CN111551532A - Metal ion detection method based on graphene quantum dot fluorescent probe array - Google Patents
Metal ion detection method based on graphene quantum dot fluorescent probe array Download PDFInfo
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Abstract
The invention discloses a metal ion detection method based on a graphene quantum dot fluorescent probe array. Firstly, preparing graphene quantum dots by a hydrothermal method, and doping the graphene quantum dots by taking the graphene quantum dots as raw materials to sequentially prepare nitrogen-doped graphene quantum dots, phosphorus-doped graphene quantum dots, sulfur-doped graphene quantum dots and boron-doped graphene quantum dots; then, a fluorescent probe array is formed by the graphene quantum dots and the doped graphene quantum dots, the change of the fluorescence intensity of the graphene quantum dots caused by various metal ions is recorded, and the metal ions are detected and distinguished by a linear discriminant analysis method. The sensor array adopted by the invention has the advantages of simple preparation method, low cost and small required sample amount; the sensor array can achieve 100% of metal ion distinguishing accuracy; can detect and distinguish various metal ions at the same time; the detection period is short, and the controllability is strong; the used instruments are simple, and the result judgment is visual.
Description
Technical Field
The invention belongs to the technical field of nano science, and particularly relates to a metal ion detection method based on a graphene quantum dot fluorescent probe array.
Background
Metals and transition metals are emphasized in the wide existence in nature, some of the metal elements play a very important role in the human life process, for example, copper element plays a very important regulatory function in tumor angiogenesis factor. The growth and development of human cells, gene transcription and nerve transmission processes can not be separated from the function of zinc ions. Some elements are very toxic to living bodies, for example, lead element can cause pathological changes of nervous system, digestive system and heart, and mercury element can cause serious damage to kidney function. Therefore, the research on the detection and identification of various metal ions is beneficial to the detection of environment-harmful metal ions and the research on the action mechanism of beneficial metal elements in organisms.
Conventional methods for detecting metal ions are generally classified into direct methods and indirect methods. The direct method directly uses the chemical and physical properties of metal ions to detect them, including atomic emission/absorption spectroscopy and ion selective electrode method. The indirect method is a method of detecting metal ions by using supramolecular interaction between an indicator and metal ions or signal change of specific chemical reaction, and includes a method of comparing a conventional metal indicator with a metal ion fluorescent molecular probe which has been recently developed.
The array-based sensing method mainly achieves the purpose of detection by distinguishing the overall characteristics of analytes, and can replace the traditional 'lock-key' detection method relying on specific recognition action to be used in the field of biological analysis. The interaction between a series of identification units in the sensor array and each analyte can generate a characteristic signal fingerprint pattern aiming at the analyte, so that the identification and classification of the analyte are realized. This particular detection method is similar to the mammalian olfactory sense and is therefore also referred to as a "chemical nose or tongue" detection method. It is an effective method for analyzing subtle differences between different samples, complex sample mixtures, and even samples to be analyzed in a biological matrix.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a metal ion detection method based on a graphene quantum dot fluorescent probe array, and the adopted sensor array is simple in preparation method, low in cost and small in required sample amount; the sensor array can achieve 100% of metal ion distinguishing accuracy; can detect and distinguish various metal ions at the same time; the detection period is short, and the controllability is strong; the used instruments are simple, and the result judgment is visual.
The technical scheme is as follows: the technical scheme adopted by the invention for solving the technical problems is as follows: firstly, preparing graphene quantum dots by a hydrothermal method, doping the graphene quantum dots by taking the graphene quantum dots as raw materials, and sequentially preparing nitrogen-doped graphene quantum dots, phosphorus-doped graphene quantum dots, sulfur-doped graphene quantum dots and boron-doped graphene quantum dots; then, a fluorescent probe array is formed by the graphene quantum dots and the doped graphene quantum dots, the change of the fluorescence intensity of the graphene quantum dots caused by various metal ions is recorded, and the metal ions are detected and distinguished by a linear discriminant analysis method.
Further, the graphene quantum dots are prepared as follows: adding 30-50mg of graphene oxide powder into 30-50mL of secondary water, placing the secondary water into an ultrasonic cleaning instrument for ultrasonic dispersion, adding 1-2mL of hydrogen peroxide, and performing uniform ultrasonic dispersion; transferring the mixed solution into a reaction kettle, sealing, and reacting at 180 ℃ for 60-90 min; and (3) filtering the reaction solution through a 0.22-micron water-based filter membrane, collecting filtrate to obtain a graphene quantum dot water dispersion, and freeze-drying.
Further, the nitrogen-doped graphene quantum dot is prepared as follows: adding 50mg of graphene quantum dots into 80-100mL of secondary water, and placing the secondary water into an ultrasonic cleaning instrument for ultrasonic dispersion for 10-15 min; then, 0.25-0.30g of melamine is added into the graphene quantum dot dispersion system, and the mixture is stirred by a glass rod until obvious settlement occurs; evaporating the solvent in the mixed system by using an electrothermal sleeve, drying overnight in vacuum, and grinding into powder; putting the powder into a quartz boat, and pyrolyzing for 30-45min under the protection of argon at the temperature of 750 plus 800 ℃; then 4-6mol/L HNO is used3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the nitrogen-doped graphene quantum dots.
Further, the phosphorus-doped graphene quantum dots are prepared as follows: uniformly mixing 50mg of graphene quantum dots, 100-200mg of triphenylphosphine and 50-100mL of ethanol, and stirring at room temperature; evaporating ethanol, drying the obtained graphene quantum dot and triphenyl phosphine mixture in vacuum overnight, and grinding into powder; putting the mixture powder into a quartz boat, and pyrolyzing for 30-45min under the protection of argon at the temperature of 750 ℃ and 800 ℃; then 4-6mol/L HNO is used3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the phosphorus-doped graphene quantum dots.
Further, the sulfur-doped graphene quantum dots are prepared as follows: mixing 50mg of graphene quantum dots, 30-40mg of dibenzyl disulfide and 50-100mL of ethanol, and placing the mixture into an ultrasonic cleaner for ultrasonic dispersion for 10-15 min; evaporating ethanol to obtain a mixture of the graphene quantum dots and the dithiobenzene, drying overnight in vacuum, and grinding into powder. Putting the mixture powder into a quartz boat, and pyrolyzing the mixture powder for 30-45min at the temperature of 750 ℃ and 800 ℃ under the protection of argon; then 4-6mol/L HNO is used3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the sulfur-doped graphene quantum dots.
Further, the boron-doped graphene quantum dots are prepared as follows: 50mg of graphene quantum dots andmixing 30-50mg of boric acid and 40-60mL of secondary water, placing the mixture into an ultrasonic cleaner, ultrasonically dispersing the mixture for 0.5-1h, uniformly mixing the mixture, drying the mixture overnight in vacuum, and grinding the mixture into powder. Putting the mixture powder into a quartz boat, and pyrolyzing for 30-45min under the protection of argon at the temperature of 750 ℃ and 800 ℃; then 4-6mol/L HNO is used3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the boron-doped graphene quantum dots.
Further, graphene quantum dots are used as fluorescent probes to distinguish metal ions: putting 50 mu L of 500 mu g/mL graphene quantum dot solution into a 4mL centrifuge tube, then adding 430 mu L secondary water and 20 mu L of 2mmol/L different metal ion solution, balancing for 5min at room temperature, and respectively recording the fluorescence intensity of the graphene quantum dots, the nitrogen-doped graphene quantum dots, the phosphorus-doped graphene quantum dots, the sulfur-doped graphene quantum dots and the boron-doped graphene quantum dots under the excitation of light with wavelength of 310 nm; each metal ion was measured in parallel 6 times and the data obtained was subjected to linear discriminant analysis using software SYSTAT 13.1.
Has the advantages that: the specific advantages of the invention are as follows:
(1) the sensor array adopted by the invention has the advantages of simple preparation method, low cost and small required sample amount;
(2) the sensor array in the invention can achieve 100% of metal ion distinguishing accuracy;
(3) the invention can simultaneously detect and distinguish various metal ions;
(4) the invention has short detection period and strong controllability;
(5) the invention has simple instrument and intuitive result judgment.
Drawings
Fig. 1 is a TEM image of graphene quantum dots of the present invention (a graphene quantum dots, b nitrogen-doped graphene quantum dots, c sulfur-doped graphene quantum dots, d phosphorus-doped graphene quantum dots, e boron-doped graphene quantum dots);
FIG. 2 is a schematic diagram of a fluorescence spectrum of the graphene quantum dot under excitation of 360 nm;
fig. 3 is a schematic diagram of 15 kinds of metal ions distinguished by four graphene quantum dot fluorescent probe arrays of graphene quantum dots, phosphorus-doped graphene quantum dots, nitrogen-doped graphene quantum dots and sulfur-doped graphene quantum dots according to the present invention;
fig. 4 is a schematic diagram of 15 kinds of metal ions distinguished by four graphene quantum dot fluorescent probe arrays of graphene quantum dots, phosphorus-doped graphene quantum dots, nitrogen-doped graphene quantum dots and boron-doped graphene quantum dots according to the present invention;
fig. 5 is a schematic diagram of 15 kinds of metal ions distinguished by four graphene quantum dot fluorescent probe arrays of graphene quantum dots, phosphorus-doped graphene quantum dots, sulfur-doped graphene quantum dots and boron-doped graphene quantum dots according to the present invention;
fig. 6 is a schematic diagram of 15 kinds of metal ions distinguished by four graphene quantum dot fluorescent probe arrays of graphene quantum dots, nitrogen-doped graphene quantum dots, sulfur-doped graphene quantum dots and boron-doped graphene quantum dots according to the present invention;
fig. 7 is a schematic diagram of the fluorescent probe array of four graphene quantum dots including a phosphorus-doped graphene quantum dot, a nitrogen-doped graphene quantum dot, a sulfur-doped graphene quantum dot and a boron-doped graphene quantum dot according to the present invention for distinguishing 15 metal ions;
fig. 8 is a schematic diagram of the graphene quantum dot, phosphorus-doped graphene quantum dot, nitrogen-doped graphene quantum dot, sulfur-doped graphene quantum dot, and sulfur-doped graphene quantum dot fluorescent probe array of the present invention for distinguishing copper ions with different concentrations.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention will be more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.
Detailed description of the preferred embodiment 1
The graphene quantum dot fluorescent probe array for detecting metal ions comprises the following steps:
(1) preparing graphene quantum dots: adding 30mg of graphene oxide powder into 30mL of secondary water, placing the secondary water into an ultrasonic cleaning instrument for ultrasonic dispersion, adding 1mL of hydrogen peroxide, and performing uniform ultrasonic dispersion. Transferring the mixed solution into a reaction kettle, sealing and reacting for 90min at 180 ℃. And (3) filtering the reaction solution through a 0.22-micron water-based filter membrane, collecting filtrate to obtain a graphene quantum dot water dispersion, and freeze-drying. The result shows that the synthesized graphene quantum dots have uniform size, the average particle size is 3.7nm (figure 1a), and the graphene quantum dots can emit fluorescence with the maximum emission wavelength of 496nm when being excited by 360nm light (figure 2).
(2) Preparing nitrogen-doped graphene quantum dots: adding 50mg of graphene quantum dots into 100mL of secondary water, and placing the secondary water into an ultrasonic cleaning instrument for ultrasonic dispersion for 15 min. Then, 0.25g of melamine was added to the graphene quantum dot dispersion and stirred with a glass rod until significant sedimentation occurred. Evaporating the solvent in the mixed system by using an electrothermal sleeve, drying overnight in vacuum, and grinding into powder. The powder is put into a quartz boat and pyrolyzed for 45min under the protection of argon at 750 ℃. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the nitrogen-doped graphene quantum dots. The result shows that the synthesized nitrogen-doped graphene quantum dots have uniform size and average particle size of 2.3nm (fig. 1 b).
(3) Preparing the phosphorus-doped graphene quantum dots: and (3) uniformly mixing 50mg of graphene quantum dots, 200mg of triphenylphosphine and 80mL of ethanol, and stirring at room temperature. Evaporating ethanol, drying the obtained graphene quantum dot and triphenyl phosphine mixture in vacuum overnight, and grinding into powder. And putting the mixture powder into a quartz boat, and pyrolyzing for 45min at 750 ℃ under the protection of argon. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the phosphorus-doped graphene quantum dots. The result shows that the synthesized phosphorus-doped graphene quantum dots have uniform size and the average particle size of 3.2nm (fig. 1 c).
(4) Preparing sulfur-doped graphene quantum dots: 50mg of graphene quantum dots and 30mg of dibenzyl disulfide were added50mL of ethanol is mixed and put into an ultrasonic cleaner for ultrasonic dispersion for 15 min. Evaporating ethanol to obtain a mixture of the graphene quantum dots and the dithiobenzene, drying overnight in vacuum, and grinding into powder. And putting the mixture powder into a quartz boat, and pyrolyzing for 45min at 750 ℃ under the protection of argon. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the sulfur-doped graphene quantum dots. The results show that the synthesized sulfur-doped graphene quantum dots are uniform in size and have an average particle size of 1.7nm (fig. 1 d).
(5) The graphene quantum dots are used as fluorescent probes to distinguish metal ions: putting 50 mu L of more than 500 mu g/mL four graphene quantum dot solutions into a 4mL centrifuge tube, then adding 430 mu L of secondary water and 20 mu L of 2mmol/L different metal ion solutions, balancing for 5min at room temperature, and respectively recording the fluorescence intensities of the graphene quantum dots, the nitrogen-doped graphene quantum dots, the phosphorus-doped graphene quantum dots and the sulfur-doped graphene quantum dots under the excitation of 360nm wavelength light. Each metal ion was measured in parallel 6 times and the data obtained was subjected to linear discriminant analysis using software SYSTAT 13.1. The 15 metal ions showed distinct fluorescent intensity response signals, and the two variation factors obtained by linear discriminant analysis were 84.6% and 9.5%, respectively, as shown in fig. 3. In the fluorescence intensity response scattergram, different metal ions are aggregated to form 15 non-overlapping data sets, indicating that the fluorescence sensor array can completely distinguish the 15 metal ions.
Specific example 2
The graphene quantum dot fluorescent probe array for detecting metal ions comprises the following steps:
(1) preparing graphene quantum dots: adding 30mg of graphene oxide powder into 30mL of secondary water, placing the secondary water into an ultrasonic cleaning instrument for ultrasonic dispersion, adding 1mL of hydrogen peroxide, and performing uniform ultrasonic dispersion. Transferring the mixed solution into a reaction kettle, sealing and reacting for 90min at 180 ℃. And (3) filtering the reaction solution through a 0.22-micron water-based filter membrane, collecting filtrate to obtain a graphene quantum dot water dispersion, and freeze-drying. The result shows that the synthesized graphene quantum dots are uniform in size and have the average particle size of 3.7 nm.
(2) Nitrogen is present inPreparing doped graphene quantum dots: adding 50mg of graphene quantum dots into 100mL of secondary water, and placing the secondary water into an ultrasonic cleaning instrument for ultrasonic dispersion for 15 min. Then, 0.25g of melamine was added to the graphene quantum dot dispersion and stirred with a glass rod until significant sedimentation occurred. Evaporating the solvent in the mixed system by using an electrothermal sleeve, drying overnight in vacuum, and grinding into powder. The powder is put into a quartz boat and pyrolyzed for 45min under the protection of argon at 750 ℃. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the nitrogen-doped graphene quantum dots. The result shows that the synthesized nitrogen-doped graphene quantum dots are uniform in size and have the average particle size of 2.3 nm.
(3) Preparing the phosphorus-doped graphene quantum dots: and (3) uniformly mixing 50mg of graphene quantum dots, 200mg of triphenylphosphine and 80mL of ethanol, and stirring at room temperature. Evaporating ethanol, drying the obtained graphene quantum dot and triphenyl phosphine mixture in vacuum overnight, and grinding into powder. And putting the mixture powder into a quartz boat, and pyrolyzing for 45min at 750 ℃ under the protection of argon. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the phosphorus-doped graphene quantum dots. The result shows that the synthesized phosphorus-doped graphene quantum dots are uniform in size and have the average particle size of 3.2 nm.
(4) Preparing boron-doped graphene quantum dots: mixing 50mg of graphene quantum dots, 30mg of boric acid and 60mL of secondary water, placing the mixture into an ultrasonic cleaning instrument, ultrasonically dispersing for 1h, uniformly mixing, carrying out vacuum drying overnight, and grinding into powder. And putting the mixture powder into a quartz boat, and pyrolyzing for 45min at 750 ℃ under the protection of argon. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the boron-doped graphene quantum dots. The results show that the synthesized boron-doped graphene quantum dots are uniform in size and have an average particle size of 2.8nm (fig. 1 e).
(5) The graphene quantum dots are used as fluorescent probes to distinguish metal ions: putting 50 mu L of more than 500 mu g/mL four graphene quantum dot solutions into a 4mL centrifuge tube, then adding 430 mu L of secondary water and 20 mu L of 2mmol/L different metal ion solutions, balancing for 5min at room temperature, and respectively recording the fluorescence intensities of the graphene quantum dots, the nitrogen-doped graphene quantum dots, the phosphorus-doped graphene quantum dots and the boron-doped graphene quantum dots under the excitation of 360nm wavelength light. Each metal ion was measured in parallel 6 times and the data obtained was subjected to linear discriminant analysis using software SYSTAT 13.1. The 15 metal ions showed distinct fluorescent intensity response signals, and the two variation factors obtained by linear discriminant analysis were 85.5% and 9.8%, respectively, as shown in fig. 4. In the fluorescence intensity response scattergram, different metal ions are aggregated to form 15 non-overlapping data sets, indicating that the fluorescence sensor array can completely distinguish the 15 metal ions.
Specific example 3
The graphene quantum dot fluorescent probe array for detecting metal ions comprises the following steps:
(1) preparing graphene quantum dots: adding 30mg of graphene oxide powder into 30mL of secondary water, placing the secondary water into an ultrasonic cleaning instrument for ultrasonic dispersion, adding 1mL of hydrogen peroxide, and performing uniform ultrasonic dispersion. Transferring the mixed solution into a reaction kettle, sealing and reacting for 90min at 180 ℃. And (3) filtering the reaction solution through a 0.22-micron water-based filter membrane, collecting filtrate to obtain a graphene quantum dot water dispersion, and freeze-drying. The result shows that the synthesized graphene quantum dots are uniform in size and have the average particle size of 3.7 nm.
(2) Preparing nitrogen-doped graphene quantum dots: adding 50mg of graphene quantum dots into 100mL of secondary water, and placing the secondary water into an ultrasonic cleaning instrument for ultrasonic dispersion for 15 min. Then, 0.25g of melamine was added to the graphene quantum dot dispersion and stirred with a glass rod until significant sedimentation occurred. Evaporating the solvent in the mixed system by using an electrothermal sleeve, drying overnight in vacuum, and grinding into powder. The powder is put into a quartz boat and pyrolyzed for 45min under the protection of argon at 750 ℃. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the nitrogen-doped graphene quantum dots. The result shows that the synthesized nitrogen-doped graphene quantum dots are uniform in size and have the average particle size of 2.3 nm.
(3) Preparing sulfur-doped graphene quantum dots: mixing 50mg of graphene quantum dots, 30mg of dibenzyl disulfide and 50mL of ethanol, and putting the mixture into an ultrasonic cleaning instrumentAnd ultrasonically dispersing for 15 min. Evaporating ethanol to obtain a mixture of the graphene quantum dots and the dithiobenzene, drying overnight in vacuum, and grinding into powder. And putting the mixture powder into a quartz boat, and pyrolyzing for 45min at 750 ℃ under the protection of argon. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the sulfur-doped graphene quantum dots. The result shows that the synthesized sulfur-doped graphene quantum dots are uniform in size and have an average particle size of 1.7 nm.
(4) Preparing boron-doped graphene quantum dots: mixing 50mg of graphene quantum dots, 30mg of boric acid and 60mL of secondary water, placing the mixture into an ultrasonic cleaning instrument, ultrasonically dispersing for 1h, uniformly mixing, carrying out vacuum drying overnight, and grinding into powder. And putting the mixture powder into a quartz boat, and pyrolyzing for 45min at 750 ℃ under the protection of argon. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the boron-doped graphene quantum dots. The result shows that the synthesized boron-doped graphene quantum dots are uniform in size and have an average particle size of 2.8 nm.
(5) The graphene quantum dots are used as fluorescent probes to distinguish metal ions: putting 50 mu L of more than 500 mu g/mL four graphene quantum dot solutions into a 4mL centrifuge tube, then adding 430 mu L of secondary water and 20 mu L of 2mmol/L different metal ion solutions, balancing for 5min at room temperature, and respectively recording the fluorescence intensities of the graphene quantum dots, the nitrogen-doped graphene quantum dots, the sulfur-doped graphene quantum dots and the boron-doped graphene quantum dots under the excitation of 360nm wavelength light. Each metal ion was measured in parallel 6 times and the data obtained was subjected to linear discriminant analysis using software SYSTAT 13.1. The 15 metal ions showed distinct fluorescent intensity response signals, with linear discriminant analysis yielding two variation factors of 91.1% and 6.9%, respectively, as shown in fig. 5. In the fluorescence intensity response scattergram, different metal ions are aggregated to form 15 non-overlapping data sets, indicating that the fluorescence sensor array can completely distinguish the 15 metal ions.
Specific example 4
The graphene quantum dot fluorescent probe array for detecting metal ions comprises the following steps:
(1) preparing graphene quantum dots: adding 30mg of graphene oxide powder into 30mL of secondary water, placing the secondary water into an ultrasonic cleaning instrument for ultrasonic dispersion, adding 1mL of hydrogen peroxide, and performing uniform ultrasonic dispersion. Transferring the mixed solution into a reaction kettle, sealing and reacting for 90min at 180 ℃. And (3) filtering the reaction solution through a 0.22-micron water-based filter membrane, collecting filtrate to obtain a graphene quantum dot water dispersion, and freeze-drying. The result shows that the synthesized graphene quantum dots are uniform in size and have the average particle size of 3.7 nm.
(2) Preparing the phosphorus-doped graphene quantum dots: and (3) uniformly mixing 50mg of graphene quantum dots, 200mg of triphenylphosphine and 80mL of ethanol, and stirring at room temperature. Evaporating ethanol, drying the obtained graphene quantum dot and triphenyl phosphine mixture in vacuum overnight, and grinding into powder. And putting the mixture powder into a quartz boat, and pyrolyzing for 45min at 750 ℃ under the protection of argon. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the phosphorus-doped graphene quantum dots. The result shows that the synthesized phosphorus-doped graphene quantum dots are uniform in size and have the average particle size of 3.2 nm.
(3) Preparing sulfur-doped graphene quantum dots: and mixing 50mg of graphene quantum dots, 30mg of dibenzyl disulfide and 50mL of ethanol, and placing the mixture into an ultrasonic cleaner for ultrasonic dispersion for 15 min. Evaporating ethanol to obtain a mixture of the graphene quantum dots and the dithiobenzene, drying overnight in vacuum, and grinding into powder. And putting the mixture powder into a quartz boat, and pyrolyzing for 45min at 750 ℃ under the protection of argon. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the sulfur-doped graphene quantum dots. The result shows that the synthesized sulfur-doped graphene quantum dots are uniform in size and have an average particle size of 1.7 nm.
(4) Preparing boron-doped graphene quantum dots: mixing 50mg of graphene quantum dots, 30mg of boric acid and 60mL of secondary water, placing the mixture into an ultrasonic cleaning instrument, ultrasonically dispersing for 1h, uniformly mixing, carrying out vacuum drying overnight, and grinding into powder. And putting the mixture powder into a quartz boat, and pyrolyzing for 45min at 750 ℃ under the protection of argon. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the boron-doped graphene quantum dots. The results show that the sizes of the synthesized boron-doped graphene quantum dots are all the sameThe average particle size was 2.8 nm.
(5) The graphene quantum dots are used as fluorescent probes to distinguish metal ions: putting 50 mu L of more than 500 mu g/mL four graphene quantum dot solutions into a 4mL centrifuge tube, then adding 430 mu L of secondary water and 20 mu L of 2mmol/L different metal ion solutions, balancing for 5min at room temperature, and respectively recording the fluorescence intensities of the graphene quantum dots, the phosphorus-doped graphene quantum dots, the sulfur-doped graphene quantum dots and the boron-doped graphene quantum dots under the excitation of light with wavelength of 360 nm. Each metal ion was measured in parallel 6 times and the data obtained was subjected to linear discriminant analysis using software SYSTAT 13.1. The 15 metal ions showed distinct fluorescent intensity response signals, and the two variation factors obtained by linear discriminant analysis were 84.2% and 9.3%, respectively, as shown in fig. 6. In the fluorescence intensity response scattergram, different metal ions are aggregated to form 15 non-overlapping data sets, indicating that the fluorescence sensor array can completely distinguish the 15 metal ions.
Specific example 5
The graphene quantum dot fluorescent probe array for detecting metal ions comprises the following steps:
(1) preparing graphene quantum dots: adding 30mg of graphene oxide powder into 30mL of secondary water, placing the secondary water into an ultrasonic cleaning instrument for ultrasonic dispersion, adding 1mL of hydrogen peroxide, and performing uniform ultrasonic dispersion. Transferring the mixed solution into a reaction kettle, sealing and reacting for 90min at 180 ℃. And (3) filtering the reaction solution through a 0.22-micron water-based filter membrane, collecting filtrate to obtain a graphene quantum dot water dispersion, and freeze-drying. The result shows that the synthesized graphene quantum dots are uniform in size and have the average particle size of 3.7 nm.
(2) Preparing nitrogen-doped graphene quantum dots: adding 50mg of graphene quantum dots into 100mL of secondary water, and placing the secondary water into an ultrasonic cleaning instrument for ultrasonic dispersion for 15 min. Then, 0.25g of melamine was added to the graphene quantum dot dispersion and stirred with a glass rod until significant sedimentation occurred. Evaporating the solvent in the mixed system by using an electrothermal sleeve, drying overnight in vacuum, and grinding into powder. The powder is put into a quartz boat and pyrolyzed for 45min under the protection of argon at 750 ℃. Then using 6mol/LHNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the nitrogen-doped graphene quantum dots. The result shows that the synthesized nitrogen-doped graphene quantum dots are uniform in size and have the average particle size of 2.3 nm.
(3) Preparing the phosphorus-doped graphene quantum dots: and (3) uniformly mixing 50mg of graphene quantum dots, 200mg of triphenylphosphine and 80mL of ethanol, and stirring at room temperature. Evaporating ethanol, drying the obtained graphene quantum dot and triphenyl phosphine mixture in vacuum overnight, and grinding into powder. And putting the mixture powder into a quartz boat, and pyrolyzing for 45min at 750 ℃ under the protection of argon. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the phosphorus-doped graphene quantum dots. The result shows that the synthesized phosphorus-doped graphene quantum dots are uniform in size and have the average particle size of 3.2 nm.
(4) Preparing sulfur-doped graphene quantum dots: and mixing 50mg of graphene quantum dots, 30mg of dibenzyl disulfide and 50mL of ethanol, and placing the mixture into an ultrasonic cleaner for ultrasonic dispersion for 15 min. Evaporating ethanol to obtain a mixture of the graphene quantum dots and the dithiobenzene, drying overnight in vacuum, and grinding into powder. And putting the mixture powder into a quartz boat, and pyrolyzing for 45min at 750 ℃ under the protection of argon. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the sulfur-doped graphene quantum dots. The result shows that the synthesized sulfur-doped graphene quantum dots are uniform in size and have an average particle size of 1.7 nm.
(5) Preparing boron-doped graphene quantum dots: mixing 50mg of graphene quantum dots, 30mg of boric acid and 60mL of secondary water, placing the mixture into an ultrasonic cleaning instrument, ultrasonically dispersing for 1h, uniformly mixing, carrying out vacuum drying overnight, and grinding into powder. And putting the mixture powder into a quartz boat, and pyrolyzing for 45min at 750 ℃ under the protection of argon. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the boron-doped graphene quantum dots. The result shows that the synthesized boron-doped graphene quantum dots are uniform in size and have an average particle size of 2.8 nm.
(6) The graphene quantum dots are used as fluorescent probes to distinguish metal ions: putting 50 mu L of more than 500 mu g/mL four graphene quantum dot solutions into a 4mL centrifuge tube, then adding 430 mu L of secondary water and 20 mu L of 2mmol/L different metal ion solutions, balancing for 5min at room temperature, and respectively recording the fluorescence intensities of the nitrogen-doped graphene quantum dots, the phosphorus-doped graphene quantum dots, the sulfur-doped graphene quantum dots and the boron-doped graphene quantum dots under the excitation of 360nm wavelength light. Each metal ion was measured in parallel 6 times and the data obtained was subjected to linear discriminant analysis using software SYSTAT 13.1. The 15 metal ions showed distinct fluorescent intensity response signals, and the two variation factors obtained by linear discriminant analysis were 82.1% and 15.3%, respectively, as shown in fig. 7. In the fluorescence intensity response scattergram, different metal ions are aggregated to form 15 non-overlapping data sets, indicating that the fluorescence sensor array can completely distinguish the 15 metal ions.
Specific example 6
The graphene quantum dot fluorescent probe array for detecting copper ions with different concentrations comprises the following steps:
(1) preparing graphene quantum dots: adding 30mg of graphene oxide powder into 30mL of secondary water, placing the secondary water into an ultrasonic cleaning instrument for ultrasonic dispersion, adding 1mL of hydrogen peroxide, and performing uniform ultrasonic dispersion. Transferring the mixed solution into a reaction kettle, sealing and reacting for 90min at 180 ℃. And (3) filtering the reaction solution through a 0.22-micron water-based filter membrane, collecting filtrate to obtain a graphene quantum dot water dispersion, and freeze-drying. The result shows that the synthesized graphene quantum dots are uniform in size and have the average particle size of 3.7 nm.
(2) Preparing nitrogen-doped graphene quantum dots: adding 50mg of graphene quantum dots into 100mL of secondary water, and placing the secondary water into an ultrasonic cleaning instrument for ultrasonic dispersion for 15 min. Then, 0.25g of melamine was added to the graphene quantum dot dispersion and stirred with a glass rod until significant sedimentation occurred. Evaporating the solvent in the mixed system by using an electrothermal sleeve, drying overnight in vacuum, and grinding into powder. The powder is put into a quartz boat and pyrolyzed for 45min under the protection of argon at 750 ℃. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the nitrogen-doped graphene quantum dots. The result shows that the synthesized nitrogen-doped graphene quantum dots have uniform size and average particle size of 2.3nm。
(3) Preparing the phosphorus-doped graphene quantum dots: and (3) uniformly mixing 50mg of graphene quantum dots, 200mg of triphenylphosphine and 80mL of ethanol, and stirring at room temperature. Evaporating ethanol, drying the obtained graphene quantum dot and triphenyl phosphine mixture in vacuum overnight, and grinding into powder. And putting the mixture powder into a quartz boat, and pyrolyzing for 45min at 750 ℃ under the protection of argon. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the phosphorus-doped graphene quantum dots. The result shows that the synthesized phosphorus-doped graphene quantum dots are uniform in size and have the average particle size of 3.2 nm.
(4) Preparing sulfur-doped graphene quantum dots: and mixing 50mg of graphene quantum dots, 30mg of dibenzyl disulfide and 50mL of ethanol, and placing the mixture into an ultrasonic cleaner for ultrasonic dispersion for 15 min. Evaporating ethanol to obtain a mixture of the graphene quantum dots and the dithiobenzene, drying overnight in vacuum, and grinding into powder. And putting the mixture powder into a quartz boat, and pyrolyzing for 45min at 750 ℃ under the protection of argon. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the sulfur-doped graphene quantum dots. The result shows that the synthesized sulfur-doped graphene quantum dots are uniform in size and have an average particle size of 1.7 nm.
(5) Preparing boron-doped graphene quantum dots: mixing 50mg of graphene quantum dots, 30mg of boric acid and 60mL of secondary water, placing the mixture into an ultrasonic cleaning instrument, ultrasonically dispersing for 1h, uniformly mixing, carrying out vacuum drying overnight, and grinding into powder. And putting the mixture powder into a quartz boat, and pyrolyzing for 45min at 750 ℃ under the protection of argon. Then using 6mol/L HNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the boron-doped graphene quantum dots. The result shows that the synthesized boron-doped graphene quantum dots are uniform in size and have an average particle size of 2.8 nm.
(6) The graphene quantum dots are used as fluorescent probes to distinguish metal ions: putting more than 50 mu L of a 500 mu g/mL solution of five graphene quantum dots into a 4mL centrifuge tube, then adding 430 mu L of secondary water and 20 mu L of copper ion solutions with different concentrations, balancing for 5min at room temperature, and respectively recording the fluorescence intensities of the graphene quantum dots, the nitrogen-doped graphene quantum dots, the phosphorus-doped nitrogen-doped graphene quantum dots, the sulfur-doped graphene quantum dots and the boron-doped graphene quantum dots under the excitation of 360nm wavelength light. Each metal ion was measured in parallel 6 times and the data obtained was subjected to linear discriminant analysis using software SYSTAT 13.1. Different concentrations of copper ions showed distinct fluorescence intensity response signals, with linear discriminant analysis yielding two variation factors of 98.6% and 0.73%, respectively, as shown in fig. 8. In the fluorescence intensity response scattergram, copper ions with different concentrations are aggregated to form 4 non-overlapping data sets, which indicates that the fluorescence sensor array can perform quantitative analysis on the copper ions.
It is apparent that the above examples are only examples for clearly illustrating the present invention, and are not to be construed as limiting the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications thereof are within the scope of the invention.
Claims (7)
1. A metal ion detection method based on a graphene quantum dot fluorescent probe array is characterized by comprising the following steps: firstly, preparing graphene quantum dots by a hydrothermal method, and doping the graphene quantum dots by taking the graphene quantum dots as raw materials to sequentially prepare nitrogen-doped graphene quantum dots, phosphorus-doped graphene quantum dots, sulfur-doped graphene quantum dots and boron-doped graphene quantum dots; then, a fluorescent probe array is formed by the graphene quantum dots and the doped graphene quantum dots, the change of the fluorescence intensity of the graphene quantum dots caused by various metal ions is recorded, and the metal ions are detected and distinguished by a linear discriminant analysis method.
2. The metal ion detection method based on the graphene quantum dot fluorescent probe array as claimed in claim 1, wherein: the preparation of the graphene quantum dot is as follows: adding 30-50mg of graphene oxide powder into 30-50mL of secondary water, placing the secondary water into an ultrasonic cleaning instrument for ultrasonic dispersion, adding 1-2mL of hydrogen peroxide, and performing uniform ultrasonic dispersion; transferring the mixed solution into a reaction kettle, sealing, and reacting at 180 ℃ for 60-90 min; and (3) filtering the reaction solution through a 0.22-micron water-based filter membrane, collecting filtrate to obtain a graphene quantum dot water dispersion, and freeze-drying.
3. The metal ion detection method based on the graphene quantum dot fluorescent probe array as claimed in claim 1, wherein: the preparation method of the nitrogen-doped graphene quantum dot comprises the following steps: adding 50mg of graphene quantum dots into 80-100mL of secondary water, and placing the secondary water into an ultrasonic cleaning instrument for ultrasonic dispersion for 10-15 min; then, 0.25-0.30g of melamine is added into the graphene quantum dot dispersion system, and the mixture is stirred by a glass rod until obvious settlement occurs; evaporating the solvent in the mixed system by using an electrothermal sleeve, drying overnight in vacuum, and grinding into powder; putting the powder into a quartz boat, and pyrolyzing for 30-45min under the protection of argon at the temperature of 750 plus 800 ℃; then 4-6mol/L HNO is used3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the nitrogen-doped graphene quantum dots.
4. The metal ion detection method based on the graphene quantum dot fluorescent probe array as claimed in claim 1, wherein: the phosphorus-doped graphene quantum dots are prepared as follows: uniformly mixing 50mg of graphene quantum dots, 100-200mg of triphenylphosphine and 50-100mL of ethanol, and stirring at room temperature; evaporating ethanol, drying the obtained graphene quantum dot and triphenyl phosphine mixture in vacuum overnight, and grinding into powder; putting the mixture powder into a quartz boat, and pyrolyzing for 30-45min under the protection of argon at the temperature of 750 ℃ and 800 ℃; then 4-6mol/L HNO is used3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the phosphorus-doped graphene quantum dots.
5. The metal ion detection method based on the graphene quantum dot fluorescent probe array as claimed in claim 1, wherein: the sulfur-doped graphene quantum dots are prepared as follows: mixing 50mg of graphene quantum dots, 30-40mg of dibenzyl disulfide and 50-100mL of ethanol, and placing the mixture into an ultrasonic cleaner for ultrasonic dispersion for 10-15 min; evaporating the ethanol to obtain a stoneAnd (3) mixing the graphene quantum dots and the dithiobenzene, drying overnight in vacuum, and grinding into powder. Putting the mixture powder into a quartz boat, and pyrolyzing the mixture powder for 30-45min at the temperature of 750 ℃ and 800 ℃ under the protection of argon; then 4-6mol/L HNO is used3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the sulfur-doped graphene quantum dots.
6. The metal ion detection method based on the graphene quantum dot fluorescent probe array as claimed in claim 1, wherein: the boron-doped graphene quantum dots are prepared as follows: mixing 50mg of graphene quantum dots, 30-50mg of boric acid and 40-60mL of secondary water, placing the mixture into an ultrasonic cleaner, ultrasonically dispersing for 0.5-1h, uniformly mixing, vacuum drying overnight, and grinding into powder. Putting the mixture powder into a quartz boat, and pyrolyzing for 30-45min under the protection of argon at the temperature of 750 ℃ and 800 ℃; then using 4-6mol/LHNO3Refluxing and evaporating HNO3And (4) dialyzing and purifying the solvent to obtain the boron-doped graphene quantum dots.
7. The metal ion detection method based on the graphene quantum dot fluorescent probe array as claimed in claim 1, wherein: the graphene quantum dots are used as fluorescent probes to distinguish metal ions: putting 50 mu L of 500 mu g/mL graphene quantum dot solution into a 4mL centrifuge tube, then adding 430 mu L secondary water and 20 mu L of 2mmol/L different metal ion solution, balancing for 5min at room temperature, and respectively recording the fluorescence intensity of the graphene quantum dots, the nitrogen-doped graphene quantum dots, the phosphorus-doped graphene quantum dots, the sulfur-doped graphene quantum dots and the boron-doped graphene quantum dots under the excitation of light with wavelength of 310 nm; each metal ion was measured in parallel 6 times and the data obtained was subjected to linear discriminant analysis using software SYSTAT 13.1.
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