Platform and method for improving detection sensitivity and efficiency of mercury ions in environment

Abstract

The invention discloses a preparation method of AgNPs-HDES, and the preparation method comprises the following steps: uniformly mixing an organic acid silver solution with an amino acid solution, preparing an AgNPs-EG solution under heating and stirring conditions, and then reacting the AgNPs-EG solution with an organic acid to prepare AgNPs-HDES; wherein the organic acid silver is used as a silver supply body, and the amino acid is used as a reducing agent; the amino acid is L-arginine, and the organic acid silver is silver acetate. Cinnamyl alcohol is selected as a hydrogen bond acceptor, an ethylene glycol solution containing AgNPs is introduced as a hydrogen bond donor for the first time, and detection is completed while enrichment is performed by utilizing the enrichment effect of a hydrophobic deep-eutectic solvent and the detection effect of AgNPs on Hg < 2 + >, so that high-flux instant sensitive detection of Hg < 2 + > in the environment is realized. The sensing platform is combined with an AI-assisted high-throughput recognition strategy, so that portable instant detection of trace Hg < 2 + > in the environment is realized, and the method has the advantages of high sensitivity, high detection speed, good selectivity and the like.

Description

Technical Field

[0001] The present application belongs to the technical field of compound preparation, and in particular, relates to a platform and method for improving the sensitivity and efficiency of mercury ion detection in the environment. Background Art

[0002] As one of the heavy metals with high toxicity to the environment and human health, the detection of mercury ions has always been a research hotspot. The long-term accumulation of mercury ions will not only cause serious damage to the human nervous system, but also lead to many diseases, such as renal failure, cognitive and action disorders. Therefore, the study of efficient, convenient and rapid mercury ion detection methods is of great significance to protecting the environment and ensuring human health. The currently developed mercury ion detection methods include electrochemical spectroscopy, atomic absorption / emission spectroscopy, and fluorescence spectroscopy. These methods have good selectivity and sensitivity, but have high requirements on instruments, require professional operators, and are expensive.

[0003] Currently, Hg 2+ Conventional detection methods include atomic fluorescence spectroscopy (AFS), ultraviolet-visible spectrophotometry (UV-Vis spectroscopy), atomic absorption spectroscopy (AAS) and inductively coupled plasma mass spectrometry (ICP-MS), which can be used to detect Hg 2+ Carry out accurate quantitative and qualitative testing.

[0004] Therefore, there is an urgent need to develop a simple, rapid and portable method for detecting mercury ions using metal-organic framework compounds. Summary of the invention

[0005] The technical problem to be solved by the present application is to overcome the defects of the prior art and provide a method. The present invention selects cinnamyl alcohol as a hydrogen bond acceptor (HBA), introduces a silver nanoparticle-ethylene glycol solution containing AgNPs (AgNPs-EG) as a hydrogen bond donor (HBD), and utilizes the enrichment effect of hydrophobic deep eutectic solvents (HDES) and the effect of AgNPs on Hg 2+The detection function is completed during enrichment, thereby constructing an integrated colorimetric sensing platform for AgNPs-HDES enrichment detection, eliminating the interference of hydrophilic substances in the sample and improving the sensitivity and accuracy of detection. The present invention prepares an ethylene glycol solution of silver nanoparticles (AgNPs-EG), which is yellow-brown and has strong light stability. 2+ Added to AgNPs-EG, Ag and Hg 2+ Zero-valent mercury is formed through redox reaction, and its peak absorbance at 420nm disappears, causing AgNPs-EG to fade rapidly within a few seconds. 2+ The color gradually fades from brown to colorless as the concentration increases. The AI-assisted detection software developed based on the YOLO v8 algorithm and convolutional neural networks (CNNs) can process multiple sample images taken by smartphones, read the colorimetric information of the samples, and then output the actual concentration, which can achieve high-throughput colorimetric detection of multiple groups of samples at the same time.

[0006] This application adopts the following technical solutions to solve the above technical problems:

[0007] The present application provides a method for preparing AgNPs-HDES, the method comprising the following steps: uniformly mixing an organic acid silver solution and an amino acid solution, preparing an AgNPs-EG solution under heating and stirring conditions, and then reacting the AgNPs-EG solution with an organic acid to prepare AgNPs-HDES;

[0008] Wherein, the organic acid silver is used as a silver donor, and the amino acid is used as a reducing agent; the amino acid is L-arginine, and the organic acid silver is silver acetate.

[0009] Preferably, the preparation method of the AgNPs-HDES satisfies at least one of the following conditions:

[0010] The organic acid silver solution is an organic acid silver glycol solution;

[0011] The mass fraction of the organic acid silver solution is about 0.0171%;

[0012] The amino acid solution is an amino acid ethylene glycol solution;

[0013] The mass fraction of the amino acid solution is about 0.108%;

[0014] Preferably, the preparation method of the AgNPs-HDES satisfies at least one of the following conditions:

[0015] The temperature of the reaction is such that the mass ratio of the silver acetate to the L-arginine is 1:1.5;

[0016] The stirring is carried out under a magnetic stirrer;

[0017] The arginine also includes an ultrasonic dispersion operation before use;

[0018] The silver acetate also includes an ultrasonic dispersion operation before use.

[0019] Preferably, the preparation method of the AgNPs-HDES satisfies at least one of the following conditions:

[0020] The organic acid solution and the amino acid solution are mixed at 45-50° C., and heated to 60-70° C. for reaction and heated and stirred. The heating time is 20-40 minutes.

[0021] Preferably, the preparation method of the AgNPs-HDES satisfies at least one of the following conditions:

[0022] The heating is carried out in a water bath, and the stirring speed is 1000 rpm;

[0023] The heating is stopped after the mixed solution becomes a light brown clear liquid.

[0024] Preferably, the preparation method of the AgNPs-HDES satisfies at least one of the following conditions:

[0025] The molar ratio of the AgNPs-EG solution to the organic acid solution is (2-4):1, for example, 3:1.

[0026] Preferably, the preparation method of the AgNPs-HDES satisfies at least one of the following conditions:

[0027] At least one of the following conditions is met:

[0028] The organic acid is cinnamic acid;

[0029] The reaction temperature is 70-90°C, for example 80°C;

[0030] The reaction time is 0.8 to 2 hours, for example 1 hour.

[0031] The present application also provides an AgNPs-HDES, which is prepared by the preparation method of AgNPs-HDES described in the above claims.

[0032] The present application also provides a method for preparing a detection agent, which uses the above-mentioned AgNPs-HDES as a hydrogen bond donor, cinnamyl alcohol as a hydrogen bond acceptor, and combines with a hydrophobic low eutectic solvent to obtain the detection agent.

[0033] The present application also provides a method for detecting Hg in the environment. 2+ detection and enrichment.

[0034] Second aspect:

[0035] The present invention selects cinnamyl alcohol as a hydrogen bond acceptor (HBA), introduces silver nanoparticle-ethylene glycol (AgNPs-EG) containing AgNPs as a hydrogen bond donor (HBD) for the first time, and utilizes the enrichment effect of hydrophobic deep eutectic solvents (HDES) and the effect of AgNPs on Hg 2+ The detection function is completed during enrichment, thereby constructing an integrated colorimetric sensing platform for AgNPs-HDES enrichment detection, eliminating the interference of hydrophilic substances in the sample and improving the sensitivity and accuracy of detection. The present invention prepares an ethylene glycol solution of silver nanoparticles (AgNPs-EG), which is yellow-brown and has strong light stability. 2+ Added to AgNPs-EG, Ag and Hg 2+ Zero-valent mercury is formed through redox reaction, and its peak absorbance at 420nm disappears, causing AgNPs-EG to fade rapidly within a few seconds. 2+ The color gradually fades from brown to colorless as the concentration increases. The AI-assisted detection software developed based on the YOLO v8 algorithm and convolutional neural networks (CNNs) can process multiple sample images taken by smartphones, read the colorimetric information of the samples, and then output the actual concentration, which can achieve high-throughput colorimetric detection of multiple groups of samples at the same time.

[0036] On the basis of conforming to the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present application.

[0037] The reagents and raw materials used in this application are commercially available.

[0038] The positive progress of the present application is that: the present application provides a specific preparation method of AgNPs, selects cinnamyl alcohol as a hydrogen bond acceptor, introduces ethylene glycol solution containing AgNPs as a hydrogen bond donor for the first time, utilizes the enrichment effect of the hydrophobic low eutectic solvent and the AgNPs to Hg 2+ The detection function was achieved during the enrichment and detection, thus constructing an integrated colorimetric sensing platform for AgNPs-HDES enrichment and detection. This detection platform has good linearity (R 2 =0.9889), the detection limit is as low as 0.23μM. Detect Hg in real samples such as lake water and soil 2+ The recovery rate can reach 93.88-111.05%, thus achieving the goal of Hg 2+ This sensing platform combined with AI-assisted high-throughput identification strategy has achieved the goal of detecting trace Hg in the environment. 2+ It is a portable instant test with the advantages of high sensitivity, fast detection speed and good selectivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] The present application can be better understood by referring to the description given below in conjunction with the accompanying drawings. The accompanying drawings, together with the following detailed description, are included in this specification and form a part of this specification, and are used to further illustrate the preferred embodiments of the present application and explain the principles and advantages of the present application.

[0040] in:

[0041] Figure 1 To prepare the test and its flow chart;

[0042] Figure 2 It is a cross-section diagram of software operation;

[0043] Figure 3 It is a schematic diagram;

[0044] Figure 4 Characterization of AgNPs, including particle size analysis, nuclear magnetic resonance images, and infrared images. DETAILED DESCRIPTION

[0045] The present application is further described below by way of examples, but the present application is not limited to the scope of the examples. The experimental methods without specific conditions in the following examples are selected according to conventional methods and conditions, or according to the product instructions.

[0046] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0047] The raw materials in the following examples are all commercially available.

[0048] Example 1

[0049] 1. Preparation of AgNPs-EG

[0050] AgNPs-EG was prepared using silver acetate as a silver donor and L-arginine as a reducing agent. First, 3.8 mg of silver acetate powder was weighed and placed in a flask, and 20 ml of EG was added and stirred with a magnetic stirrer until the solution was in a suspension state. Then, according to the molar ratio of L-arginine:AgAc 1.5:1, 6.0 mg of L-arginine solid powder was weighed, dissolved in 5 ml of EG and ultrasonicated until a colorless, clear and transparent L-arginine-EG solution was obtained. When the temperature in the magnetic stirrer reached 45°C, the L-arginine-EG solution was slowly added dropwise to the flask containing AgAc, and the reaction solution was gradually heated to 60°C and stirred and heated in a water bath for 30 minutes. At this time, it can be observed that the solution changes from a suspension to a clear solution, accompanied by a color change, and the reaction solution changes from colorless to light yellow and finally to light brown. After the reaction is completed, stop heating, transfer the reaction solution to a container for cooling, and store it at room temperature or in a refrigerator at 4°C.

[0051] 2. Preparation of AgNPs-HDES

[0052] The prepared AgNPs-EG solution was used as HBD, and n-decanoic acid was used as HBA, with a molar ratio of HBD:HBA of 3:1, and the mixture was mixed and stirred at 80°C for 1 h, and finally a brown-yellow AgNPs-HDES solution was synthesized.

[0053] Comparative Example 1

[0054] The preparation method comprises:

[0055] AgNPs were produced by a simple and easy-to-use chemical reduction method using a silver precursor, a capping agent, and a reducing agent as follows:

[0056] Silver nanoparticles: Add an appropriate amount of deionized (DI) water to a reaction flask, then add the Ag precursor (silver nitrate) and coating agent (trisodium citrate dihydrate) and mix, then introduce a reducing agent (sodium borohydride) to produce a solution of AgNPs. Mix the above solutions in proportion under vigorous stirring (50mL of 0.1mM silver nitrate and 1mM trisodium citrate solution, quickly add 2mL of 10mM sodium borohydride solution), and observe the color change (usually from colorless to yellow or brown, indicating the formation of silver nanoparticles, the reaction time is 20 minutes). Once the reaction is complete, store the solution at low temperature and away from light.

[0057] Effect Example 1

[0058] according to Figure 3 The product prepared in Example 1 was tested for Hg2+ Recovery rate, among which, the effect data is shown in Table 1:

[0059] Table 1

[0060]

[0061]

[0062] As shown in Table 1, by utilizing this platform, the Hg concentrations of all samples in a single image captured at a high resolution of 4096 × 3072 pixels, as well as the corresponding sample IDs and average RGB values, can be identified and annotated within 377 milliseconds. This efficiency is significantly higher than that of traditional methods while maintaining a recovery rate of 90.28%-123.2%. For single sample detection, the recovery rate was 82.76-113.0%.

[0063] Figure 1 Describe the detection flow chart of the integrated colorimetric sensing platform for AgNPs-HDES enrichment detection.

[0064] Figure 2 Illustration: (a) A self-designed graphical user interface (GUI) application that displays relevant information at appropriate locations; (b) annotated image with final detection results.

[0065] Figure 3 Description: Preparation of AgNPs-HDES and Hg 2+ Detection process diagram: AgNPs-EG is prepared by the reaction of silver acetate and L-arginine in ethylene glycol. AgNPs-EG, as one of the components of DES, reacts with cinnamyl alcohol under heating conditions at 80°C to synthesize AgNPs-HDES. After vortexing, standing and separating with the sample, AI-assisted detection and UV detection are performed respectively.

[0066] Figure 4 Description: Characterization of the properties of AgNPs-HDES (SEM, IR, 1H-NMR). (ac) The SEM images of the prepared AgNP-HDES show that the magnification increases from left to right, and it can be observed that the AgNP particles have an almost spherical structure, and the structure has no obvious changes. The particle size is about 13nm, and the dispersion is good. The average particle size of the AgNP in the figure is 12.94±2.32nm. (d) The components of HDES were analyzed by Fourier transform infrared spectroscopy. The -OH peak shifted from 3534.91cm-1 to 3484.77cm-1, and the -OH peak was broadened to a certain extent, indicating that EG-AgNPs and DES have a certain combination, and the hydrogen bond formed leads to the displacement of the -OH peak and the broadening of the peak shape. (e) The components of HDES were analyzed by nuclear magnetic resonance spectroscopy. The -OH part of CA moved from 4.994ppm to 4.919ppm, and the H on the C connected to the hydroxyl group moved from 4.184ppm to 4.129ppm. This is because after the hydrogen bond is formed, the shielding effect of electrons on active hydrogen atoms will be weakened, and the chemical shift of active H will increase.

[0067] Finally, it should be noted that in this application, the terms "comprises", "includes" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also other elements that are not explicitly listed, or also includes elements that are inherent to such process, method, article or apparatus.

[0068] Although the present application has been disclosed above through the description of the specific embodiments of the present application, it should be understood that those skilled in the art can design various modifications, improvements or equivalents to the present application within the spirit and scope of the attached scheme. These modifications, improvements or equivalents should also be considered to be included in the scope of protection claimed in the present application.

Claims

1. A method for preparing AgNPs-HDES, characterized in that: The preparation method comprises the following steps: uniformly mixing an organic acid silver solution and an amino acid solution to prepare an AgNPs-EG solution under heating and stirring conditions, and then reacting the AgNPs-EG solution with an organic acid to prepare AgNPs-HDES; Wherein, the organic acid silver is used as a silver donor, and the amino acid is used as a reducing agent; the amino acid is L-arginine, and the organic acid silver is silver acetate.

2. The method for preparing AgNPs-HDES according to claim 1, characterized in that: At least one of the following conditions is met: The organic acid silver solution is an organic acid silver glycol solution; The mass fraction of the organic acid silver solution is about 0.0171%; The amino acid solution is an amino acid ethylene glycol solution; The mass fraction of the amino acid solution is about 0.108%.

3. The method for preparing AgNPs-HDES according to claim 1, characterized in that: At least one of the following conditions is met: The temperature of the reaction is such that the mass ratio of the silver acetate to the L-arginine is 1:1.5; The stirring is carried out under a magnetic stirrer; The arginine also includes an ultrasonic dispersion operation before use; The silver acetate also includes an ultrasonic dispersion operation before use.

4. The method for preparing AgNPs-HDES according to claim 1, characterized in that: The organic acid solution and the amino acid solution are mixed at 45-50° C., and heated to 60-70° C. for reaction and heated and stirred. The heating time is 20-40 minutes.

5. The method for preparing AgNPs-HDES according to claim 4, characterized in that: The heating is carried out in a water bath, and the stirring speed is 1000 rpm; The heating is stopped after the mixed solution becomes a light brown clear liquid.

6. The method for preparing AgNPs-HDES according to claim 1, characterized in that: The molar ratio of the AgNPs-EG solution to the organic acid solution is (2-4):1, for example, 3:

1.

7. The method for preparing AgNPs-HDES according to claim 1, characterized in that: At least one of the following conditions is met: The organic acid is cinnamyl alcohol; The reaction temperature is 70-90°C, for example 80°C; The reaction time is 0.8 to 2 hours, for example 1 hour.

8. An AgNPs-HDES, characterized in that: The AgNPs-HDES is prepared by the preparation method of any one of claims 1 to 7.

9. A method for preparing a detection agent, comprising using the AgNPs-HDES described in claim 8 as a hydrogen bond donor, using cinnamyl alcohol as a hydrogen bond acceptor, and combining them with a hydrophobic low eutectic solvent to obtain the detection agent.

10. A detection agent according to claim 9, characterized in that Used for Hg in the environment 2+ detection and enrichment.

Images