Quaternary quantum dot ZnCuInSe / CuInSe and preparation method and application thereof
By preparing core-shell structured quaternary quantum dots ZnCuInSe/CuInSe, the problems of poor stability and toxicity of binary and ternary quantum dots were solved, and sensitive detection of chloroiodohydroxyquine was achieved with a detection limit of 3.33 μM.
Patent Information
- Application Number
- CN202511168022.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-20
- Publication Date
- 2025-11-18
AI Technical Summary
Existing binary quantum dots contain toxic heavy metal elements, have poor stability and low fluorescence efficiency, and ternary quantum dots have many surface defects, affecting their optical properties; long-term use of chloroquine may cause neurotoxicity, so there is a need to develop low-cost, rapid and accurate quantitative analysis methods.
A core-shell quaternary quantum dot ZnCuInSe/CuInSe was prepared using an aqueous phase method. By coating the ZnCuInSe surface with a CuInSe shell, defects were passivated and the carrier recombination rate was reduced, and a fluorescent probe was constructed for the detection of chloroiodohydroxyquine.
Sensitive detection of chloroiodohydroxyquine was achieved with a detection limit of 3.33 μM. The quantum dots exhibit good water solubility and stability, long fluorescence lifetime, low toxicity, and enhanced fluorescence performance.
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Figure CN120966479A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of nanomaterials, and particularly relates to a quaternary quantum dot ZnCuInSe / CuInSe and a preparation method and application thereof. BACKGROUND
[0002] Semiconductor fluorescent quantum dots, simply referred to as quantum dots (QDs), are nanocrystals made of semiconductor materials. The quantum dots are generally spherical or spherical-like, and the diameter is often between 2-20 nm. The quantum dots are a new type of inorganic fluorescent nanomaterials, and have excellent physical and chemical properties, such as a wide excitation wavelength, a narrow emission spectrum, good stability, and a long fluorescence lifetime. The quantum dots have a great application prospect in biomedical applications, and are widely used in various fields, such as biological imaging, drug delivery, cancer treatment, and biosensors. The binary quantum dots often contain toxic heavy metal elements, which have a great harm to the human body and the environment. The ternary quantum dots have a large number of defects, and thus have a low fluorescence efficiency. In order to solve the problems of poor stability and low emission efficiency of the ternary quantum dots, the technical personnel in the field will introduce Zn 2+ Zn-I-III-VI quaternary quantum dots are formed by directly doping I-III-VI quantum dots into a lattice, and the introduction of Zn 2+ can reduce surface defects, inhibit non-radiative recombination, and make the lattice structure more stable, thereby effectively improving the luminescent efficiency of the quantum dots. However, the small size of the quantum dots makes the surface of the quantum dots present a high-density defect state, and too many defect states will affect the optical properties of the quantum dots.
[0003] Chloroquine iodine (5-chloro-8-hydroxy-7-iodoquinoline, CQ) is a halogenated hydroxyquinoline compound with antifungal, antiparasitic and potential anticancer activity. Its cream preparation can also be used for the treatment of various skin diseases, and thus is concerned in the fields of medical and pharmaceutical research. However, long-term or excessive use of CQ may cause neurotoxicity and lead to adverse reactions such as retinopathy and subacute myelo-optic neuropathy. Therefore, there is an urgent need to develop a new type of sensor with low cost, rapid response and simple operation to realize the accurate quantitative analysis of CQ. SUMMARY
[0004] To solve the above technical problems, the application provides a quaternary quantum dot ZnCuInSe / CuInSe (ZCISe / CISe) and a preparation method and application thereof. The quaternary quantum dot ZnCuInSe / CuInSe prepared by the application can detect chloroquine iodine, and can realize sensitive detection of chloroquine iodine.
[0005] To achieve the above purpose, the application provides the following technical solutions.
[0006] The application provides a preparation method of quaternary quantum dots ZnCuInSe / CuInSe.
[0007] Step 1, zinc salt, copper salt, indium salt and mercaptopropionic acid (MPA) aqueous solution are mixed, nitrogen is introduced under magnetic stirring, after heating, the first NaHSe precursor solution is added under stirring, and the reflux reaction is carried out under nitrogen protection, to obtain a ZnCuInSe (ZCISe) dispersion liquid;
[0008] Step 2, copper salt and indium salt are added again in the ZCISe dispersion liquid, the second NaHSe precursor solution is added after reaction, and the reaction is cooled to room temperature, isopropanol is added, centrifugal washing is carried out, and drying is carried out, to obtain the quaternary quantum dots ZnCuInSe / CuInSe, which is recorded as ZCISe / CISe.
[0009] The application first prepares the core-shell structure quaternary quantum dots ZCISe / CISe by the aqueous phase synthesis method, the core-shell structure can effectively passivate the surface defects of the quantum dots and reduce the carrier recombination rate, so that the carrier lifetime is prolonged, the prepared quaternary quantum dots have low toxicity and unique optical properties (after the ZCISe shell is coated on the CISe, the fluorescence emission peak is significantly red-shifted), and then the fluorescence probe is constructed based on the prepared core-shell structure quaternary quantum dots ZCISe / CISe, so that sensitive detection of chloroiodoxyquinol can be realized.
[0010] Further, in step 1, the preparation method of the first NaHSe precursor solution is that Se powder is mixed with NaBH4, water is added, nitrogen is introduced and stirred, and the reaction is carried out until the solution is clear and colorless, to obtain the first NaHSe precursor solution.
[0011] Further, in step 1, the mass ratio of the Se powder to NaBH4 is 1:2.
[0012] And / or, the water is air-removed water.
[0013] Further, in step 1, the preparation method of the first NaHSe precursor solution is that 0.1180g Se powder is mixed with 0.2g NaBH4 and added into a 25mL three-necked flask, 10mL deionized water which has been air-removed is added into the three-necked flask, nitrogen is introduced and stirred at room temperature, and the reaction is carried out for 20min until the solution is clear and colorless, to obtain the first NaHSe precursor solution.
[0014] Further, in step 1, the mass ratio of the zinc salt, the copper salt and the indium salt is 0.0275:0.0299:0.3503. Exemplarily, the zinc salt is selected from Zn(CH3COO)2, the copper salt is selected from Cu(CH3COO)2, and the indium salt is selected from In(CH3COO)3.
[0015] Further, in step 1, the temperature of the reflux reaction is 100℃, and the reflux reaction time is 240 min.
[0016] Further, in step 2, the mass ratio of the copper salt and the indium salt added again is 0.0299:0.0438.
[0017] Further, in step 2, the reaction time after adding the copper salt and the indium salt is 30 min, and the reaction time after adding the second NaHSe precursor solution is 60 min.
[0018] The application further provides a quaternary quantum dot ZnCuInSe / CuInSe prepared by the above method, which is a core-shell structure, has a morphology close to a sphere, a particle size distribution of 1.6-5.5 nm, and a lattice stripe with a resolution of 0.33 nm.
[0019] The application further provides an application of the above quaternary quantum dot ZnCuInSe / CuInSe in detecting chloroiodoxyquinol (CQ).
[0020] The application further provides a method for detecting CQ by using the above quaternary quantum dot ZnCuInSe / CuInSe, which comprises the following steps: mixing Zn 2+ solution with the quaternary quantum dot ZnCuInSe / CuInSe, adding a to-be-detected solution containing CQ to obtain a mixed solution, and detecting the fluorescence emission spectrum of the mixed solution under excitation of a wavelength of 550 nm.
[0021] Compared with the prior art, the application has the following advantages and technical effects:
[0022] The quaternary quantum dot ZCISe / CISe prepared by the water phase method has good water solubility and stability, and has a longer fluorescence lifetime than ZnCuInSe. 2+ Adsorbed to the surface of the quaternary quantum dot ZCISe / CISe, CQ can enhance the fluorescence performance of the quantum dot. 2+ Since CQ and Zn 2+ have a strong binding force, CQ can compete with Zn Thus, the fluorescence probe constructed by the quaternary quantum dot ZCISe / CISe prepared by the application can realize sensitive detection of chloroiodoxyquinol, and the detection limit is 3.33 µM. BRIEF DESCRIPTION OF DRAWINGS
[0023] The accompanying drawings, which form a part of this application, are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification. The illustrations are shown schematically in the drawings where:
[0024] Figure 1 Fluorescence spectrum of the quaternary quantum dot ZCISe prepared for Comparative Example 1 in water;
[0025] Figure 2 Fluorescence spectrum of the quaternary quantum dot ZCISe prepared for Comparative Example 2 in water;
[0026] Figure 3 Fluorescence spectrum of the quaternary quantum dot ZCISe / CISe prepared for Example 1 in water;
[0027] Figure 4 Transmission electron microscope image of the quaternary quantum dot ZCISe / CISe prepared for Example 1;
[0028] Figure 5 Survival rate of HeLa cells after the quaternary quantum dot ZCISe / CISe prepared for Example 1 was treated for 12 h;
[0029] Figure 6 Fluorescence intensity change diagram of the quaternary quantum dot ZCISe prepared for Comparative Example 1 and ZCISe / CISe prepared for Example 1 dispersed in water within 15 days;
[0030] Figure 7 Fluorescence decay curve diagram of the quaternary quantum dot ZCISe prepared for Comparative Example 1 and ZCISe / CISe prepared for Example 1;
[0031] Figure 8 Fluorescence spectrum and linear diagram of CQ concentration and fluorescence intensity ratio of CQ detection in Application Example 1, wherein (A) is the fluorescence spectrum of CQ detection, and (B) is the linear diagram of CQ concentration and fluorescence intensity ratio. DETAILED DESCRIPTION
[0032] Various illustrative embodiments of the present application are now described in detail. The detailed description is made with reference to the accompanying drawings, of which:
[0033] It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. Additionally, for a range of values of, an intermediate value of is specifically contemplated. Each of these intermediate values is also encompassed within the scope of the present application. The upper and lower limits of these smaller ranges can independently be included or excluded in the ranges.
[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, preferred methods and materials are described. All publications mentioned in this specification are herein incorporated by reference to disclose and describe the methods and / or materials in connection with which the publications are cited. The citation of any reference is not construed as an admission that it is prior art with respect to the present application.
[0035] Many modifications and variations of this application can be made in the light of the above teachings without departing from the spirit and scope thereof. Additional implementations of the application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. The examples and embodiments described herein are exemplary only and are not intended to be limiting.
[0036] As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having", "contains", "containing", or variations thereof, are intended to be open-ended terms that mean including, but not limited to.
[0037] Embodiments of the present application provide a method for preparing a quaternary quantum dot ZnCuInSe / CuInSe, comprising the following steps:
[0038] Step 1, zinc salt, copper salt, indium salt and mercaptopropionic acid (MPA) aqueous solution are mixed, nitrogen is introduced under magnetic stirring, after heating, the first NaHSe precursor solution is added under stirring, and the reflux reaction is carried out under nitrogen protection, to obtain a ZCISe dispersion liquid;
[0039] Step 2, copper salt and indium salt are added again in the ZCISe dispersion liquid, the second NaHSe precursor solution is added after reaction, and the reaction is cooled to room temperature, isopropanol is added, centrifugal washing and drying are carried out, to obtain a quaternary quantum dot ZnCuInSe / CuInSe (ZCISe / CISe).
[0040] The application first prepares core-shell structure quaternary quantum dots ZCISe / CISe by an aqueous phase synthesis method, the core-shell structure can effectively passivate quantum dot surface defects and reduce carrier recombination rate, thereby prolonging carrier lifetime, and the core-shell structure quaternary quantum dots ZCISe / CISe have low toxicity and unique optical properties; then a fluorescence probe is constructed based on the prepared core-shell structure quaternary quantum dots ZCISe / CISe, and the fluorescence probe can detect chloroiodoxyquin, and sensitive detection of chloroiodoxyquin can be realized.
[0041] In the embodiment of the application, in step 1, the preparation method of the first NaHSe precursor solution is as follows: Se powder and NaBH4 are mixed at a mass ratio of 1:2, deionized water is added, nitrogen is bubbled at room temperature, and the solution is clear and colorless after reaction for 20 min, thereby obtaining the first NaHSe precursor solution.
[0042] In the embodiment of the application, in step 1, the mass ratio of the zinc salt, the copper salt and the indium salt is 0.0275:0.0299:0.3503. For example, the zinc salt is selected from Zn(CH3COO)2, the copper salt is selected from Cu(CH3COO)2, and the indium salt is selected from In(CH3COO)3.
[0043] In the embodiment of the application, in step 1, the stirring rate is 1000-1200 rpm when the first NaHSe precursor solution is added.
[0044] In the embodiment of the application, in step 1, the concentration of the MPA aqueous solution is 0.1 M.
[0045] In the embodiment of the application, in step 1, the temperature of the reflux reaction is 100°C, and the reflux reaction time is 240 min.
[0046] In the embodiment of the application, in step 2, the mass ratio of the copper salt and the indium salt is 0.0299:0.0438. For example, the zinc salt is selected from Zn(CH3COO)2, the copper salt is selected from Cu(CH3COO)2, and the indium salt is selected from In(CH3COO)3.
[0047] In the embodiment of the application, in step 2, the preparation method of the second NaHSe precursor solution is as follows: Se powder and NaBH4 are mixed at a mass ratio of 1:10, deionized water is added, nitrogen is bubbled at room temperature, and the solution is clear and colorless after reaction for 20 min, thereby obtaining the second NaHSe precursor solution.
[0048] In the embodiment of the application, in step 2, the reaction time after the copper salt and the indium salt are added is 30 min, and the reaction time after the second NaHSe precursor solution is added is 60 min.
[0049] In the embodiment of the application, in step 2, the centrifugal washing is performed for 3 times, and the drying is vacuum drying for 4 h.
[0050] The embodiment of the present application also provides a quaternary quantum dot ZnCuInSe / CuInSe prepared according to the above method, which is a core-shell structure, has a morphology close to a sphere, a particle size distribution between 1.6-5.5 nm, and has a well-resolved lattice fringe with a spacing of 0.33 nm.
[0051] The embodiment of the present application also provides an application of the above quaternary quantum dot ZnCuInSe / CuInSe in detecting chloroquine (CQ).
[0052] The embodiment of the present application also provides a method for detecting chloroquine by using the above quaternary quantum dot ZnCuInSe / CuInSe, which comprises the following steps: 2+ mixing the solution with the quaternary quantum dot ZnCuInSe / CuInSe, adding a to-be-detected solution containing chloroquine, obtaining a mixed solution, and detecting a fluorescence emission spectrum of the mixed solution under excitation of a wavelength of 550 nm.
[0053] In the embodiment of the present application, the final concentrations of the quaternary quantum dot ZnCuInSe / CuInSe and the Zn 2+ solution in the mixed solution are 2 mg / mL and 30 μM respectively; and the final concentration of the CQ solution is 0-600 μM, and the concentration of the CQ solution is not 0.
[0054] In the embodiment of the present application, the Zn 2+ solution is selected from a Zn(CH3COO)2 solution.
[0055] In the present application, in order to detect the concentration of CQ in an actual sample, chloroquine cream (Jin Yao Heping Pharmaceutical Co., Ltd.) purchased from a pharmacy is used as a real sample for CQ determination.
[0056] Unless otherwise specified, the room temperature in the present application is 25±2 ℃.
[0057] The raw materials used in the embodiment of the present application are all purchased from the market.
[0058] It should be noted that the parts not described in detail in the present application are all conventional operation means in the art, and are not the focus of the present application.
[0059] The technical solutions of the present application are further described below through examples.
[0060] Comparative Example 1
[0061] A preparation method of a quaternary quantum dot ZnCuInSe, comprising the following steps:
[0062] (1) Preparation of NaHSe precursor solution: 0.1180 g Se powder and 0.2 g NaBH4 were mixed and added into a 25 mL three-neck flask, 10 mL deionized water with air removed was added into the three-neck flask, and the reaction was stirred at room temperature for 20 min until the solution was clear and colorless, obtaining 0.15M NaHSe precursor solution, which was stored in an air-tight container and used later;
[0063] (2) 0.0275 g Zn(CH3COO)2, 0.0299 g Cu(CH3COO)2, 0.3503 g In(CH3COO)3 and 50 mL MPA aqueous solution (0.1M) with air removed by nitrogen were added into the three-neck flask, and the solution was stirred at 800 rpm under nitrogen for 30 min, then the solution was heated to 100°C, and 10 mL 0.15M NaHSe precursor solution was rapidly added under vigorous stirring (1100 rpm), and the reaction was refluxed under nitrogen for 240 min, obtaining a dispersion solution containing quaternary quantum dots ZnCuInSe, 20 mL isopropyl alcohol was added, and the solution was centrifuged and washed for 3 times, and vacuum dried for 4 h, obtaining quaternary quantum dots ZnCuInSe, which was denoted as ZCISe.
[0064] Figure 1 The fluorescence spectrum of the quaternary quantum dots ZCISe prepared in the present comparative example in water, wherein n Zn :n Cu = 1:1, the fluorescence emission peak of the quaternary quantum dots ZCISe was located at about 620 nm, and the fluorescence intensity was high.
[0065] Comparative Example 2
[0066] A method for preparing quaternary quantum dots ZnCuInSe, comprising the following steps:
[0067] (1) Preparation of NaHSe precursor solution: 0.1180 g Se powder and 0.2 g NaBH4 were mixed and added into a 25 mL three-neck flask, 10 mL deionized water with air removed was added into the three-neck flask, and the reaction was stirred at room temperature for 20 min until the solution was clear and colorless, obtaining 0.15M NaHSe precursor solution, which was stored in an air-tight container and used later;
[0068] (2) 0.0275 g Zn(CH3COO)2, 0.1794 g Cu(CH3COO)2, 0.3503 g In(CH3COO)3 and 50 mL MPA aqueous solution (0.1 M) which had been deaerated with nitrogen were added into a three-necked flask, and the solution was heated to 100°C under nitrogen protection after stirring at 800 rpm for 30 min. Then, 10 mL 0.15 M NaHSe precursor solution was added rapidly under stirring at 1100 rpm, and the solution was refluxed for 240 min under nitrogen protection. Then, 20 mL isopropyl alcohol was added, and the solution was centrifuged for 3 times and dried in vacuum for 4 h to obtain the quaternary quantum dots ZnCuInSe, which was denoted as ZCISe;
[0069] Figure 2 The fluorescence spectrum of the quaternary quantum dots ZCISe prepared in the present comparative example in water was shown in FIG. 1, wherein n Zn :n Cu = 1:6, and the fluorescence emission peak was red-shifted to about 760 nm, but the fluorescence intensity was very weak.
[0070] Example 1
[0071] A preparation method of quaternary quantum dots ZnCuInSe / CuInSe, comprising the following steps:
[0072] (1) Preparation of NaHSe precursor solution: ① Preparation of 0.03 M NaHSe precursor solution: 0.0236 g Se powder and 0.2 g NaBH4 were mixed and added into a 25 mL three-necked flask, and 10 mL deionized water which had been deaerated was added into the three-necked flask. The solution was stirred at room temperature under nitrogen protection for 20 min until the solution was clear and colorless, thereby obtaining the 0.03 M NaHSe precursor solution which was stored in an air-tight container;
[0073] ② Preparation of 0.15 M NaHSe precursor solution: 0.1180 g Se powder and 0.2 g NaBH4 were mixed and added into a 25 mL three-necked flask, and 10 mL deionized water which had been deaerated was added into the three-necked flask. The solution was stirred at room temperature under nitrogen protection for 20 min until the solution was clear and colorless, thereby obtaining the 0.15 M NaHSe precursor solution which was stored in an air-tight container;
[0074] (2) 0.0275 g Zn(CH3COO)2, 0.0299 g Cu(CH3COO)2, 0.3503 g In(CH3COO)3 and 50 mL MPA aqueous solution (0.1 M) which has been deaerated by nitrogen were added into a three-necked flask, and the solution was heated to 100°C under nitrogen protection after stirring at 800 rpm for 30 min. Then, 10 mL 0.15 M NaHSe precursor solution was added rapidly under stirring at 1100 rpm, and the reaction was carried out under reflux for 240 min to obtain a dispersion of quaternary quantum dots ZnCuInSe (ZCISe dispersion) ;
[0075] (3) 0.0299 g Cu(CH3COO)2 and 0.0438 g In(CH3COO)3 were added into the obtained ZCISe dispersion, and the reaction was carried out for 30 min. Then, 0.03 M NaHSe precursor solution was added rapidly, and the reaction was carried out for 60 min. After cooling to room temperature, 20 mL isopropanol was added, and the precipitate was washed by centrifugation for 3 times to obtain quaternary quantum dots ZCISe / CISe. After vacuum drying for 4 h, quaternary quantum dots ZnCuInSe / CuInSe were obtained, which were denoted as ZCISe / CISe and dispersed in deionized water.
[0076] Figure 3 The fluorescence spectrum of the quaternary quantum dots ZCISe / CISe prepared in this example in water showed that the fluorescence emission peak of the quaternary quantum dots ZCISe / CISe was significantly red-shifted after the CuInSe shell was coated on the quaternary quantum dots ZCISe. This phenomenon might be due to the narrow band gap of the CuInSe shell. Meanwhile, the fluorescence intensity of the quaternary quantum dots ZCISe / CISe was increased, which might be due to the effective regulation of the internal defect state level of the quaternary quantum dots ZCISe during the growth of the shell.
[0077] Figure 4 The transmission electron microscopy (TEM) image of the quaternary quantum dots ZCISe / CISe prepared in this example showed that the morphology of the quaternary quantum dots ZCISe / CISe was approximately spherical, and the particle size distribution was between 1.6 nm and 5.5 nm. The quaternary quantum dots ZCISe / CISe had clear lattice fringes with a spacing of 0.33 nm.
[0078] Figure 5 The survival rate of HeLa cells after treatment with the quaternary quantum dots ZCISe / CISe prepared in Example 1 for 12 h showed that when the concentration of the quaternary quantum dots ZCISe / CISe reached 1 mg / mL, the survival rate of HeLa cells was still greater than 85%, indicating that the prepared quaternary quantum dots had low toxicity.
[0079] Figure 6The fluorescence intensity change graph of the quaternary quantum dots ZCISe prepared in Comparative Example 1 and the quaternary quantum dots ZCISe / CISe prepared in the present example within 15 days of dispersion in water can be seen that the fluorescence intensity of ZCISe and ZCISe / CISe within 15 days has no obvious change, indicating that the two quaternary quantum dots have good stability in water.
[0080] Figure 7 The fluorescence decay curve graph of the quaternary quantum dots ZCISe prepared in Comparative Example 1 and the quaternary quantum dots ZCISe / CISe prepared in the present example. As shown in Figure 7 , the average fluorescence lifetime of the quaternary quantum dots ZCISe is calculated to be 74.89 ns, and the average fluorescence lifetime of the core-shell quaternary quantum dots ZCISe / CISe is 123.28 ns. It can be seen that the core-shell quaternary quantum dots ZCISe / CISe have a longer fluorescence lifetime than ZCISe.
[0081] Application Example 1 Detection of chloroiodoxyquinol
[0082] (1) The quaternary quantum dots ZCISe / CISe prepared in Example 1 were mixed with Zn(CH3COO)2 solution, and different concentrations of CQ solution were added to make the final concentration of the quaternary quantum dots ZCISe / CISe and Zn 2+ solution 2 mg / mL and 30 μM respectively, and the final concentration of the CQ solution 0-600 μM. The fluorescence emission spectrum of the sample was detected under excitation at 550 nm.
[0083] (2) The chloroiodoxyquinol cream (1.0 g) was diluted with ethanol (20.0 mL), then filtered through a 0.22 μM filter membrane, diluted 100 times, and the CQ in the filtrate was detected using the constructed method. The fluorescence emission spectrum of the sample was detected under excitation at 550 nm.
[0084] Figure 8 The fluorescence spectrum and linear graph for CQ detection, wherein (A) is the fluorescence spectrum for CQ detection, and (B) is the linear graph of the CQ concentration and the fluorescence intensity ratio. As shown in Figure 8 (A), with the increase of the CQ concentration, the fluorescence intensity of the quaternary quantum dots ZCISe / CISe gradually decreases, and the detection limit of chloroiodoxyquinol is 3.33 μM. As shown in Figure 8 (B), there is a good linear relationship in the range of 0-600 μM. The linear regression equation is (F-F0) / F0=0.001C CQ +0.0193 (R 2 =0.997) (F0 represents the fluorescence intensity of the detection system without adding CQ).
[0085] Table 1 is the recovery rate of CQ detected in the chloroquine iodine hydroxy cream.
[0086] Table 1
[0087]
[0088] As shown in Table 1, the recovery rate of CQ in the cream is between 96.30% and 103.5%, and the standard deviation (RSD) is between 0.464% and 4.196%, indicating that the method of the present application has no obvious systematic error, and confirming that testing CQ in actual samples has great potential.
[0089] The above, only for the preferred specific embodiments of the present application, but the scope of protection of the present application is not limited to this, any skilled in the art of the technical personnel in the technical range disclosed by the present application, can easily think of changes or replacement, should be covered within the scope of protection of the present application.
Claims
1. A method for preparing quaternary quantum dots ZnCuInSe / CuInSe, characterized in that, Includes the following steps: Step 1: Mix zinc salt, copper salt, indium salt and mercaptopropionic acid aqueous solution, introduce nitrogen gas under magnetic stirring, heat and add first NaHSe precursor solution under stirring, and carry out reflux reaction under nitrogen protection to obtain ZnCuInSe dispersion. Step 2: Add copper salt and indium salt to the ZnCuInSe dispersion again, add a second NaHSe precursor solution after the reaction, cool to room temperature after the reaction, add isopropanol, centrifuge and wash, and dry to obtain the quaternary quantum dot ZnCuInSe / CuInSe.
2. The method for preparing quaternary quantum dots ZnCuInSe / CuInSe according to claim 1, characterized in that, In step 1, the preparation method of the first NaHSe precursor solution is as follows: Se powder is mixed with NaBH4, water is added, nitrogen gas is passed through and stirred, and the reaction is carried out until the solution is clear and colorless, thus obtaining the first NaHSe precursor solution.
3. The method for preparing quaternary quantum dots ZnCuInSe / CuInSe according to claim 2, characterized in that, In the preparation method of the first NaHSe precursor solution, the mass ratio of Se powder to NaBH4 is 1:2; And / or, the water is water from which air has been removed.
4. The method for preparing quaternary quantum dots ZnCuInSe / CuInSe according to claim 1, characterized in that, In step 1, the mass ratio of the zinc salt, copper salt, and indium salt is 0.0275:0.0299:0.3503.
5. The method for preparing quaternary quantum dots ZnCuInSe / CuInSe according to claim 1, characterized in that, In step 1, the reflux reaction temperature is 100°C and the reflux reaction time is 240 min.
6. The method for preparing quaternary quantum dots ZnCuInSe / CuInSe according to claim 1, characterized in that, In step 2, the mass ratio of the copper salt and indium salt added again is 0.0299:0.0438.
7. The method for preparing quaternary quantum dots ZnCuInSe / CuInSe according to claim 1, characterized in that, In step 2, the reaction time after adding copper salt and indium salt is 30 min; the reaction time after adding the second NaHSe precursor solution is 60 min.
8. A quaternary quantum dot ZnCuInSe / CuInSe, characterized in that, It is prepared according to any one of claims 1 to 7.
9. The application of the quaternary quantum dot ZnCuInSe / CuInSe as described in claim 8 in the detection of chloroiodohydroxyquine.
10. A method for detecting chloroiodohydroxyquine using the quaternary quantum dot ZnCuInSe / CuInSe as described in claim 8, characterized in that, Includes the following steps: Zn 2+ The solution was mixed with the quaternary quantum dot ZnCuInSe / CuInSe, and a test solution containing chloroiodohydroxyquine was added to obtain a mixed solution. The fluorescence emission spectrum of the mixed solution was detected under excitation at a wavelength of 550 nm.