The above results show that the Fe 3+ doped carbon point provided by the invention can specifically detect In 3+.
Test example 6
This test example provides a fluorescence lifetime test of the carbon dots of example 2 in an indium ion containing solution.
100. Mu.L of the carbon dot prepared in example 2 was taken and a carbon dot solution of 0.5mg/ml concentration was prepared for testing. The fluorescence lifetime was measured by a fluorescence spectrophotometer at room temperature at different excitation wavelengths, see fig. 6 for the results.
Test example 7
This test example provides a test of the relationship between the fluorescence intensity of the carbon dots of example 2 and the concentration of indium ions in the solution.
100. Mu.L of the carbon dot prepared in example 2, a carbon dot solution of 0.5mg/ml concentration was prepared for testing. At room temperature, in 3+ has a good linear relationship with carbon point (R 2 = 0.9747) In the detection range of 7-40nmol/L as determined by fluorescence spectrophotometer. The results are shown in FIG. 7.
FIG. 7 shows that the carbon spot can perform double-response fluorescence detection on In 3+ under 380nm excitation, the detection range is 7-40nmol/L, and the low detection limit is 12nmol/L.
Test example 8
This test example provides a test for the ability of the carbon dots prepared In example 2 to detect In 3+ concentration In cells.
The testing process comprises the following steps: LO2 cells were incubated in DMEM with 10% FBS and then transferred onto glass substrates overnight. After 12h incubation In a glass matrix, different concentrations of In 3+ (0.0, 15, 45, 90 nmol/L) and 0.5mg/mL carbon spots were incubated and injected into the cells at room temperature (37 ℃). Cells were cultured in a CO 2 air incubator for 4h, and to prevent interference by other factors, the cells were kept active at an appropriate pH, PBS buffer was selected, and the cultured cells were washed 3 times. Confocal fluorescence images were then obtained using an Olympus Zeiss 710 Laser Scanning Confocal Microscope (LSCM).
FIG. 8 is a graph of the image of cells with carbon dots prepared in example 2 under excitation light conditions of different wavelengths. Wherein, when the excitation light wavelength is 340nm and the emission light condition is 340nm-414nm, the carbon point emits blue fluorescence; when the excitation light wavelength is 380nm and the light emitting condition is 380nm-446nm, the carbon point emits green fluorescence; when the excitation light wavelength is 380nm and the light emitting condition is 380nm-538nm, the carbon dot emits yellow fluorescence; when the excitation light wavelength is 490nm and the light emitting condition is 490-615 nm, the carbon point emits red fluorescence.
As can be seen from fig. 8, the fluorescence intensity increases with an increase in the indium ion concentration under excitation at 340 nm; in contrast, at excitation at 380nm and 490nm, the green, yellow and red fluorescence of the cells gradually decreased with increasing In 3+ content, with the green fluorescence effect being optimal, so 380nm was chosen.
Claims (15)
1. A method for preparing a ferric ion doped carbon dot, the method comprising: mixing cyclodextrin compounds, phenylenediamine and ferric salt in an organic solvent to form a raw material solution, and reacting to obtain carbon points doped with ferric ions;
wherein the mass ratio of the cyclodextrin compound to the phenylenediamine to the ferric salt is 1-2:0.1-1:1-4;
The organic solvent comprises a first solvent and a second solvent, wherein the first solvent comprises acetic acid and the second solvent comprises N, N-dimethylformamide;
the pH value of the raw material solution is 4-6;
The temperature of the reaction is 160-240 ℃, and the reaction time is 6-20 h.
2. The preparation method of claim 1, wherein the ferric salt comprises one or a combination of more than two of ferric chloride, ferric sulfate, and ferric nitrate.
3. The preparation method of claim 1, wherein the cyclodextrin compound comprises one or more than two of beta-cyclodextrin, alpha-cyclodextrin and gamma-cyclodextrin.
4. The method according to claim 1, wherein the phenylenediamine comprises one or a combination of two or more of o-phenylenediamine, p-phenylenediamine, and m-phenylenediamine.
5. The production method according to claim 1, wherein a ratio of a total mass of the cyclodextrin compound, phenylenediamine, and ferric salt to a volume of the organic solvent is 1.6 to 2.0g:7-9mL.
6. An Fe 3+ -doped carbon dot obtained by the production process according to any one of claims 1 to 5.
7. The Fe 3+ -doped carbon dot of claim 6, wherein the particle size of the Fe 3+ -doped carbon dot is 2-2.6nm.
8. The Fe 3+ -doped carbon dot of claim 6, wherein the fluorescence emitted by the Fe 3+ -doped carbon dot comprises one or a combination of two or more of green, yellow, blue, red.
9. A fluorescent probe comprising the Fe 3+ -doped carbon dot of any one of claims 6-8.
10. A fluorescence detection method for indium ions, the method comprising detecting indium ions in a test solution using the fluorescent probe according to claim 9.
11. The fluorescence detection method of claim 10, wherein the test solution comprises indium ions.
12. The fluorescence detection method according to claim 11, wherein the test solution further comprises one or a combination of two or more of L-methionine, histidine, glutamic acid, threonine, and Hf 4+、PO4 3+、Mn2+.
13. The fluorescence detection method of claim 10, wherein the excitation light wavelength of the fluorescence detection method is 340-490nm.
14. The fluorescence detection method of claim 13, wherein the excitation light wavelength of the fluorescence detection method is 380nm.
15. The fluorescence detection method according to claim 10 or 11, wherein the detection limit of indium ions by the fluorescence detection method is 12nmol/L.
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