CN113480731A - Detectable Cu2+And ClO-Preparation method of fluorescent carbon dot and hydrogel - Google Patents
Detectable Cu2+And ClO-Preparation method of fluorescent carbon dot and hydrogel Download PDFInfo
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 30
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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Abstract
The invention discloses a detectable Cu2+And ClO‑The preparation method of the fluorescent carbon dot and the hydrogel comprises the following steps: dissolving polyethyleneimine in secondary water, and then adding 2, 4-dihydroxybenzoic acid into the solution for ultrasonic dispersion; placing the solution after ultrasonic treatment in a high-temperature reaction kettle, reacting at 160-200 ℃ for 4-10 hours, cooling the solution after reaction to room temperature, dialyzing for 2-5 days by using a dialysis bag, taking out the dialysate in the dialysis bag, and freeze-drying the dialysate to obtain pure fluorescent carbon dots; the carbon dot has the advantages of good water solubility, simple synthesis, short detection time and the like, and provides a very effective method for bidirectionally detecting copper ions and hypochlorite ions in a water body.
Description
Technical Field
The invention belongs to the technical field of fluorescence analysis and detection, and particularly relates to a detectable Cu2+And ClO-The preparation method of the fluorescent carbon dot and the hydrogel.
Background
Fluorescence sensing plays an essential role in the field of environmental and biological systems. The traditional micromolecular carbon dots are widely researched due to high quantum yield, various fluorescence colors and clear luminescence mechanism. However, they tend to be complicated to synthesize, accompanied by the use of organic solvents, and have poor water solubility, which severely limits their applications. Therefore, the development of new fluorescent materials through a simple and environmentally friendly preparation method remains a challenge and key to the material scientist.
In recent years, carbon dots have been favored by many researchers because of their unique advantages, such as good water solubility and biosafety, in the micro-scale dimensions. Most of the carbon dots are modified at the molecular level, so that a nano-grade luminescent material is prepared and used for detecting various substances such as active oxygen, metal ions, antibiotics, enzymes and the like. However, bifunctional water-soluble fluorescent carbon dots capable of efficiently detecting metal ions and anions simultaneously in an aqueous solution are very rare.
Most of carbon dots are identified in a single way, the identification efficiency is low, the function is single, the construction of the dual-function fluorescent carbon dots capable of effectively and simultaneously detecting metal ions and anions in the aqueous solution can carry out two-way identification on target ions, and compared with single-function carbon dots, the multifunctional application of the fluorescent carbon dots is realized.
Disclosure of Invention
The object of the present invention is to provide a detectable Cu2+And ClO-The preparation method of the fluorescent carbon dots and the hydrogel solves the problem that the existing carbon dots can not detect Cu2+And can detect ClO-To a problem of (a).
The invention adopts the following technical scheme: detectable Cu2+And ClO-The preparation method of the fluorescent carbon dot comprises the following steps:
dissolving polyethyleneimine in secondary water, and then adding 2, 4-dihydroxybenzoic acid into the solution for ultrasonic dispersion;
the solution after ultrasonic treatment is placed in a high-temperature reaction kettle and reacts for 4 to 10 hours at the temperature of 160-200 ℃,
and cooling the solution after reaction to room temperature, dialyzing for 2-5 days by using a dialysis bag, taking out the dialysate in the dialysis bag, and freeze-drying the dialysate to obtain pure fluorescent carbon dots.
Further, the amount of the polyethyleneimine and 2, 4-dihydroxybenzoic acid used was in the range of 1ml:0.5-2.5 g.
Further, the cut-off molecular weight of the dialysis bag is 3500-6000 Da.
Further, the fluorescent carbon dots are prepared into a solution and then used for treating Cu in water2+And ClO-Carrying out quantitative or qualitative detection.
Further, the fluorescent carbon dots are prepared into a solution and then used for treating Cu in Hela cells2+Carrying out quantitative or qualitative detection.
Cu detection by using fluorescent carbon dots2+And ClO-The preparation method of the hydrogel comprises the steps of dissolving the fluorescent carbon dots, acrylamide, acrylic acid, alpha-ketoglutaric acid and N, N-methylene bisacrylamide in water, preparing a gel precursor solution after performing ultrasonic treatment for 15 minutes, injecting the precursor solution into a gel mold, and curing for 40min under an ultraviolet lamp to obtain the hydrogelTo fluorescent hydrogels.
The invention has the beneficial effects that: the carbon dot has the advantages of good water solubility, simple synthesis, short detection time and the like, and provides a very effective method for bidirectionally detecting copper ions and hypochlorite ions in a water body; the preparation method disclosed by the invention is simple and environment-friendly in synthesis, only one-step reaction is needed in a reaction kettle, the fluorescent carbon dots have good dispersibility and water solubility in an aqueous solution, the optical performance is stable, and the storage time is long; high sensitivity to target, short response time and capability of bidirectionally identifying Cu2+And ClO-Low toxicity, can be applied to Cu in living cells2+According to the detection, although a lot of hydrogels in the prior art can realize the adsorption of metal ions, the adsorption process of the metal ions is difficult to detect, and the acrylic acid/acrylamide system is a carrier, and the pure gel can be endowed with fluorescence detection performance by doping carbon dots, so that the dual effects of the detection and the adsorption of copper ions are realized.
Drawings
FIG. 1 is a microscopic morphology image of a fluorescent carbon dot of the present invention under a transmission electron microscope, and FIG. 1(a) is a TEM image of the fluorescent carbon dot; FIG. 1(b) is an infrared spectrum of a fluorescent carbon dot;
FIG. 2 is a fluorescence emission spectrum and a linear relationship of the fluorescent carbon dots of the present invention after reaction with copper ions of different concentrations;
FIG. 3 is a fluorescence emission spectrum and a linear relationship of the fluorescent carbon dots of the present invention after reaction with hypochlorite ions of different concentrations;
FIG. 4 is a graph of the selectivity of fluorescent carbon dots of the present invention for copper ions and hypochlorite ions;
FIG. 5 is a biological image of the fluorescent carbon dots of the present invention detecting copper ions in Hela cells; FIG. 5(a) is a fluorescent photograph of HeLa cells cultured with the fluorescent carbon spots of the present invention under a green channel; FIG. 5(b) is a photograph of fluorescence imaging of cells cultured with fluorescent carbon spots and Hela cells cultured with copper ions (100. mu.M);
FIG. 6 shows a fluorescent hydrogel of the present inventionFor Cu2+Adsorption experiment of (1); FIG. 6(a) is a schematic view of fluorescent hydrogel adsorption; FIG. 6(b) shows the detection of target ions (100. mu.M) in the fluorescent hydrogel; FIG. 6(c) is a photograph of gels at different adsorption times; FIG. 6(d) shows fluorescence gel vs. Cu2+Adsorption capacity of ion.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention discloses a detectable Cu2+And ClO-The preparation method of the fluorescent carbon dot comprises the following steps:
dissolving polyethyleneimine in secondary water, and then adding 2, 4-dihydroxybenzoic acid into the solution for ultrasonic dispersion; the amounts of polyethyleneimine and 2, 4-dihydroxybenzoic acid used ranged from 1ml to 0.5-2.5 g.
The solution after ultrasonic treatment is placed in a high-temperature reaction kettle and reacts for 4 to 10 hours at the temperature of 160-200 ℃,
and cooling the solution after the reaction to room temperature, dialyzing for 2-5 days by using a dialysis bag, taking out the dialysate in the dialysis bag, and freeze-drying the dialysate to obtain pure fluorescent carbon dots, wherein the cut-off molecular weight of the dialysis bag is 3500-6000 Da.
The fluorescent carbon dots prepared by the preparation method of the invention are strongly green in water body and can be used for Cu2+And ClO-Has obvious recognition effect. Meanwhile, the fluorescent carbon dots have good selectivity and high sensitivity, and can be used for Cu2+And ClO-Detection of (3).
The fluorescent carbon dots are prepared into a solution and then used for treating Cu in water2+And ClO-Performing quantitative or qualitative detection, and using the fluorescent carbon dots to detect Cu in Hela cells after being prepared into solution2+Carrying out quantitative or qualitative detection.
The invention also discloses a method for detecting Cu by using the fluorescent carbon dots2+And ClO-The preparation method of the hydrogel comprises the steps of dissolving the fluorescent carbon dots, acrylamide, acrylic acid, alpha-ketoglutaric acid and N, N-methylene bisacrylamide in water, preparing a gel precursor solution after ultrasonic treatment for 15 minutes,and then injecting the precursor liquid into a gel mold, and curing for 40min under an ultraviolet lamp to prepare the fluorescent hydrogel.
Example 1
Dissolving 2mL of polyethyleneimine in 45mL of secondary distilled water, and then adding 1g of 2, 4-dihydroxybenzoic acid into the solution for ultrasonic dispersion; the amount of polyethyleneimine and 2, 4-dihydroxybenzoic acid is 1ml:0.5 g; placing the prepared solution in a high-temperature reaction kettle, reacting at 160 ℃ for 8 hours, cooling the reacted solution to room temperature, dialyzing for three days by using a dialysis bag (3500Da), and taking dialysate in the dialysis bag; after freeze-drying the dialyzate, pure fluorescent carbon dots were obtained, the absolute quantum yield of which was 2.36% as measured by QuantaMater8000 fluorometer.
Example 2
Dissolving 2ml of polyethyleneimine in 45ml of secondary water, and then adding 2g of 2, 4-dihydroxybenzoic acid into the solution for ultrasonic dispersion; the amount of polyethyleneimine and 2, 4-dihydroxybenzoic acid is 1ml:1 g; placing the prepared solution in a high-temperature reaction kettle, reacting at 180 ℃ for 8 hours, cooling the reacted solution to room temperature, dialyzing for three days by using a dialysis bag (3500Da), and taking dialysate in the dialysis bag; after freeze-drying the dialyzate, pure fluorescent carbon dots were obtained, and the absolute quantum yield thereof was 7.44% as measured by a QuantaMater8000 fluorometer.
The fluorescent carbon dots prepared in this example were characterized as shown in fig. 1, and transmission electron microscopy showed that the carbon dots had good dispersibility and a small particle size, with an average diameter of about 3.16 nm. The infrared spectrum confirms the formation of C ═ O double bonds, and further proves the successful synthesis of the fluorescent carbon dots.
Fluorescent carbon dot pairs Cu prepared in this example2+The quantitative determination of (2) is shown in FIG. 2, along with Cu2+The fluorescence exhibits a quenching phenomenon with increasing concentration. By detecting the fluorescence intensity, when Cu2+The carbon point is aligned with Cu at a concentration of 0-30 μ M2+Has excellent linear response. The linear relationship curve is: y is 0.0186x-0.0331 (R)20.9980), which shows that the carbon dots can be realized for Cu2+Is determined bySex and quantitative detection.
Fluorescent carbon dot pairs ClO prepared in this example-As shown in FIG. 2, with ClO-The fluorescence exhibits a quenching phenomenon with increasing concentration. By detecting the intensity of fluorescence when ClO-At a concentration of 0-30 μ M, the carbon dot pairs to ClO-Has excellent linear response. The linear relationship curve is: y is 0.0094x-0.0158 (R)20.9979) to illustrate that this carbon dot can be implemented on ClO-Qualitative and quantitative detection.
The ion competition experiment of the fluorescent carbon dot prepared in this example is shown in FIG. 3, and FIG. 3(a) shows that the carbon dot pair is directed to Cu in metal ions2+FIG. 3(b) shows that this carbon point pair is directed to ClO in the relevant analyte-Specific response of (2). In FIG. 3, only Cu can be found2+And ClO-The fluorescent carbon dots can be effectively quenched. Through ion competition experiments, the fluorescent carbon dots can be applied to Cu2+And ClO-Has good specificity and sensitivity.
The cell image of the fluorescent carbon dot prepared in this example is shown in fig. 4, and after Hela cells were incubated with the carbon dot solution, green fluorescence was observed; then with Cu2+After incubation of the solution, the green fluorescence disappeared. The fluorescent carbon dots can be used for Cu in cells through the change of fluorescence intensity in cell imaging2+Detection of (3).
The fluorescent carbon dots prepared in the embodiment are doped to be capable of detecting and adsorbing Cu2+Such as the bifunctional hydrogel of (a) as shown in figure 6. FIG. 6(a) shows gel adsorption of Cu2+FIG. 6(b) is a schematic view showing that the fluorescent hydrogel detects 100. mu.M Cu respectively2+And ClO-FIG. 6(c) shows the detection of 100. mu.M Cu by fluorescent hydrogel, respectively2+And ClO-FIG. 6(d) shows fluorescent hydrogel vs. Cu2+Study of adsorption Properties. The fluorescent hydrogel can identify target ions and can also identify Cu in the fluorescent hydrogel2+The equilibrium adsorption capacity of (A) was 75.76 mg/g. The preparation of the adsorption hydrogel shows that the carbon point-doped hydrogel can realize the effect on Cu2+Effective sensing and adsorption.
Example 3
Dissolving 2ml of polyethyleneimine in 45ml of secondary water, and then adding 1.5g of 2, 4-dihydroxybenzoic acid into the solution for ultrasonic dispersion; the amount of polyethyleneimine and 2, 4-dihydroxybenzoic acid used is 1ml:1.5 g; placing the prepared solution in a high-temperature reaction kettle, reacting at 200 ℃ for 8 hours, cooling the reacted solution to room temperature, dialyzing for three days by using a dialysis bag (3500Da), and taking dialysate in the dialysis bag; after freeze-drying the dialyzate, pure fluorescent carbon dots were obtained, and the absolute quantum yield thereof was 5.64% as measured by a QuantaMater8000 fluorometer.
Example 4
0.05g of fluorescent carbon dots, 5.2g of acrylamide, 3ml of acrylic acid, 0.004g of alpha-ketoglutaric acid and 0.0045g of N, N-methylene bisacrylamide are dissolved in 9ml of water, and the gel precursor solution is prepared after 15 minutes of ultrasonic treatment. And then injecting the precursor solution into a gel mold, and curing for 40min under an ultraviolet lamp of 150kV/h to prepare the fluorescent hydrogel.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. Detectable Cu2+And ClO-The preparation method of the fluorescent carbon dot is characterized by comprising the following steps:
dissolving polyethyleneimine in secondary water, and then adding 2, 4-dihydroxybenzoic acid into the solution for ultrasonic dispersion;
the solution after ultrasonic treatment is placed in a high-temperature reaction kettle and reacts for 4 to 10 hours at the temperature of 160-200 ℃,
and cooling the solution after reaction to room temperature, dialyzing for 2-5 days by using a dialysis bag, taking out the dialysate in the dialysis bag, and freeze-drying the dialysate to obtain pure fluorescent carbon dots.
2. The detectable Cu of claim 12+And ClO-The method for preparing a fluorescent carbon dot of (1), wherein the amount of the polyethyleneimine and 2, 4-dihydroxybenzoic acid is in the range of 1ml to 0.5-2.5 g.
3. A detectable Cu according to claim 22+And ClO-The preparation method of the fluorescent carbon dot is characterized in that the cut-off molecular weight of the dialysis bag is 3500-6000 Da.
4. A detectable Cu according to claim 32+And ClO-The use of the fluorescent carbon dot of (1), wherein the fluorescent carbon dot is used for Cu in water after being prepared into a solution2+And ClO-Carrying out quantitative or qualitative detection.
5. A detectable Cu according to claim 32+And ClO-The use of fluorescent carbon dots of (a), wherein said fluorescent carbon dots are used in solution for the treatment of Cu in Hela cells2+Carrying out quantitative or qualitative detection.
6. Cu detection by using fluorescent carbon dots2+And ClO-The preparation method of the hydrogel is characterized in that the fluorescent carbon dots, acrylamide, acrylic acid, alpha-ketoglutaric acid and N, N-methylene bisacrylamide are dissolved in water, gel precursor liquid is prepared after ultrasonic treatment for 15 minutes, then the precursor liquid is injected into a gel mould, and the fluorescent hydrogel is prepared by curing for 40 minutes under an ultraviolet lamp.
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