CN116083076A - Rhodamine B and gold-coated silver nanoparticle-based fluorescence sensor and detection application thereof to organophosphorus pesticides - Google Patents

Rhodamine B and gold-coated silver nanoparticle-based fluorescence sensor and detection application thereof to organophosphorus pesticides Download PDF

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CN116083076A
CN116083076A CN202211582332.6A CN202211582332A CN116083076A CN 116083076 A CN116083076 A CN 116083076A CN 202211582332 A CN202211582332 A CN 202211582332A CN 116083076 A CN116083076 A CN 116083076A
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fluorescence
organophosphorus pesticide
rhodamine
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蒋长龙
林丹
杨亮
徐诗皓
刘明利
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Hefei Intelligent Agriculture Collaborative Innovation Research Institute Of China Science And Technology
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Abstract

The invention develops a simple and efficient open type fluorescent nano sensor by combining gold-coated silver nano particles and rhodamine B, which is used for sensitive detection of organophosphorus pesticide residues. Rhodamine B is used as a fluorescent source to emit orange light, and the gold-coated silver nano-particles are used as a quencher to quench the orange light fluorescence. The addition of the organophosphorus pesticide leads to aggregation of the gold-coated silver nano particles and recovery of orange emission, thereby realizing detection of the organophosphorus pesticide based on a fluorescence opening principle. Meanwhile, a smart phone sensing platform can be established, and an RGB analysis method is adopted to quantitatively detect organophosphorus pesticide residues in actual samples. The designed nano sensor responds to a detection signal by means of fluorescence opening, shows obvious change from dark fluorescence intensity to bright orange fluorescence, effectively improves the visual effect of the sensor, realizes quantitative detection by combining with a smart phone, and expands the application of on-site in-situ organophosphorus pesticide residue detection and food safety.

Description

Rhodamine B and gold-coated silver nanoparticle-based fluorescence sensor and detection application thereof to organophosphorus pesticides
Technical Field
The invention relates to a fluorescent nano sensor based on rhodamine B and gold-coated silver nano particle composite material and a high-sensitivity fluorescent visual detection method for organophosphorus pesticide residues in an actual water sample and on surfaces of fruits and vegetables.
Background
Organophosphorus pesticides (organophosphorus pesticide, OPs) bind to acetylcholinesterase after entering organisms, which causes the excessive accumulation of acetylcholine in the nerve conduction of organisms without hydrolysis, thus causing nerve to be stimulated, and the toxic symptoms and serious cases to die directly. Therefore, importance of pesticide residue detection must be paid attention to. The fluorescence detection method has the advantages of quick and simple reaction and high sensitivity, and is a powerful tool for detecting organophosphorus pesticide residues. However, most of the current fluorescence sensors for organophosphorus pesticide detection are based on enzyme inhibition, and have a certain short plate in terms of detection conditions, time, cost and the like; some special practical detection environments have interference effects on detection results, so that the detection results are false positive or false negative. Moreover, most quantitative fluorescence detection methods require specialized technicians and expensive, complex and heavy instrumentation, which makes field detection difficult. Thus, there is an urgent need for portable, rapid, on-site, cost-effective detection techniques.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and aims to design a fluorescent nano sensor based on rhodamine B and gold-coated silver nano particle composite material for quantitatively detecting organophosphorus pesticide residues with high sensitivity. The method has the characteristics of high selectivity, high sensitivity, visual quantitative detection and the like.
The invention combines gold-coated silver nano particles and rhodamine B dye to design and develop a fluorescent nano sensor for sensitively detecting organophosphorus pesticide residues. The fluorescent nano sensor is obtained by uniformly mixing a gold-coated silver nano particle solution and a rhodamine B dye solution. Specific:
the nano sensor provided by the invention is composed of a composite system of gold-coated silver nanoparticle solution and rhodamine B dye. The concentration of the gold-coated silver nanoparticle solution in the composite system is 0.8-1 mg/mL, and the concentration of rhodamine B solution is 90-100 mu M respectively.
Preferably, the preparation method of the composite system of rhodamine B and gold-coated silver nano particles comprises the steps of preparing silver nano particles Ag NPs by adopting a trisodium citrate reduction method, adding the silver nano particles Ag NPs into a system for preparing gold nano particles Au NPs by adopting an ascorbic acid reduction method to obtain gold-coated silver nano particles Ag@Au NPs, and then mixing the gold-coated silver nano particles Ag@Au NPs with rhodamine B.
Preferably, the silver nano-particle Ag NPs prepared by adopting the trisodium citrate reduction method is prepared by uniformly mixing a silver nitrate aqueous solution and a trisodium citrate aqueous solution, then adding a freshly prepared sodium borohydride aqueous solution, quickly injecting a hydrogen peroxide solution, observing that the color of a reactant turns blue, centrifuging, separating, washing and dispersing in ultrapure water for standby.
Preferably, the gold-coated silver nano particles Ag@Au NPs are prepared by dissolving ascorbic acid and polyvinylpyrrolidone in ultrapure water, adding silver nano particles, adjusting the pH value to 10-12, adding chloroauric acid solution, observing that the color of the reaction mixture solution turns into pink, centrifugally separating, washing and dispersing in the ultrapure water for later use.
Preferably, the gold-coated silver nano particles Ag@Au NPs and rhodamine B are mixed by adding rhodamine B solution and gold-coated silver nano particle stock solution into PBS buffer solution, and finally, the pH value of the mixture solution is 7.0-7.4, so that the fluorescent nano sensor is formed.
More preferably, the fluorescent nanosensor of the invention may comprise the steps of:
(1) Preparation of silver nanoparticles
Uniformly mixing 3-4 mL of 0.008-0.01 mol/L silver nitrate aqueous solution and 5-6 mL of 0.08-0.1 mol/L citric acid three, adding ultrapure water to enable the final volume to reach 35-40 mL, adding 3-4 mL of freshly prepared 90-100 mmol/L sodium borohydride aqueous solution, and rapidly injecting 0.8-1 mL of 25-40wt% hydrogen peroxide solution; observing the blue color of the reactant, centrifugally separating, washing, and dispersing in ultrapure water for standby;
(2) Preparation of gold-coated silver nanoparticles
Dissolving 95-100 mg of ascorbic acid and 60-66.6 mg of polyvinylpyrrolidone in 13-15 mL of ultrapure water, adding 4-5 mL of prepared silver nanoparticle stock solution, and regulating the pH value to 10-12; slowly adding 90-100 mu L of 0.08-0.1 mol/L chloroauric acid solution, observing the color of the reaction solution to be pink, centrifugally separating, washing and dispersing in ultrapure water for standby;
(3) Preparation of fluorescent nanosensor
180 to 200. Mu.L of rhodamine B solution with the concentration of 0.08 to 0.12mM and 180 to 200. Mu.L of gold-coated silver nanoparticle stock solution are added into 10mM PBS buffer solution, so that the pH value of the final mixture solution is 7.0.
Preferably, the aqueous solution of sodium borohydride in step (1) should be ready for use; in step (2)Trisodium citrate is Na with 2 crystal waters 3 C 6 H 5 O 7 ·2H 2 O, chloroauric acid is HAuCl with 3 crystal waters 4 ·3H 2 O; the molecular weight of the polyvinylpyrrolidone in step (3) is 8000-80000, preferably 20000-60000, most preferably 55000; the PBS buffer in step (3) has a pH of 7.0-7.5.
More specifically, the preparation method of the nano sensor of the invention can adopt the following steps:
(1) Preparation of silver nanoparticles
First, 3-4 mL of silver nitrate aqueous solution (0.008-0.01 mol/L) and 5-6 mL of trisodium citrate aqueous solution (0.08-0.1 mol/L) are stirred and mixed uniformly in a beaker. Secondly, adding ultrapure water to enable the final volume of the reaction solution to reach 35-40 mL, magnetically stirring for 9-10 min, adding 3-4 mL of freshly prepared sodium borohydride aqueous solution (90-100 mmol/L) under the condition of continuous stirring, and then rapidly injecting 0.8-1 mL of 30% hydrogen peroxide solution. The reaction was observed to change color from pale yellow to red, then green, and finally blue over 3 to 4min, ensuring the reaction was complete. Subsequently, silver nanoparticles (Ag NPs) dispersible in water are centrifugally separated at 9000 to 10000r/min, and repeatedly washed with ethanol and ultrapure water 2 to 3 times. Finally, the treated silver nanoparticles were dispersed in a refrigerator at 4 ℃ with 18-20 mL of ultrapure water for further use.
(2) Preparation of gold-coated silver nanoparticles
95-100 mg of ascorbic acid and 60-66.6 mg of polyvinylpyrrolidone are dissolved in 13-15 mL of ultrapure water, and the mixture is stirred by magnetic force to be completely dissolved. Then adding 4-5 mL of prepared silver nano particles in sequence, and then adding 0.4-0.5 mL of NaOH aqueous solution (0.18-0.2 mol/L) to adjust the pH value of the reaction mixture to 11. Subsequently, 90 to 100. Mu.L of chloroauric acid solution (0.08 to 0.1 mol/L) was slowly added at a rate of 8 to 10. Mu.L/min with continuous stirring, while observing the change of the color of the reaction mixture solution from deep blue to pink, ensuring complete formation of gold-coated silver nanoparticles (Ag@Au NPs). Finally, the Ag@Au NPs which can be dispersed in water are separated by centrifugation for 13 to 15 minutes at the rotating speed of 9000 to 10000r/min, and repeatedly washed by ultrapure water for 2 to 3 times. Finally, the treated Ag@Au NPs were dispersed in 18-20 mL of ultrapure water in a refrigerator at 4℃for further use.
(3) Preparation of fluorescent nanosensor
4.5 to 4.79mg of rhodamine B is dissolved in 90 to 100mL of ultrapure water to prepare 0.08 to 0.1mM of rhodamine B solution. 180 to 200 mu L of rhodamine B solution and 180 to 200 mu L of gold-coated silver nanoparticle stock solution are added into PBS buffer solution (10 mM), and the pH value of the final mixture solution is 7.0. And uniformly mixing the composite solution to form a sensing system. And then adding the organophosphorus pesticide solution into the sensor solution, and uniformly stirring. Calculating the final concentration of the organophosphorus pesticide to be 0.001, 0.01, 0.1, 0.4, 0.8, 1, 10, 50 and 100 mu M, incubating for 18-20 min at 30 ℃, and recording the fluorescence spectrum of the probe solution in the range of 450-750nm by using 320-350nm excitation light to finish the fluorescence detection of the organophosphorus pesticide.
The fluorescent nano sensor can be applied to qualitative detection in organophosphorus pesticide detection, specifically, an organophosphorus pesticide solution can be added into the sensor solution, incubated for 18-20 min at 27-30 ℃, and whether the fluorescence of the solution is changed into orange yellow or not is observed under a 350nm ultraviolet lamp, so that whether the organophosphorus pesticide component is contained or not can be qualitatively analyzed. The inventor researches and discovers that the excitation light with the wavelength of 320-350nm has fluorescence on the excitation of the fluorescence of the sensor, but the fluorescence intensity is high when the excitation light with the wavelength of 350nm is the optimal excitation state of the probe solution. The organophosphorus pesticides of the present invention include, but are not limited to, trichlorfon, dichlorvos, omethoate, malathion, phoxim, chlorpyrifos, ethyl paraoxon, and the like.
The fluorescent nano sensor can also be applied to quantitative detection in organophosphorus pesticide detection, specifically, an organophosphorus pesticide standard solution is added into a sensor solution, incubation is carried out for 18-20 min at 27-30 ℃, the fluorescence spectrum of the recorded solution is observed under a 350nm ultraviolet lamp, a standard curve is produced, the relationship between the fluorescence intensity and the organophosphorus pesticide concentration is obtained, a fluorescence test is carried out on a sample to be detected containing the organophosphorus pesticide according to the correlation, and the organophosphorus pesticide concentration in the sample to be detected is calculated according to the fluorescence intensity.
In addition, the fluorescent nano sensor can be further combined with the smart phone to be applied to the intelligent sensing platform, so that the detection process is more portable and economical. Specifically, an organophosphorus pesticide standard solution is added into a sensor solution, incubated for 18-20 min at 27-30 ℃, fluorescence of the recorded solution is observed under a 350nm ultraviolet lamp, the fluorescent color recognition software is further decomposed into RGB values, a linear relation curve of a G/R ratio and the organophosphorus pesticide concentration is established, and quantitative detection is realized by using the obtained G/R ratio. And (3) quantitatively detecting the intelligent mobile phone sensing platform, wherein the number of the color reading sites is 3, and the reading results are averaged.
Fluorescent colors are obtained through a smart phone or a smart camera, and an intelligent sensing platform is established, wherein the intelligent sensing platform comprises a porous plate, a dark cavity, a 350nm ultraviolet lamp and the smart phone or the smart camera; the application method of the intelligent sensing platform comprises the steps of adding fluorescent nano sensor solution into a porous plate, then adding organophosphorus pesticide solutions with different concentrations, obtaining fluorescence in a dark environment through a smart phone or a smart camera, further decomposing the fluorescence into RGB values through color recognition application software, establishing a linear relation curve of G/R ratio and organophosphorus pesticide concentration, and utilizing the obtained G/R ratio to realize quantitative detection.
The invention provides a simple and efficient open-type fluorescent nano sensor which can be used for sensitive detection of organophosphorus pesticide residues. Rhodamine B is used as a fluorescent source to emit orange light, and the gold-coated silver nano-particles are used as a quencher to quench the orange light fluorescence. The addition of the organophosphorus pesticide leads to aggregation of the gold-coated silver nano particles and recovery of orange emission, thereby realizing detection of the organophosphorus pesticide based on a fluorescence opening principle. The fluorescent nano sensor has a good detection effect on organophosphorus pesticides, and the detection limit in a fluorescent mode is 7.89nM. In addition, the intelligent mobile phone sensing platform is utilized, and an RGB analysis method is adopted to quantitatively detect organophosphorus pesticide residues in actual samples. The designed nano sensor responds to a detection signal by means of fluorescence opening, shows obvious change from dark fluorescence intensity to bright orange fluorescence, effectively improves the visual effect of the sensor, realizes quantitative detection by combining with a smart phone, and expands the application of on-site in-situ organophosphorus pesticide residue detection and food safety.
The invention has the advantages and positive effects that:
1. according to the invention, the fluorescence of rhodamine B is used as a fluorescence detection signal of organophosphorus pesticide residues, and obvious fluorescence intensity change is displayed based on a fluorescence opening strategy, so that visual detection is realized.
2. The detection limit of the fluorescent probe solution on the organophosphorus pesticide residues on a fluorescence spectrometer is 7.89nM, which is lower than the allowable limit of the organophosphorus pesticide residues.
3. The invention adopts rhodamine B purchased commercially, and omits a complex preparation process.
4. By introducing the smart phone sensing platform, the fluorescent nano sensor can quantitatively detect organophosphorus pesticide residues in real time/on site visually, so that the detection process is portable, quick and low in cost.
Drawings
Fig. 1 is a transmission electron microscope image of gold-coated silver nanoparticles. In the figure, the gold-coated silver nanoparticles are dispersed so that rhodamine B is fluorescence quenched.
Fig. 2 is a transmission electron microscope image of the gold-coated silver nanoparticle after adding the organophosphorus pesticide. After organophosphorus pesticide residues are added in the graph, particles are aggregated, so that rhodamine B fluorescence recovery is facilitated.
Fig. 3 (a) is a graph of fluorescence and color change of organophosphorus pesticides with different concentrations on a gold-coated silver nanoparticle/rhodamine B mixed system. As the concentration of organophosphorus pesticide increases (0.001, 0.01, 0.1, 0.4, 0.8, 1, 10, 50, 100. Mu.M, in sequence from left to right), the orange-yellow fluorescence of the solution gradually lightens from dark. FIG. 3 (B) is a graph showing the relationship between the fluorescence intensity and the concentration of the organophosphorus pesticide, and the inset is a graph showing the relationship between the fluorescence intensity and the concentration of the organophosphorus pesticide in a linear manner, wherein the concentration of the organophosphorus pesticide is 0-100. Mu.M.
Fig. 4 is a schematic operation diagram and a visual detection effect diagram of the smart phone sensing platform. (A) Adding the fluorescent nano sensor solution into a porous plate, and then adding organophosphorus pesticide solutions with different concentrations; (B) Fluorescent light is obtained through a smart phone in a dark environment, the fluorescent light is further decomposed into RGB values through installation of a color recognition Application (APP), a linear relation curve of the ratio of G to R and the concentration of organic phosphorus is established, and quantitative detection is achieved through the obtained ratio of G to R.
FIG. 5 is a graph of optimal pH for a fluorescence sensing system. (A) At pH values of 2 to 12, the change of the fluorescence spectrum of the sensing system; (B) And after the organophosphorus pesticide is added, the pH value is subjected to an influence diagram of fluorescent probe detection. As can be seen from the graph, the sensor solution has maximum fluorescence intensity at 580nm at pH 7.0; after the organophosphorus pesticide is added, the sensor solution has the maximum fluorescence intensity at 580nm when the pH is 7.0, which indicates that the detection effect is best under the condition of the pH of 7.0.
FIG. 6 is a graph of optimal reaction time for a fluorescent sensing system, with the reaction stable over 15 minutes.
The specific embodiment is as follows:
the following examples are further illustrative of the technical content of the present invention, but the essential content of the present invention is not limited to the examples described below, and those skilled in the art can and should know that any simple changes or substitutions based on the essential spirit of the present invention should fall within the scope of the present invention as claimed. In order to verify the effectiveness of the present invention, ethyl paraoxone was used as an organophosphorus pesticide test sample in the following examples, but it is apparent that the present invention is not limited thereto.
Example 1
(1) Preparation of silver nanoparticles
First, 3-4 mL of silver nitrate aqueous solution (0.008-0.01 mol/L) and 5-6 mL of trisodium citrate aqueous solution (0.08-0.1 mol/L) are stirred and mixed uniformly in a beaker. Secondly, adding ultrapure water to enable the final volume of the reaction solution to reach 35-40 mL, magnetically stirring for 9-10 min, adding 3-4 mL of freshly prepared sodium borohydride aqueous solution (90-100 mmol/L) under the condition of continuous stirring, and then rapidly injecting 0.8-1 mL of 30% hydrogen peroxide solution. The reaction was observed to change color from pale yellow to red, then green, and finally blue over 3 to 4min, ensuring the reaction was complete. Subsequently, silver nanoparticles (Ag NPs) dispersible in water are centrifugally separated at 9000 to 10000r/min, and repeatedly washed with ethanol and ultrapure water 2 to 3 times. Finally, the treated silver nanoparticles were dispersed in a refrigerator at 4 ℃ with 18-20 mL of ultrapure water for further use.
(2) Preparation of gold-coated silver nanoparticles
95-100 mg of ascorbic acid and 60-66.6 mg of polyvinylpyrrolidone are dissolved in 13-15 mL of ultrapure water, and the mixture is stirred by magnetic force to be completely dissolved. Then adding 4-5 mL of prepared silver nano particles in sequence, and then adding 0.4-0.5 mL of NaOH aqueous solution (0.18-0.2 mol/L) to adjust the pH value of the reaction mixture to 11. Subsequently, 90 to 100. Mu.L of chloroauric acid solution (0.08 to 0.1 mol/L) was slowly added at a rate of 8 to 10. Mu.L/min with continuous stirring, while observing the change of the color of the reaction mixture solution from deep blue to pink, ensuring complete formation of gold-coated silver nanoparticles (Ag@Au NPs). Finally, the Ag@Au NPs which can be dispersed in water are separated by centrifugation for 13 to 15 minutes at the rotating speed of 9000 to 10000r/min, and repeatedly washed by ultrapure water for 2 to 3 times. Finally, the treated Ag@Au NPs were dispersed in 18-20 mL of ultrapure water in a refrigerator at 4℃for further use. See fig. 1 for a transmission photograph.
(3) Preparation of fluorescent nanosensor
4.5 to 4.79mg of rhodamine B dye is dissolved in 90 to 100mL of ultrapure water to prepare 0.08 to 0.1mM of rhodamine B solution. 180-200. Mu.L of rhodamine B solution and 200. Mu.L of gold-coated silver nanoparticle stock solution are added to PBS buffer (10 mM), and the pH of the final mixture solution is 7.0. And uniformly mixing the composite solution to form a sensing system. And then adding the organophosphorus pesticide solution into the sensor solution, and uniformly stirring. The final concentration of the organophosphorus pesticide is calculated to be 0.001, 0.01, 0.1, 0.4, 0.8, 1, 10, 50 and 100 mu M, after incubation for 20min at 30 ℃, the fluorescence spectrum of the probe solution is recorded by using 350nm excitation light, and the fluorescence detection of the organophosphorus pesticide is completed. The fluorescence spectrum and the visual photograph are shown in fig. 3. In fig. 3 (a) is a graph of fluorescence spectrum and color change of the mixed system of the gold-coated silver nanoparticle/rhodamine B by the organophosphorus pesticide with different concentrations, it can be seen that the orange-yellow fluorescence of the solution gradually becomes bright from dark as the concentration of the organophosphorus pesticide increases (0.001, 0.01, 0.1, 0.4, 0.8, 1, 10, 50, 100 μm in sequence from left to right). (B) The graph is a linear relationship graph between the fluorescence intensity and the concentration of the organophosphorus pesticide, and the inset graph is a linear relationship graph between the fluorescence intensity and the concentration of the organophosphorus pesticide, wherein the concentration of the organophosphorus pesticide is 0-100 mu M.
(4) Smart mobile phone sensing platform
The smart phone sensing platform comprises a porous plate, a dark cavity, a 350nm ultraviolet lamp and a smart phone. For the operation of a smart phone sensing platform, firstly, adding a fluorescent nano sensor solution into a porous plate, then adding organophosphorus pesticide solutions with different concentrations, obtaining fluorescence through a smart phone in a dark environment, further decomposing into RGB values by installing a color recognition Application (APP), establishing a linear relation curve of the ratio of G to R and the organophosphorus concentration, and utilizing the obtained ratio of G to R to realize quantitative detection. The operation flow is shown in fig. 4.
(5) Sample detection
First, 400. Mu.L of the probe solution was diluted to 2mL with PBS buffer (10 mM, pH=7.4), and then 200. Mu.L of the sample solution was added to the probe solution for measurement. The corresponding fluorescence image is captured by a mobile phone or a camera, and the data is recorded by a fluorescence spectrometer. Further decomposing into RGB values through color recognition Application (APP), calculating the ratio of G to R, and obtaining the concentration of the organic phosphorus according to the linear relation curve in the step (4).

Claims (10)

1. A fluorescent nano sensor based on rhodamine B and gold-coated silver nanoparticle composite material is characterized in that the nano sensor is composed of a rhodamine B solution and gold-coated silver nanoparticle solution composite system; the concentration of the gold-coated silver nanoparticle solution in the composite system is 0.8-1 mg/mL, and the concentration of the rhodamine B solution is 90-100 mu M.
2. The fluorescent nanosensor of claim 1, wherein the preparation method of the composite system of rhodamine B and gold-coated silver nanoparticles comprises the steps of preparing silver nanoparticle Ag NPs by a trisodium citrate reduction method, adding the silver nanoparticle Ag NPs into a system of preparing gold nanoparticle Au NPs by an ascorbic acid reduction method to obtain gold-coated silver nanoparticle Ag@Au NPs, and then mixing the gold-coated silver nanoparticle Ag@Au NPs with rhodamine B.
3. The fluorescent nanosensor of claim 2, wherein the silver nanoparticle Ag NPs prepared by the trisodium citrate reduction method is prepared by uniformly mixing a silver nitrate aqueous solution and a trisodium citrate aqueous solution, adding a freshly prepared sodium borohydride aqueous solution, rapidly injecting a hydrogen peroxide solution, observing the color of a reactant to be blue, centrifuging, washing, and dispersing in ultrapure water for later use.
4. The fluorescent nanosensor of claim 2, wherein the gold-coated silver nanoparticles ag@au NPs are prepared by dissolving ascorbic acid and polyvinylpyrrolidone in ultrapure water, adding silver nanoparticles, adjusting the pH to 10-12, adding chloroauric acid solution, observing the color of the reaction mixture solution to pink, centrifuging, washing, and dispersing in ultrapure water.
5. The fluorescent nanosensor of claim 2, wherein the gold-coated silver nanoparticles ag@au NPs are mixed with rhodamine B by adding rhodamine B solution and gold-coated silver nanoparticle stock solution to PBS buffer, and the final mixture solution pH is 7.0-7.4, to form the fluorescent nanosensor.
6. The fluorescent nanosensor of claim 2, comprising the steps of:
(1) Preparation of silver nanoparticles
Uniformly mixing 3-4 mL of 0.008-0.01 mol/L silver nitrate aqueous solution and 5-6 mL of 0.08-0.1 mol/L citric acid three, adding ultrapure water to enable the final volume to reach 35-40 mL, adding 3-4 mL of freshly prepared 90-100 mmol/L sodium borohydride aqueous solution, and rapidly injecting 0.8-1 mL of 25-40wt% hydrogen peroxide solution; observing the blue color of the reactant, centrifugally separating, washing, and dispersing in ultrapure water for standby;
(2) Preparation of gold-coated silver nanoparticles
Dissolving 95-100 mg of ascorbic acid and 60-66.6 mg of polyvinylpyrrolidone in 13-15 mL of ultrapure water, adding 4-5 mL of prepared silver nanoparticle stock solution, and regulating the pH value to 10-12; slowly adding 90-100 mu L of 0.08-0.1 mol/L chloroauric acid solution, observing the color of the reaction solution to be pink, centrifugally separating, washing and dispersing in ultrapure water for standby;
(3) Preparation of fluorescent nanosensor
180 to 200. Mu.L of rhodamine B solution with the concentration of 0.08 to 0.12mM and 180 to 200. Mu.L of gold-coated silver nanoparticle stock solution are added into 10mM PBS buffer solution, so that the pH value of the final mixture solution is 7.0.
7. Use of the fluorescent nanosensor of any one of claims 1-6 in the detection of organophosphorus pesticides, characterized in that organophosphorus pesticide solution is added to the sensor solution, incubated for 18-20 min at 27-30 ℃, and the change of fluorescent color of the solution is observed under 350nm ultraviolet lamp.
8. The use of the fluorescent nanosensor of any one of claims 1-6 in detection of organophosphorus pesticides, characterized in that an organophosphorus pesticide standard solution is added into the sensor solution, incubated for 18-20 min at 27-30 ℃, the fluorescence spectrum of the recorded solution is observed under a 350nm ultraviolet lamp, a standard curve is made, the relationship between the fluorescence intensity and the organophosphorus pesticide concentration is obtained, a fluorescence test is performed on a sample to be detected containing the organophosphorus pesticide according to the correlation, and the organophosphorus pesticide concentration in the sample to be detected is calculated according to the fluorescence intensity.
9. The application of the fluorescent nano sensor in the detection of organophosphorus pesticides according to any one of claims 1-6, wherein an organophosphorus pesticide standard solution is added into the sensor solution, incubated for 18-20 min at 27-30 ℃, fluorescence of the recorded solution is observed under a 350nm ultraviolet lamp, a linear relation curve of G/R ratio and organophosphorus pesticide concentration is established by further decomposing fluorescence color recognition software into RGB values, and quantitative detection is realized by using the obtained G/R ratio.
10. The use of claim 9, wherein the fluorescent color is obtained by a smart phone or smart camera, and a smart sensor platform is established, the smart sensor platform comprising a porous plate, a dark cavity, a 350nm ultraviolet lamp, and the smart phone or smart camera; the application method of the intelligent sensing platform comprises the steps of adding fluorescent nano sensor solution into a porous plate, then adding organophosphorus pesticide solutions with different concentrations, obtaining fluorescence in a dark environment through a smart phone or a smart camera, further decomposing the fluorescence into RGB values through color recognition application software, establishing a linear relation curve of G/R ratio and organophosphorus pesticide concentration, and utilizing the obtained G/R ratio to realize quantitative detection.
CN202211582332.6A 2021-12-13 2022-12-09 Rhodamine B and gold-coated silver nanoparticle-based fluorescence sensor and detection application thereof to organophosphorus pesticides Pending CN116083076A (en)

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