CN116478688B - Carbon quantum dot for detecting mercury ions, synthesis method thereof, mercury ion detection kit and application thereof - Google Patents
Carbon quantum dot for detecting mercury ions, synthesis method thereof, mercury ion detection kit and application thereof Download PDFInfo
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- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 59
- -1 mercury ions Chemical class 0.000 title claims abstract description 58
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000001514 detection method Methods 0.000 title claims abstract description 49
- 238000001308 synthesis method Methods 0.000 title claims abstract description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 36
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- 231100000053 low toxicity Toxicity 0.000 description 1
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
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- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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Abstract
The invention provides a carbon quantum dot for detecting mercury ions, a synthesis method thereof, a mercury ion detection test and application thereof, wherein citric acid, urea and L-cysteine are used as raw materials, the carbon quantum dot is prepared by a hydrothermal method, the excitation wavelength of the prepared carbon quantum dot is 325-425 nm, blue fluorescence with the wavelength of 400-550 nm can be emitted, the synthesis method is simple and rapid, and the prepared carbon quantum dot has excellent fluorescence performance. By utilizing the carbon quantum dot, the detection of mercury ions in the solution can be realized through a molecular fluorescence spectrophotometer, and the detection method is sensitive and quick. Meanwhile, the portable mercury ion detection method is also provided, and the detection method is convenient and simple.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a carbon quantum dot for detecting mercury ions, a synthesis method thereof, a mercury ion detection kit and application thereof.
Background
As one of the most common heavy metals in the environment, mercury ions can be enriched into human bodies through food chains, and the harm is large. Therefore, trace detection of mercury ions is of great importance. Traditional mercury ion detection methods mainly comprise atomic fluorescence spectrometry, inductively coupled plasma emission spectrometry, inductively coupled plasma mass spectrometry and the like. However, these methods have the disadvantages of time consuming sample processing, high cost, need for professional handling, etc., and are difficult to meet the requirements of portable detection under new circumstances, which severely limits their practical application. Fluorescent nano-materials are widely applied to trace determination of heavy metal ions due to high sensitivity and excellent specificity. The carbon quantum dots are used as novel fluorescent nano materials, and have the advantages of simple synthesis, excellent optical properties and low toxicity.
Disclosure of Invention
In order to overcome the technical problems in the prior art, the invention provides the carbon quantum dot for detecting the mercury ions, the synthesis method thereof, the mercury ion detection kit and the application thereof, the synthesis method is simple, the fluorescence spectrometry and the portable rapid detection of the mercury ions can be realized by utilizing the synthesized carbon quantum dot, and the kit is high in sensitivity and excellent in specificity.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the first aspect of the invention provides a carbon quantum dot for detecting mercury ions, wherein the excitation wavelength of the carbon quantum dot is 325-425 nm, and the carbon quantum dot can emit blue fluorescence with the wavelength of 400-550 nm.
As an alternative embodiment, in the carbon quantum dot provided by the invention, blue fluorescence with an optimal wavelength of 450nm can be emitted.
As an alternative embodiment, in the carbon quantum dot provided by the invention, the ultraviolet absorption peaks of the carbon quantum dot are 230nm and 340nm.
As an alternative embodiment, in the carbon quantum dot provided by the invention, when the pH value of the solution is greater than 4, the fluorescence of the carbon quantum dot at 450nm is stable.
The second aspect of the invention provides a method for synthesizing carbon quantum dots for detecting mercury ions, which comprises the steps of dissolving citric acid, urea and L-cysteine in water, and reacting by adopting a hydrothermal method to obtain the carbon quantum dots.
In the invention, citric acid is used as a carbon source for synthesizing carbon quantum dots and improving fluorescence intensity, urea and L-cysteine are used as nitrogen sources and sulfur sources, and respond to mercury ions.
As an alternative implementation mode, in the synthesis method provided by the invention, the molar ratio of the citric acid to the urea to the L-cysteine is (2.0-10.0): 10.0-40.0): 0.5-1.5.
In the present invention, the ratio of the three substances is limited to the above range, and too low or too high a ratio may affect the maximum fluorescence intensity and wavelength of the carbon quantum dots.
In an alternative embodiment, in the synthesis method provided by the invention, the reaction temperature of a hydrothermal method is 180 ℃ and is heated for 3 hours, and after the reaction, the reaction is subjected to centrifugation and filtration treatment.
As an alternative embodiment, in the synthesis method provided by the invention, the pore size of the filter membrane used for filtration is 0.22 μm.
In a third aspect, the invention provides a mercury ion detection kit comprising carbon quantum dots as described above.
In an optional embodiment, the kit further comprises a buffer solution, wherein the buffer solution is one of potassium hydrogen phthalate buffer solution or potassium hydrogen tartrate and other acidic buffer solutions, and the volume ratio of the buffer solution to the carbon quantum dot solution is 20:1-1:1.
Preferably, the buffer solution is potassium hydrogen phthalate buffer solution, and the volume ratio of the buffer solution to the carbon quantum dot solution is 9:1.
The fourth aspect of the invention provides an application of the carbon quantum dot or the detection kit in detecting mercury ions.
In an alternative embodiment, in the application provided by the present invention, the method for detecting mercury ions comprises the steps of:
s1, taking a carbon quantum dot solution, a buffer solution and mercury ion standard solutions with different concentrations, mixing, and standing at room temperature.
S2, measuring fluorescence intensity F of the fluorescent material at 450nm at 365nm of excitation wavelength by using a molecular fluorescence spectrophotometer, and recording different valuesFluorescence intensity F of soluble mercury ions and fluorescence intensity F of blank solution 0 The ratio between them to obtain F/F 0 And (3) obtaining a standard curve by linear relation between the standard curve and the concentration of the mercury ion standard solution.
S3, mixing the mercury ion solution to be detected, the carbon quantum dot solution and the buffer solution, standing, and measuring the fluorescence intensity F of the mercury ion solution to be detected at 450nm at 365nm excitation wavelength by using a molecular fluorescence spectrophotometer 1 And (3) calculating to obtain the solubility of the mercury ion solution to be measured by using the standard curve obtained in the step (S2).
In the present invention, since the fluorescence intensity (450 nm) at 365nm excitation wavelength is maximum, the fluorescence intensity F is used as an index for detection.
In an alternative embodiment, in the application provided by the invention, the carbon quantum dot solution in the step S1 is a solution obtained by diluting the synthetic solution by 50-150 times, and the detection concentration of mercury ions is as low as 0.39 mu M.
As an alternative embodiment, in the method for detecting mercury ions provided by the invention, the concentration of the mercury ion standard solution ranges from 0 mu M to 300 mu M.
In an alternative embodiment, in the application provided by the present invention, the method for portable detection of mercury ions comprises the steps of:
(1) And (3) uniformly mixing the carbon quantum dot solution and the buffer solution in a container, immersing cotton fiber paper in the solution, taking out the solution after full absorption, drying at room temperature, and putting the solution into the bottom of the fluorescent ELISA plate.
(2) And (3) uniformly mixing mercury ion standard solutions and buffer solutions with different concentrations, adding the mixed solution into the fluorescent ELISA plate in the step (1), keeping the fluorescent ELISA plate for 0.25-1.5h in a dark place, placing a portable ultraviolet lamp in a direction which forms an angle of 45 degrees with the fluorescent ELISA plate, irradiating the fluorescent ELISA plate, and taking a photo right above the fluorescent ELISA plate through a smart phone to obtain a color fluorescent photo.
(3) Splitting a color fluorescence photograph into a photograph of three channels of blue, green and red by ImageJ software according to the change rate B/B of the blue channel 0 Obtaining B/B 0 Linear relation with the concentration of the mercury ion standard solution to obtain a standard curve。
(4) Taking mercury ion solution to be detected, and obtaining the change rate B of the blue channel by using the methods of the steps (2) and (3) 1 And (3) calculating to obtain the solubility of the mercury ion solution to be measured by using the standard curve obtained in the step (3).
As an alternative embodiment, in the application provided by the invention, the detection concentration of mercury ions is as low as 0.78 mu M by the portable method for detecting mercury ions.
As an alternative embodiment, in the application provided by the invention, the use solubility of the carbon quantum dot solution is the stock solution of the synthesis solution.
In an alternative embodiment, the portable method for detecting mercury ions provided by the invention has a concentration of the mercury ion standard solution ranging from 0 to 400 mu M.
In an alternative implementation manner, in the portable method for detecting mercury ions provided by the invention, the filter paper in the step (1) is cut into a round shape with the diameter of 1cm after being dried, and then the round shape is placed at the bottom of a small hole of a 96-hole fluorescent ELISA plate after being subjected to quartering, and then mercury ion standard solution and buffer solution are added for mixing.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the carbon quantum dot which has the excitation wavelength of 325-425 nm and can emit blue fluorescence with the optimal wavelength of 450nm is obtained for the first time.
(2) The synthesis method disclosed by the invention takes citric acid, urea and L-cysteine as raw materials, and the carbon quantum dot is prepared by a hydrothermal method, and the synthesis method is simple and quick, and the prepared carbon quantum dot has excellent fluorescence performance.
(3) In the invention, mercury ions are detected by utilizing a fluorescence spectrum method, and the detection method is sensitive and rapid. The portable method is used for detecting mercury ions, and the detection method is convenient and simple.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an ultraviolet absorption spectrum of the carbon quantum dots prepared in example 1;
FIG. 2 is a graph showing fluorescence emission properties of the carbon quantum dots prepared in example 1 without excitation wavelength adjustment;
FIG. 3 is a graph showing pH-adjusted fluorescence emission properties of the carbon quantum dots prepared in example 1;
FIG. 4 is a graph of the photo-bleaching resistance of the carbon quantum dots prepared in example 1;
fig. 5 is a fourier infrared spectrum of the carbon quantum dot prepared in example 1;
FIG. 6 is an X-ray photoelectron spectrum of the carbon quantum dot prepared in example 1;
FIG. 7 is a schematic diagram of the principle of fluorescence spectrometry for detecting mercury ions;
FIG. 8 is a fluorescence spectrum and a linear fitting graph of mercury ion detection by fluorescence spectrometry;
FIG. 9 is a graph of the results of specific detection of mercury ions by fluorescence spectrometry;
FIG. 10 is a schematic diagram of portable detection of mercury ions;
FIG. 11 is a time optimized graph of portable detection of mercury ions (199.4. Mu.M);
FIG. 12 is a linear fit of portable detection of mercury ions, with the inset being a fluorescence photograph of the response of different concentrations of mercury ions;
FIG. 13 is a specific diagram of portable detection of mercury ions, with the inset being a fluorescence photograph of the response of different species of heavy metal ions;
FIG. 14 is a transmission electron microscope image of the carbon quantum dots before and after binding to mercury ions (99.70. Mu.M);
FIG. 15 is a graph showing the result of detecting mercury ions by using a carbon quantum dot fluorescence spectrometry prepared in comparative example 1;
fig. 16 is a graph showing a specific detection result of mercury ions by using the carbon quantum dot fluorescence spectrometry prepared in comparative example 2.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
A synthesis method of carbon quantum dots comprises the following steps:
(1) 0.10g of citric acid, 0.11g of urea and 0.01g of L-cysteine are respectively weighed according to the molar ratio of 5.8:22.2:1.0, and dispersed in 5mL of secondary water by ultrasonic treatment for 10min.
(2) The solution was transferred to a high-pressure reactor, heated at 180℃for 3 hours, and cooled to room temperature. Centrifuging at 6000rpm/min for 10min, treating with a filter membrane with pore diameter of 0.22 μm, and storing the treated solution in a refrigerator at 4deg.C.
Example 2
A synthesis method of carbon quantum dots comprises the following steps:
(1) 0.15g of citric acid, 0.30g of urea and 0.02g of L-cysteine are respectively weighed according to the molar ratio of 4.7:30.3:1.0, and dispersed in 5mL of secondary water by ultrasonic treatment for 10min.
(2) The solution was transferred to a high-pressure reactor, heated at 150℃for 4 hours, and cooled to room temperature. Centrifuging at 6000rpm/min for 10min, treating with a filter membrane with pore diameter of 0.22 μm, and storing the treated solution in a refrigerator at 4deg.C.
Example 3
1. Detection of mercury ions by fluorescence spectrometry
The principle is shown in fig. 7, after the carbon quantum dot solution synthesized by citric acid, urea and L-cysteine in example 1 is diluted 100 times, blue fluorescence can be quenched by mercury ions under an ultraviolet lamp. Based on this phenomenon, a fluorescence spectroscopy detection test was performed. The method comprises the following specific steps:
(1) 100. Mu.L of the carbon quantum dot solution prepared in example 1 was diluted 100 times, 200. Mu.L of potassium hydrogen phthalate buffer solution (pH 4.0), and 100. Mu.L of mercury ion standard solutions with different concentrations (0.097. Mu.M, 0.19. Mu.M, 0.39. Mu.M, 0.78. Mu.M, 1.56. Mu.M, 3.12. Mu.M, 179.45. Mu.M, 199.40. Mu.M, respectively) were taken. Respectively mixing, and standing at room temperature for 10min.
(2) The fluorescence intensity F at 450nm was determined by means of a molecular fluorescence spectrophotometer at an excitation wavelength of 365 nm. When Hg is 2+ As the concentration gradually increases, the fluorescence intensity F gradually decreases, as shown in fig. 8A. By recording the fluorescence intensity F of F and blank solution 0 The ratio between them is explored F/F 0 With Hg 2+ The linear relationship between standard solution concentrations, as shown in fig. 8B, the standard curve is as follows: y= -0.00436x+1.00448, r 2 = 0.99723, where Y is the rate of change of the fluorescence intensity of the carbon quantum dots, X is the mercury ion concentration, R 2 Is a linear fitting constant. The linear range of the method is 0.39-79.76 mu M, and the detection limit is 0.29 mu M.
(3) 100. Mu.L of mercury ion solution to be detected, 100. Mu.L of carbon quantum dot solution prepared in example 1 and 200. Mu.L of potassium hydrogen phthalate buffer solution (pH 4.0) are diluted by 100 times, and the mixture is uniformly mixed and then left at room temperature for 10min. The fluorescence intensity F at 450nm was measured at an excitation wavelength of 365nm by means of a molecular fluorescence spectrophotometer 1 And calculating according to a standard curve Y= -0.00436X+1.00448 to obtain the mercury ion concentration of the sample to be detected. The specific detection concentrations are shown in Table 1.
2. Specific test of mercury ion detection method by fluorescence spectrum method
(1) Preparation of 79.76. Mu.M of other ions (Ag + 、Al 3+ 、As 3+ 、Ca 2+ 、Cd 2+ 、Co 2+ 、Cr 3+ 、Cr 6+ 、Cu 2+ 、Fe 3+ 、Mg 2+ 、Ni 2+ 、Zn 2+ 、Pb 2+ ) Standard ofAnd (5) carrying out detection specificity investigation on the solution.
(2) 100. Mu.L of the carbon quantum dot solution prepared in example 1 diluted 100 times, 200. Mu.L of potassium hydrogen phthalate buffer solution (pH 4.0) and 100. Mu.L of the 14 ion standard solutions were respectively removed, mixed, allowed to stand at room temperature for 10min, and the fluorescence intensity F at 450nm was measured at an excitation wavelength of 365 nm. As a result, as shown in FIG. 9A, only Hg was used 2+ The fluorescence intensity of the carbon quantum dots can be induced to decrease. Record fluorescence intensity F of F and blank solution 0 The ratio between them. Further F/F 0 The result shows that the fluorescent probe carbon quantum dot has higher specificity for mercury ion measurement, and the result is shown in figure 9B.
3. Accuracy test of mercury ion detection method by fluorescence spectrum method
The method for carrying out the standard adding recovery test on mercury ions in drinking water, tap water and river water comprises the following specific steps:
(1) Filtering drinking water, laboratory tap water and Liuyang river water with 0.22 μm filter membrane, and adding different concentrations of mercury ion standard solution to obtain solutions with concentrations of 1.00 μm,12.46 μm and 49.85 μm.
(2) 100. Mu.L of the carbon quantum dot solution prepared in example 1 diluted by 100 times, 200. Mu.L of potassium hydrogen phthalate buffer solution (pH 4.0) and 100. Mu.L of the above-mentioned labeled sample were removed, and the labeled recovery rate of mercury ions was detected by fluorescence spectrometry.
The results are shown in table 1, and the results show that the fluorescence spectrometry is used for detecting the standard recovery rate of mercury ions in drinking water, tap water and river water, namely 97.4% -105.2%, and the method has higher accuracy in detecting mercury ions in actual samples.
Example 4
1. Portable mercury ion detection method
The principle is shown in fig. 10, and the experiment is carried out according to the phenomenon that the fluorescence of the carbon quantum dot solution is quenched by mercury ions. And adding the mercury ion to-be-detected kit immersed with the carbon quantum dot filter paper into the kit in advance, adding a to-be-detected mercury ion and potassium hydrogen phthalate buffer solution (pH 4.0), and realizing portable and rapid detection of mercury ions by analyzing the intensity change of a color fluorescent photo by means of a portable ultraviolet lamp and a smart phone photographing function. The method comprises the following specific steps:
(1) 1mL of the carbon quantum dot solution synthesized in example 1 was mixed with 9mL of potassium hydrogen phthalate buffer solution (pH 4.0), placed in a plastic petri dish, and a piece of filter paper was slowly immersed therein, and after 10min, the filter paper was taken out and dried at room temperature. And uniformly shearing the dried filter paper into a round shape with the diameter of 1cm, and then putting the round shape into the bottom of a small hole of a 96-hole fluorescent ELISA plate after quartering to serve as a mercury ion detection kit.
(2) Respectively transferring 150 mu L of mercury ion standard solution and 150 mu L of potassium hydrogen phthalate buffer solution (pH4.0) with different concentrations (the concentrations are respectively 0.097 mu M, 0.19 mu M, 0.39 mu M, 0.78 mu M, 1.56 mu M, 3.12 mu M, 179.45 mu M, 199.40 mu M and 399.80 mu M) into a mercury ion kit to be detected, stirring and mixing uniformly, placing in a dark and light-proof environment for 30min (the light-proof time optimization result is shown in figure 11), placing a portable ultraviolet lamp in a direction at an angle of 45 degrees with a plane, irradiating the mercury ion kit to be detected, and photographing right above the kit by a smart phone to obtain color fluorescence intensity information.
(3) Splitting a color fluorogram into three-channel photographs of blue (B), green (G) and red (R) by imageJ software, the rate of change of the blue channel (B/B) 0 ) There is a linear relationship with mercury ion concentration, and the results are shown in fig. 12, with the standard curves as follows: y= -0.00096x+0.93622, r 2 = 0.98542. The linear range of the method is 0.78-199.40 mu M, and the detection limit is 0.55 mu M.
(4) Taking mercury ion solution to be detected, and obtaining the change rate B of the blue channel by using the methods of the steps (2) and (3) 1 And (3) calculating the solubility of the mercury ion solution of the sample to be detected by using the standard curve Y= -0.00096X+0.93622 obtained in the step (3). The specific detection concentrations are shown in Table 1.
2. Specificity test of portable mercury ion detection method
(1) Preparation of 199.40. Mu.M other ions (Ag + 、Al 3+ 、As 3+ 、Ca 2+ 、Cd 2+ 、Co 2+ 、Cr 3+ 、Cr 6+ 、Cu 2+ 、Fe 3+ 、Mg 2+ 、Ni 2+ 、Zn 2+ 、Pb 2+ ) And (5) standard solution, and performing detection specificity investigation.
(2) 1mL of the carbon quantum dot solution synthesized in example 1 was mixed with 9mL of potassium hydrogen phthalate buffer solution (pH 4.0), placed in a plastic petri dish, and a piece of filter paper was slowly immersed therein, and after 10min, the filter paper was taken out and dried at room temperature. And uniformly shearing the dried filter paper into a round shape with the diameter of 1cm, and putting the round shape into the bottom of a small hole of a 96-hole fluorescent ELISA plate after quartering to serve as a kit to be detected.
(3) And respectively transferring 150 mu L of the solutions of different ions and 150 mu L of potassium hydrogen phthalate buffer solution (pH 4.0) into the kit to be detected, stirring and mixing uniformly, placing in a dark and light-proof environment for 30min, placing a portable ultraviolet lamp in a direction forming an angle of 45 degrees with a plane, irradiating the kit to be detected, and photographing right above the kit by a smart phone to obtain color fluorescence intensity information. The results are shown in FIG. 13, and the mobile phone photographing results show that the blue fluorescence of all the solutions in the kit is hardly reduced. The carbon quantum dots in the invention can be specifically used for detecting mercury ions.
3. Accuracy test of portable mercury ion detection method
The method for carrying out the standard adding recovery test on mercury ions in drinking water, tap water and river water comprises the following specific steps:
(1) Filtering drinking water, tap water and river water with 0.22 μm filter membrane, and adding different concentrations of mercury ion standard solution to obtain solutions with concentrations of 1.00 μm,12.46 μm and 49.85 μm.
(2) And respectively transferring 150 mu L of the marked sample and 150 mu L of potassium hydrogen phthalate buffer solution (pH 4.0) into a kit to be detected, and measuring the marked recovery rate of mercury ions in the marked sample under the same condition by virtue of a smart phone and a portable ultraviolet lamp.
The results are shown in table 1, and the results show that the fluorescence spectrometry is used for detecting the standard recovery rate of the mercury ions in the drinking water, tap water and river water by 95.1-110.8%, and the method has higher accuracy in detecting the mercury ions in actual samples.
Table 1: fluorescence spectroscopy and portable detection method in actual sample labeled recovery results
Comparative example 1
Carbon quantum dots were synthesized using citric acid, melamine (instead of urea), and L-cysteine as precursors, and then their specificity for mercury ions was detected by fluorescence spectroscopy in the same manner as in example 1.
100. Mu.L of the prepared carbon quantum dot solution diluted 100 times, 200. Mu.L of potassium hydrogen phthalate buffer solution (pH 4.0), 100. Mu.L of 14 ions (Ag) with a concentration of 79.76. Mu.M were removed + 、Al 3+ 、As 3+ 、Ca 2+ 、Cd 2+ 、Co 2+ 、Cr 3+ 、Cr 6 + 、Cu 2+ 、Fe 3+ 、Mg 2+ 、Ni 2+ 、Zn 2+ 、Pb 2+ ) The standard solution was allowed to stand at room temperature for 10 minutes after mixing, and the fluorescence intensity F at 450nm was measured at an excitation wavelength of 365 nm. As shown in fig. 15, the mercury ions did not induce a decrease in fluorescence intensity of the carbon quantum dots, and the specificity to mercury ions was poor.
Comparative example 2
Carbon quantum dots were synthesized using citric acid, urea, and glutathione (instead of L-cysteine) as precursors, and then their specificity for mercury ions was detected by fluorescence spectroscopy in the same manner as in example 1.
100. Mu.L of the prepared carbon quantum dot solution diluted 100 times, 200. Mu.L of potassium hydrogen phthalate buffer solution (pH 4.0), 100. Mu.L of 14 ions (Ag) with a concentration of 79.76. Mu.M were removed + 、Al 3+ 、As 3+ 、Ca 2+ 、Cd 2+ 、Co 2+ 、Cr 3+ 、Cr 6 + 、Cu 2+ 、Fe 3+ 、Mg 2+ 、Ni 2+ 、Zn 2+ 、Pb 2+ ) The standard solution was allowed to stand at room temperature for 10 minutes after mixing, and the fluorescence intensity F at 450nm was measured at an excitation wavelength of 365 nm. As shown in fig. 16, the mercury ions did not induce a decrease in fluorescence intensity of the carbon quantum dots, and the specificity to mercury ions was poor.
Performance detection
The carbon quantum dots prepared in example 1 were subjected to ultraviolet absorption spectrum detection, and as shown in fig. 1, the ultraviolet absorption peaks are at 230nm and 340nm, which are respectively attributed to pi-pi transition of c=c bond and n-pi transition of c=o bond.
The fluorescence emission of the carbon quantum dot prepared in example 1 was measured without adjustment of the excitation wavelength, and as shown in fig. 2, the fluorescence emission peak of the carbon quantum dot hardly moved when the excitation wavelength was increased from 325nm to 425 nm; when the excitation wavelength is increased from 325nm to 425nm, the emission wavelength range is 400-550 nm, and the maximum emission wavelength is 450nm.
For the fluorescence emission conditions of the carbon quantum dots prepared in example 1 under different pH values, the result is shown in FIG. 3, when the pH value of the solution is greater than 4, the fluorescence of the carbon quantum dots at 450nm is stable, and when the pH value is less than 4, the fluorescence intensity is gradually reduced.
The photo-bleaching resistance of the carbon quantum dot prepared in example 1 is tested, and the result is shown in fig. 4, and the fluorescence intensity of the carbon quantum dot solution at 450nm is basically unchanged under the irradiation of 365nm excitation light for 1h, which shows that the carbon quantum dot solution has higher photo-bleaching resistance.
The result of Fourier infrared spectrum detection of the carbon quantum dots prepared in example 1 is shown in FIG. 5, which shows 625.79cm -1 、1102.34cm -1 、1194.59cm -1 、1435.94cm -1 、1568.99cm -1 、3065.01cm -1 、3204.56cm -1 The peaks of (a) correspond to the stretching vibration of C-S, S-O, C-O, C-N, C = O, C-H and-OH groups respectively, indicating that the surface of the carbon quantum dot has carboxyl, hydroxyl, sulfhydryl and other groups.
The result of performing X-ray photoelectron detection on the carbon quantum dot prepared in example 1 is shown in fig. 6, wherein peaks of 285.03eV, 400.19eV, 532.2eV and 168.51eV can be respectively attributed to C1S, N1S, O1S and S2p, which indicates that the carbon quantum dot is mainly composed of elements such as C, N, O and S.
And carrying out transmission electron microscope detection on the carbon quantum dots and the carbon quantum dot-mercury ions (99.70 mu M). The results are shown in FIG. 14, wherein A is a transmission electron micrograph of CDs, which are approximately spherical and have good monodispersity, and the average diameter of the carbon quantum dots in the inset is 2.28nm. B is a transmission electron microscope image of the carbon quantum dots combined with 99.7 mu M mercury ions, and the average diameter of the carbon quantum dots is increased to 3.23nm, which shows that the mercury ions can induce the carbon quantum dots to agglomerate, thereby leading the carbon quantum dots to be fluorescence quenched.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (5)
1. A method for portable detection of mercury ions, comprising the steps of:
(1) Uniformly mixing a carbon quantum dot solution and a buffer solution in a container, immersing cotton fiber paper in the solution, taking out the solution after full absorption, drying at room temperature, and putting the solution into the bottom of a fluorescent ELISA plate;
(2) Uniformly mixing mercury ion standard solutions and buffer solutions with different concentrations, adding the mixed solution into the fluorescent ELISA plate in the step (1), keeping the fluorescent ELISA plate in a dark place for 0.25-1.5h, placing a portable ultraviolet lamp in a direction forming an angle of 45 degrees with the fluorescent ELISA plate, irradiating the fluorescent ELISA plate, and taking a photo right above the fluorescent ELISA plate through a smart phone to obtain a color fluorescent photo;
(3) Splitting a color fluorescent photo into photos of three channels of blue, green and red through Image J software, and obtaining a linear relation between the change rate of the blue channel and the concentration of mercury ion standard solution according to the change rate of the blue channel to obtain a standard curve, wherein the standard curve is as follows: y= -0.00096x+0.93622, r 2 = 0.98542, where Y is the rate of change of the blue channel and X is the mercury ion concentration;
(4) Obtaining a change rate of a blue channel by using the mercury ion solution to be detected and using the methods of the steps (2) and (3), and calculating the solubility of the mercury ion solution to be detected by using the standard curve obtained in the step (3);
the excitation wavelength of the carbon quantum dots is 325 nm-425 nm, and the carbon quantum dots can emit blue fluorescence with the wavelength of 400-550 nm.
2. The portable mercury ion detection method according to claim 1, wherein the synthesis method of the carbon quantum dots is characterized in that citric acid, urea and L-cysteine are dissolved in water, and the carbon quantum dots are obtained after the reaction is carried out by a hydrothermal method.
3. The portable mercury ion detection method according to claim 2, wherein the molar ratio of the citric acid, urea and L-cysteine is (2.0-10.0): 10.0-40.0): 0.5-1.5;
the reaction temperature is 150-200 ℃ and the reaction time is 2-4 h by adopting a hydrothermal method, and the reaction is treated by centrifugation and filtration.
4. The portable mercury ion detection method according to claim 1, wherein the buffer solution is one of potassium hydrogen phthalate buffer solution and potassium hydrogen tartrate buffer solution, and the volume ratio of the buffer solution to the carbon quantum dot solution is 20:1-1:1.
5. The method of claim 1, wherein the portable method of detecting mercury ions detects mercury ions at a concentration as low as 0.78 μm.
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