CN110835528B - Preparation of composite fluorescent nano probe and detection method of hydrogen peroxide by using composite fluorescent nano probe - Google Patents
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Abstract
The invention discloses a preparation method of a CdSe @ ZnS/AgNCs composite fluorescent nano probe, which comprises the following steps of: mixing the CdSe @ ZnS quantum dots and the nano silver clusters under a certain pH condition to prepare a CdSe @ ZnS/AgNCs composite fluorescent nano probe; after mixing, the concentration of the CdSe @ ZnS quantum dots is 0.032mg/mL, and the concentration of the nano silver clusters is 0.015 mg/mL. The CdSe @ ZnS/AgNCs composite fluorescent nano-probe is constructed by directly mixing CdSe @ ZnS quantum dots and nano-silver clusters, and has the advantage of simple synthesis method. The constructed CdSe @ ZnS/AgNCs composite fluorescent nano probe decomposes silver clusters through hydrogen peroxide oxidation, silver ions are released, the silver ions have a quenching effect on CdSe @ ZnS quantum dot fluorescence, and the high-efficiency detection target of hydrogen peroxide is realized, so that the technical problems of long detection reaction time, slow response and insufficient detection lower limit in the traditional technology are solved.
Description
Technical Field
The invention relates to the technical field of nanoprobes, in particular to a preparation method of a composite fluorescent nanoprobe and a detection method of the composite fluorescent nanoprobe on hydrogen peroxide.
Background
In recent decades, the food safety problem has attracted people's attention and has been on schedule. The food is rich in nutrient substances, and provides a good living environment for the growth of microorganisms. Since hydrogen peroxide has a high fresh-keeping function for foods, a food additive, hydrogen peroxide, has been developed for the purpose of food freshness. The hydrogen peroxide can inhibit the growth of microorganisms in the food, so that the aim of keeping the food fresh for a long time is fulfilled, but the residual hydrogen peroxide in the food seriously harms the health of human beings. Hydrogen peroxide, one of the important members of active oxygen, can cause DNA damage and body aging, and the increase of hydrogen peroxide level is closely related to diseases such as cancer, stroke, alzheimer disease, parkinson syndrome and arteriosclerosis. The high reactivity of hydrogen peroxide makes it harmful even at low concentrations. Therefore, it is necessary to develop a highly efficient and sensitive detection method for selectively detecting hydrogen peroxide.
According to the national food safety standard, namely the determination of the residual amount of hydrogen peroxide in food, hydrogen peroxide can be used as an adjuvant for food production, but the residual amount of hydrogen peroxide needs to be decomposed or removed before the product is finished. According to the national standard GB/T23499-.
Therefore, the construction of a composite fluorescent nanoprobe and the realization of the efficient, accurate, rapid and sensitive detection of hydrogen peroxide become a problem which needs to be solved urgently.
Disclosure of Invention
It is an object of the present invention to address at least the above-mentioned deficiencies and to provide at least the advantages which will be described hereinafter.
The invention also aims to provide a preparation method of the CdSe @ ZnS/AgNCs composite fluorescent nano-probe with a simple synthesis method, and the prepared CdSe @ ZnS/AgNCs composite fluorescent nano-probe can be used for efficiently detecting hydrogen peroxide.
The invention also aims to provide a method for detecting hydrogen peroxide by the CdSe @ ZnS/AgNCs composite fluorescent nano probe, which has good detection effect and good detection selectivity.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing a CdSe @ ZnS/AgNCs composite fluorescent nanoprobe, comprising: mixing the CdSe @ ZnS quantum dots and the nano silver clusters under a certain pH condition to prepare a CdSe @ ZnS/AgNCs composite fluorescent nano probe;
after mixing, the concentration of the CdSe @ ZnS quantum dots is 0.016-0.040mg/mL, and the concentration of the nano silver clusters is 0.009-0.018 mg/mL.
In the scheme, the CdSe @ ZnS/AgNCs composite fluorescent nano-probe is constructed by directly mixing CdSe @ ZnS quantum dots and nano-silver clusters, and the synthesis method has the advantage of simplicity.
The constructed CdSe @ ZnS/AgNCs composite fluorescent nano probe decomposes silver clusters through hydrogen peroxide oxidation, silver ions are released, the silver ions have a quenching effect on CdSe @ ZnS quantum dot fluorescence, and the high-efficiency detection target of hydrogen peroxide is realized, so that the technical problems of long detection reaction time and slow response in the traditional technology are solved.
Preferably, in the preparation method of the CdSe @ ZnS/AgNCs composite fluorescent nanoprobe, the preparation method of the CdSe @ ZnS quantum dots comprises the following steps:
adding CdCl2·2H2Dissolving O and N-acetyl-L-cysteine in ultrapure water, mixing and stirring uniformly, adjusting the pH of the solution to 9 by using NaOH, adding NaHSe solution, stirring at the room temperature of 20-25 ℃ for 2h, transferring to 100 ℃, heating for 6h, and then adding Zn (OAc)2·2H2O and Na2S·9H2And O, obtaining the CdSe @ ZnS quantum dot.
Using CdCl2·2H2O, N-acetyl-L-cysteine and the like are used as raw materials to react and synthesize the CdSe @ ZnS quantum dots, and the method is simple and easy to realize.
Preferably, in the preparation method of the CdSe @ ZnS/AgNCs composite fluorescent nano-probe, the preparation method of the nano-silver cluster is as follows:
dissolving DL-lipoic acid in ultrapure water, adding NaOH solution, stirring until the DL-lipoic acid is completely dissolved, and adding NaBH4Solution and AgNO3And (4) preparing a solution to obtain the nano silver cluster.
The preparation method of the nano silver cluster is simple, the raw materials are easy to obtain, and the preparation cost of the CdSe @ ZnS/AgNCs composite fluorescent nano probe is reduced.
Preferably, Zn (OAc) is added into the preparation method of the CdSe @ ZnS/AgNCs composite fluorescent nano probe2·2H2O and Na2S·9H2The reaction time for O was 2 hours.
Preferably, in the preparation method of the CdSe @ ZnS/AgNCs composite fluorescent nanoprobe, the pH condition is provided by a Tris-HCl solution with pH of 7.4.
A method for detecting hydrogen peroxide by using a CdSe @ ZnS/AgNCs composite fluorescent nano probe comprises the following steps:
acquiring a standard curve of the corresponding relation between the concentration of the hydrogen peroxide and the fluorescence intensity;
and (3) mixing the solution to be detected with the CdSe @ ZnS/AgNCs composite fluorescent nano probe, observing the fluorescence intensity under a specific wavelength, and substituting the fluorescence intensity into the standard curve to obtain the concentration of hydrogen peroxide in the solution to be detected.
Preferably, in the method for detecting hydrogen peroxide by using the composite fluorescent nanoprobe, the method for obtaining the standard curve is as follows:
taking 2mL of CdSe @ ZnS/AgNCs composite fluorescent nanoprobe, respectively adding hydrogen peroxide solutions with different volumes into the CdSe @ ZnS/AgNCs composite fluorescent nanoprobe to obtain mixed reaction systems, wherein the concentrations of hydrogen peroxide in the mixed reaction systems are respectively 0 mu M, 0.2 mu M, 0.5 mu M, 1 mu M, 2 mu M, 5 mu M, 10 mu M, 20 mu M, 30 mu M, 40 mu M, 50 mu M, 60 mu M, 70 mu M, 80 mu M, 90 mu M and 100 mu M, reacting for a period of time at room temperature of 20-25 ℃, respectively determining the fluorescence intensity of each mixed reaction system at 510nm, and obtaining a hydrogen peroxide concentration-fluorescence intensity standard curve by taking the concentration of hydrogen peroxide as a horizontal coordinate and the fluorescence intensity as a vertical coordinate.
Preferably, in the method for detecting hydrogen peroxide by using the composite fluorescent nano-probe, the specific wavelength is 510 nm.
Preferably, in the method for detecting hydrogen peroxide by using the composite fluorescent nanoprobe, the reaction time is 12 minutes at room temperature.
Preferably, in the method for detecting hydrogen peroxide by using the composite fluorescent nanoprobe, the concentrations of the CdSe @ ZnS quantum dots and AgNCs in a solution obtained by mixing the solution to be detected and the CdSe @ ZnS/AgNCs composite fluorescent nanoprobe are 0.032mg/mL and 0.015mg/mL respectively.
The invention at least comprises the following beneficial effects:
the composite fluorescent nano probe can be used for detecting residual hydrogen peroxide in food, has simple synthesis method and easier later purification process, and can obtain a high-purity probe material.
The invention discovers the effect mechanism of the composite nano fluorescent probe on hydrogen peroxide for the first time, and the effect mechanism is that silver clusters are decomposed by hydrogen peroxide oxidation to release silver ions, and the silver ions have a quenching effect on CdSe @ ZnS quantum dot fluorescence, so that the high-efficiency detection target of the hydrogen peroxide is realized.
The invention realizes the fluorescent quantitative analysis of the hydrogen peroxide, has better detection effect in a wider pH range and has good detection selectivity; meanwhile, the lower limit of detection can be as low as 0.3 mu M, and the method can be applied to trace analysis of hydrogen peroxide in practical samples.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a transmission electron micrograph of the CdSe @ ZnS quantum dots synthesized in example 1 with the particle size distribution inset.
FIG. 2 is a transmission electron micrograph of the silver clusters synthesized in example 2, with the particle size distribution being shown in the inset.
FIG. 3 is the effect of CdSe @ ZnS quantum dot concentration on composite nano fluorescent probe in example 4.
FIG. 4 is the silver cluster concentration vs. composite nano fluorescent probe detection H in example 52O2The influence of (c).
FIG. 5 shows the pH value versus the detection H of the composite nano fluorescent probe in example 62O2The influence of (c).
FIG. 6 is the reaction time vs. composite nano fluorescent probe detection H in example 72O2The influence of (c).
FIG. 7 is a histogram of fluorescence quenching efficiency at 510nm for CdSe @ ZnS/AgNCs composite fluorescent nanoprobes after addition of different types of interfering substances in example 8.
FIG. 8 is a fluorescence spectrum of the CdSe @ ZnS/AgNCs composite fluorescent nanoprobe after adding hydrogen peroxide in example 9.
FIG. 9 is a linear regression plot of hydrogen peroxide concentration versus CdSe @ ZnS/AgNCs composite fluorescent nanoprobes fluorescence intensity at 510nm over the linear range in example 9.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
Example 1 Synthesis of CdSe @ ZnS Quantum dots
Adding CdCl2·2H2O (38.4mg) and NAC (27.5mg) were dissolved in 80mL of ultrapure water, mixed and stirred well, the pH of the solution was adjusted to 9 with NaOH, 170. mu.L of NaHSe solution was added, the reaction solution was stirred at room temperature for 2 hours, then transferred to 100 ℃ and heated for 6 hours, followed by the addition of 3mL of Zn (OAc)2·2H2O and 3mL of Na2S·9H2And O solution to obtain the CdSe @ ZnS quantum dots.
Wherein the concentration of NaOH is 1mol/L, and the NaHSe solution is prepared from Se powder (39.5mg) and NaBH4(40mg) in 2mL of ultrapure water to give Zn (OAc)2·2H2O and Na2The concentration of S was 11.5mg/mL and 12mg/mL, respectively.
As shown in fig. 1, the prepared CdSe @ ZnS quantum dots showed good dispersibility and were morphologically spherical, and the corresponding gaussian fitting results of the histograms obtained from the TEM images of the CdSe @ ZnS quantum dots showed that the synthesized quantum dots had a size distribution in the range of 2.5 to 3.9nm and an average size of 3.2 nm.
Example 2 Synthesis of AgNCs
52.6mg of DL-lipoic acid was weighed out and dissolved in 20mL of ultrapure water, 400. mu.L of NaOH solution (1mol/L) was added, and after stirring was completed, 2mL of NaBH was added4(0.24mg/mL) solution and 0.5mL of AgNO3(25mM) solution to prepare the nano silver clusters.
As shown in FIG. 2, the synthesized nano silver clusters are spherical and have good dispersibility, and the particle size is 1.7 +/-0.5 nm.
Example 3: construction of CdSe @ ZnS/AgNCs composite fluorescent nano probe
And (3) carrying out volume metering on 20 mu L of CdSe @ ZnS quantum dot solution (3.2mg/mL) and 20 mu L of AgNCs solution (1.5mg/mL) by using Tris-HCl (pH 7.4) solution, and then incubating for 10min together to prepare the CdSe @ ZnS/AgNCs composite fluorescent nano-probe.
Example 4 optimum Quantum dot concentration experiment of composite Nano fluorescent Probe for Hydrogen peroxide detection
The fluorescence quenching efficiency was calculated by controlling the variable method by adding CdSe @ ZnS quantum dot solutions at concentrations of 0.008, 0.016, 0.024, 0.032, 0.04, 0.048, 0.056, 0.064, 0.072, 0.08, 0.088, 0.096, 0.104mg/mL, fixing the volume to 2mL with Tris-HCL (pH 7.4) solution, adding 10 μ M silver ion solution with a microsyringe, measuring the fluorescence spectrum of the silver ion added CdSe @ ZnS quantum dots, and by the ratio of the fluorescence quenching intensity of the CdSe @ ZnS quantum dots after silver ion addition to the fluorescence intensity of the CdSe @ ZnS quantum dots before silver ion addition.
The result is shown in fig. 3, the fluorescence quenching effect of the silver ions on the CdSe @ ZnS quantum dots is closely related to the concentration of the CdSe @ ZnS quantum dots, and when the concentration of the CdSe @ ZnS quantum dots is 0.032mg/mL, the fluorescence quenching effect of the silver ions on the CdSe @ ZnS quantum dots is the best, which indicates that the best concentration of the CdSe @ ZnS quantum dots is 0.032 mg/mL.
Example 5 optimal silver Cluster concentration experiment of composite Nano fluorescent Probe for Hydrogen peroxide detection
The CdSe @ ZnS/AgNCs composite fluorescent nanoprobe is constructed by taking the optimum quantum dot concentration (C ═ 0.032mg/mL), adding silver cluster solution with concentration of 0.003, 0.006, 0.009, 0.012, 0.015, 0.018, 0.021, 0.024, 0.027mg/mL and CdSe @ ZnS quantum dot solution of 20 μ L (3.2mg/mL), and making up a volume of 2mL with Tris-HCL (pH 7.4) solution, after which 2 μ L of 0.05mol/L H is added2O2Solution, determination of H addition2O2The fluorescence spectrum of the CdSe @ ZnS/AgNCs composite fluorescence nanoprobe before and after the solution is obtained by adding H2O2Fluorescence quenching intensity of post-CdSe @ ZnS/AgNCs composite fluorescent nano probe and addition of H2O2And calculating the fluorescence quenching efficiency by using the ratio of the fluorescence intensity of the front CdSe @ ZnS/AgNCs composite fluorescent nano probe.
The results are shown in FIG. 4, H2O2The fluorescence of the CdSe @ ZnS/AgNCs composite fluorescent nano probe can be effectively quenched, when the concentration of the silver clusters is in the range of 0.003-0.015mg/mL, the fluorescence quenching efficiency of the CdSe @ ZnS/AgNCs composite fluorescent nano probe continuously increases along with the increase of the concentration of the silver clusters, when the concentration of the silver clusters exceeds 0.015mg/mL, the fluorescence quenching efficiency of the CdSe @ ZnS/AgNCs composite fluorescent nano probe continuously decreases along with the increase of the concentration of the silver clusters, and the optimal concentration of the silver clusters on the surface is 0.015 mg/mL.
Example 6 optimal pH test of composite Nanofluorescent Probe for Hydrogen peroxide detection
The optimum CdSe @ ZnS quantum dot concentration (C0.032 mg/mL) and the optimum silver cluster concentration (C0.015 mg/mL) were adjusted to 2mL with Tris-HCl solutions having pHs of 3.4, 4.4, 5.4, 6.4, 7.4, 8.4, 9.4, 10.4 and 11.4, respectively, and then 2. mu.L of 0.05mol/L H was added to the solution2O2Solution, and related data are determined.
The results are shown in fig. 5, from which it can be derived that: when the pH of the solution is in the neutral range, H2O2The composite fluorescent nano probe has a good fluorescence quenching effect on the CdSe @ ZnS/AgNCs composite fluorescent nano probe.
Example 7 optimal reaction time experiment of composite Nanofluorescent Probe for Hydrogen peroxide detection
Taking the optimal quantum dot concentration (C0.032 mg/mL), the optimal silver cluster concentration (C0.015 mg/mL) and the optimal pH (pH 7.4 and Tris-HCL solution), fixing the volume to 2mL, and measuring and adding 20 mu M H2O2Before and after the solution, the fluorescence spectra of the CdSe @ ZnS/AgNCs composite fluorescence nanoprobe in different time periods are obtained by adding H2O2Fluorescence quenching intensity of post-CdSe @ ZnS/AgNCs post-composite fluorescent nano-probe and addition of H2O2The fluorescence quenching efficiency is calculated by the ratio of the fluorescence intensity of the front CdSe @ ZnS/AgNCs composite fluorescent nano probe, and the influence of the reaction time is measured.
The results are shown in FIG. 6, without addition of H2O2The fluorescence quenching efficiency of the composite fluorescent nanoprobe is not obviously changed along with the time extension and is about 0, which shows that the CdSe @ ZnS/AgNCs composite fluorescent nanoprobe has better fluorescence stability, and once H is added2O2Then, the fluorescence quenching efficiency of the CdSe @ ZnS/AgNCs composite fluorescent nano probe is increased along with the prolonging of time, and the quenching efficiency is basically kept unchanged at 12min, which indicates that the optimal reaction time is 12 min.
Example 8: selective experiment for detecting hydrogen peroxide by composite nano fluorescent probe
The optimal quantum dot concentration (C ═ 0.032mg/mL), the optimal silver cluster concentration (C ═ 0.015mg/mL), and the optimal pH (pH ═ 7.4, Tris-HCL solution) were taken and the volume was adjusted to 2mL, and 2 μ L of 0.1mol/L Glutathione (GSH) and Na were added to each of the solutionNO2、Ca2+、Na+、K+Equal interfering substances and 2. mu.L of 0.05mol/L H2O2Then, measuring the fluorescence spectrum of the CdSe @ ZnS/AgNCs composite fluorescent nano probe, calculating the fluorescence quenching efficiency by the ratio of the fluorescence quenching intensity of the CdSe @ ZnS/AgNCs composite fluorescent nano probe after the interference substance is added to the fluorescence intensity of the CdSe @ ZnS/AgNCs composite fluorescent nano probe before the interference substance is added, and verifying the CdSe @ ZnS/AgNCs composite fluorescent nano probe against H2O2Selectivity of (2).
The result is shown in FIG. 7, the fluorescence quenching efficiency of the interference substance on the CdSe @ ZnS/AgNCs composite fluorescent nano-probe is low, which indicates that the composite fluorescent nano-probe is on H2O2Has better selectivity.
Example 9: working curve for detecting hydrogen peroxide by composite nano fluorescent probe
Taking the optimal quantum dot concentration (C is 0.032mg/mL), the optimal silver cluster concentration (C is 0.015mg/mL) and the optimal pH (pH is 7.4 and Tris-HCL solution), fixing the volume to 2mL, adding hydrogen peroxide solutions with different concentrations (0, 0.2, 0.5, 1, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 and 100 mu M) respectively, waiting for 12 minutes, setting the excitation wavelength to 440nm, and collecting the fluorescence signal intensity at the wavelength of 510 nm; and drawing a working curve by taking the concentration of the hydrogen peroxide as an abscissa and the fluorescence intensity at 510nm as an ordinate. Its linear dependency parameter R2Good linear correlation was shown at 0.993 (see fig. 9), indicating that the composite nano fluorescent probe can be applied to trace analysis of hydrogen peroxide.
The results are shown in FIGS. 8 and 9, FIG. 8 is a fluorescence spectrum of CdSe @ ZnS/AgNCs composite fluorescent nanoprobe after hydrogen peroxide addition, from which H can be seen2O2Has stronger quenching effect on the fluorescence of the CdSe @ ZnS/AgNCs composite fluorescent nano probe at 510nm and is accompanied with H2O2The fluorescence intensity of the composite fluorescent nano probe is continuously reduced when the concentration is increased. From the results of the linear fitting (FIG. 9), it can be concluded that the composite nano-fluorescent probe is directed to H2O2The linear range of detection is 0.5-60 mu M, the detection limit is 0.3 mu M, and the result is superior to the current levelParagraph most of reported H2O2A fluorescent nanoprobe.
While embodiments of the invention have been disclosed above, it is not intended to be limited to the uses set forth in the specification and examples. It can be applied to all kinds of fields suitable for the present invention. Additional modifications will readily occur to those skilled in the art.
Claims (6)
1. A preparation method of a CdSe @ ZnS/AgNCs composite fluorescent nano probe comprises the following steps: mixing the CdSe @ ZnS quantum dots and the nano silver clusters under a certain pH condition to prepare a CdSe @ ZnS/AgNCs composite fluorescent nano probe;
after mixing, the concentration of the CdSe @ ZnS quantum dots is 0.016-0.040mg/mL, and the concentration of the nano silver clusters is 0.009-0.018 mg/mL;
the preparation method of the CdSe @ ZnS quantum dot comprises the following steps:
adding CdCl2·2H2Dissolving O and N-acetyl-L-cysteine in ultrapure water, mixing and stirring uniformly, adjusting the pH of the solution to 9 by using NaOH, adding NaHSe solution, stirring at the room temperature of 20-25 ℃ for 2h, transferring to 100 ℃, heating for 6h, and then adding Zn (OAc)2·2H2O and Na2S·9H2Reacting for 2 hours to obtain the CdSe @ ZnS quantum dots;
the preparation method of the nano silver cluster comprises the following steps:
dissolving DL-lipoic acid in ultrapure water, adding NaOH solution, stirring until the DL-lipoic acid is completely dissolved, and adding NaBH4Solution and AgNO3Preparing a solution to obtain the nano silver clusters;
the pH conditions are provided by Tris-HCl solution at pH 7.4.
2. A method for detecting hydrogen peroxide by using the CdSe @ ZnS/AgNCs composite fluorescent nanoprobe prepared by the preparation method of claim 1, which comprises the following steps:
acquiring a standard curve of the corresponding relation between the concentration of the hydrogen peroxide and the fluorescence intensity;
and (3) mixing the solution to be detected with the CdSe @ ZnS/AgNCs composite fluorescent nano probe, observing the fluorescence intensity under a specific wavelength, and substituting the fluorescence intensity into the standard curve to obtain the concentration of hydrogen peroxide in the solution to be detected.
3. The method for detecting hydrogen peroxide by using the composite fluorescent nano-probe as claimed in claim 2, wherein the standard curve is obtained by:
taking 2mL of CdSe @ ZnS/AgNCs composite fluorescent nanoprobe, respectively adding hydrogen peroxide solutions with different volumes into the CdSe @ ZnS/AgNCs composite fluorescent nanoprobe to obtain mixed reaction systems, wherein the concentrations of hydrogen peroxide in the mixed reaction systems are respectively 0 mu M, 0.2 mu M, 0.5 mu M, 1 mu M, 2 mu M, 5 mu M, 10 mu M, 20 mu M, 30 mu M, 40 mu M, 50 mu M, 60 mu M, 70 mu M, 80 mu M, 90 mu M and 100 mu M, reacting for a period of time at room temperature of 20-25 ℃, respectively determining the fluorescence intensity of each mixed reaction system at 510nm, and obtaining a hydrogen peroxide concentration-fluorescence intensity standard curve by taking the concentration of hydrogen peroxide as a horizontal coordinate and the fluorescence intensity as a vertical coordinate.
4. The method for detecting hydrogen peroxide using a multiplex fluorescent nanoprobe according to claim 3, wherein the specific wavelength is 510 nm.
5. The method for detecting hydrogen peroxide by using the composite fluorescent nano-probe according to claim 4, wherein the reaction time is 12 minutes at room temperature.
6. The method for detecting hydrogen peroxide by using a composite fluorescent nanoprobe according to claim 5, wherein the concentrations of the CdSe @ ZnS quantum dots and AgNCs in the solution to be detected and the solution obtained by mixing the CdSe @ ZnS/AgNCs composite fluorescent nanoprobe are 0.032mg/mL and 0.015mg/mL respectively.
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| KR100858765B1 (en) * | 2007-03-26 | 2008-09-16 | 재단법인서울대학교산학협력재단 | A multi-color tuning method of semiconductor quantum-dots from single source semiconductors by oxidation in the solution |
| CN103940788A (en) * | 2013-01-17 | 2014-07-23 | 华东理工大学 | Application of nano silver cluster in detection of hypochloric acid content, and detection method |
| JP6164637B2 (en) * | 2013-03-22 | 2017-07-19 | 国立大学法人名古屋大学 | Fluorescent probe for labeling biological samples |
| EP3379252B1 (en) * | 2017-03-20 | 2022-10-26 | National Cheng Kung University | Molecular probe for signal amplification and assay using the same |
| CN107216882B (en) * | 2017-07-21 | 2020-01-10 | 安徽师范大学 | Preparation and application of AgNPs @ PDA-CdSe quantum dot nano assembly |
| CN108318438B (en) * | 2018-01-19 | 2021-10-01 | 广东工业大学 | Silver-doped fluorescent carbon quantum dot, preparation method thereof and cholesterol detection method |
| CN109517595B (en) * | 2018-10-18 | 2022-07-22 | 临沂大学 | Dual-response-ratio fluorescent probe constructed based on dual detection mechanism and construction method thereof |
| CN109181690B (en) * | 2018-11-02 | 2019-06-25 | 青岛大学 | Preparation method based on double emissive quantum dots/nano grain of silver compound cymoxanil ratio fluorescent probe |
| CN110376176A (en) * | 2019-08-27 | 2019-10-25 | 青岛大学 | Codope metal organic framework compound ratio fluorescent scutellaria glycosides probe preparation method |
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2019
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