CN115386367A - Fluorescent paper sensor - Google Patents
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Abstract
The invention provides a fluorescent paper sensor, which is formed by reducing a chloroauric acid solution by using glutathione to carry out gold nanocluster solution and then loading the gold nanocluster solution on a paper sensor consisting of a cellulose acetate membrane. The gold nanocluster solution formed by reducing chloroauric acid by glutathione has the advantages that on one hand, the glutathione can generate a monomolecular protective layer to protect the gold nanoclusters, so that the stability of the gold nanoclusters is improved, and the yield and the environmental interference resistance of the gold nanoclusters can be obviously improved compared with other thiol compounds in the prior art; on the other hand, the cellulose acetate membrane has the characteristics of low background influence and small required sample volume, and can be used as a fluorescence analysis carrier to load gold nanocluster solution, so that the obtained fluorescent paper sensor can achieve the effect of rapid detection.
Description
Technical Field
The invention relates to the field of food safety, in particular to a fluorescent paper sensor.
Background
The fluorescence analysis method is an important method for testing heavy metal pollution in the field of food at present, and the rapid detection of a specific detection substance is realized by taking a fluorescent paper material as a carrier, loading a fluorescent probe solution on the fluorescent paper material and performing visual/colorimetric design on the fluorescent probe; compared with the currently commonly used raman spectroscopy, electrochemical analysis and the like, the method has the advantages of high selectivity, high sensitivity, low cost, easiness in operation and the like, and becomes the key point of the current research.
At present, a lot of fluorescent probe solutions are used for detecting heavy metals in food, common fluorescent molecules take acetonitrile, acridone derivatives, pyrrole group-containing molecules and the like as fluorescent signals, and the heavy metals are detected, so that a good effect is obtained, but most of the fluorescent molecules have high toxicity and are not suitable for direct detection in the field of food; at present, it is common in the food field that novel environment-friendly fluorescent nano materials such as carbon dots, gold nanoclusters and graphene oxide are designed and synthesized to form novel fluorescent sensing molecules so as to realize high-sensitivity rapid detection of heavy metal ions. The gold nanoclusters are gold nanocluster solution formed by reducing chloroauric acid by using a reducing agent, and can realize rapid detection of heavy metals in food after being loaded on a paper sensor. The choice of the reducing agent is different according to different detected heavy metals, and the reducing agent commonly used at present is a thiol reducing agent such as cysteine and dihydrolipoic acid in order to ensure the safety of food detection.
However, in the existing research, there is no reducing agent specially for the rapid detection of lead ions in food, and meanwhile, the existing sensor using gold nanocluster solution as a fluorescent probe has weak environmental interference resistance, and the detection accuracy is reduced in response under the condition of pH and temperature change or the presence of other metal ions, so that the defects of inaccurate detection result, incapability of adapting to most environments and the like are caused.
Disclosure of Invention
Based on the above problems, the present invention aims to provide a fluorescent paper sensor, wherein a fluorescent probe of the fluorescent paper sensor comprises a gold nanocluster solution obtained by reducing chloroauric acid with glutathione, a load carrier of the fluorescent paper sensor is a paper sensor composed of a cellulose acetate membrane, and the fluorescent paper sensor is obtained by loading the fluorescent probe on the paper sensor; the obtained fluorescent paper has high-efficiency detection capability on food and agricultural products and also has strong environmental interference resistance.
In order to achieve the aim, the technical scheme of the invention firstly provides a gold nanocluster solution which is obtained by reducing chloroauric acid by glutathione;
preferably, the glutathione is reduced glutathione.
Further, the specific preparation method of the gold nanocluster comprises the following steps: mixing a chloroauric acid solution and a glutathione solution, and heating in a water bath to obtain a gold nanocluster solution;
further, in the preparation method, the concentrations of the chloroauric acid solution and the glutathione solution are both 0.1mol/L;
the addition amount of the chloroauric acid solution and the glutathione solution is 4:6 volume ratio;
the heating temperature of the water bath is 80 ℃, and the heating time is 24h.
The technical scheme of the invention provides a fluorescent probe solution, which comprises the gold nanocluster solution;
further, the preparation method of the fluorescent probe solution comprises the following steps: adding a copper chloride solution into the gold nanocluster solution to obtain a fluorescent probe solution;
further, the solution concentration of the copper chloride solution is 1mol/L, and the addition amount of the gold nanocluster solution to the copper chloride solution is 50.
The technical scheme of the invention also provides a fluorescent paper sensor which is composed of a load material and a fluorescent probe solution loaded on the load material;
the load material is a paper sensor composed of a cellulose acetate membrane;
the fluorescent probe solution is the above fluorescent probe solution and comprises the above gold nanocluster solution;
further, the preparation method of the paper sensor comprises the following steps: soaking a cellulose acetate membrane in a dilute hydrochloric acid solution, soaking in a dithizone-chloroform buffer solution, and drying to obtain the cellulose acetate membrane;
further, the mass fraction of the dithizone-chloroform buffer solution is 0.005%;
further, immersing the paper sensor in the fluorescent probe solution, taking out after stabilizing for 0.5h, and drying in the shade to obtain the fluorescent paper sensor.
The invention has the following beneficial effects:
the method comprises the steps of reducing a chloroauric acid solution by using glutathione to obtain a gold nanocluster solution, and loading the gold nanocluster solution on a paper sensor consisting of a cellulose acetate membrane to form the fluorescent paper sensor. The gold nanocluster solution formed by reducing chloroauric acid by glutathione has the advantages that on one hand, the glutathione can generate a monomolecular protective layer to protect the gold nanoclusters, so that the stability of the gold nanoclusters is improved, and the yield and the environmental interference resistance of the gold nanoclusters can be obviously improved compared with other thiol compounds in the prior art; on the other hand, the cellulose acetate membrane has the characteristics of low background influence and small required sample volume, and can be used as a fluorescence analysis carrier to load gold nanocluster solution, so that the obtained fluorescent paper sensor can achieve the effect of rapid detection.
Drawings
FIG. 1: the influence of the pH value change on the test stability of the fluorescent paper sensor is tested;
FIG. 2 is a drawing: the influence of temperature change on the test stability of the fluorescent paper sensor is tested;
FIG. 3: influence of metal ion interference on testing stability of the glutathione-gold nanocluster fluorescent paper sensor;
FIG. 4 is a drawing: influence of metal ion interference on testing stability of the cysteine-gold nanocluster fluorescent paper sensor;
FIG. 5 is a drawing: influence of metal ion interference on the stability of the dihydrolipoic acid-gold nanocluster fluorescent paper sensor test;
FIG. 6: influence of metal ion interference on testing stability of the dithiothreitol-gold nanocluster fluorescent paper sensor;
FIG. 7: influence of metal ion interference on the test stability of the 2,3-dithiosuccinic acid-gold nanocluster fluorescent paper sensor.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions of the embodiments of the present disclosure are described below clearly and completely. It is to be understood that the described embodiments are only a few embodiments of the present disclosure, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the disclosure without inventive step, are within the scope of protection of the disclosure.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this disclosure belongs.
The first embodiment of the application discloses a gold nanocluster solution obtained by reducing chloroauric acid with reduced glutathione.
Glutathione is divided into two configurations of reduction type and oxidation type, and in the patent, gold nanoclusters need to be reduced by glutathione, so that the glutathione related in the application is reduced glutathione.
In this embodiment, glutathione plays a role in reducing chloroauric acid, and generally, when a gold nanocluster solution is prepared from chloroauric acid, a reducing agent needs to be added to reduce chloroauric acid so as to stabilize the properties of chloroauric acid. Glutathione can generate a monomolecular protective layer to protect the gold nanoclusters, so that the stability of the gold nanoclusters is improved, and the environmental interference resistance of the gold nanoclusters can be remarkably improved compared with other thiol compounds (such as cysteine, dihydrolipoic acid, dithiothreitol and the like) in the prior art.
In some embodiments, the gold nanoclusters are prepared by a specific method comprising: mixing a chloroauric acid solution and a reduced glutathione solution, and heating in a water bath to obtain a gold nanocluster solution; .
In some specific embodiments, in the preparation method, the concentrations of the chloroauric acid solution and the glutathione solution are both 0.1mol/L;
the addition amount of the chloroauric acid solution and the glutathione solution is 4:6 volume ratio;
the heating temperature of the water bath is 80 ℃, and the heating time is 24h.
The second embodiment of the application discloses a fluorescent probe solution, which comprises the gold nanocluster solution; the gold nanocluster solution is obtained by reducing a chloroauric acid solution with glutathione, so that the environmental interference resistance of the obtained fluorescent probe solution is particularly improved.
In some embodiments, the method for preparing the fluorescent probe solution comprises: and adding a copper chloride solution into the gold nanocluster solution to obtain a fluorescent probe solution.
In some embodiments, the solution concentration of the copper chloride solution is 1mol/L, and the addition amount of the gold nanocluster solution to the copper chloride solution is 50.
The third embodiment of the application discloses a fluorescent paper sensor, which consists of a loading material and a fluorescent probe solution loaded on the loading material; the load material is a paper sensor composed of a cellulose acetate membrane; the fluorescent probe solution is the above fluorescent probe solution, and includes the above gold nanocluster solution.
The cellulose acetate membrane has the characteristics of low background influence and small required sample volume, can be used as a fluorescence analysis carrier to load the gold nanocluster solution, can enable the obtained fluorescent paper sensor to achieve the effect of rapid detection, and meanwhile, the gold nanocluster solution comprises reduced glutathione, so that the especially prepared fluorescent paper sensor also has strong environmental interference resistance.
In some embodiments, the paper sensor is prepared by: soaking a cellulose acetate membrane in a dilute hydrochloric acid solution, soaking in a dithizone-chloroform buffer solution, and drying to obtain the cellulose acetate membrane;
soaking the cellulose acetate membrane for 1h by using dilute hydrochloric acid, washing the cellulose acetate membrane for 3 times by using ultrapure water till the cellulose acetate membrane is neutral, and drying the cellulose acetate membrane at 40 ℃; cutting the dried acetic acid fibrous membrane into a rectangular sheet with the length of 5cm and the width of 1 cm; then placing the cut slices into a dithizone-chloroform buffer solution with the mass fraction of 0.005% for loading, standing, taking out after stabilizing for 0.5h, and drying in a ventilating way to obtain a paper sensor;
in this embodiment, the preparation method of the 0.005% dithizone-chloroform solution comprises the following steps: weighing 0.005g of dithizone to dissolve in 1L of chloroform solution, stirring and dissolving, and then carrying out ultrasonic vibration for 30min, wherein the dithizone is easy to decompose under the action of light, so that the prepared dithizone-chloroform solution is stored in a brown reagent bottle.
The environmental interference resistance of the gold nanoclusters of the present application will be verified by specific examples below, and it is apparent that the described examples are a part of the disclosure, not all of the examples. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the disclosure without any inventive step, are within the scope of protection of the disclosure.
Example 1 preparation of fluorescent paper sensor
(1) Soaking a cellulose acetate membrane for 1 hour by using dilute hydrochloric acid, then washing the cellulose acetate membrane for 3 times by using ultrapure filtered water until the cellulose acetate membrane is neutral, and drying the cellulose acetate membrane at 40 ℃;
(2) Cutting: cutting the dried cellulose acetate film into rectangular sheets with the length of 5cm and the width of 1 cm;
(3) Loading: and placing the cut cellulose acetate membrane into a buffer solution with the mass fraction of 0.005% dithizone-chloroform for loading, standing, taking out after stabilizing for 0.5h, and drying in a ventilated and dry place to obtain the paper sensor.
2. Preparation of fluorescent Probe solution
(1) Preparing a gold nanocluster solution: mixing 0.1mol/L chloroauric acid solution and 0.1mol/L glutamic acid solution according to the proportion of 4:6, and heating in 80 ℃ water bath for 24 hours to obtain gold nanocluster solution;
(2) Adding 1mol/L of copper chloride solution into the gold nanocluster solution, wherein the adding ratio of the gold nanocluster solution to the copper chloride solution is 50.
(3) And immersing the paper sensor in the fluorescent probe solution, stabilizing for 0.5h, taking out, and drying in the shade to obtain the fluorescent paper sensor.
Comparative example 1 preparation of fluorescent paper sensor
The preparation method is the same as example 1, except that in comparative example 1, cysteine is used instead of glutathione.
Comparative example 2 preparation of fluorescent paper sensor
The preparation method is the same as example 1 except that in comparative example 2, dihydrolipoic acid is used instead of glutathione.
Comparative example 3 preparation of fluorescent paper sensor
The preparation method is the same as that of example 1, except that in comparative example 2, dithiothreitol is used instead of glutathione.
Comparative example 4 preparation of fluorescent paper sensor
The preparation method is the same as example 1, except that in comparative example 2, 2,3-dithiosuccinic acid is used instead of glutathione.
Test example 1 test for environmental interference resistance
The environmental interference resistance is one of the key indexes for evaluating the test stability of the fluorescent paper sensor, and the main environmental influence factors are pH, temperature and a mixed solution (Ca) of various metal ions 2+ 、Mg 2+ 、Fe 2+ 、Cu 2+ 、Ba 2+ 、Co 2+ 、Pb 2+ 、Cd 2+ 、Zn 2 + 、Se 2+ 、Ni 2+ 、Hg 2+ ) The fluorescence response value of (1). Therefore, the test evaluates the strength of the different gold nanocluster solutions against environmental interference by testing the difference of the fluorescence response values of the fluorescent paper sensors prepared from the gold nanocluster solutions of example 1 and comparative examples 1 to 4 in different pH, temperature and multi-metal ions.
The test method comprises the following steps:
1.1 Experimental reagent
Chloroauric acid tetrahydrate, analytically pure, national chemical group, chemical reagents, ltd; reduced glutathione, cysteine, dihydrolipoic acid, dithiothreitol, 2,3-dithiosuccinic acid, analytically pure, alatin reagent (shanghai) ltd; calcium chloride, magnesium sulfate, ferrous sulfate heptahydrate, copper chloride, barium chloride, cobalt chloride hexahydrate, lead nitrate, cadmium chloride, zinc chloride, selenium chloride, nickel chloride hexahydrate and mercury nitrate monohydrate, analytically pure, chemical reagents of the national drug group, ltd; nitric acid and hydrochloric acid, and superior purity to Doctorong; potassium dihydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium chloride, analytically pure, national drug group chemical reagents ltd.
1.2 Laboratory apparatus
UV-2000 UV-vis spectrophotometer, you Nike shanghai instruments & equipment; f4500 A fluorescence spectrophotometer manufactured by Hitachi, japan; PHS3C type pH meter, shanghai rainbow instruments and meters ltd; NEXION 1000G inductively coupled plasma mass spectrometer, PE corporation, usa; RV-10 rotary evaporator, guangzhou Instrument laboratory (Tech factory); TD-4Z desk high speed centrifuge, sichuan instruments ltd; UX220H precision balance, shimadzu corporation, japan; KQ5200B ultrasonic instrument, kunshan ultrasonic instruments ltd; DZKK-S-6 electric heating constant temperature water bath, yongguang instruments works in Beijing; thermo F3 micropipette gun, sehmer technologies, usa.
1.3 Optimization process of pH value
The preparation method of the phosphate buffer solution with the pH value of 6.0 to 8.0 is as follows, weighingPotassium dihydrogen phosphate 9.08 g, dissolving with purified water, transferring into 1000 mL volumetric flask, and metering to obtain solution A; weighing 9.47g of disodium hydrogen phosphate, dissolving with purified water, transferring into a 1000 mL volumetric flask for constant volume to obtain solution B, wherein the pH value is 6.0, and the volume ratio of the solution A to the solution B is 12.2 mL:87.8 mL mixed, likewise pH 7, 8 by volume 61.1 mL:38.9 mL, 94.7 mL:5.3 mL; when the pH value is 3.0 to 5.0, weighing 100 g of monopotassium phosphate, adding 800 mL of water, adjusting the pH value by using hydrochloric acid or sodium hydroxide, diluting the solution to 1000 mL by using water, and reading by using a pH meter in the period; when the pH value is 9.0, 100 g sodium dihydrogen phosphate is weighed, 800 mL is added, and then the pH value is adjusted by sodium hydroxide, wherein a pH meter is used for reading. Mixing 20 μ L stock solution of different gold nanocluster systems with 980 μ L phosphate buffer solution with different pH values, reacting for 3 min, and adding Pb 2+ The fluorescence spectrum of the solution having a concentration of 10. Mu. Mol/L was measured by a fluorescence spectrophotometer, and the excitation wavelength was 365 nm and the slit width was 10 nm.
The experimental results are as follows: see fig. 1.
And (4) analyzing results: as can be seen from FIG. 1, in example 1, pb increased from 3.0 to 5.0 in the pH of the solution 2+ The fluorescence quenching degree of the glutathione-gold nanocluster system is enhanced along with the increase of the pH value, and when the pH value of the solution is more than 6.0, pb exists 2+ The fluorescence quenching degree of the glutathione-gold nanocluster system is reduced in a small range, and the fluorescence quenching degree reaches the maximum when the pH = 6.0. Thus, the glutathione-gold nanocluster system is aligned to Pb at pH =6.0 2+ The detection effect is optimal. Meanwhile, compared with a cysteine-gold nanocluster system (comparative example 1), a dihydrolipoic acid-gold nanocluster system (comparative example 2), a dithiothreitol-gold nanocluster system (comparative example 3) and a 2,3-dithiosuccinic acid-gold nanocluster system (comparative example 4), the glutathione-gold nanocluster system is less influenced by a pH value, a fluorescence reaction is more obvious, and the glutathione-gold nanocluster system is more stable in an acid/alkaline environment.
Experiment 2. Influence of temperature variation on test stability of fluorescent paper sensor
The test method comprises the following steps: the temperature of the to-be-tested reagent is set to be 15 ℃, 20, 25, 30, 35, 40, 45 and 50 ℃, and then the content of lead ions in the to-be-tested reagent is tested by using a fluorescent paper sensor, and the fluorescence quenching degree of the to-be-tested reagent is observed.
Experimental reagents and apparatus As shown in experiment 1, according to the result of experiment 1, phosphate buffer solution with pH value of 6.0 was selected for experiment. Placing a stock solution of a glutathione-gold nanocluster system (example 1), a cysteine-gold nanocluster system (comparative example 1), a dihydrolipoic acid-gold nanocluster system (comparative example 2), a dithiothreitol-gold nanocluster system (comparative example 3), a 2,3-dithiosuccinic acid-gold nanocluster system (comparative example 4) and a phosphate buffer solution in a refrigerator at 5 ℃ for refrigeration overnight, controlling the temperature to be 15, 20, 25, 30, 35, 40, 45 and 50 ℃ (± 1 ℃) by utilizing the heating function of an electric heating constant temperature water bath kettle, stabilizing for 3 min after the reaction temperature is reached, and adding Pb 2+ Solution with a concentration of 10. Mu. Mol/L. The fluorescence spectrum was measured at an excitation wavelength of 365 nm and a slit width of 10 nm using a fluorescence spectrophotometer, and the degree of influence of temperature on the reaction system was examined.
The experimental results are as follows: see fig. 2.
And (4) analyzing results: the glutathione-gold nanocluster system (example 1), the cysteine-gold nanocluster system (comparative example 1), the dihydrolipoic acid-gold nanocluster system (comparative example 2), the dithiothreitol-gold nanocluster system (comparative example 3) and the 2,3-dithiosuccinic acid-gold nanocluster system (comparative example 4) have stable reaction at 15 to 35 ℃ and have better reaction effect along with the increase of temperature in the glutathione-gold nanocluster system (example 1); when the temperature exceeds 40 ℃, the fluorescence response value of the cysteine-gold nanocluster system (comparative example 1), the dihydrolipoic acid-gold nanocluster system (comparative example 2), the dithiothreitol-gold nanocluster system (comparative example 3) and the 2,3-dithiosuccinic acid-gold nanocluster system (comparative example 4) is greatly reduced, the glutathione-gold nanocluster system only starts to change greatly when the temperature exceeds 45 ℃, and the response value of the glutathione-gold nanocluster system to lead ions is equivalent to the response value of other systems under the optimal condition, so that the glutathione-gold nanocluster system has better tolerance to temperature change.
The test method comprises the following steps: lead ions and other metal ions are selected to prepare a mixed solution (Ca) 2+ 、Mg 2+ 、Fe 2+ 、Cu 2+ 、Ba 2+ 、Co 2+ 、Pb 2+ 、Cd 2+ 、Zn 2+ 、Se 2+ 、Ni 2+ 、Hg 2+ ) The effect of the reaction in the presence of interfering ions was examined.
Experimental reagents and instruments As shown in experiment 1 and experiment 2, according to the experimental results, phosphate buffer solution with pH value of 6.0 was selected for experiments, and the temperature was set to 35 ℃. Common divalent metal ion Ca is selected in the experiment 2+ 、Mg 2+ 、Fe 2+ 、Cu 2+ 、Ba 2+ 、Co 2+ 、Cd 2+ 、Zn 2+ 、Se 2+ 、Ni 2+ 、Hg 2+ ) As interfering ions, fluorescent paper sensors including glutathione-gold nanocluster, cysteine-gold nanocluster (comparative example 1), dihydrolipoic acid-gold nanocluster (comparative example 2), dithiothreitol-gold nanocluster (comparative example 3), 2,3-dithiosuccinic acid-gold nanocluster (comparative example 4) system were examined for detection of Pb 2+ Influence of concentration of Pb contained therein 2+ The concentration was set at 10. Mu. Mol/L and the concentration of other interfering ions was set at 50. Mu. Mol/L. Glutathione-gold nanoclusters, cysteine-gold nanoclusters (comparative example 1), dihydrolipoic acid-gold nanoclusters (comparative example 2), dithiothreitol-gold nanoclusters (comparative example 3), 2,3-dithiosuccinic acid-gold nanocluster (comparative example 4) system were measured for the common divalent metal ion Ca according to the methods of experiment 1 and experiment 2, respectively 2+ 、Mg 2+ 、Fe 2+ 、Cu 2+ 、Ba 2+ 、Co 2+ 、Cd 2+ 、Zn 2+ 、Se 2+ 、Ni 2 + 、Hg 2+ ) The fluorescence reaction of (4) was repeated three times, and the results were compared with a blank (here, the blank refers to the fluorescence intensity detected when the cluster system does not contain any metal ion).
The experimental results are as follows: see fig. 3-7.
And (4) analyzing results: the experimental result shows that the glutathione-gold nanocluster (example 1) system has higher absorbance on lead ions and is lower in interference degree of the ions in the reaction. And the absorption values of the cysteine-gold nanocluster (comparative example 1), the dihydrolipoic acid-gold nanocluster (comparative example 2), the dithiothreitol-gold nanocluster (comparative example 3) and the 2,3-dithiosuccinic acid-gold nanocluster (comparative example 4) are obviously reduced in the presence of other interfering ions, which shows that the other systems have a certain specific reaction on lead ions, but the absorption values are more easily shielded in the presence of other interfering ions.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, those skilled in the art will appreciate that; the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A gold nanocluster solution is characterized in that the gold nanocluster solution is obtained by reducing chloroauric acid with glutathione;
preferably, the glutathione is reduced glutathione.
2. The gold nanocluster solution as claimed in claim 1, wherein the specific preparation method of the gold nanoclusters is as follows: and mixing the chloroauric acid solution and the glutathione solution, and heating in a water bath to obtain the gold nanocluster solution.
3. The gold nanocluster solution as claimed in claim 2, wherein in the preparation method, the concentration of the chloroauric acid solution and the concentration of the glutathione solution are both 0.1mol/L;
the addition amount of the chloroauric acid solution and the glutathione solution is 4:6 volume ratio;
the heating temperature of the water bath is 80 ℃, and the heating time is 24h.
4. A fluorescent probe solution comprising the gold nanocluster solution of any one of claims 1 to 3.
5. The fluorescent probe solution as set forth in claim 4, wherein the fluorescent probe solution is prepared by: and adding a copper chloride solution into the gold nanocluster solution to obtain a fluorescent probe solution.
6. The fluorescent paper sensor according to claim 5, wherein the solution concentration of the copper chloride solution is 1mol/L, and the addition amount of the gold nanocluster solution to the copper chloride solution is 50.
7. The fluorescent paper sensor is characterized by comprising a loading material and a fluorescent probe solution loaded on the loading material;
the load material is a paper sensor composed of a cellulose acetate membrane;
the fluorescent probe solution is the fluorescent probe solution as described in any one of claims 4 to 6, which includes the gold nanocluster solution as described in any one of claims 1 to 3.
8. The fluorescent paper sensor of claim 7, wherein the paper sensor is prepared by: soaking a cellulose acetate membrane in a dilute hydrochloric acid solution, soaking in a dithizone-chloroform buffer solution, and drying to obtain the cellulose acetate membrane.
9. The fluorescent paper sensor according to claim 8, wherein the dithizone-chloroform buffer solution is 0.005% by mass.
10. The fluorescent paper sensor of claim 7, wherein the paper sensor is immersed in the fluorescent probe solution, stabilized for 0.5h, removed, and dried in the shade to obtain the fluorescent paper sensor.
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