CN109777405B - Red-blue dual-emission fluorescent carbon dot and method for simultaneously detecting Al3+And Cu2+Method for fluorescence analysis of ions - Google Patents
Red-blue dual-emission fluorescent carbon dot and method for simultaneously detecting Al3+And Cu2+Method for fluorescence analysis of ions Download PDFInfo
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Abstract
The invention relates to a red and blue dual-emission fluorescent carbon dot and a method for simultaneously detecting Al3+And Cu2+A method for fluorescence analysis of ions. Grinding dry tea leaves into powder, adding the powder into a reaction solvent to form a mixture, carrying out ultrasonic treatment at room temperature, heating and reacting at the temperature of 140 ℃ and 250 ℃ for 1-24 hours, naturally cooling to room temperature after the reaction is finished, centrifuging to remove large particles, filtering by using a 0.22 mu m microporous filter membrane, and removing the solvent by rotary evaporation to obtain the red-blue dual-emission fluorescent carbon dot3+Ion content, fluorescence quenching in the red emission region enables highly sensitive and highly selective detection of Cu2+The ion content can realize the simultaneous detection of two ions without mutual interference.
Description
Technical Field
The invention relates to a preparation method of fluorescent carbon dots and Al detection based on the fluorescent carbon dots3+Ions and Cu2+A method for fluorescence analysis of ions.
Background
Aluminum is the most abundant metal element in the earth, and is commonly used in the industries of aluminum materials for aerospace, electronic appliances, packaging, buildings and the like because of various excellent properties, particularly the use of aluminum potassium sulfate and aluminum ammonium sulfate in the food industry, so that human beings are exposed to the environment with high aluminum concentration for a long time. However, a number of studies have demonstrated that the intake of aluminum in humans causes serious health problems, such as alzheimer's disease, parkinson's disease, and renal failure. Therefore, accurate detection of the aluminum ion content is of great significance to food safety and human health.
Copper ions are important transition metal ions in human bodies, and the presence of copper ions can react with certain proteins to form metalloproteins, which play a functional role in the form of enzymes which are vital to life processes, and the high or low content of copper ions can have great influence on the body, resulting in serious neurodegenerative diseases, such as: alzheimer's disease and wilson's disease. Therefore, the establishment of a high-sensitivity and high-selectivity analysis method for detecting copper ions is very important.
At present, for Al3+Ions and Cu2+Ion detection usually adopts atomic absorption spectrometry, inductively coupled plasma, electrochemical methods, chromatography and the like, and although some methods have high sensitivity, the application of the methods is limited to a certain extent by complicated operation processes, complicated instruments and long detection time. In contrast, the fluorescence analysis method based on the fluorescent carbon dots has the characteristics of high sensitivity and easiness in operation, and has the advantages of simplicity in material preparation and good specificity, so that the method is widely used for detecting metal ions. However, most of the probes can only be used for detecting single metal ions so far, and no literature report about simultaneous detection of Al exists3+Ions and Cu2+A method for fluorescence analysis of ions. Compared with single metal ion detection, the double-emission peak position-based multi-ion detection can more effectively realize simultaneous detection of two or more metal ions, and is beneficial to practical analysis and practical application.
Disclosure of Invention
The invention aims to solve the technical problem of providing a red and blue dual-emission fluorescent carbon dot and a method for simultaneously detecting Al3+And Cu2+A method for fluorescence analysis of ions.
To solve the above technical problems, according to an aspect of the present invention, a method for preparing a red and blue dual-emission fluorescent carbon dot is provided.
A preparation method of a red and blue dual-emission fluorescent carbon dot comprises the following steps: grinding dry tea leaves into powder, adding the powder into a reaction solvent to form a mixture, carrying out ultrasonic treatment at room temperature for 5-15min, transferring the mixture into a high-pressure reaction kettle, heating the mixture to react at the temperature of 140-250 ℃ for 1-24 h, naturally cooling the mixture to the room temperature after the reaction is finished, centrifuging the mixture at the temperature of 8000-12000 rpm to remove large particles, filtering the mixture by using a 0.22 mu m microporous filter membrane, and carrying out rotary evaporation to remove the solvent to obtain the red-blue dual-emission fluorescent carbon dot.
Further, the solvent is absolute ethyl alcohol, acetone or a mixed solution of the absolute ethyl alcohol and the acetone.
Further, the mixture is subjected to ultrasonic treatment for 10min at room temperature; after the reaction was completed and cooled to room temperature, large particles were removed by centrifugation at 10000 rpm.
Further, the obtained red and blue dual-emission fluorescent carbon dots are dispersed into required concentration by absolute ethyl alcohol and stored at 4 ℃ for later use.
According to another aspect of the present invention, there is provided a red-blue dual emission fluorescent carbon dot prepared by any one of the above methods.
According to another aspect of the present invention, there is provided a method of detecting Al3+A method of ionizing, comprising the steps of:
(1) mixing AlCl3Dissolving in absolute ethyl alcohol, and preparing Al with different concentrations in sequence3+Ionic ethanol solution; dispersing the red and blue dual-emission fluorescent carbon dots into absolute ethyl alcohol to obtain a fluorescent carbon dot ethyl alcohol solution with the concentration of 0.2 mg/mL;
(2) will have different concentrations of Al3+Adding the ionic ethanol solution into 2.0 mL of fluorescent carbon dot ethanol solution to prepare a mixed solution, reacting at room temperature for 1-5 min, measuring the fluorescence spectrum under the excitation condition of 410 nm, and drawing ln (F/F) at the emission wavelength of 478 nm0) With Al3+A standard curve between ion concentrations; f0Is in the absence of Al3+Fluorescence intensity in the presence of ions, F being the presence of Al3+Fluorescence intensity at ion time;
(3) taking the fluorescence of step (1)Light carbon point ethanol solution containing Al to be detected3+Preparing an ionic ethanol solution into a mixed solution, measuring and calculating ln (F/F) according to the test conditions in the step (2)0) Then, Al is calculated according to the standard curve in the step (2)3+The concentration of the ions.
According to another aspect of the present invention, there is provided a method of detecting Cu2+A method of ionizing, comprising the steps of:
(1) adding CuCl2Dissolving in absolute ethyl alcohol, and sequentially preparing Cu with different concentrations2+Ionic ethanol solution; dispersing the red and blue dual-emission fluorescent carbon dots into absolute ethyl alcohol to obtain a fluorescent carbon dot ethyl alcohol solution with the concentration of 0.2 mg/mL;
(2) will have different concentrations of Cu2+Adding the ionic ethanol solution into 2.0 mL of fluorescent carbon dot ethanol solution to prepare a mixed solution, reacting at room temperature for 30-120 min, measuring the fluorescence spectrum under the excitation condition of 410 nm, and drawing the fluorescence intensity ratio F/F at the emission wavelength of 671 nm0And Cu2+A standard curve between ion concentrations; f0Is in the absence of Cu2+Fluorescence intensity in the presence of ions, F being the presence of Cu2+Fluorescence intensity at ion time;
(3) taking the fluorescent carbon dot ethanol solution in the step (1) and containing Cu to be detected2+Preparing the ionic ethanol solution into a mixed solution, measuring and calculating F/F according to the test conditions in the step (2)0Then calculating Cu according to the standard curve in the step (2)2+The concentration of the ions.
According to another aspect of the present invention, there is provided a method of simultaneously detecting Al3+Ions and Cu2+A method of ionizing, comprising the steps of:
(1) mixing AlCl3Dissolving in absolute ethyl alcohol, and preparing Al with different concentrations in sequence3+Ionic ethanol solution; adding CuCl2Dissolving in absolute ethyl alcohol, and sequentially preparing Cu with different concentrations2+Ionic ethanol solution; dispersing the red and blue dual-emission fluorescent carbon dots into absolute ethyl alcohol to obtain a fluorescent carbon dot ethyl alcohol solution with the concentration of 0.2 mg/mL;
(2) will have different concentrations of Al3+Adding the ionic ethanol solution into 2.0 mL of fluorescent carbon dot ethanol solution to prepare a mixed solution, reacting at room temperature for 1-5 min, measuring the fluorescence spectrum under the excitation condition of 410 nm, and drawing ln (F/F) at the emission wavelength of 478 nm0) With Al3+A standard curve between ion concentrations; f0Is in the absence of Al3+Fluorescence intensity in the presence of ions, F being the presence of Al3+Fluorescence intensity at ion time;
will have different concentrations of Cu2+Adding the ionic ethanol solution into 2.0 mL of fluorescent carbon dot ethanol solution to prepare a mixed solution, reacting at room temperature for 30-120 min, measuring the fluorescence spectrum under the excitation condition of 410 nm, and drawing the fluorescence intensity ratio F/F at the emission wavelength of 671 nm0And Cu2+A standard curve between ion concentrations; f0Is in the absence of Cu2+Fluorescence intensity in the presence of ions, F being the presence of Cu2+Fluorescence intensity at ion time;
(3) taking the fluorescent carbon dot ethanol solution in the step (1) and containing Al to be detected3+Ions and Cu2+Preparing the ionic ethanol solution into mixed solution, respectively measuring and calculating Al according to the test conditions in the step (2)3+Ion corresponding ln (F/F)0) And Cu2+F/F corresponding to ion0Then respectively calculating Al according to the standard curve in the step (2)3+Ions and Cu2+The concentration of the ions.
Further, Al is detected3+In the ionic method, in the step (2), the reaction time is preferably 1 to 2 min.
Further, in detecting Cu2+In the ionic method, in the step (2), the reaction time is preferably 45 to 90 min.
The invention provides a preparation method of red and blue dual-emission fluorescent carbon dots and a method for simultaneously detecting Al3+And Cu2+Compared with the prior art, the ion fluorescence analysis method has the beneficial effects that: firstly, the synthesis of the fluorescent probe has the advantages of simple steps, environmental protection and the like, and the synthesized probe has the characteristics of single excitation and double emission; fluorescence of blue emission regionThe light enhancement can detect Al with high sensitivity and high selectivity3+(ii) an ion content; ③ the fluorescence quenching of the red emission area can detect Cu with high sensitivity and high selectivity2 +(ii) an ion content; and fourthly, the simultaneous detection of two ions can be realized without mutual interference.
Drawings
FIG. 1 is a transmission electron micrograph of a red-blue dual-emission fluorescent carbon dot.
FIG. 2 shows XPS photoelectron spectra of red and blue dual-emission fluorescent carbon dots (a), high resolution C1s (b), O1s (C) and N1s (d).
FIG. 3 shows emission spectra in the presence of different metal ions.
FIG. 4 is a comparison of the relative fluorescence intensity in the presence of different metals at the emission wavelength of 671 nm.
FIG. 5 is a comparison of the relative fluorescence intensity in the presence of different metals at an emission wavelength of 478 nm.
FIG. 6 shows different solvent pairs for Al3+The effect of ion detection.
FIG. 7 shows different solvent pairs for Cu2+The effect of ion detection.
FIG. 8 shows different Al concentrations3+And (3) a fluorescence spectrum of the red and blue dual-emission fluorescent carbon dot ethanol solution in the presence of ions.
FIG. 9 is Al3+Standard curve for ion detection.
FIG. 10 shows Cu concentrations2+And (3) a fluorescence spectrum of the red and blue dual-emission fluorescent carbon dot ethanol solution in the presence of ions.
FIG. 11 is Cu2+Standard curve for ion detection.
Detailed Description
The invention provides a preparation method of a red-blue dual-emission fluorescent carbon dot, which comprises the following steps: grinding dry tea leaves into powder, adding the powder into a reaction solvent to form a mixture, carrying out ultrasonic treatment at room temperature for 5-15min, transferring the mixture into a high-pressure reaction kettle, and carrying out heating reaction at the temperature of 140-; the heating reaction time may be 1 to 6 hours, 6 to 12 hours, 12 to 18 hours, 18 to 24 hours. Naturally cooling to room temperature after the reaction is finished, centrifuging at 8000-12000 rpm to remove large particles, filtering by using a 0.22 mu m microporous filter membrane, and removing the solvent by rotary evaporation to obtain the red-blue dual-emission fluorescent carbon dot.
According to the embodiment, the prepared red-blue dual-emission fluorescent carbon dot has the characteristics of single excitation and dual emission, and can detect Al in a blue emission area with high sensitivity and high selectivity3+Ion content, high sensitivity and high selectivity detection of Cu in red emission region2+Ion content. The preparation method of the double-emission carbon dots provided by the invention is simple, low in cost and environment-friendly. In the preparation process, the dry tea can be any one or a mixture of several of black tea, green tea, dark tea and other tea.
In a preferred embodiment, the solvent is absolute ethyl alcohol, acetone or a mixed solution thereof.
In a preferred embodiment, the mixture is sonicated at room temperature for 10 min; after the reaction was completed and cooled to room temperature, large particles were removed by centrifugation at 10000 rpm.
In a preferred embodiment, the obtained red and blue dual-emission fluorescent carbon dots are dispersed to a desired concentration by using absolute ethanol, and stored at 4 ℃ for later use.
Based on the fluorescence enhancement of the red-blue dual-emission fluorescent carbon dots in the blue emission area, Al detection is provided3+A method of fluorescence analysis of ion content; meanwhile, based on the fluorescence quenching of the red-blue dual-emission fluorescent carbon dot in a red emission area, the method for detecting Cu is provided2+The fluorescence analysis method of the ion content can obtain the detection effect with high sensitivity and high selectivity. Especially in the presence of Al3+Ions and Cu2+The contents of the ions in the mixed solution can be detected simultaneously and are not interfered with each other.
The present embodiment provides a method for detecting Al3+A method of ionizing, comprising the steps of:
(1) mixing AlCl3Dissolving in absolute ethyl alcohol, and preparing Al with different concentrations in sequence3+Ionic ethanol solution; dispersing the red and blue dual-emission fluorescent carbon dots into absolute ethyl alcohol to obtain a fluorescent carbon dot ethyl alcohol solution with the concentration of 0.2 mg/mL;
(2) will have different concentrations of Al3+Adding the ionic ethanol solution into 2.0 mL of fluorescent carbon dot ethanol solution to prepare a mixed solution, and reacting at room temperature for 1-5 min, preferably for 1-2 min. Measuring fluorescence spectrum under the excitation condition of 410 nm, and plotting ln (F/F) at the emission wavelength of 478 nm0) With Al3+A standard curve between ion concentrations; f0Is in the absence of Al3+Fluorescence intensity in the presence of ions, F being the presence of Al3+Fluorescence intensity at ion time;
(3) taking the fluorescent carbon dot ethanol solution in the step (1) and containing Al to be detected3+Preparing an ionic ethanol solution into a mixed solution, measuring and calculating ln (F/F) according to the test conditions in the step (2)0) Then, Al is calculated according to the standard curve in the step (2)3+The concentration of the ions.
The present embodiment provides a method for detecting Cu2+A method of ionizing, comprising the steps of:
(1) adding CuCl2Dissolving in absolute ethyl alcohol, and sequentially preparing Cu with different concentrations2+Ionic ethanol solution; dispersing the red and blue dual-emission fluorescent carbon dots into absolute ethyl alcohol to obtain a fluorescent carbon dot ethyl alcohol solution with the concentration of 0.2 mg/mL;
(2) will have different concentrations of Cu2+Adding the ionic ethanol solution into 2.0 mL of fluorescent carbon dot ethanol solution to prepare a mixed solution, and after reacting for 30-120 min at room temperature, preferably reacting for 45-90 min. Measuring its fluorescence spectrum under the excitation condition of 410 nm, and plotting the fluorescence intensity ratio F/F at the emission wavelength of 671 nm0And Cu2+A standard curve between ion concentrations; f0Is in the absence of Cu2+Fluorescence intensity in the presence of ions, F being the presence of Cu2+Fluorescence intensity at ion time;
(3) taking the fluorescent carbon dot ethanol solution in the step (1) and containing Cu to be detected2+Preparing the ionic ethanol solution into a mixed solution according to the step (a)2) The test conditions are measured and calculated to obtain F/F0Then calculating Cu according to the standard curve in the step (2)2+The concentration of the ions.
The present embodiment provides a method for producing Al3+Ions and Cu2+Detecting Al simultaneously in the ion mixed solution3+Ions and Cu2+A method of ionizing, comprising the steps of:
(1) mixing AlCl3Dissolving in absolute ethyl alcohol, and preparing Al with different concentrations in sequence3+Ionic ethanol solution; adding CuCl2Dissolving in absolute ethyl alcohol, and sequentially preparing Cu with different concentrations2+Ionic ethanol solution; dispersing the red and blue dual-emission fluorescent carbon dots into absolute ethyl alcohol to obtain a fluorescent carbon dot ethyl alcohol solution with the concentration of 0.2 mg/mL;
(2) will have different concentrations of Al3+Adding the ionic ethanol solution into 2.0 mL of fluorescent carbon dot ethanol solution to prepare a mixed solution, and after reacting for 1-5 min at room temperature, preferably reacting for 1-2 min. Measuring fluorescence spectrum under the excitation condition of 410 nm, and plotting ln (F/F) at the emission wavelength of 478 nm0) With Al3+A standard curve between ion concentrations; f0Is in the absence of Al3+Fluorescence intensity in the presence of ions, F being the presence of Al3+Fluorescence intensity at ion time;
will have different concentrations of Cu2+Adding the ionic ethanol solution into 2.0 mL of fluorescent carbon dot ethanol solution to prepare a mixed solution, and after reacting for 30-120 min at room temperature, preferably reacting for 45-90 min. Measuring its fluorescence spectrum under the excitation condition of 410 nm, and plotting the fluorescence intensity ratio F/F at the emission wavelength of 671 nm0And Cu2+A standard curve between ion concentrations; f0Is in the absence of Cu2+Fluorescence intensity in the presence of ions, F being the presence of Cu2+Fluorescence intensity at ion time;
(3) taking the fluorescent carbon dot ethanol solution in the step (1) and containing Al to be detected3+Ions and Cu2+Preparing the ionic ethanol solution into mixed solution, respectively measuring and calculating Al according to the test conditions in the step (2)3+Ion corresponding ln (F/F)0) And Cu2+F/F corresponding to ion0Then respectively calculating Al according to the standard curve in the step (2)3+Ions and Cu2+The concentration of the ions.
The embodiments of the present invention will be described below with reference to the accompanying drawings, and the preferred embodiments described herein are only for the purpose of illustrating and explaining the present invention and are not to be construed as limiting the present invention.
The first embodiment is as follows: preparation of red and blue dual-emission fluorescent carbon dots
Grinding 300 mg of clovershrub into powder, adding the powder into 10 mL of acetone solvent, carrying out ultrasonic treatment at room temperature for 10min, transferring the mixture into a 25 mL high-pressure reaction kettle, heating the mixture at 180 ℃ for reaction for 1 hour, naturally cooling the mixture to room temperature after the reaction is finished, centrifuging the mixture at 10000 rpm to remove large particles, filtering the mixture by using a 0.22 mu m microporous filter membrane, and carrying out rotary evaporation to remove the solvent to obtain the red-blue dual-emission fluorescent carbon dot. When in use, the extract is dispersed into required concentration by absolute ethyl alcohol, and stored at 4 ℃ for later use. The morphology of the red and blue dual-emission fluorescent carbon dots is shown in figure 1, the dots are in a quasi-spherical morphology, and the sizes of the dots are distributed in a range of 2 nm to 4 nm. The quantum yield of the prepared red-blue dual-emission fluorescent carbon dot in an acetone solvent is 6.06% and can reach 8.93% in a DMF solvent by taking rhodamine 6G as a reference standard within the range of 600-800 nm. With tiopronin as a reference standard within the range of 400-600 nm, the quantum yield of the blue emission band of the prepared red-blue dual-emission fluorescent carbon dot in an ethanol solvent is 0.80%. Fig. 2 shows a photoelectron spectrum of the prepared red-blue dual-emission fluorescent carbon dot, which indicates that the red-blue dual-emission fluorescent carbon dot contains three elements of carbon, oxygen and nitrogen, and C-H, C-C/C = C, C-N, C-OH, C = O, pyridine N, pyrrole N, graphitized N and N-H bonds are mainly present.
The red and blue dual-emission fluorescent carbon dots prepared by the embodiment are used as fluorescent probes to study the selectivity of the red emission band and the blue emission band to different metal ions and the selectivity of the solvent to Cu2+Ions and Al3+The effect of ion detection.
Specificity of metal ion detection
Adding ethanol solutions of different metal ions with the same concentration into 2.0 mL respectivelyPreparing a mixed solution in an ethanol solution containing 0.2 mg/mL double-emission carbon dots, reacting for 30 min, and measuring the fluorescence emission spectrum under the excitation wavelength of 410 nm. As shown in FIGS. 3, 4 and 5, Cu is present at 671 nm2+The presence of ions can cause significant fluorescence quenching, while the effect of other metal ions can be negligible; at 478 nm, Al3+The existence of ions can cause obvious fluorescence enhancement, and the influence of other metal ions is small, which indicates that the prepared red-blue dual-emission fluorescent carbon dots have a small influence on Cu2+Ions and Al3+The ions have good selectivity, can be used for the separate detection of the ions and the ions, and do not generate any interference.
(II) solvent to Cu2+Ions and Al3+Influence of ion detection
The same amount of AlCl3And CuCl2Respectively dissolving in DMSO, ethanol, acetone, DMF, acetonitrile and THF to obtain stock solution. The double-emitting carbon dot solution is also respectively dissolved in DMSO, ethanol, acetone, DMF, acetonitrile and THF to prepare the required stock solution. Taking the same amount of the above Cu2+Ions or Al3+Adding the ionic DMSO solutions into 2.0 mL DMSO solutions containing 0.2 mg/mL double-emitting carbon dots respectively to prepare mixed solutions, reacting for 30 min, and measuring the fluorescence emission spectrum at 410 nm excitation wavelength. Several other solvents such as ethanol, acetone, DMF, acetonitrile and THF were performed as described above. As shown in fig. 6 and 7, the change in fluorescence intensity is most pronounced in ethanol solvent, followed by acetone solvent.
Example two: preparation of red and blue dual-emission fluorescent carbon dots
Grinding 500 mg of Tieguanyin into powder, adding the powder into 10 mL of ethanol solvent, carrying out ultrasonic treatment at room temperature for 10min, transferring the mixture into a 25 mL high-pressure reaction kettle, heating the mixture at 200 ℃ for reaction for 3 hours, naturally cooling the mixture to room temperature after the reaction is finished, centrifuging the mixture at 10000 rpm to remove large particles, filtering the mixture by using a 0.22-micron microporous filter membrane, and carrying out rotary evaporation to remove the solvent to obtain the red-blue dual-emission fluorescent carbon dot. When in use, the extract is dispersed into required concentration by absolute ethyl alcohol, and stored at 4 ℃ for later use.
Example three: preparation of red and blue dual-emission fluorescent carbon dots
Grinding 1 g of Anhua black brick tea into powder, adding the powder into 15 mL of acetone solvent, carrying out ultrasonic treatment at room temperature for 10min, transferring the mixture into a 25 mL high-pressure reaction kettle, heating the mixture at 160 ℃ for reaction for 3 hours, naturally cooling the mixture to room temperature after the reaction is finished, centrifuging the mixture at 10000 rpm to remove large particles, filtering the mixture by using a 0.22 mu m microporous filter membrane, and carrying out rotary evaporation to remove the solvent to obtain the red-blue dual-emission fluorescent carbon dot. When in use, the extract is dispersed into required concentration by absolute ethyl alcohol, and stored at 4 ℃ for later use.
Example four: preparation of red and blue dual-emission fluorescent carbon dots
Grinding 300 mg of clovershrub into powder, adding the powder into 10 mL of acetone solvent, carrying out ultrasonic treatment at room temperature for 5min, transferring the mixture into a 25 mL high-pressure reaction kettle, heating the mixture at 140 ℃ for reaction for 24 h, naturally cooling the mixture to room temperature after the reaction is finished, centrifuging the mixture at 8000 rpm to remove large particles, filtering the mixture by using a 0.22-micron microporous filter membrane, and carrying out rotary evaporation to remove the solvent to obtain the red-blue dual-emission fluorescent carbon dot. When in use, the extract is dispersed into required concentration by absolute ethyl alcohol, and stored at 4 ℃ for later use.
Example five: preparation of red and blue dual-emission fluorescent carbon dots
Grinding 300 mg of clovershrub into powder, adding the powder into 10 mL of acetone solvent, carrying out ultrasonic treatment at room temperature for 15min, transferring the mixture into a 25 mL high-pressure reaction kettle, heating the mixture at 250 ℃ for reaction for 10 h, naturally cooling the mixture to room temperature after the reaction is finished, centrifuging the mixture at 12000 rpm to remove large particles, filtering the mixture by using a 0.22 mu m microporous filter membrane, and carrying out rotary evaporation to remove the solvent to obtain the red-blue dual-emission fluorescent carbon dot. When in use, the extract is dispersed into required concentration by absolute ethyl alcohol, and stored at 4 ℃ for later use.
Example six: al (Al)3+Analytical detection of ions
In the embodiment, the red and blue dual-emission fluorescent carbon dots prepared in the first embodiment are used as fluorescent probes to realize the alignment of Al3+And (4) analyzing and detecting ions.
Step (1) of mixing AlCl3Dissolving in absolute ethyl alcohol, and preparing Al with different concentrations in sequence3+Ion BAn alcohol solution; dispersing the red and blue dual-emission fluorescent carbon dots into absolute ethyl alcohol to obtain a fluorescent carbon dot ethyl alcohol solution with the concentration of 0.2 mg/mL;
step (2) of adding Al with different concentrations3+The ionic ethanol solution was added to 2.0 mL of the above fluorescent carbon dot ethanol solution to prepare a mixed solution, and after 1 min of reaction at room temperature, the fluorescence spectrum was measured under the excitation condition of 410 nm, as shown in FIG. 8. Then, ln (F/F) at an emission wavelength of 478 nm was plotted0) With Al3+Standard Curve between ion concentrations, F0Is in the absence of Al3+Fluorescence intensity in the presence of ions, F being the presence of Al3+Fluorescence intensity at ion. The results show that: ln (F/F)0) With Al3+The ion concentration is in a good linear relationship in the range of 0-20 mu M and 25-100 mu M.
Step (3), taking 0.2 mg/mL of fluorescent carbon dot ethanol solution containing Al to be detected3+Preparing mixed solution from ionic ethanol solution, reacting at room temperature for 1 min, measuring fluorescence spectrum under the excitation condition of 410 nm, and measuring ln (F/F) at the emission wavelength of 478 nm0) And ln (F/F)0) With Al3+Calculating Al from standard curve between ion concentrations3+The ion concentration.
Example seven: cu2+Analytical detection of ions
In the embodiment, the red and blue dual-emission fluorescent carbon dots prepared in the first embodiment are used as fluorescent probes to realize the detection of Cu2+And (4) analyzing and detecting ions.
Step (1), adding CuCl2Dissolving in absolute ethyl alcohol, and sequentially preparing Cu with different concentrations2+Ionic ethanol solution; dispersing the red and blue dual-emission fluorescent carbon dots into absolute ethyl alcohol to obtain a fluorescent carbon dot ethyl alcohol solution with the concentration of 0.2 mg/mL;
step (2) to have different concentrations of Cu2+The ionic ethanol solution was added to 2.0 mL of the above fluorescent carbon dot ethanol solution to prepare a mixed solution, and after reacting at room temperature for 30 min, the fluorescence spectrum was measured under the excitation condition of 410 nm, as shown in FIG. 10. Then, the fluorescence intensity ratio F/F at the emission wavelength of 671 nm was plotted0And Cu2+Ion concentrationA standard curve between degrees; f0Is in the absence of Cu2+Fluorescence intensity in the presence of ions, F being the presence of Cu2+Fluorescence intensity at ion. The results show that: F/F0And Cu2+The ion concentration is in a good linear relation within the range of 0.1-50 mu M.
Step (3) taking the ethanol solution containing the to-be-detected Cu of the fluorescent carbon dots2+Preparing mixed solution from ionic ethanol solution, reacting at room temperature for 30 min, measuring fluorescence spectrum under 410 nm excitation condition, and measuring F/F ratio at 671 nm emission wavelength0And F/F0And Cu2+Standard curve between ion concentrations, calculating Cu2+The ion concentration.
Example eight: simultaneous detection of Al3+Ions and Cu2+Ion(s)
In the embodiment, the red and blue dual-emission fluorescent carbon dots prepared in the first embodiment are used as fluorescent probes to realize the purpose of detecting Al in the mixed solution3+Ions and Cu2+And (4) analyzing and detecting ions.
Step (1) of mixing AlCl3Dissolving in absolute ethyl alcohol, and preparing Al with different concentrations in sequence3+Ionic ethanol solution; adding CuCl2Dissolving in absolute ethyl alcohol, and sequentially preparing Cu with different concentrations2+Ionic ethanol solution; dispersing the red and blue dual-emission fluorescent carbon dots into absolute ethyl alcohol to obtain a fluorescent carbon dot ethyl alcohol solution with the concentration of 0.2 mg/mL;
step (2) of adding Al with different concentrations3+Adding the ionic ethanol solution into 2.0 mL of the fluorescent carbon dot ethanol solution to prepare a mixed solution, reacting at room temperature for 5min, measuring the fluorescence spectrum under the excitation condition of 410 nm, and drawing ln (F/F) at the emission wavelength of 478 nm0) With Al3+A standard curve between ion concentrations; f0Is in the absence of Al3+Fluorescence intensity in the presence of ions, F being the presence of Al3+Fluorescence intensity at ion time;
will have different concentrations of Cu2+Adding ionic ethanol solution into 2.0 mL of the above fluorescent carbon dot ethanol solution to prepare mixed solution, reacting at room temperature for 120 min, and exciting at 410 nmThe fluorescence spectrum was measured, and the F/F ratio of the fluorescence intensity at the emission wavelength of 671 nm was plotted0And Cu2+A standard curve between ion concentrations; f0Is in the absence of Cu2+Fluorescence intensity in the presence of ions, F being the presence of Cu2+Fluorescence intensity at ion time;
step (3) taking the ethanol solution containing the to-be-detected Al and the fluorescent carbon dots in the step (1)3+Ions and Cu2+Preparing an ionic ethanol solution into a mixed solution; reacting at room temperature for 5min, taking part of the solution, measuring its fluorescence spectrum under the excitation condition of 410 nm, and determining ln (F/F) at the emission wavelength of 478 nm0) And ln (F/F)0) With Al3+Calculating Al from standard curve between ion concentrations3+The ion concentration. After the reaction is carried out for 120 min at room temperature, the fluorescence spectrum of the rest solution is measured under the excitation condition of 410 nm, and the fluorescence intensity ratio F/F is determined according to the emission wavelength of 671 nm0And F/F0And Cu2+Standard curve between ion concentrations, calculating Cu2 +The ion concentration.
Example nine: the difference from the sixth example is that in the step (2) and the step (3), the reaction time at room temperature is 2 min.
Example ten: the difference from the seventh example is that in the step (2) and the step (3), the reaction time at room temperature was 45 min.
Example eleven: the difference from example eight is that: analysis and detection of Al3+When the ion concentration is high, the reaction time is 4min at room temperature in the step (2) and the step (3); analytical detection of Cu2+When the ion concentration is high, the reaction time is 90min at room temperature in the step (2) and the step (3).
Claims (4)
1. Detect Al3+A method of ionizing, characterized by:
grinding 300 mg of clovershrub into powder, adding the powder into 10 mL of acetone solvent, carrying out ultrasonic treatment at room temperature for 10min, transferring the mixture into a 25 mL high-pressure reaction kettle, heating the mixture at 180 ℃ for reaction for 1 hour, naturally cooling the mixture to room temperature after the reaction is finished, centrifuging the mixture at 10000 rpm to remove large particles, filtering the mixture by using a 0.22 mu m microporous filter membrane, and carrying out rotary evaporation to remove the solvent to obtain the red-blue double-emission fluorescent carbon dots;
the method comprises the following steps:
(1) mixing AlCl3Dissolving in absolute ethyl alcohol, and preparing Al with different concentrations in sequence3+Ionic ethanol solution; dispersing the red and blue dual-emission fluorescent carbon dots into absolute ethyl alcohol to obtain a fluorescent carbon dot ethyl alcohol solution with the concentration of 0.2 mg/mL;
(2) will have different concentrations of Al3+Adding the ionic ethanol solution into 2.0 mL of fluorescent carbon dot ethanol solution to prepare a mixed solution, reacting at room temperature for 1-5 min, measuring the fluorescence spectrum under the excitation condition of 410 nm, and drawing ln (F/F) at the emission wavelength of 478 nm0) With Al3+A standard curve between ion concentrations; f0Is in the absence of Al3+Fluorescence intensity in the presence of ions, F being the presence of Al3+Fluorescence intensity at ion time;
(3) taking the fluorescent carbon dot ethanol solution in the step (1) and containing Al to be detected3+Preparing the ionic ethanol solution into a mixed solution, measuring and calculating ln (F/F) according to the test conditions of the step (2)0) Then, Al is calculated according to the standard curve in the step (2)3+The concentration of the ions.
2. Detect Al simultaneously3+Ions and Cu2+A method for the production of ions, characterized in that,
grinding 300 mg of clovershrub into powder, adding the powder into 10 mL of acetone solvent, carrying out ultrasonic treatment at room temperature for 10min, transferring the mixture into a 25 mL high-pressure reaction kettle, heating the mixture at 180 ℃ for reaction for 1 hour, naturally cooling the mixture to room temperature after the reaction is finished, centrifuging the mixture at 10000 rpm to remove large particles, filtering the mixture by using a 0.22 mu m microporous filter membrane, and carrying out rotary evaporation to remove the solvent to obtain the red-blue double-emission fluorescent carbon dots;
the method comprises the following steps:
(1) mixing AlCl3Dissolving in absolute ethyl alcohol, and preparing Al with different concentrations in sequence3+Ionic ethanol solution; adding CuCl2Dissolving in absolute ethyl alcohol, and sequentially preparing Cu with different concentrations2+Ion BAn alcohol solution; dispersing the red and blue dual-emission fluorescent carbon dots into absolute ethyl alcohol to obtain a fluorescent carbon dot ethyl alcohol solution with the concentration of 0.2 mg/mL;
(2) will have different concentrations of Al3+Adding the ionic ethanol solution into 2.0 mL of fluorescent carbon dot ethanol solution to prepare a mixed solution, reacting at room temperature for 1-5 min, measuring the fluorescence spectrum under the excitation condition of 410 nm, and drawing ln (F/F) at the emission wavelength of 478 nm0) With Al3+A standard curve between ion concentrations; f0Is in the absence of Al3+Fluorescence intensity in the presence of ions, F being the presence of Al3+Fluorescence intensity at ion time;
will have different concentrations of Cu2+Adding the ionic ethanol solution into 2.0 mL of fluorescent carbon dot ethanol solution to prepare a mixed solution, reacting at room temperature for 30-120 min, measuring the fluorescence spectrum under the excitation condition of 410 nm, and drawing the fluorescence intensity ratio F/F at the emission wavelength of 671 nm0And Cu2+A standard curve between ion concentrations; f0Is in the absence of Cu2+Fluorescence intensity in the presence of ions, F being the presence of Cu2+Fluorescence intensity at ion time;
(3) taking the fluorescent carbon dot ethanol solution in the step (1) and containing Al to be detected3+Ions and Cu2+Preparing the ionic ethanol solution into mixed solution, respectively measuring and calculating Al according to the test conditions in the step (2)3+Ion corresponding ln (F/F)0) And Cu2+F/F corresponding to ion0Then respectively calculating Al according to the standard curve in the step (2)3+Ions and Cu2+The concentration of the ions.
3. The method according to claim 1 or 2, characterized in that: in detecting Al3+In the ionic method, in the step (2), the reaction time is 1-2 min.
4. The method of claim 2, wherein: in detecting Cu2+In the ionic method, in the step (2), the reaction time is 45-90 min.
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