A method for the ratiometric fluorescence detection of clioquinol based on AuNCs / CDs@SiO2

Abstract

The present invention discloses a method for detecting clioquinol by ratio fluorescence based on AuNCs / CDs@SiO2. In the present invention, gold nanoclusters and carbon dots coated with silica are compounded to prepare AuNCs / CDs@SiO2. A CuCl2 solution, clioquinol solutions with different concentrations, and H2O are added to a centrifuge tube for reaction; AuNCs / CDs@SiO2 is added to the reaction mixture for reaction; after the reaction, a fluorescence photometer is used to measure the fluorescence emission spectrum of the resulting mixed solution, excited under an Xe lamp, and the fluorescence intensities at wavelengths of 420 nm and 595 nm are recorded; and a standard working curve is plotted with the CQ concentration as the abscissa and the fluorescence intensity ratio at 420 nm and 595 nm as the ordinate; the above steps are repeated for the clioquinol sample to be tested, and the fluorescence intensity ratio after the reaction of the sample to be tested with the system is measured respectively by a fluorescence photometer, and the concentration of clioquinol CQ to be tested is obtained through calculation. Using the method of the present invention to detect clioquinol, both the sensitivity and the accuracy are relatively high.

Description

I. Technical Field:

[0001] The present invention relates to an analytical detection method for clioquinol, belonging to the technical field of analytical chemistry, and specifically relates to a method for detecting clioquinol by ratio fluorescence based on AuNCs / CDs@SiO2. II. Background Art:

[0002] Clioquinol (5-chloro-8-hydroxy-7-iodoquinoline, CQ), as a widely used drug in the pharmaceutical field, has various pharmacological effects such as antifungal, antiparasitic, antiviral, and anti-inflammatory effects. CQ has attracted much attention as a potential therapeutic drug for human prostate cancer and neurodegenerative diseases (such as Alzheimer's disease, Parkinson's disease, and Huntington's disease). However, long-term or excessive use of CQ may lead to serious toxic effects, such as neurotoxicity and cytotoxicity. Accurately detecting the concentration of CQ in drugs can timely monitor the medication situation of patients and avoid adverse reactions caused by excessive or long-term use of drugs. Therefore, establishing a simple, rapid, and accurate CQ detection method is crucial for reducing its adverse consequences.

[0003] Currently, the CQ detection methods disclosed in the prior art mainly include electrochemistry, colorimetry, fluorescence, and high-performance liquid chromatography techniques. In particular, fluorescence sensing methods based on nanomaterials have become effective alternative methods, with higher sensitivity, cost-effectiveness, and the ability for rapid analysis. However, the currently disclosed fluorescence sensing methods based on nanomaterials only rely on the change of a single fluorescence signal and may be easily interfered by uncontrollable factors such as probe concentration, photobleaching, and environmental condition changes. To overcome the difficulties faced by single-emission fluorescence methods, using ratio fluorescence sensing methods is the most effective strategy. Ratio fluorescence can use multiple fluorescence output signals as detection indicators and has a self-calibration function, improving the detection accuracy. However, due to the lack of effective functional nanomaterials and sensor mechanism design, ratio fluorescence methods for CQ detection have not been developed yet. III. Summary of the Invention:

[0004] The technical problem to be solved by the present invention is: Based on the technical problems existing in the current CQ detection methods and the urgent need for ratio fluorescence methods for CQ detection, the present invention provides a method for detecting clioquinol by ratio fluorescence based on AuNCs / CDs@SiO2. Using the technical solution of the present invention to detect clioquinol, both its sensitivity and accuracy are relatively high.

[0005] To solve the above problems, the technical solution adopted by the present invention is:

[0006] The present invention provides a preparation method for AuNCs / CDs@SiO2, and the preparation method includes the following steps:

[0007] a. At 25 °C, add chloroauric acid HAuCl4 to H2O, and dropwise add glutathione GSH under gentle stirring for mixing reaction. Then heat to 60 - 80 °C and continue the reaction for 24 h. Then purify the obtained AuNCs solution through a dialysis process (using a dialysis bag with MWCO 1000 Da) to obtain AuNCs;

[0008] b. Mix and stir NH4OH, ethanol, and carbon dots CDs. Under vigorous stirring, add tetraethyl orthosilicate TEOS and react for 3 - 5 h, then add (3-aminopropyl)triethoxysilane APTES and react for 12 - 14 h. After the reaction, perform centrifugation, and then repeatedly wash the product with ethanol and ultrapure water. After washing, dry it to obtain CDs@SiO2;

[0009] c. Add the obtained CDs@SiO2 to H2O and perform ultrasonic treatment. Then add the AuNCs obtained in step a and Tris-HCl buffer solution, and react at room temperature. After the reaction, collect the formed AuNC / CDs@SiO2 complex by centrifugation. Wash the complex with H2O, and finally perform freeze-drying to obtain the AuNCs / CDs@SiO2 solid.

[0010] According to the above preparation method of AuNCs / CDs@SiO2, in step a, the addition amount of chloroauric acid is 2 mL, the concentration is 10 mM; the addition amount of H2O is 7.7 mL; the stirring rate is 400 - 700 rpm; the addition amount of glutathione is 300 μL, the concentration is 100 mM; the mixing reaction time is 5 min; the purification time is 24 h.

[0011] According to the above preparation method of AuNCs / CDs@SiO2, in step b, the addition amount of NH4OH is 0.4 mL, the addition amount of ethanol is 50 mL, the addition amount of carbon dots is 1.5 - 3 mL, the addition amount of tetraethyl orthosilicate is 200 μL, and the addition amount of (3-aminopropyl)triethoxysilane is 200 μL.

[0012] According to the above preparation method of AuNCs / CDs@SiO2, in step b, the mixing and stirring time is 15 min, the stirring speed during vigorous stirring is 500 - 800 rpm; during the drying process, the temperature is 60 - 80 °C and the time is 12 - 24 h.

[0013] According to the above preparation method of AuNCs / CDs@SiO2, the addition amount of the CDs@SiO2 described in step c is 2.0 - 3.5 mg, the addition amount of H2O is 8.5 mL, the addition amount of the AuNCs obtained in step a is 1 mL and its concentration is 1.0 mg / mL, the addition amount of the Tris-HCl buffer solution is 0.5 mL, its concentration is 100 mM, and the pH is 6.0.

[0014] According to the above preparation method of AuNCs / CDs@SiO2, the time of the ultrasonic treatment in step c is 15 min, the reaction is carried out at room temperature for 2 h, the conditions during centrifugation are 9000 - 10000 r / min for 10 min, the number of times of washing the complex with H2O is 3 times, during the freeze-drying process, the temperature is -80 °C and the time is 24 - 36 h; the obtained AuNCs / CDs@SiO2 solid is a nanospherical material with a particle size of 90 - 110 nm.

[0015] In addition, a method for ratiometric fluorescence detection of clioquinol based on AuNCs / CDs@SiO2 is provided, and the method includes the following steps:

[0016] 1) Add 200 μL of 0.1 mM CuCl2 solution, 200 μL of clioquinol CQ solutions with different concentrations and 100 μL of H2O into a 1.5 mL centrifuge tube, and react at room temperature for 30 - 60 minutes (preferably 40 minutes);

[0017] The concentrations of the clioquinol CQ solutions with different concentrations added before the reaction are 0 μM, 0.5 μM, 2.5 μM, 5 μM, 25 μM, 50 μM, 100 μM, 150 μM, 200 μM, 250 μM, 300 μM, 350 μM, 400 μM, 450 μM, 500 μM, 600 μM and 700 μM respectively; the addition amount of each concentration of clioquinol CQ solution is 200 μL;

[0018] After the reaction, the final concentrations of clioquinol CQ in the reaction system are 0 μM, 0.1 μM, 0.5 μM, 1 μM, 5 μM, 10 μM, 20 μM, 30 μM, 40 μM, 50 μM, 60 μM, 70 μM, 80 μM, 90 μM, 100 μM, 120 μM and 140 μM respectively;

[0019] 2) Add 500 μL of the AuNCs / CDs@SiO2 obtained in claim 1 with a concentration of 0.4 mg / mL into the reaction mixture obtained in step 1), and react at room temperature for 5 - 15 min (preferably 10 min);

[0020] 3) Use a fluorometer to measure the fluorescence emission spectrum of the mixed solution obtained in step 2). Excite it under a Xe lamp and record the fluorescence intensities at wavelengths of 420 nm and 595 nm; and plot a standard working curve with the CQ concentration as the abscissa and the ratio of the fluorescence intensities at 420 nm and 595 nm as the ordinate.

[0021] 4) Repeat steps 1) - 3) for the chlorquinaldol CQ sample to be measured. Use a fluorometer to measure the ratio of the fluorescence intensities after the reaction of the sample to be measured with the system respectively. Through calculation and comparison with the standard working curve, obtain the concentration of the chlorquinaldol CQ to be measured.

[0022] According to the above method for ratio fluorescence detection of chlorquinaldol based on AuNCs / CDs@SiO2, the excitation wavelength of the Xe lamp in step 3) is 365 nm.

[0023] According to the above method for ratio fluorescence detection of chlorquinaldol based on AuNCs / CDs@SiO2, the detection concentration range of the chlorquinaldol CQ sample to be measured in step 4) is 0.1 - 60 μM.

[0024] The positive and beneficial effects of the present invention:

[0025] 1. In the technical solution of the present invention, AuNCs / CDs@SiO2 is prepared by compounding gold nanoclusters with carbon dots coated with silica, and the method for ratio fluorescence detection of chlorquinaldol based on AuNCs / CDs@SiO2 of the present invention is developed. First, Cu 2+ can quench the fluorescence of AuNCs in AuNCs / CDs@SiO2, but does not quench the fluorescence of CDs; secondly, Cu 2+ can form a complex with CQ, thus preventing Cu 2+ from quenching the fluorescence of AuNCs; after adding CQ, the fluorescence of AuNCs at 595 nm is restored, and the fluorescence of CDs at 420 nm does not change. Therefore, this detection platform can realize the ratio fluorescence determination of CQ by using the change of the fluorescence intensity ratio (F 420 / F 595 ).

[0026] 2. The present invention uses the AuNCs / CDs@SiO2 nanomaterial as a dual-emission fluorescence probe to realize the ratio fluorescence detection of CQ. The detection method is convenient, low-cost, and simple to operate. Based on AuNCs / CDs@SiO2 for detecting CQ, the detectable range is as wide as 0.1 - 60 μM. Based on AuNCs / CDs@SiO2 to realize the ratio detection of CQ, it is sensitive to CQ, and the measurement results of actual samples are accurate and reliable, realizing the detection of CQ in commercially available commercial creams.

[0027] 3. Detecting clioquinol using the technical solution of the present invention has relatively high sensitivity and accuracy. IV. Description of the Drawings:

[0028] Figure 1 Fluorescence emission spectrum of AuNCs / CDs@SiO2 prepared in the embodiment of the present invention;

[0029] Figure 2 Fluorescence emission spectra of AuNCs / CDs@SiO2 prepared in the embodiment of the present invention at different CuCl2 concentrations;

[0030] Figure 3 Quantitative detection of the concentration of CQ by ratio fluorescence detection in the AuNCs / CDs@SiO2 system of the present invention;

[0031] Figure 4 Selectivity of the AuNCs / CDs@SiO2 system of the present invention for detecting CQ. V. Specific Embodiments:

[0032] In order to more clearly illustrate the technical solution of the present invention, the following further detailed description of the present invention is provided in conjunction with the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and do not limit the protection scope of the technical solution of the present invention.

[0033] Example 1:

[0034] The preparation method of AuNCs / CDs@SiO2 of the present invention is as follows in detail:

[0035] a. At 25 °C, add 2 mL of 10 mM HAuCl4 to 7.7 mL of H2O, and dropwise add 300 μL of 100 mM glutathione GSH at a stirring speed of 500 rpm. The mixture reacts for 5 minutes; then heat to 70 °C and continue to react for 24 hours; then purify the obtained AuNCs solution by dialysis (through a dialysis bag with a MWCO of 1000 Da) for 24 hours to obtain AuNCs after purification;

[0036] b. Mix 0.4 mL of NH4OH, 50 mL of ethanol, and 2 mL of carbon dot CDs solution and stir for 15 minutes; then, under the condition of a stirring speed of 500 rpm, add 200 μL of tetraethyl orthosilicate TEOS and react for 3 h, and then add 200 μL of (3-aminopropyl)triethoxysilane (APTES) and react for 12 h; after the reaction, centrifuge, and then wash the product several times with ethanol and ultrapure water, and dry (at a temperature of 60 °C for 20 h) to obtain CDs@SiO2;

[0037] c. Add 3.0 mg of CDs@SiO2 to 8.5 mL of H2O and sonicate for 15 minutes; then add 1 mL of 1.0 mg / mL AuNCs and 0.5 mL of 100 mM Tris-HCl buffer solution (pH 6.0), and react at room temperature for 2 hours; after the reaction, collect the formed AuNC / CDs@SiO2 complex by centrifugation (9000 r / min, 10 min); wash three times with H2O; finally, perform freeze-drying (temperature -80 °C, time 30 h) to obtain the AuNCs / CDs@SiO2 solid after drying.

[0038] The AuNCs / CDs@SiO2 solid prepared in this example is a nanospherical material with a particle size of 90 - 110 nm.

[0039] The fluorescence emission spectrum of AuNCs / CDs@SiO2 prepared in Example 1 of the present invention is shown in detail in the appendix Figure 1 , Figure 1 which shows that AuNCs / CDs@SiO2 has two characteristic fluorescence emission peaks at 425 nm and 595 nm.

[0040] Example 2:

[0041] The AuNCs / CDs@SiO2 prepared in the present invention has a fluorescence response to Cu 2+ :

[0042] 1) Add 500 μL of CuCl2 solutions with different concentrations (the different concentrations are 0 μM, 0.01 μM, 0.02 μM, 0.1 μM, 0.2 μM, 1 μM, 2 μM, 4 μM, 6 μM, 8 μM, 10 μM, 12 μM, 16 μM, 20 μM, 24 μM, 28 μM, 32 μM, 36 μM, 40 μM, 44 μM, 48 μM) and 500 μL of 0.4 mg / mL AuNCs / CDs@SiO2 to a 1.5 mL centrifuge tube and react at room temperature for 10 min;

[0043] The final concentration of the Cu 2+ in the system after the reaction is 0 μM, 0.005 μM, 0.01 μM, 0.05 μM, 0.1 μM, 0.5 μM, 1 μM, 2 μM, 3 μM, 4 μM, 5 μM, 6 μM, 8 μM, 10 μM, 12 μM, 14 μM, 16 μM, 18 μM, 20 μM, 22 μM, 24 μM respectively;

[0044] 2) Use a fluorescence photometer to measure the fluorescence emission spectrum of the reaction mixture solution, excite at 365 nm, and record the fluorescence emission spectrum.

[0045] In this example, the fluorescence emission spectra of AuNCs / CDs@SiO2 at different Cu 2+ concentrations can be found in the appendix Figure 2 . As Figure 2 shown, as the Cu 2+ content increases from 0 to 24 μM, the fluorescence of AuNCs / CDs@SiO2 at 595 nm gradually decreases, and the fluorescence at 420 nm remains basically unchanged.

[0046] Example 3:

[0047] The method for detecting the concentration of clioquinol based on the ratio fluorescence of AuNCs / CDs@SiO2 in the present invention is as follows in detail:

[0048] 1) Add 200 μL of 0.1 mM CuCl2 solution, 200 μL of clioquinol CQ solutions with different concentrations (the different concentrations are 0 μM, 0.5 μM, 2.5 μM, 5 μM, 25 μM, 50 μM, 100 μM, 150 μM, 200 μM, 250 μM, 300 μM, 350 μM, 400 μM, 450 μM, 500 μM, 600 μM, 700 μM) and 100 μL of H2O into a 1.5 mL centrifuge tube, and react at room temperature for 40 minutes;

[0049] The final concentrations of clioquinol CQ in the reaction system after reaction are 0 μM, 0.1 μM, 0.5 μM, 1 μM, 5 μM, 10 μM, 20 μM, 30 μM, 40 μM, 50 μM, 60 μM, 70 μM, 80 μM, 90 μM, 100 μM, 120 μM, 140 μM respectively;

[0050] 2) Add 500 μL of 0.4 mg / mL AuNCs / CDs@SiO2 prepared in Example 1 into the reaction mixture obtained in step 1), and react at room temperature for 10 min;

[0051] 3) Use a fluorescence photometer to measure the fluorescence emission spectrum of the mixed solution obtained in step 2), excite at 365 nm, and record the fluorescence intensities at wavelengths of 420 nm and 595 nm; and plot a standard working curve with the CQ concentration as the abscissa and the fluorescence intensity ratio at 420 nm and 595 nm as the ordinate.

[0052] The results of quantitatively detecting the concentration of CQ by using the ratio fluorescence detection of the AuNCs / CDs@SiO2 system can be found in the appendix Figure 3 A. As Figure 3 shown in A, as the CQ content increases from 0 to 140 μM, the fluorescence of AuNCs / CDs@SiO2 at 595 nm gradually increases, and the fluorescence at 420 nm remains basically unchanged; Figure 3B is the fitting straight line of the fluorescence intensity ratio (F 420 / F 595 ), indicating that the detectable range of this method for CQ is 0.1 - 60 μM, and it has excellent detection effect.

[0053] Example 4:

[0054] Detect the selectivity for CQ using the reaction system:

[0055] 1) Add CuCl2 solution (200 μL, 0.1 mM), different kinds of amino acids (serine Ser, methionine Met, aspartic acid Asp, proline Pro, glycine Gly, valine Val, tyrosine Tyr), ions (Na + , K + , Mg 2+ , Mn 2+ , NH4 + , Cl - , I - , NO3 - , SO4 2- ), other drugs (chloramphenicol CPL, ibuprofen IBU, aspirin asp) and biomolecules (urea urea, creatinine Cr, cholesterol CHOL, glucose GLU, galactose Gal, sucrose SUC) (200 μL, 250 μM) and 100 μL H2O into 1.5 mL centrifuge tubes, and react at room temperature for 40 minutes;

[0056] 2) Add AuNCs / CDs@SiO2 (500 μL, 0.4 mg / mL) to the above mixture, and react at room temperature for 10 minutes;

[0057] 3) Measure the fluorescence emission spectrum of the mixed solution with a fluorescence photometer, excite at 365 nm, and record the fluorescence intensities at wavelengths of 420 nm and 595 nm.

[0058] The detection results are as Figure 4 shown; the fluorescence intensity ratio (F 420 / F 595 ) of the system decreases significantly only in the presence of CQ. In the absence of CQ, the fluorescence intensity ratio (F 420 / F 595 ) does not change significantly, indicating that this sensing system has high selectivity for CQ.

[0059] Example 5:

[0060] Detect the concentration of CQ in actual samples using the reaction system:

[0061] 1) Add CuCl2 solution (200 μL, 0.1 mM), 200 μL of the actual sample to be tested, and 100 μL of H2O into a 1.5 mL centrifuge tube respectively, and react at room temperature for 40 minutes;

[0062] 2) Add AuNCs / CDs@SiO2 (500 μL, 0.4 mg / mL) to the above mixture and react at room temperature for 10 min;

[0063] 3) Measure the fluorescence emission spectrum of the mixed solution with a fluorescence photometer, excite at 365 nm, record the fluorescence intensities at wavelengths of 420 nm and 595 nm, and calculate the fluorescence intensity ratio (F 420 / F 59 5). By calculation and comparison with the standard working curve, the CQ concentration can be obtained. The detected data results are shown in Table 1.

[0064] The recovery rate of CQ is 99.6 - 100.9%, and the relative standard deviation is less than 7%. The results show that this ratiometric fluorescence sensing method has high accuracy and reliability and can be used for the analysis and detection of CQ in actual samples.

[0065] Table 1 Detection results in CQ cream

[0066]

Claims

1. A method for ratiometric fluorescence detection of clioquinol based on AuNCs / CDs@SiO2, characterized in that, The method includes the following steps: 1) Add 200 μL of 0.1 mM CuCl2 solution, 200 μL of chloroiodoquine CQ solutions with different concentrations, and 100 μL of H2O into a 1.5 mL centrifuge tube, and react at room temperature for 30 - 60 minutes; The concentrations of the chloroiodoquine CQ solutions with different concentrations added before the reaction are 0 μM, 0.5 μM, 2.5 μM, 5 μM, 25 μM, 50 μM, 100 μM, 150 μM, 200 μM, 250 μM, 300 μM, 350 μM, 400 μM, 450 μM, 500 μM, 600 μM, and 700 μM respectively; the addition amount of each concentration of chloroiodoquine CQ solution is 200 μL; After the reaction, the final concentrations of chloroiodoquine CQ in the reaction system are 0 μM, 0.1 μM, 0.5 μM, 1 μM, 5 μM, 10 μM, 20 μM, 30 μM, 40 μM, 50 μM, 60 μM, 70 μM, 80 μM, 90 μM, 100 μM, 120 μM, and 140 μM respectively; 2) Add 500 μL of 0.4 mg / mL AuNCs / CDs@SiO2 into the reaction mixture obtained in step 1), and react at room temperature for 5 - 15 min; The preparation method of the AuNCs / CDs@SiO2 is as follows: a. At 25 °C, add chloroauric acid HAuCl4 into H2O, dropwise add glutathione GSH under gentle stirring for mixing reaction, then heat to 60 - 80 °C and continue the reaction for 24 h; then purify the obtained AuNCs solution through the dialysis process to obtain AuNCs; b. Mix and stir NH4OH, ethanol, and carbon dots CDs; under vigorous stirring, add tetraethyl orthosilicate TEOS and react for 3 - 5 h, then add (3-aminopropyl)triethoxysilane APTES and react for 12 - 14 h; after the reaction, centrifuge, then repeatedly wash the product with ethanol and ultrapure water, and dry after washing to obtain CDs@SiO2; c. Add the obtained CDs@SiO2 into H2O for ultrasonic treatment; then add the AuNCs obtained in step a and Tris-HCl buffer solution, and react at room temperature; after the reaction, collect the formed AuNC / CDs@SiO2 complex by centrifugation; wash the complex with H2O, and finally perform freeze-drying to obtain the AuNCs / CDs@SiO2 solid; 3) Use a fluorescence photometer to measure the fluorescence emission spectrum of the mixed solution obtained in step 2), excite under a Xe lamp, and record the fluorescence intensities at wavelengths of 420 nm and 595 nm; and plot a standard working curve with the CQ concentration as the abscissa and the fluorescence intensity ratio at 420 nm and 595 nm as the ordinate; 4) Repeat steps 1) - 3) for the chloroiodoquine CQ sample to be measured, use a fluorescence photometer to measure the fluorescence intensity ratio of the sample to be measured after reacting with the system respectively, and compare with the standard working curve through calculation to obtain the concentration of the chloroiodoquine CQ to be measured.

2. The method for ratiometric fluorescence detection of clioquinol based on AuNCs / CDs@SiO2 according to claim 1, wherein: In step a of the preparation method of AuNCs / CDs@SiO2 described in step 2), the addition amount of chloroauric acid is 2 mL and the concentration is 10 mM; the addition amount of H2O is 7.7 mL; the stirring rate is 400 - 700 rpm; the addition amount of glutathione is 300 μL and the concentration is 100 mM; the time for the mixed reaction is 5 min; the time for purification is 24 h.

3. The method for ratiometric fluorescence detection of clioquinol based on AuNCs / CDs@SiO2 according to claim 1, characterized in that: In step b of the preparation method of AuNCs / CDs@SiO2 described in step 2), the addition amount of NH4OH is 0.4 mL, the addition amount of ethanol is 50 mL, the addition amount of carbon dots is 1.5 - 3 mL, the addition amount of tetraethyl orthosilicate is 200 μL, and the addition amount of (3-aminopropyl)triethoxysilane is 200 μL.

4. The method for ratiometric fluorescence detection of clioquinol based on AuNCs / CDs@SiO2 according to claim 1, wherein: In step b of the preparation method of AuNCs / CDs@SiO2 described in step 2), the time for the mixed stirring is 15 min, the stirring speed during vigorous stirring is 500 - 800 rpm; during the drying process, the temperature is 60 - 80 °C and the time is 12 - 24 h.

5. The method for ratiometric fluorescence detection of clioquinol based on AuNCs / CDs@SiO2 according to claim 1, characterized in that: In step c of the preparation method of AuNCs / CDs@SiO2 described in step 2), the addition amount of CDs@SiO2 is 2.0 - 3.5 mg, the addition amount of H2O is 8.5 mL, the addition amount of AuNCs obtained in step a is 1 mL and its concentration is 1.0 mg / mL, the addition amount of Tris-HCl buffer solution is 0.5 mL, its concentration is 100 mM, and the pH is 6.

0.

6. The method for ratiometric fluorescence detection of clioquinol based on AuNCs / CDs@SiO2 according to claim 1, characterized in that: In step c of the preparation method of AuNCs / CDs@SiO2 described in step 2), the time for ultrasonic treatment is 15 min, the reaction is carried out at room temperature for 2 h, the conditions for centrifugation are 9000 - 10000 r / min for 10 min, the number of times for washing the complex with H2O is 3 times, during the freeze-drying process, the temperature is -80 °C and the time is 24 - 36 h; the obtained AuNCs / CDs@SiO2 solid is a nanospherical material with a particle size of 90 - 110 nm.

7. The method for ratiometric fluorescence detection of clioquinol based on AuNCs / CDs@SiO2 according to claim 1, characterized in that: In step 3), the excitation wavelength of the Xe lamp is 365 nm.

8. The method for ratiometric fluorescence detection of clioquinol based on AuNCs / CDs@SiO2 according to claim 1, characterized in that: In step 4), the detection concentration range of the chlorquinaldol CQ sample to be measured is 0.1 - 60 μM.

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