CN111171808A - Preparation method of butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe, product and application thereof - Google Patents
Preparation method of butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe, product and application thereof Download PDFInfo
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- CN111171808A CN111171808A CN202010029852.9A CN202010029852A CN111171808A CN 111171808 A CN111171808 A CN 111171808A CN 202010029852 A CN202010029852 A CN 202010029852A CN 111171808 A CN111171808 A CN 111171808A
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Abstract
The invention discloses a preparation method of a butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe, which comprises the steps of dissolving butyric acid-4-methylumbelliferone and citrulline in an aqueous solution, reacting for 10-13 hours at 220-250 ℃, centrifuging, removing large particles, filtering supernate with a 0.20 mu m filter membrane, taking supernate, dialyzing, freeze-drying, and detecting Fe in an aqueous phase by using the product3+The fluorescent probe can be used for Fe in aqueous solution3+The content detection has high sensitivity, avoids the use of organic solvent, and is beneficial to the practical application of the content detection in organisms and water body environments.
Description
Technical Field
The invention belongs to the field of metal ion detection, and particularly relates to a preparation method of a butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe, and a product and application thereof.
Background
Iron ions are widely distributed in nature and are one of the important transition metal species in many biological systems and chemicals. However, when the content of water or food is too high after the water or food is polluted by iron ions and enters a human body after drinking or eating, the water or food can cause great damage to the heart, the liver and the pancreas, and even cause life danger in serious cases. Therefore, it is very important to achieve a fast and sensitive detection of iron ions in aqueous media. In recent years, small molecule organic fluorescent probes have attracted much attention from the scientific community because they can react with a specific target analyte and then change the fluorescent signal to detect the specific target analyte. The existing fluorescent probe for iron ion detection has the defects of fewer types and unobvious detection signals, and can realize the iron ion detection in an aqueous medium. Therefore, the design and research of the fluorescent probe which can carry out quantitative detection on the iron ions in the water system and has the characteristics of specific selectivity, high sensitivity, quick response time and the like have important practical significance.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe, and a product and application thereof. In order to achieve the purpose, the invention provides the following technical scheme:
1. a preparation method of a butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe comprises the steps of dissolving butyric acid-4-methylumbelliferone and citrulline in an aqueous solution, reacting for 10-13 hours at 220-250 ℃, centrifuging, removing large particles, filtering supernate with a 0.20-micron filter membrane, taking supernate, dialyzing and freeze-drying.
Furthermore, the cut-off molecular weight of the dialysis is 200Da, and the time is 4-5 hours.
Furthermore, the molar ratio of butyric acid-4-methylumbelliferone to citrulline is 1: 1.
Further, the rotating speed of the centrifugal separator is 21000 r/min.
2. The butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe prepared by the preparation method.
3. The application of the butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe in detecting Fe3+ in a water phase.
The invention has the beneficial effects that:
1. according to the invention, the butyric acid-4-methylumbelliferone/citrulline carbon dot hybrid composite material is successfully prepared by a simple one-step hydrothermal synthesis method, citrulline forms a carbon dot by itself, and butyric acid-4-methylumbelliferone is used as an additive to form a hybrid material. The butyric acid-4-methylumbelliferone/citrulline carbon-point hybrid composite material and Fe3+The electron transfer process between the two leads to butyric acid-4-methylumbelliferone/citrulline carbon-point hybrid composite material-Fe3+The generation of complexes and the phenomenon of fluorescence quenching.
2. The butyric acid-4-methyl umbelliferone/citrulline carbon-point hybrid composite material prepared based on a hydrothermal method can be used as a fluorescent probe for detecting iron ions, the preparation method is simple and easy to control, products are easy to separate, the yield is high, the purity is high, and the defects of complex structure, complex synthesis steps or purification steps, low yield and the like of the existing iron ion probe molecules are overcome.
3. The butyric acid-4-methyl umbelliferone/citrulline carbon dot hybrid composite material is used as a fluorescent probe for detecting Fe in various common metal ions3+Has high selectivity, is not interfered by other common ions, has high sensitivity and is resistant to Fe3 +The detection limit is 0.30-300 mu M.
4. The butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe is used for Fe in aqueous solution3+The content detection is carried out, and the testing solvent is a pure water solvent, so that the use of an organic solvent is avoided, and the practical application of the organic solvent in organisms and water body environments is facilitated.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 is a fluorescence spectrum of a butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe mixed with different metal cations.
FIG. 2 shows butyric acid-4-methylumbelliferone/melonAmino acid carbon point fluorescent probe and Fe with different concentrations3+Fluorescence spectrum at excitation wavelength λ 378nm after mixing.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1
0.5mmol of butyric acid-4-methylumbelliferone and 0.5mmol of citrulline are dissolved in 10mL of pure water and dispersed with stirring. Transferring the mixture into a stainless steel autoclave, heating the autoclave to 220 deg.C for 13h, naturally cooling to room temperature, centrifuging the suspension at 21000 rpm for 10min to remove large particles, and filtering the supernatant with 0.20 μm water membrane to further completely remove the large particles. Finally, the crude solution was diluted with 10ml of ultrapure water and dialyzed (molecular weight cut-off 200Da) for 4 hours to obtain a purified product. After freeze-drying, yellow brown powder is collected to obtain butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe (BMUK-CIT1) which is prepared into stock solution with the concentration of 0.5 mg/mL.
Example 2
0.3mmol of butyric acid-4-methylumbelliferone and 0.3mmol of citrulline are dissolved in 10mL of pure water and dispersed with stirring. Transferring the mixture into a stainless steel autoclave, heating the autoclave to 230 deg.C for 12h, naturally cooling to room temperature, centrifuging the suspension at 21000 rpm for 10min to remove large particles, and filtering the supernatant with 0.20 μm water membrane to further completely remove the large particles. Finally, the crude solution was diluted with 10ml of ultrapure water and dialyzed (molecular weight cut-off 200Da) for 5 hours to obtain a purified product. After freeze-drying, yellow brown powder is collected to obtain butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe (BMUK-CIT2) which is prepared into stock solution with the concentration of 0.5 mg/mL.
Example 3
0.7mmol of butyric acid-4-methylumbelliferone and 0.7mmol of citrulline are dissolved in 15mL of pure water and dispersed with stirring. Transferring the mixture into a stainless steel autoclave, heating the autoclave to 240 deg.C for 12h, naturally cooling to room temperature, centrifuging the suspension at 21000 rpm for 10min to remove large particles, and filtering the supernatant with 0.20 μm water membrane to further completely remove the large particles. Finally, the crude solution was diluted with 10ml of ultrapure water and dialyzed (molecular weight cut-off 200Da) for 4 hours to obtain a purified product. After freeze-drying, yellow brown powder is collected to obtain butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe (BMUK-CIT3) which is prepared into stock solution with the concentration of 0.5 mg/mL.
Example 4
0.8mmol of butyric acid-4-methylumbelliferone and 0.8mmol of citrulline are dissolved in 15mL of pure water and dispersed with stirring. Transferring the mixture into a stainless steel autoclave, heating the autoclave to 250 deg.C for 12h, naturally cooling to room temperature, centrifuging the suspension at 21000 rpm for 10min to remove large particles, and filtering the supernatant with 0.20 μm water membrane to further completely remove the large particles. Finally, the crude solution was diluted with 10ml of ultrapure water and dialyzed (molecular weight cut-off 200Da) for 5 hours to obtain a purified product. After freeze-drying, yellow brown powder is collected to obtain butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe (BMUK-CIT4) which is prepared into stock solution with the concentration of 0.5 mg/mL.
Test example 1 ion detection and Selective analysis
250 μ L of BMUK-CIT1 (concentration 0.25mg/mL) and 250 μ L of Fe3+After the solution (concentration: 1mM) was added to 2ml tris-HCl buffer (pH: 7.0,10mM) and the like at room temperature for 2 minutes, the resulting solution was transferred to a quartz cuvette (1 × 1cm), and the fluorescence spectrum was measured at an excitation wavelength λ 378. Under the similar conditions as described above, the absence of Fe was also measured3+And the effect of adding other metal cations (concentration ═ 1mM) on the fluorescence intensity of BMUK-CIT1 solutions, the results are shown in fig. 1.
As can be seen from FIG. 1, common metal ions such as Ca2+,Zn2+,Mg2+,Cu2+,Ba2+,Ag+,Mn2+,Mg2+,Al3+Etc., while the fluorescence intensity was hardly changed only by adding Fe3+The later change is obvious, so that other metal ions do not generate any interference on the detection result, and the higher selectivity of the fluorescent probe on iron ions can be proved.
Test example 2 sensitivity detection
BMUK-CIT1 pair Fe was systematically studied by fluorescence titration3+The detection sensitivity of (3). mu.L of BMUK-CIT1 solution (0.25mg/mL) was mixed with 2mL of Tris-HCl buffer (pH 7.0,10mm) and then Fe was added at various concentrations3+And (3) solution, so that the total volume of the mixed solution is kept constant. All samples (as BMUK-CIT1-Fe3+Meter) were measured at an excitation wavelength of 378nm, and the results are shown in fig. 2.
As can be seen from FIG. 2a, with Fe3+Increasing the concentration (0-250 μ M), the fluorescence intensity of BMUK-CIT1 solution gradually decreased at λ 483 nm. Finally, the fluorescence intensity reaches a constant value which does not follow Fe3+The concentration was increased and varied (concentration 400-700. mu.M).
Adding Fe with different concentrations under the irradiation of ultraviolet light (lambda is 365nm)3+Before and after the whole fluorescence quenching process is recorded, the fluorescence intensity and Fe of the BMUK-CIT1 probe are researched3+Ion concentration relationship. Using the fluorescence quenching ratio (F)0/F) q, i.e. BMUK-CIT1 solution in the absence of Fe3+And has Fe3+The ratio of the existing initial fluorescence intensity to the current fluorescence intensity, as shown in FIG. 2b, is fit by computer and processed to obtain the corresponding linear equation and correlation index. Apparently, these results confirm that (F) is in the range of 0.30-300. mu.M0/F) q and Fe3+There is a good linear relationship between the concentrations.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (6)
1. A preparation method of a butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe is characterized by dissolving butyric acid-4-methylumbelliferone and citrulline in an aqueous solution, reacting for 10-13 hours at 220-250 ℃, centrifuging, removing large particles, filtering a supernatant through a 0.20 mu m filter membrane, taking the supernatant, dialyzing and freeze-drying.
2. The preparation method of the butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe according to claim 1, characterized in that: the cut-off molecular weight of the dialysis is 200Da, and the time is 4-5 hours.
3. The preparation method of the butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe according to claim 1, characterized in that: the molar ratio of butyric acid-4-methylumbelliferone to citrulline is 1: 1.
4. The preparation method of the butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe according to claim 1, characterized in that: the rotating speed of the centrifuge is 21000 r/min.
5. A butyrate-4-methylumbelliferone/citrulline carbon dot fluorescent probe prepared according to the preparation method of any one of claims 1-4.
6. The butyric acid-4-methylumbelliferone/citrulline carbon dot fluorescent probe as claimed in claim 5, for detecting Fe in aqueous phase3+The use of (1).
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CN115248243A (en) * | 2021-12-15 | 2022-10-28 | 重庆工程职业技术学院 | Method for detecting AFP (alpha fetoprotein) based on sandwich electrochemical immunoassay mode of hyperbranched polyethyleneimine |
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CN115248243A (en) * | 2021-12-15 | 2022-10-28 | 重庆工程职业技术学院 | Method for detecting AFP (alpha fetoprotein) based on sandwich electrochemical immunoassay mode of hyperbranched polyethyleneimine |
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