CN116925755A - 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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- CN116925755A CN116925755A CN202310894554.XA CN202310894554A CN116925755A CN 116925755 A CN116925755 A CN 116925755A CN 202310894554 A CN202310894554 A CN 202310894554A CN 116925755 A CN116925755 A CN 116925755A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910001449 indium ion Inorganic materials 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 17
- 238000001917 fluorescence detection Methods 0.000 title claims abstract description 16
- 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000001514 detection method Methods 0.000 claims abstract description 32
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
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- 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
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- 229940080345 gamma-cyclodextrin Drugs 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
- 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
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- 229910052738 indium Inorganic materials 0.000 description 7
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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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- 235000013922 glutamic acid Nutrition 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-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
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- 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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- 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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- G01N21/62—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: cyclodextrin compounds, phenylenediamine and ferric salt with the mass ratio of 1:0.1:1-2:1:4 are mixed in an organic solvent to form a raw material solution, and the raw material solution reacts to obtain Fe 3+ Doped carbon dots; the reaction temperature is 160-240 ℃ and the reaction time is 6-20h. The invention also provides Fe 3+ Doped carbon dots, which are obtained by the above-described preparation method. The invention also provides a method for preparing the Fe 3+ Fluorescent probe of doped carbon point and fluorescent detection of indium ion by using the fluorescent probeMeasuring method. Fe provided by the invention 3+ The doped carbon dots have good physicochemical properties, small and uniform size and good biocompatibility, and have 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, while the fluorescence probe is stable in alkaline environments (pH>8) Lower indium ion with In (OH) 3 Is precipitated in the form of (2). 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, an object of the present invention is to provide a method for producing ferric ions (hereinafter, fe 3+ ) A preparation method of doped carbon dots and a fluorescence detection method of fluorescent probes and indium ions. Fe provided by the invention 3+ The doped carbon dot has good physicochemical property, 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 Fe 3+ A method of preparing a 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 the Fe 3+ Doped carbon dots; 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. The method of the invention can obtain Fe by solvothermal reaction between raw materials without adding modifying agents such as citric acid 3+ Doped carbon dots.
Conventional carbon sites require modification of the starting materials used in the synthesis to effect a change in the color of the emitted fluorescence; the invention provides the Fe 3+ At least some of the doped carbon dots can emit fluorescence of different colors by changing the excitation light conditions, and the doped carbon dots 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 Fe 3+ Doped carbon dots, which are obtained by the above-described 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 Fe 3+ The particle size of the 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+ The doped carbon dots can fluoresce in the visible light band (400-700 nm). In some embodiments, the Fe 3+ The fluorescence emitted by the doped carbon dots comprises one or more of green (wavelength 500-560 nm), yellow (580-595 nm), blue (450-480 nm) and red (605-700 nm). In some embodiments, the above Fe 3+ The doped carbon dots can be full spectrum carbon dots, can emit multicolor fluorescence under different excitation light conditions, and can emit a combination of more than two 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 dots. In some embodiments, the above Fe 3+ The doped carbon dots can be used for the selective detection of indium ions, i.e. the full spectrum carbon dots can specifically identify indium ions in different ions and detect the concentration of the indium ions.
In some embodiments, a green color may be emittedColor and/or yellow Fe 3+ The doped carbon dots act as fluorescent probes. Further, compared with Fe with yellow fluorescence 3+ Doped carbon dots, fe with green fluorescence 3+ The indium ion detection effect of the doped carbon dots is good. 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. Fe of the above 3+ The doped carbon dots serving as fluorescent probes have a specific recognition effect on indium ions, have 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 test solution may include indium ions, and may further include L-Met (L-methionine), his (histidine), glu (glutamic acid), thr (threonine), and Hf 4+ 、PO 4 3+ 、Mn 2+ One or a combination of two or more of them. The invention has found that the solution to be tested contains L-Met, his, glu, thr, hf 4+ 、PO 4 3+ 、Mn 2+ In the case of indium ions and at least one of the above, the invention provides Fe 3+ The fluorescence intensity of the doped carbon dots may decrease as the indium ion concentration increases. Therefore, the fluorescent probe may contain indium ions and L-Met, his, glu, thr, hf 4+ 、PO 4 3+ And Mn of 2+ Specifically identifying a solution containing indium ions in the aqueous solution of (A) or L-Met, his, glu, thr, hf can be contained in the aqueous solution 4+ 、PO 4 3+ And Mn of 2+ The detection of indium ions in a solution of indium ions and at least one of them indicates Fe 3+ The doped full spectrum carbon dot has higher sensitivity and selectivity to indium ions.
In some embodiments, the fluorescence detection method described above may be used to dope Fe 3+ The carbon point of (2) is responsive to the fluorescence intensity of the presence of indium ions, and the absence of indium ionsThe fluorescence intensity is used as a reference signal for fluorescence test, so that the specificity detection of indium ions in an environmental water sample and cells is realized. The fluorescence detection method specifically comprises the following steps: configuration of Fe 3+ The concentration of the doped aqueous solution of the full spectrum carbon point 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; to Fe 3+ Adding an indium-containing solution into the doped carbon dot aqueous solution to form a solution to be detected, and measuring the fluorescence spectrum of the solution to be detected under the excitation light condition of the wavelength of 340nm-490nm (such as 380 nm), 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 Fe is at a wavelength of 380nm as compared to an excitation light at a wavelength of 340nm, 490nm 3+ The fluorescence intensity of the doped carbon dots is obviously reduced with the increase of the concentration of indium ions, and the sensitivity and the accuracy of indium ion detection are higher. In some embodiments, the above fluorescence detection methods can be performed at room temperature.
The beneficial effects of the invention include:
1. fe provided by the invention 3+ The preparation method of the doped carbon dots has the advantages of simplicity, low cost and simple and convenient 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. Fe provided by the invention 3+ The doped carbon dots have excellent biocompatibility, easy surface functionalization and good physicochemical properties.
3. Fe provided by the invention 3+ The doped carbon dots have the advantages of good stability, high detection rate, high sensitivity, high detection accuracy and high selective identification performance on indium ions. The Fe is 3+ The doped carbon dots can detect indium ions in aqueous solution and cells, and have wide application prospects in the field of analysis and detection of indium ions.
Drawings
FIG. 1 shows the present inventionFe of (2) 3+ Schematic representation of the preparation process of doped carbon dots.
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 shows Fe in example 2 in time 3+ Test data graph of the effect of fluorescence properties of doped full spectrum carbon dots.
FIG. 4B shows the concentration of Fe in example 2 3+ Test data graph of the effect of fluorescence properties of doped full spectrum carbon dots.
FIG. 4C is the pH vs. Fe of example 2 3+ Test data graph of the effect of fluorescence properties of doped full spectrum carbon dots.
FIG. 5 is a diagram of Fe of example 2 in the presence of different metal ions 3+ The change in fluorescence intensity of the doped carbon dots at 380nm.
FIG. 6 is Fe of example 2 3+ Fluorescence decay curve of doped full spectrum carbon dots in indium ion-containing aqueous solution.
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 present embodiment provides a Fe 3+ The main process of the preparation method of the doped carbon dots 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 are mixed and dissolved in 8mL of an organic solvent (pH 5.5) composed of 7mL of DMF and1mL of acetic acid with concentration of 1%. Transferring the mixed solution into an autoclave chamber lined with polytetrafluoroethylene, heating at 200deg.C for 12 hr, cooling to room temperature, centrifuging in a centrifuge to remove impurities (specifically, filtering the supernatant after centrifuging with chemical analysis filter paper, and performing spin drying and freeze drying to obtain red solid, and purifying to obtain purified Fe 3+ Doped carbon dots; 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 present embodiment provides a Fe 3+ The main process of the preparation method of the doped full spectrum carbon point 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 with polytetrafluoroethylene lining, heating at 200deg.C for 12 hr, cooling to room temperature, centrifuging in a centrifuge to remove impurities to obtain red liquid, spin drying and freeze drying to obtain red solid, and purifying to obtain purified Fe 3+ Doped carbon dots; 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 2.5nm.
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 present embodiment provides a Fe 3+ The main process of the preparation method of the doped carbon dots is shown in figure 1The 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 with polytetrafluoroethylene lining, heating at 200deg.C for 12 hr, cooling to room temperature, centrifuging in a centrifuge to remove impurities to obtain red liquid, spin drying and freeze drying to obtain red solid, and purifying to obtain purified Fe 3+ Doped carbon dots; 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
This comparative example provides a Zn 2+ A doped carbon dot, the method of making comprising:
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 with polytetrafluoroethylene lining, heating at 200deg.C for 12 hr, cooling to room temperature, centrifuging in a centrifuge to remove impurities to obtain red liquid, spin drying and freeze drying to obtain red solid, and purifying to obtain purified Zn 2+ Doped carbon dots; and dissolving the carbon dots by high-purity water to obtain a carbon dot solution.
Comparative example 2
This comparative example provides a Cu 2+ A doped carbon dot, the method of making comprising:
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. The mixed solution is then transferred to an inner liner of polytetrafluoroethyleneHeating ethylene in an autoclave at 200deg.C for 12 hr, cooling the solution to room temperature, centrifuging in a centrifuge to remove impurities to obtain red liquid, spin drying and freeze drying to obtain red solid, and purifying to obtain purified Cu 2+ Doped carbon dots; and dissolving the carbon dots by high-purity water to obtain a carbon dot solution.
Comparative example 3
This comparative example provides a Fe 3+ The main process of the preparation method of the doped carbon dots 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 with polytetrafluoroethylene lining, heating at 200deg.C for 12 hr, cooling to room temperature, centrifuging in a centrifuge to remove impurities to obtain red liquid, spin drying and freeze drying to obtain red solid, and purifying to obtain purified Fe 3+ Doped carbon dots; 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 corresponding fluorescence response value delta F/F 0 Linear relationship with indium ion content, wherein:
ΔF＝F 0 -F，F 0 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 of the carbon dot after adding the solutionAnd (3) a change.
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.
The Fe prepared in example 2 3+ Characterization testing was performed on the doped full spectrum carbon dots.
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, fe prepared in example 2 3+ The doped full spectrum carbon dot 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, fe prepared in example 2 3+ The fluorescence intensity of the doped full spectrum carbon dot is basically unchanged with the increase of time, which indicates that the fluorescence performance of the carbon dot provided by the 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, fe prepared in example 2 3+ The fluorescence intensity of the doped full-spectrum carbon dots is basically kept unchanged with the increase of the salt solution concentration, which indicates that the carbon dots provided by the invention have 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, fe 3+ The fluorescence intensity of the doped full spectrum carbon point is kept stable in a solution with pH value of 3-10, and is equivalent to the light stability of the conventional carbon point.
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. Adding 0.0001g/ml L-Met solution, his solution, glu solution, thr solution, and Hf solution into each carbon dot solution at room temperature 4+ Solution, PO 4 3+ Solution, in 3+ Solution and Mn 2+ The solution (20 mu L is added dropwise each time), the change of the fluorescence intensity of the carbon dots is observed, the fluorescence of the carbon dots is not obviously changed after the ions to be detected of samples 1-6 and 8 are added dropwise, and the solutions to be detected are added dropwise 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. Final concentration of ions in carbon dot solutionThe degree (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 -5 g/ml |
| Sample 2 | His | 6.0×10 -5 g/ml |
| Sample 3 | Glu | 6.0×10 -5 g/ml |
| Sample 4 | Thr | 6.0×10 -5 g/ml |
| Sample 5 | Hf 4+ | 6.0×10 -5 g/ml |
| Sample 6 | PO 4 3+ | 6.0×10 -5 g/ml |
| Sample 7 | In 3+ | 1.6×10 -4 g/ml |
| Sample 8 | Mn 2+ | 6.0×10 -5 g/ml |
As can be seen from FIG. 5, in is added 3+ After that, fe 3+ The fluorescence intensity of the doped full spectrum carbon dots is reduced, and the addition of other amino acids or ions has no obvious effect on the fluorescence intensity of the carbon dots. The above results indicate that the invention provides Fe 3+ The doped carbon dots 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. In the detection range of 7-40nmol/L as measured by a fluorescence spectrophotometer at room temperature 3+ Has good linear relation with carbon point (R 2 = 0.9747). The results are shown in FIG. 7.
FIG. 7 shows that the carbon dot energy is specific to In under 380nm excitation 3+ Performing double responseFluorescence detection, wherein the detection range is 7-40nmol/L, and the low detection limit is 12nmol/L.
Test example 8
This test example provides a method for preparing In carbon dot pair cells from example 2 3+ Testing of the detection ability of the concentration.
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 glass matrix, different concentrations of In at room temperature (37 ℃) 3+ (0.0, 15, 45, 90 nmol/L) and 0.5mg/mL carbon spots were co-incubated and injected into cells. Cell in CO 2 The cells were cultured in an air incubator for 4 hours, and in order to prevent interference by other factors, the cells were kept active at a suitable 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; conversely, under excitation at 380nm and 490nm, in contrast, with In 3+ The green, yellow and red fluorescence of the cells gradually decrease with increasing content, wherein the green fluorescence effect is optimal, so 380nm is selected.
Claims (10)
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 1:0.1:1-2:1:4;
the temperature of the reaction is 160-240 ℃, and the reaction time is 6-20h.
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 preparation method according to claim 1, wherein the pH of the raw material solution is 4 to 6.
6. The production method according to claim 1, wherein 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;
preferably, the ratio of the total mass of the cyclodextrin compound, phenylenediamine, and ferric salt to the volume of the organic solvent is 1.6 to 2.0g:7-9mL.
7. Fe (Fe) 3+ A doped carbon dot obtained by the production process according to any one of claims 1 to 6;
preferably, the Fe 3+ The particle size of the doped carbon dots is 2-2.6nm.
8. The Fe of claim 7 3+ A doped carbon dot, wherein the Fe 3+ The fluorescence emitted by the doped carbon dots comprises one or more of green, yellow, blue and redTwo or more kinds are combined.
9. A fluorescent probe comprising the Fe as set forth in claim 7 or 8 3+ Doped carbon dots.
10. A fluorescence detection method of indium ions, the method comprising detecting indium ions in a solution to be detected using the fluorescent probe of claim 9;
preferably, the solution to be tested comprises indium ions; more preferably, the test solution further comprises L-Met, his, glu, thr, hf 4+ 、PO 4 3+ 、Mn 2+ One or a combination of two or more of them;
preferably, the excitation light wavelength of the fluorescence detection method is 340-490nm, more preferably 380nm;
preferably, the detection limit of the fluorescence detection method on indium ions is 12nmol/L.
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