Disclosure of Invention
The invention aims to solve the technical problem of providing a method for identifying various metal ions through fluorescent carbon dots, which utilizes the difference phenomenon of the fluorescent response of the fluorescent emission intensity of the carbon dots to different metal ions under different excitation wavelengths to realize the detection and identification of various metal ions, thereby being suitable for the detection and analysis of multi-substrate samples under complex environments in practical application.
In order to solve the above technical problems, an aspect of the present invention provides a method for identifying a plurality of metal ions through a fluorescent carbon dot, including:
providing N kinds of fluorescent carbon dots (N is more than or equal to 1), wherein the N kinds of fluorescent carbon dots are provided with a plurality of fluorescence emission channels in total;
providing N groups of metal ion aqueous solutions with equal concentration, and correspondingly adding one aqueous solution of the fluorescent carbon dots into each group of metal ion aqueous solutions; wherein each group of the aqueous solution of metal ions is selected from Al3+,Fe3+,Co2+,Ni2+,Cu2+,Zn2+,Hg2+,Cd2+,Ca2+,Mg2+、Ba2+、Na+、Cr2+、Ni2+、Mn2+、Ce3+、Pb2+At least one of aqueous solutions of (a);
detecting the fluorescence intensity value of the solution under each fluorescence emission channel before and after adding the metal ion aqueous solution, performing principal component analysis on the obtained fluorescence intensity change data, and establishing a standard principal component analysis chart; and
providing N groups of solutions to be detected, correspondingly adding one aqueous solution of the fluorescent carbon dots into each group of solutions to be detected, detecting the fluorescence intensity value of the solutions under each fluorescence emission channel before and after the solutions to be detected are added, carrying out principal component analysis on the obtained fluorescence intensity change data, and identifying the detection substrate in the solutions to be detected according to the positions of the obtained values in a standard principal component analysis diagram.
Further, the at least one fluorescent carbon dot is a single peak fluorescent carbon dot and a double peak fluorescent carbon dot.
Further, the preparation method of the aqueous solution of the single-peak fluorescent carbon dot comprises the following steps: dissolving a carbon source in ethanol to obtain a reaction precursor; carrying out hydrothermal reaction on the obtained reaction precursor at 120-240 ℃ for 2-12 h to obtain a single-peak fluorescent carbon dot aqueous solution;
the preparation method of the aqueous solution of the bimodal fluorescent carbon dots comprises the following steps: dissolving a carbon source in ethanol, and adding a reductive nitrogen source to obtain a reaction precursor; and carrying out hydrothermal reaction on the obtained reaction precursor at 120-240 ℃ for 2-12 h to obtain the multimodal fluorescent carbon dot aqueous solution.
Further, the carbon source is selected from one of 5-aminoisophthalic acid, 2-aminoisophthalic acid, 4-aminoisophthalic acid, 2-aminoterephthalic acid, 2, 5-diaminoterephthalic acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 3-aminophthalic acid, and 4-aminophthalic acid.
Further, the reducing nitrogen source is selected from one of ethylenediamine, ammonia water, ethanolamine, propylamine, 1, 2-propylenediamine, 1, 3-propylenediamine, hydrazine hydrate, triethylamine and diethylamine.
Further, the molar ratio of the carbon source to the reductive nitrogen source is 1: 1-1: 10.
Further, the method also comprises the step of carrying out post-treatment on the obtained fluorescent carbon dot aqueous solution; the post-treatment comprises the following steps: and centrifuging the fluorescent carbon dot aqueous solution to remove large-particle impurities, and then carrying out rotary evaporation to obtain powdery fluorescent carbon dots dissolved in deionized water.
Furthermore, the concentration of the fluorescent carbon dot aqueous solution is 0.001-0.01 g/L, and the concentration of the metal ion aqueous solution is 0.5-5 mM.
Furthermore, the volume ratio of the aqueous solution of the fluorescent carbon dots to the aqueous solution of the metal ions is 1: 1-1: 10.
According to another aspect of the present application, there is provided a detector that implements any of the above-described methods of identifying a plurality of metal ions.
The invention has the beneficial effects that:
1. the method synthesizes carbon dots by a solvothermal method, has simple operation, is easy to synthesize and is convenient for practicality.
2. According to the invention, multiple carbon point emission peaks under different excitation wavelengths are combined, and the detection and analysis of multiple metal ions are realized through the difference of responses of the combination to each metal ion under multiple emission states, so that the detection and analysis of multiple substrate samples under complex environments in practical application can be realized. The method realizes simultaneous detection and discrimination of at most 17 metal cations by using only 1-2 carbon dots, avoids complex synthesis process, simplifies detection process, and has excellent environmental friendliness and chemical economy.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
As described in the background, the conventional "lock-and-key" type "single-to-single" chemical detection is difficult to meet the higher requirements of complex system detection in real life, and thus, the detection of multiple substrates for researching carbon spots is particularly important. In order to solve this technical problem, the present application provides a solution that can identify a plurality of metal ions through fluorescent carbon dots.
The method specifically comprises the following steps:
providing N kinds of fluorescent carbon dots (N is more than or equal to 1), wherein the N kinds of fluorescent carbon dots are provided with a plurality of fluorescence emission channels in total;
providing N groups of metal ion aqueous solutions with equal concentration, and correspondingly adding one aqueous solution of the fluorescent carbon dots into each group of metal ion aqueous solutions; wherein each group of the aqueous solution of metal ions is selected from Al3+,Fe3+,Co2+,Ni2+,Cu2+,Zn2+,Hg2+,Cd2+,Ca2+,Mg2+、Ba2+、Na+、Cr2+、Ni2+、Mn2+、Ce3+、Pb2+At least one of aqueous solutions of (a);
detecting the fluorescence intensity value of the solution under each fluorescence emission channel before and after adding the metal ion aqueous solution, performing principal component analysis on the obtained fluorescence intensity change data, and establishing a standard principal component analysis chart; and
providing N groups of solutions to be detected, correspondingly adding one aqueous solution of the fluorescent carbon dots into each group of solutions to be detected, detecting the fluorescence intensity value of the solutions under each fluorescence emission channel before and after the solutions to be detected are added, carrying out principal component analysis on the obtained fluorescence intensity change data, and identifying the detection substrate in the solutions to be detected according to the positions of the obtained values in a standard principal component analysis diagram.
The N fluorescent carbon dots in the present application have a plurality of fluorescence emission channels (alternatively referred to as fluorescence emission peaks) in total, and preferably have at least 3 fluorescence emission channels. The principle is as follows: the detection and identification of various metal ions are realized through the differentiation phenomenon of the responsiveness of a plurality of fluorescence emission peaks to different metal ions.
In an exemplary embodiment of the present application, the N fluorescent carbon dots are a single-peak fluorescent carbon dot and a double-peak fluorescent carbon dot, and have a total of 3 fluorescent emission channels. Preferably, the particle size of the monomodal fluorescent carbon dot and the bimodal fluorescent carbon dot used is 1 to 10 nm.
The application also provides a preparation method of the aqueous solution of the monomodal fluorescent carbon dot and the aqueous solution of the bimodal fluorescent carbon dot. The preparation method of the monomodal fluorescent carbon dot aqueous solution comprises the following steps: dissolving a carbon source in ethanol to obtain a reaction precursor; and carrying out hydrothermal reaction on the obtained reaction precursor at 120-240 ℃ for 2-12 h to obtain a brown-yellow single-peak fluorescent carbon dot aqueous solution.
The preparation method of the aqueous solution of the bimodal fluorescent carbon dots comprises the following steps: dissolving a carbon source in ethanol, and adding a reductive nitrogen source to obtain a reaction precursor; and carrying out hydrothermal reaction on the obtained reaction precursor at 120-240 ℃ for 2-12 h to obtain a brown-yellow multi-peak fluorescent carbon dot aqueous solution.
In the preparation method, the carbon source is a molecule containing a benzene ring, an amino group and a carboxyl group structure. Preferably, the carbon source is selected from one of 5-aminoisophthalic acid, 2-aminoisophthalic acid, 4-aminoisophthalic acid, 2-aminoterephthalic acid, 2, 5-diaminoterephthalic acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 3-aminophthalic acid, and 4-aminophthalic acid. The reductive nitrogen source is selected from one of ethylenediamine, ammonia water, ethanolamine, propylamine, 1, 2-propane diamine, 1, 3-propane diamine, hydrazine hydrate, triethylamine and diethylamine. Preferably, the molar ratio of the carbon source to the reductive nitrogen source is 1: 1-1: 10.
In order to reduce the impurity content in the prepared fluorescent carbon dots and improve the purity, the method preferably further comprises the step of carrying out post-treatment on the obtained unimodal fluorescent carbon dot solution and the multimodal fluorescent carbon dot solution. The post-treatment may be: centrifuging the prepared fluorescent carbon dot solution to remove large-particle impurities in the solution; the solution of the initial product is then subjected to rotary evaporation and the powder obtained is dissolved in deionized water.
In the application, the concentration of the fluorescent carbon dot aqueous solution is preferably 0.001-0.01 g/L, and more preferably 0.005 g/L. The concentration of the metal ion aqueous solution is preferably 0.5-5 mM. The volume ratio of the fluorescent carbon dot aqueous solution to the metal ion aqueous solution is preferably 1: 1-1: 10.
In the application, the used excitation wavelength is 265-415 nm in the measurement process of fluorescence intensity. Preferably, the excitation wavelength of the single-peak fluorescent carbon dot is near 315nm, and the wave peak of the fluorescence emission peak is near 415 nm. Preferably, when the excitation wavelength of the bimodal fluorescent carbon dot is near 315nm, the fluorescence emission peak is near 415 nm; when the excitation wavelength is near 390nm, the fluorescence emission peak is near 510 nm.
In another embodiment of the present application, there is provided a detector capable of detecting and identifying a plurality of metal ions, the detector implementing any of the above-described methods for identifying a plurality of metal ions by fluorescent carbon dots.
The scheme of the present application will be further described with reference to the following examples.
Example 1
(1) Weighing 0.3g of 5-amino isophthalic acid, placing the 5-amino isophthalic acid in a beaker, adding 30mL of ethanol, stirring until the solid is completely dissolved, and obtaining 2 different precursors by parallel experiments without adding a nitrogen source and adding 1mL of ethylenediamine; respectively transferring the uniformly dispersed precursor solution to a hydrothermal reaction kettle with a polytetrafluoroethylene inner container, and reacting in an oven at the reaction temperature: 180 ℃, reaction time: obtaining 2 different carbon point solutions after 10 hours; centrifuging the resulting solution to remove large particle impurities; and then carrying out rotary evaporation on the primary product solution to obtain powder, and dissolving the powder by using deionized water for later use.
Taking a monomodal fluorescent carbon dot CD1 without ethylenediamine as an example, the particle size of the monomodal fluorescent carbon dot is characterized by a transmission electron microscope, and the particle size ranges from 2nm to 5nm (see attached figure 2); the fluorescence emission peak of the fluorescent carbon dot CD1 is 415nm (see FIG. 3); the bimodal fluorescent carbon dot CD2 obtained by adding ethylenediamine for reaction has 2 fluorescence emission peaks under different excitations, wherein the fluorescence emission peak is 415nm when the excitation wavelength is 315nm, and the fluorescence emission peak is 510nm when the excitation wavelength is 390nm (see figure 4).
(2) Respectively adding the fluorescent carbon dot aqueous solution into a certain amount of metal ion aqueous solution with the same concentration, and testing the fluorescence intensity of the solution before and after the addition; the ratio of the change in fluorescence before and after addition of metal ions was calculated, and the ratio of the change in fluorescence intensity before and after addition of metal ions was taken as the abscissa and the ordinate, and a bar graph of the fluorescence response of carbon dots to different metal ions was established (see fig. 5). And (3) obtaining the grouping and component similarity result and identification analysis of each detection substrate by performing statistical Principal Component Analysis (PCA) on the calculated change ratio of the fluorescence before and after the metal ions are added. For Al3+,Fe3 +,Co2+,Ni2+,Cu2+,Zn2+,Hg2+,Cd2+,Ca2+,Mg2+、Ba2+、Na+、Cr2+、Ni2+、Mn2+、Ce3+、Pb2+The 17 metal cation detection can be completely distinguished and grouped after 3 times of repeated experiments (see figure 6).
Example 2
(1) Weighing 0.5g of 2-aminoterephthalic acid, placing the 2-aminoterephthalic acid in a beaker, adding 50mL of ethanol, stirring until the solid is completely dissolved, obtaining 2 different precursors by adding 1.2mL of hydrazine hydrate without adding a nitrogen source through a parallel experiment, respectively transferring the uniformly dispersed precursor solutions to a hydrothermal reaction kettle with a polytetrafluoroethylene inner container, and reacting in an oven at the reaction temperature: 180 ℃, reaction time: obtaining 2 different carbon point solutions after 8 hours; centrifuging the resulting solution to remove large particle impurities; and then carrying out rotary evaporation on the primary product solution to obtain powder, and dissolving the powder by using deionized water for later use.
(2) Respectively adding the fluorescent carbon dot aqueous solution into a certain amount of metal ion aqueous solution with the same concentration, and testing the fluorescence intensity of the mixed solution; calculating the change ratio of the fluorescence before and after adding the metal ions, taking different metal ions as the abscissa and the change ratio of the fluorescence intensity before and after adding the metal ions as the ordinate, and establishing a bar graph of the fluorescence response of the carbon points to different metal ions; and (3) obtaining the grouping and component similarity result and identification analysis of each detection substrate by performing statistical Principal Component Analysis (PCA) on the calculated change ratio of the fluorescence before and after the metal ions are added.
Example 3
(1) Weighing 0.3g of 4-aminophthalic acid, placing the 4-aminophthalic acid in a beaker, adding 30mL of ethanol, stirring until the solid is completely dissolved, obtaining 2 different precursors by a parallel experiment without adding a nitrogen source and adding 0.8mL of ethanolamine, respectively transferring the uniformly dispersed precursor solutions to a hydrothermal reaction kettle with a polytetrafluoroethylene inner container, and reacting in an oven at the reaction temperature: 200 ℃, reaction time: obtaining 2 different carbon point solutions after 10 hours; centrifuging the resulting solution to remove large particle impurities; and then carrying out rotary evaporation on the primary product solution to obtain powder, and dissolving the powder by using deionized water for later use.
(2) Respectively adding the fluorescent carbon dot aqueous solution into a certain amount of metal ion aqueous solution with the same concentration, and testing the fluorescence intensity of the mixed solution; calculating the change ratio of the fluorescence before and after adding the metal ions, taking different metal ions as the abscissa and the change ratio of the fluorescence intensity before and after adding the metal ions as the ordinate, and establishing a bar graph of the fluorescence response of the carbon points to different metal ions; and (3) obtaining the grouping and component similarity result and identification analysis of each detection substrate by performing statistical Principal Component Analysis (PCA) on the calculated change ratio of the fluorescence before and after the metal ions are added.
Example 4
(1) Weighing 0.5g of p-aminobenzoic acid, placing the p-aminobenzoic acid in a beaker, adding 50mL of ethanol, stirring until the solid is completely dissolved, obtaining 2 different precursors by adding 1.0mL of 1, 2-propane diamine and not adding a nitrogen source in a parallel experiment, respectively transferring the uniformly dispersed precursor solutions to a hydrothermal reaction kettle with a polytetrafluoroethylene inner container, and reacting in an oven at the reaction temperature: 200 ℃, reaction time: obtaining 2 different carbon point solutions after 6 hours; centrifuging the resulting solution to remove large particle impurities; and then carrying out rotary evaporation on the primary product solution to obtain powder, and dissolving the powder by using deionized water for later use.
(2) Respectively adding the fluorescent carbon dot aqueous solution into a certain amount of metal ion aqueous solution with the same concentration, and testing the fluorescence intensity of the mixed solution; calculating the change ratio of the fluorescence before and after adding the metal ions, taking different metal ions as the abscissa and the change ratio of the fluorescence intensity before and after adding the metal ions as the ordinate, and establishing a bar graph of the fluorescence response of the carbon points to different metal ions; and (3) obtaining the grouping and component similarity result and identification analysis of each detection substrate by performing statistical Principal Component Analysis (PCA) on the calculated change ratio of the fluorescence before and after the metal ions are added.
Example 5
(1) Weighing 0.4g of 2, 5-diamino terephthalic acid, placing the 2, 5-diamino terephthalic acid in a beaker, adding 40mL of ethanol, stirring until the solid is completely dissolved, obtaining 2 different precursors by adding no nitrogen source and 1.0mL of triethylamine through a parallel experiment, respectively transferring the uniformly dispersed precursor solutions to a hydrothermal reaction kettle with a polytetrafluoroethylene inner container, and reacting in an oven at the reaction temperature: 200 ℃, reaction time: obtaining 2 different carbon point solutions after 8 hours; centrifuging the resulting solution to remove large particle impurities; and then carrying out rotary evaporation on the primary product solution to obtain powder, and dissolving the powder by using deionized water for later use.
(2) Respectively adding the fluorescent carbon dot aqueous solution into a certain amount of metal ion aqueous solution with the same concentration, and testing the fluorescence intensity of the mixed solution; calculating the change ratio of the fluorescence before and after adding the metal ions, taking different metal ions as the abscissa and the change ratio of the fluorescence intensity before and after adding the metal ions as the ordinate, and establishing a bar graph of the fluorescence response of the carbon points to different metal ions; and (3) obtaining the grouping and component similarity result and identification analysis of each detection substrate by performing statistical Principal Component Analysis (PCA) on the calculated change ratio of the fluorescence before and after the metal ions are added.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.