Preparation method of phenylboronic acid functionalized silicon quantum dot fluorescent probe and application of phenylboronic acid functionalized silicon quantum dot fluorescent probe in detection of mercury ions and methyl mercury ions
By preparing phenylboronic acid-functionalized silicon quantum dot fluorescent probes and combining them with smartphones to detect mercury ions and methylmercury ions in environmental water, the problems of high detection cost and complex operation in existing technologies have been solved, achieving portable and highly sensitive detection results.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- EAST CHINA SEA FISHERIES RES INST CHINESE ACAD OF FISHERY SCI
- Filing Date
- 2025-12-24
- Publication Date
- 2026-05-01
AI Technical Summary
Existing Hg2+ and CH3Hg+ detection technologies rely on expensive instruments and complex operations, making it difficult to achieve portable, highly sensitive, and highly selective rapid on-site detection.
Using phenylboronic acid-functionalized silicon quantum dot fluorescent probes, B-SiQDs were prepared by a microwave-assisted method. Combined with the acquisition of fluorescent images by a smartphone and conversion into grayscale values, a portable and rapid detection of mercury ions and methylmercury ions in environmental water bodies was achieved.
It enables rapid detection of mercury ions and methylmercury ions in environmental water bodies with high sensitivity, portability, simplicity, and high accuracy, and is suitable for smartphone platforms.
Smart Images
Figure CN121950296A_ABST
Abstract
Description
Preparation method of phenylboronic acid functionalized silicon quantum dot fluorescent probe and its application in the detection of mercury ions and methylmercury ions. Technical Field
[0001] This invention relates to the field of mercury ion and methylmercury ion detection technology in environmental water bodies, specifically to a method for detecting mercury ions and methylmercury ions in environmental water bodies by combining a phenylboronic acid-functionalized silicon quantum dot fluorescent probe with a smartphone sensing platform. Background Technology
[0002] Mercury ions (Hg) 2+ ) and methylmercury ions (CH3Hg) + Pollutants are ubiquitous and highly toxic pollutants in the environment. Contaminated water resources pose a significant exposure risk to humans, easily causing adverse effects on the digestive, nervous, endocrine, and other physiological systems. Given their high toxicity and trace lethality, there is an urgent need for highly sensitive, selective, portable, and cost-effective in-situ environmental monitoring methods.
[0003] Common Hg tests 2+ and CH3Hg + The technologies mainly include high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS), atomic fluorescence spectrometry (AFS), and chemical sensing methods. However, these methods rely on expensive instruments and complex operations, are time-consuming, and have high detection costs, making it difficult to achieve rapid on-site detection.
[0004] Chemical sensing methods based on nanomaterials have attracted widespread attention for the detection of mercury or methylmercury due to their advantages such as ease of preparation, low cost, and simple operation. However, in the case of Hg... 2+ and CH3Hg + Challenges remain in achieving highly selective and portable detection. Summary of the Invention
[0005] This invention provides a phenylboronic acid-functionalized silicon quantum dot fluorescent probe and its preparation method. Based on this phenylboronic acid-functionalized silicon quantum dot (B-SiQDs) fluorescent probe, a portable and rapid detection of mercury ions and methylmercury ions in environmental water can be achieved. This invention utilizes a microwave-assisted method to rapidly prepare B-SiQDs, which possess excellent optical properties, but [the following is unclear due to incomplete sentence fragments]. 2+ and CH3Hg + In its presence, its fluorescence is quenched, via B-SiQDs-Hg 2+ and B-SiQDs-CH3Hg + The system combines smartphones to collect fluorescence photos, obtain RGB values, and convert them into grayscale values, enabling portable, rapid, and highly sensitive detection of mercury ions and methylmercury ions in environmental water bodies.
[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: In the first aspect, the present invention provides a method for preparing B-SiQDs fluorescent probes, comprising the following steps: (1) adding the reducing agent tyrosine and the functionalizing reagent 4-aminophenylborate salt to the solvent glycerol, wherein the ratio of the three is 10~100:10~100:5-15, and stirring magnetically to fully dissolve the tyrosine and 4-aminophenylborate salt to obtain a homogeneous mixed solution; (2) introducing an inert gas into the mixed solution obtained in step (1) to remove oxygen from the solution, and then adding a 3-aminopropyltriethoxysilane solution with a mass-volume ratio of 1-5, and continuing to stir in an inert gas atmosphere for 5-30 min; (3) transferring the solution obtained in step (2) to a microwave reactor and reacting at 50-250℃ for 5-90 min. min, to obtain a phenylboronic acid functionalized silicon quantum dot (B-SiQDs) solution; (4) use a dialysis bag with a molecular cutoff of 500-1500 to purify the B-SiQDs solution obtained in step (3), change the water every 4-8 h, and the total dialysis time is 18-36 h to obtain a pure B-SiQDs solution.
[0007] In a second aspect, the present invention provides a B-SiQDs fluorescent probe prepared by the above method. Detection results show that the prepared fluorescent probe is a regular spherical shape with a particle size of approximately 3.00 nm, and its surface has abundant functional groups.
[0008] In a third aspect, the present invention provides the use of the prepared B-SiQDs fluorescent probe, primarily for the detection of mercury ions and methylmercury ions in environmental water bodies.
[0009] In a fourth aspect, this invention provides a method for detecting mercury ions and methylmercury ions in environmental water. This method combines B-SiQDs fluorescent probes with a smartphone to achieve portable and rapid detection of mercury ions and methylmercury ions in environmental water. After incubation with different concentrations of mercury ions and methylmercury ions, the fluorescence intensity of the B-SiQDs fluorescent probe decreases. A smartphone is used to capture fluorescence images of the B-SiQDs, extract RGB values, and convert them to grayscale values for detection. The steps are as follows: After mixing the B-SiQDs fluorescent probe with the water to be tested, it is irradiated with 365 nm ultraviolet light. The RGB values are obtained using color recognition software, converted to grayscale values, and then the content of mercury ions and methylmercury in the environmental water is quantitatively determined according to the standard curve method.
[0010] The formula for converting RGB values to grayscale values is: Grayscale value = R*0.299 + G*0.587 + B*0.144.
[0011] This detection method can detect Hg concentrations of 0–120 nmol / L in environmental water bodies. 2+and 0~200 μmol / L CH3Hg + Concentration detection.
[0012] The beneficial safeguards and effects of this invention are as follows: The phenylboronic acid-functionalized silicon quantum dots (B-SiQDs) prepared in this invention have good fluorescence properties, and in Hg 2+ and CH3Hg + In the presence of B-SiQDs, fluorescence is quenched. The method for detecting mercury and methylmercury ions in water using a sensing platform built on smartphones and B-SiQDs offers advantages such as ease of operation, rapid feedback, high sensitivity and repeatability, good stability, high accuracy, and portability. It enables direct, real-time, portable, and rapid determination of mercury and methylmercury ions in environmental water samples, broadening the application of nanomaterials in environmental monitoring. Attached Figure Description
[0013] Figure 1 is a schematic diagram of the preparation method of phenylboronic acid functionalized modified silicon quantum dots according to the present invention.
[0014] Figure 2 is a schematic diagram of the method for detecting mercury ions and methylmercury ions based on phenylboronic acid functionalized silicon quantum dots according to the present invention. Detailed Implementation
[0015] The present invention will now be described in detail with reference to the embodiments and accompanying drawings, but the implementation of the present invention is not limited thereto. Embodiment 1
[0016] I. Preparation of Phenylboronic Acid Functionalized Silicon Quantum Dot Fluorescent Probes (See Figure 1). The preparation method includes: 1) Adding the reducing agent tyrosine and the functionalizing reagent 4-aminophenylboronic acid salt to the solvent glycerol, with a ratio of tyrosine to 4-aminophenylboronic acid salt and glycerol of 80 mg: 30 mg: 8 mL, and magnetically stirring for 10 min to fully dissolve the tyrosine and 4-aminophenylboronic acid salt to obtain a homogeneous mixed solution; 2) Passing argon gas into the mixed solution for 10 min to remove oxygen from the solution, and then adding 2 mL of 3-aminopropyltriethoxysilane, and continuing to stir under an argon atmosphere for 15 min; 3) Transferring the above solution to a microwave reactor and reacting at 180 °C for 50 min to obtain a phenylboronic acid functionalized silicon quantum dot solution; 4) Purifying the above solution using a dialysis bag with a molecular cutoff of 1000, changing the water every 6 h for a total of 4 water changes, with a total dialysis time of 24 hours. h, pure phenylboronic acid-functionalized silicon quantum dots (B-SiQDs) were obtained.
[0017] II. Detection of mercury ions and methylmercury ions at different concentrations: Refer to Figure 2. Take a certain amount of B-SiQDs and add Hg... 2+ The solution was diluted with buffer solution to a final volume of 1.0 mL, so that the Hg concentration in the test solution was [missing value]. 2+The ion concentrations were 20 nmol / L, 40 nmol / L, 60 nmol / L, 80 nmol / L, 100 nmol / L, 120 nmol / L, 140 nmol / L, 160 nmol / L, 180 nmol / L, and 200 nmol / L, respectively. After standing for 1 min, the prepared solutions were placed in a UV dark chamber and irradiated with a 365 nm UV lamp. The fluorescence images were photographed using a smartphone, and the RGB values were extracted. The grayscale value was converted to a grayscale value using the formula: Grayscale value = R*0.299 + G*0.587 + B*0.144. A correlation between grayscale value and Hg was established. 2+ The linear relationship of concentration was shown in the results, R. 2 =0.991, which proves that the method for detecting mercury ions in environmental water bodies using a smartphone sensing platform based on phenylboronic acid-functionalized silicon quantum dot fluorescent probes has high sensitivity, repeatability, stability and accuracy, and can intuitively realize portable and rapid determination of mercury ions in environmental water samples.
[0018] Take a certain amount of B-SiQDs and add CH3Hg + The solution was diluted with buffer solution to a final volume of 1.0 mL, so that the CH3Hg concentration in the test solution was [missing value]. + The concentrations of ions were 10 mmol / L, 20 mmol / L, 30 mmol / L, 40 mmol / L, 50 mmol / L, 60 mmol / L, 70 mmol / L, 80 mmol / L, 90 mmol / L, 100 mmol / L, 120 mmol / L, 140 mmol / L, 160 mmol / L, 180 mmol / L, and 200 mmol / L. After standing for 1 min, the prepared solutions were placed in a UV dark chamber and photographed with a smartphone under 365 nm UV light. The RGB values of the fluorescence images were extracted, and the grayscale value was converted to a grayscale value using the formula: grayscale value = R*0.299 + G*0.587 + B*0.144. A correlation between grayscale value and Hg was established. 2+ and CH3Hg + The linear relationship of concentration was shown in the results, R. 2 =0.998, demonstrating that the method for detecting methylmercury ions in environmental water using a smartphone sensing platform based on phenylboronic acid-functionalized silicon quantum dot fluorescent probes in this invention exhibits high sensitivity, repeatability, stability, and accuracy, enabling portable and rapid determination of mercury ions in environmental water samples. Example 2
[0019] Unlike Example 1: In step 1), the ratio of tyrosine to 4-aminophenylboronic acid salt and glycerol was 10 mg: 10 mg: 15 mL. The mixture was magnetically stirred for 30 min to fully dissolve the tyrosine and 4-aminophenylboronic acid salt, resulting in a homogeneous mixed solution. In step 2), argon gas was introduced into the mixed solution for 10 min to remove oxygen, and then 1 mL of 3-aminopropyltriethoxysilane was added. Stirring continued for 30 min under an argon atmosphere. In step 3), the solution was transferred to a microwave reactor and reacted at 50 °C for 90 min to obtain a phenylboronic acid-functionalized silicon quantum dot solution. In step 4), the solution was purified using a dialysis bag with a molecular weight cutoff of 500. Water was changed every 4 h for a total of 4 water changes, with a total dialysis time of 36 h, yielding pure phenylboronic acid-functionalized silicon quantum dots (B-SiQDs). Example 3
[0020] Unlike Examples 1 and 2: In step 1), the ratio of tyrosine to 4-aminophenylboronic acid salt and glycerol was 100 mg: 10 mg: 5 mL. The mixture was magnetically stirred for 5 min to ensure complete dissolution of the tyrosine and 4-aminophenylboronic acid salt, resulting in a homogeneous mixed solution. In step 2), argon gas was introduced into the mixed solution for 10 min to remove oxygen, and then 5 mL of 3-aminopropyltriethoxysilane was added. Stirring continued for 10 min under an argon atmosphere. In step 3), the solution was transferred to a microwave reactor and reacted at 250 °C for 5 min to obtain a phenylboronic acid-functionalized silicon quantum dot solution. In step 4), the solution was purified using a dialysis bag with a molecular weight cutoff of 1500. Water was changed every 8 h for a total of 4 water changes, with a total dialysis time of 18 h, yielding pure phenylboronic acid-functionalized silicon quantum dots (B-SiQDs). Example 4
[0021] The difference from Examples 1-3 is as follows: In step 1), the ratio of tyrosine to 4-aminophenylboronic acid salt and glycerol is 50 mg: 100 mg: 10 mL. The mixture is magnetically stirred for 20 min to fully dissolve the tyrosine and 4-aminophenylboronic acid salt, resulting in a homogeneous mixed solution. In step 2), argon gas is introduced into the mixed solution for 10 min to remove oxygen from the solution. Then, 3 mL of 3-aminopropyltriethoxysilane is added, and the mixture is stirred for another 20 min under an argon atmosphere. In step 3), the above solution is transferred to a microwave reactor and reacted at 100 °C for 60 min to obtain a phenylboronic acid-functionalized silicon quantum dot solution. In step 4), the above solution is purified using a dialysis bag with a molecular cutoff of 500. The water is changed every 5 h for a total of 4 water changes, and the total dialysis time is 30 h, resulting in pure phenylboronic acid-functionalized silicon quantum dots (B-SiQDs).
[0022] It should be further noted that the above embodiments are merely for understanding the technical solution of the present invention and are not intended to limit the scope of protection of the present invention. In the various embodiments of the preparation method of the present invention, the design of reactants, dosages, and process conditions does not include all possible selections, but any combination within the corresponding range can achieve the purpose of the present invention and achieve the expected technical effect. Similarly, in the detection method of the present invention, RGB values are obtained after collecting fluorescence images, and further analyzed by comparing their grayscale values with Hg... 2+ and CH3Hg + The linear relationship between concentrations enables the detection of mercury ions and methylmercury ions in water. The acquisition of fluorescence images is not solely achieved through a smartphone; the smartphone is used only for convenience. The acquisition of fluorescence images is not limited to any image acquisition device other than a smartphone. Therefore, this invention is not limited to the described embodiments. Those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit of this invention, and all such equivalent modifications or substitutions are included within the scope defined by the claims of this application.
Claims
1. A method for preparing phenylboronic acid-functionalized silicon quantum dot fluorescent probes, characterized in that: (1) Add the functionalizing reagent 4-aminophenylboronic acid salt and the reducing agent tyrosine to the solvent glycerol, and stir magnetically to fully dissolve the tyrosine to obtain a homogeneous mixed solution; (2) Pass an inert gas into the mixed solution to remove oxygen from the solution, and then add 3-aminopropyltriethoxysilane, and continue stirring to mix the reactants evenly; (3) Transfer the solution obtained in step (2) to a microwave reactor and react at a certain temperature for a certain time to obtain a phenylboronic acid functionalized silicon quantum dot solution; (4) Dialyze the supernatant of the phenylboronic acid functionalized silicon quantum dot solution with a dialysis bag to obtain a pure phenylboronic acid functionalized silicon quantum dot solution; wherein, in step (1), the mass-volume ratio of the reducing agent tyrosine to the functionalizing reagent 4-aminophenylboronic acid salt and the solvent glycerol is 10~100:10~100:5-15; the volume of 3-aminopropyltriethoxysilane added in step (2) is 1-5 mL.
2. The detection method according to claim 1, characterized in that: The magnetic stirring time in step (1) is 5-30 min. In step (2), the inert gas used is nitrogen or argon. The stirring time in step (2) is 5-30 min.
3. The preparation method according to claim 1, characterized in that: In step (3), the reaction temperature is 50-250℃ and the reaction time is 5-90 min.
4. The preparation method according to claim 1, characterized in that: In step (4), the molecular weight cutoff of the dialysis bag is 500-1500, the water is changed every 4-8 hours during dialysis, and the total dialysis time is 18-36 hours.
5. A phenylboronic acid-functionalized silicon quantum dot fluorescent probe, characterized in that: It is prepared by the method described in any one of claims 1-4.
6. The application of the phenylboronic acid functionalized silicon quantum dot fluorescent probe according to claim 5 in the detection of mercury ions and methylmercury ions in environmental water.
7. The application according to claim 6, characterized in that: The method for detecting mercury ions and methylmercury ions in environmental water using a phenylboronic acid-functionalized silicon quantum dot fluorescent probe is as follows: The phenylboronic acid-functionalized silicon quantum dot fluorescent probe is used to capture mercury ions and methylmercury ions, and the detection is achieved by combining the grayscale values converted from RGB values. The steps are as follows: After mixing the phenylboronic acid-functionalized silicon quantum dot fluorescent probe with the water to be tested, and then irradiating it with ultraviolet light, the RGB values are obtained through color recognition software, converted into grayscale values, and the concentrations of mercury ions and methylmercury ions in the water are quantitatively determined. The formula for converting RGB values into grayscale values is: Grayscale value = R*0.299 + G*0.587 + B*0.
144.
8. The application according to claim 7, characterized in that: In the detection method, the phenylboronic acid functionalized silicon quantum dot fluorescent probe is mixed with the water to be tested and then irradiated with a 365 nm ultraviolet lamp.
9. The application according to claim 7, characterized in that: In the detection method, RGB values are obtained after collecting fluorescence images.