CN114088668B - Preparation method and application of ratio type fluorescent paper-based sensor - Google Patents
Preparation method and application of ratio type fluorescent paper-based sensor Download PDFInfo
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Abstract
The invention belongs to the fields of nano science and fluorescence sensing, and particularly relates to a preparation method and application of a ratio type fluorescent paper-based sensor. The method comprises the following steps: firstly preparing a CNQDs solution, mixing the CNQDs solution with penicillamine to obtain a penicillamine mixed solution, adding a copper nitrate trihydrate solution, stirring to generate white precipitate, collecting a precipitate, centrifugally washing the precipitate with methanol for a plurality of times, and freeze-drying the centrifuged product to obtain CuNCs/CNQDs; and then dissolving the obtained CuNCs/CNQDs in a methanol solution to obtain a CuCNs/CNQDs solution, dripping the CuCNs/CNQDs solution on filter paper, and drying and loading the CuCNs/CNQDs solution on the filter paper by nitrogen blowing to obtain the ratio type fluorescent paper-based sensor. The ratio type fluorescent probe prepared by the invention has the advantages of low toxicity, high selectivity and low cost, is convenient to carry, and has wide application prospect in detecting hydrogen sulfide gas in food.
Description
Technical Field
The invention belongs to the fields of nano science and fluorescence sensing, and particularly relates to a preparation method and application of a ratio type fluorescent paper-based sensor.
Background
Hydrogen sulfide (H) 2 S) hydrogen sulfide is a colorless, slightly sweet, odorous, irritating choking gas. In the food industry, it is often used to treat spoiled fish, meat, eggs, dredge guts, clean pickle in a manure kiln, and even some sulfides such as sodium sulfide are needed to ensure the appearance of the food in some food processing processes. Such as: and removing iron element in monosodium glutamate by utilizing sodium sulfide. In addition, hydrogen sulfide gas is also generated in the food fermentation process, and the hydrogen sulfide gas and other fermentation gases are harmful to human bodies. However, due to the complexity and variety of food ingredients, it is still difficult to eliminate interference of one or more gas components to perform nondestructive detection of hydrogen sulfide gas in food. Therefore, the preparation of the selective probe with high sensitivity has important significance for detecting the hydrogen sulfide.
Currently, conventional methods for measuring hydrogen sulfide include electrochemical methods, colorimetry, gas chromatography, and the like. But these techniques typically require destruction of the required sample, limiting further applications. While the method of detecting hydrogen sulfide using organic fluorescent probes is generally rapid, its use in the food industry is limited due to its relatively high biotoxicity. In contrast, fluorescent detection using such low biotoxicity fluorescent probes as metal clusters, thereby achieving high sensitivity, high selectivity, low cost, and real-time visual detection, has become an increasingly popular research direction.
Metal nanoclusters are composed of several to about one hundred metal atoms, which fill the gap between the atoms and the nanocrystals. Due to their specific size, metal nanoclusters are capable of exhibiting discrete electronic structures and molecular-like structures, such as size-dependent HOMO-LUMO transitions and luminescence. Unlike general organic fluorescent probes, which have high biotoxicity and complex synthesis processes, various sulfide-protected or template-stabilized CuNCs have good chemical stability and low biotoxicity, and have simpler synthesis steps. The novel fluorescent probe not only has the electrochemical detection method and the rapid and accurate detection characteristic of the organic fluorescent probe, but also has good development prospect in cell sensing and food packaging sensing. However, the preparation of stable copper clusters is a significant challenge due to the difficulty in controlling ultra-small size synthesis and the oxidative sensitivity of copper clusters to exposure to air. Meanwhile, compared with the enhanced fluorescent probe, the ratio fluorescent probe has the characteristic of dual-wavelength emission, and the change of the wavelength ratio value is independent of the probe concentration and the light source intensity, so that the interference of other detection conditions can be greatly reduced. However, most of these probes are soluble in liquids, which limits their utility and portability.
Paper-based sensors, however, offer unique advantages over other detection methods, including low cost, simplicity, low sample and reagent consumption, good biocompatibility, and ease of use, as a very promising biosensing platform in recent years.
In the prior art, the patent "a near infrared fluorescent probe for identifying hydrogen sulfide and a preparation method and application thereof" (CN 109836394A) discloses a near infrared fluorescent probe with high selectivity and high sensitivity, but the preparation process of the probe is complicated and the preparation time is long. The patent 'a coumarin-based hydrogen sulfide fluorescent probe, a preparation method and application thereof' (CN 111763187A) provides a fluorescent detection probe with high sensitivity and simple synthesis method, but coumarin based on the probe has higher biotoxicity, and cannot monitor hydrogen sulfide gas in food in real time. Therefore, the combination of the fluorescent probe and the paper base has important significance in developing a simple, rapid, accurate, portable and easy-to-operate biosensor.
Disclosure of Invention
Aiming at the defects of the existing hydrogen sulfide fluorescent molecular probe, the invention provides the ratio type fluorescent probe with strong specificity, high sensitivity and low biotoxicity, on one hand, the Cu-S effect between hydrogen sulfide and the nano copper cluster is utilized to destroy the process of the transition of the original electron from the ligand on the surface of the copper cluster to the metal nucleus, thereby leading to fluorescence quenching. The ratio type fluorescent substance is combined with a paper base to obtain the hydrogen sulfide paper base sensor. On the other hand, the paper-based sensor can well adsorb hydrogen sulfide gas molecules due to the large specific surface area and the high porosity, so that the detection effect of the biosensor on the hydrogen sulfide gas is improved.
The invention synthesizes CuNCs/CNQDs with stable fluorescence emission and low biotoxicity through two steps, and obtains the ratio type fluorescent paper-based sensor with high selectivity and high sensitivity by utilizing paper-based load.
In order to achieve the above object, the present invention comprises the following specific steps:
(1) Preparing a Carbon Nitride Quantum Dot (CNQDs) solution; mixing sodium citrate, ammonium chloride and water, transferring to an autoclave, placing the autoclave in an oven for reaction, and naturally cooling to room temperature after the reaction to obtain a mixture; loading the obtained mixture into a dialysis membrane, and standing in a dialysis solution for a period of time for purification to remove unreacted precursor substances; centrifuging the purified mixture to remove insoluble large-particle solutes, and taking a supernatant as a purified CNQDs solution;
(2) Preparing CuNCs/CNQDs ratio type fluorescent substance; mixing penicillamine with the CNQDs solution obtained in the step (1) to obtain penicillamine mixed solution, mixing and stirring the obtained penicillamine mixed solution and copper nitrate trihydrate solution at a certain temperature to generate white precipitate, collecting a precipitate product, centrifugally washing the precipitate product with methanol for a plurality of times, and freeze-drying the centrifuged product to obtain a final product, namely CuNCs/CNQDs; (long-term preservation at-20 ℃ C.)
(3) Preparing a ratio type fluorescent paper-based sensor by using a filter paper loaded fluorescent probe; dissolving the CuNCs/CNQDs obtained in the step (2) in a methanol solution to obtain a CuCNs/CNQDs solution; and then dripping CuNCs/CNQDs solution on the filter paper, and drying and loading the solution on the filter paper by nitrogen blowing to obtain the ratio type fluorescent paper-based sensor.
Preferably, the dosage ratio of sodium citrate, ammonium chloride and water in step (1) is 10g:53g:500ml.
Preferably, the temperature at which the reaction in the oven in step (1) is carried out is 180℃for 4 hours.
Preferably, the molecular weight of the dialysis membrane in the step (1) is 1000Da, and the dialysate is ultrapure water, distilled water or deionized water; the standing time is 24 hours; the centrifugation conditions are 8000rpm, 5-10min.
Preferably, in the step (2), the concentration of the CNQDs solution is 0.25-1mg/ml; the concentration of the penicillamine in the penicillamine mixed solution is 10mM; the volume ratio of the penicillamine mixed solution to the copper nitrate trihydrate solution is 100:1, and the concentration of the copper nitrate trihydrate solution is 100mM.
Preferably, in the step (2), the certain temperature condition is 20-25 ℃; the mixing and stirring time is 25-30 min.
Preferably, the concentration of the CNQDs solution in the step (3) is 30-50 mg/ml.
Preferably, the amount of the CuNCs/CNQDs solution dropwise added to the filter paper in the step (3) is as follows: every 1cm 2 For the filter paper of (C), 50. Mu.l of CuNCs/CNQDs solution was used.
Preferably, the nitrogen blowing time in the step (3) is 5-10min.
The ratio type fluorescent paper-based sensor prepared by the invention is used for detecting hydrogen sulfide gas.
The beneficial effects are that:
(1) The copper nanocluster is used as a novel fluorescent material and has special size and stable light stability. Unlike general organic fluorescent probes, metal clusters have lower biotoxicity. The detection limit of the CuNCs/CNQDs fluorescent probe on the sulfide ion is 65.7nM, and the CuNCs/CNQDs fluorescent probe does not react with substances such as sodium nitrite, copper ions, bromide ions, glutathione and the like; therefore, the novel probe with high selectivity and sensitivity is obtained, and has good research prospect in real-time detection and cell sensing of food harmful substances.
(2) Unlike the cumbersome synthetic steps of a general organic fluorescent probe, the fluorescent complex is obtained by a two-step synthesis method, and the synthesis time is short. Meanwhile, the paper-based sensor is different from the limitation of the liquid probe, and is suitable for detecting hydrogen sulfide gas in gas phase. The paper-based sensor of the invention still maintains good light stability at 70 ℃ for 2 hours.
(3) The ratio type fluorescent probe prepared by the invention has the advantages of low toxicity, high selectivity and low cost, is convenient to carry, and has wide application prospect in detecting hydrogen sulfide gas in food.
Drawings
In FIG. 1, a and b are emission spectra of CNQDs and CuNCs/CNQDs, respectively, and an illustration is a fluorescence picture of CNQDs and CuNCs/CNQDs;
FIG. 2 is a graph showing fluorescence of CuNCs/CNQDs with different concentrations of sodium sulfide solution added;
FIG. 3 shows the fluorescence intensity ratio (I 645 /I 440 ) A standard curve is established;
FIG. 4 is a graph showing fluorescence ratios of CuNCs/CNQDs solutions reacted with different solutions;
FIG. 5 is a fluorescence photograph of a ratiometric fluorescent paper-based sensor placed at 70℃for 2 h;
FIG. 6 is a graph of a ratio fluorescent paper-based sensor (R-R 0 ) And (3) establishing a standard curve of the value/B and the concentration of hydrogen sulfide.
Detailed Description
Example 1:
(1) Synthesis of CNQDs;
mixing sodium citrate with a mass of 0.1g, ammonium chloride with a mass of 0.53g and water with 5ml and transferring the mixture to a Teflon stainless steel autoclave, placing the autoclave in an oven at 180 ℃ for 4 hours, naturally cooling the autoclave to room temperature, purifying the mixture in ultra pure water with a dialysis membrane having a molecular weight of 1000Da for 24 hours to remove unreacted precursors; centrifuging the purified mixture at 8000rpm for 5 minutes to remove insoluble large-particle solutes, and taking supernatant to obtain purified CNQDs solution; stored in an environment at 4 ℃.
(2) Preparing CuNCs/CNQDs ratio type fluorescent substance;
penicillamine and the CNQDs solution obtained in the step (1) (concentration is 0.25 mg/ml) are mixed to obtain penicillamine mixed solution (concentration of penicillamine in mixed solution is 10 mM), the obtained penicillamine mixed solution and copper nitrate trihydrate solution (concentration is 100 mM) are mixed according to a volume ratio of 100:1 to obtain a mixture, the mixture is stirred at 25 ℃ for 25 minutes, white precipitate is generated, the precipitate is collected by centrifugation at 8000rpm for 10 minutes, the precipitate is washed with methanol for 3 times, and then the mixture is frozen and dried in vacuum and stored at-20 ℃ for a long time.
(3) Preparing a ratio type fluorescent paper-based sensor by using a filter paper loaded fluorescent probe;
dissolving dried CuNCs/CNQDs in methanol solution to obtain 50mg/ml CuNCs/CNQDs solution, and dripping 50 μl of CuNCs/CNQDs solution at 1cm 2 And (3) blowing nitrogen on the filter paper for 5min to dry and load the filter paper, thus obtaining the ratio-type fluorescence sensor.
And (3) performance detection:
1. firstly, detecting sodium sulfide by using the CuNCs/CNQDs ratio fluorescent material prepared in the example 1;
the sodium sulfide aqueous solution is a strongly alkaline solution, hydrogen sulfide gas with the odor of foul eggs is released when the sodium sulfide aqueous solution is exposed to air and reacts with strong acid, and the feasibility of detecting the hydrogen sulfide gas by taking CuNCs/CNQDs fluorescent materials as the basis of the ratio type fluorescent paper-based sensor is verified by the reaction of CuNCs/CNQDs and sulfur ions in the sodium sulfide aqueous solution, and the specific operation is as follows:
(1) An aqueous solution of CuNCs/CNQDs was prepared at 50mg/ml.
(2) Preparation of sodium sulfide aqueous solution: in view of the instability of aqueous sodium sulfide solutions, sodium sulfide was dissolved in PBS buffer at pH 10.5 and a series of different concentrations of aqueous sodium sulfide solutions (specifically 20, 30, 40, 50, 60, 70. Mu.M) were prepared prior to each test.
(3) The fluorescence change curve was observed at a maximum excitation wavelength of 365nm by adding 50. Mu.l of an aqueous sodium sulfide solution to 1ml of an aqueous solution of 50mg/ml CuNCs/CNQDs, and it was found from the fluorescence spectrum that the emission peak at 645nm was continuously decreased with an increase in the concentration of the aqueous sodium sulfide solution, while the emission peak at 440nm was almost unchanged with an increase in the concentration of the aqueous sodium sulfide solution.
The fluorescence intensities at 645nm and 440nm after adding the ratio CuNCs/CNQDs fluorescent material with different concentrations of sodium sulfide were recorded, and the ratio (I 645 /I 440 ) The relation between them establishes a standard curve (figure 3) for detecting sodium sulfide, the equation of the standard curve is y= -0.3906x+1.2661 (R 2 = 0.9923). The result shows that the standard curve has a good linear relation, thereby achieving the purpose of detecting the sodium sulfide aqueous solution.
(4) To further verify that the prepared CuNCs/CNQDs fluorescent material had higher selectivity for hydrogen sulfide, 1ml of a 50mg/ml CuNCs/CNQDs solution was mixed with 50. Mu.l of 100. Mu.M cysteine (Cys), and its fluorescence change curve was observed at a maximum excitation wavelength of 365 nm.
Similarly, cu (NO 3 ) 2 EDTA-2Na, glutathione (GSH), na 2 CO 3 、NaAC、NaCl、NaBr、NaF、NaNO 2 、(NH 4 ) 2 SO 4 、NaH 2 PO 4 And a buffer solution (blank) having a pH of 10.5 was mixed with CuNCs/CNQDs under the same conditions, and the fluorescence change profile thereof was observed. As shown in FIG. 4, the ratio of fluorescence intensity of the ratio-type fluorescent substance to that of sodium sulfide and other ions is shown, and the ratio of fluorescence is not interfered by substances such as sodium nitrite, copper ions, glutathione, bromide ions, ammonium sulfate and the like, so that the fluorescent composite material has better selectivity.
2. The CuNCs/CNQDs paper-based sensor prepared in example 1 was used in a hydrogen sulfide gas detection method;
(1) The hydrogen sulfide gas concentration was detected using the paper-based sensor produced in example 1, and the paper-based sensor concentration was calculated by the following formula
c (CuNCs/CNQDs) is the concentration of the fluorescent composite material;
v (CuNCs/CNQDs) is the volume of the fluorescent composite;
a (paper) is the area of the filter paper;
(2) Fixing the dried CuNCs/CNQDs paper-based sensor on a self-made gas generator upper cover, adding sodium sulfide water solutions with different concentrations (0, 10, 20, 30, 50 and 70 mu M) into the hole, adding 200 mu l of dilute sulfuric acid solution through a micro-injector, heating the obtained sample cell to 70 ℃, and calculating the concentration of hydrogen sulfide in the gas phase by the following formula
R-molar gas constant; t-reaction ambient temperature; n (H) 2 S, g) -molar amount of hydrogen sulfide in the gas phase; v (H) 2 S, g) -container volume; k (K) B -henry constant; n (Na) 2 S) -molar sodium sulfide; v (H) 2 O) -total volume of solution; ρ (H) 2 O) -density of water; m (H) 2 O) -the relative molecular mass of water;
KB＝0.551Pa，
(H2S in water,343.15K),R＝8.314J/(mol·K)，T＝343.15K，
V(H2O)＝V(H2SO4)+V(Na2S)，
V(H2S,g)＝0.3927L，
M(H2O)＝18g/mol，M(H2S)＝34g/mol。
(3) After 24 hours, the fluorescence color of the paper base under the 365nm ultraviolet lamp is recorded by the smart phone, the paper base is replaced once for each recording of the paper base fluorescence image change under one concentration to observe the next concentration (namely, one CuNCs/CNQDs paper base sensor corresponds to one concentration), and the process is repeated three times under each concentration. The ratio of the R value to the B value is calculated by extracting the RGB value of the image to quantitatively analyze the hydrogen sulfide gas. According to (R-R 0 ) B (R-value of paper-based picture collected after reaction, R 0 -paper-based picture R value collected before reaction) and H 2 The relationship of S establishes a standard curve (fig. 6) with the standard curve equation y =2.7032x+0.0289(R 2 = 0.9981), the limit of detection was 4.52ppt. As shown by the results, the standard curve has good linear relation, low detection limit and good detection of H 2 S effect.
Further, according to theory (R-R 0 ) B and actual (R-R) 0 ) Comparison of the values of/B establishes Table 1, and it can be seen from Table 1 that RSD is below 5%, so that the ratio-type fluorescent paper-based sensor has good detection accuracy and good application in hydrogen sulfide detection.
TABLE 1
Description: the above embodiments are only for illustrating the present invention and not for limiting the technical solution described in the present invention; thus, although the present invention has been described in detail with reference to the above embodiments, it will be understood by those skilled in the art that the present invention may be modified or equivalent; all technical solutions and modifications thereof that do not depart from the spirit and scope of the present invention are intended to be covered by the claims of the present invention.
Claims (4)
1. The use of a ratio-type fluorescent paper-based sensor for hydrogen sulfide gas detection is characterized in that the ratio-type fluorescent paper-based sensor is prepared by the following steps:
(1) Mixing sodium citrate, ammonium chloride and water, transferring the mixture into an autoclave, wherein the dosage ratio of the sodium citrate to the ammonium chloride to the water is 10g to 53g to 500mL, and then placing the autoclave into an oven for reaction at 180 ℃ for 4 hours; naturally cooling to room temperature after the reaction to obtain a mixture; loading the obtained mixture into a dialysis membrane, and standing in a dialysis solution for a period of time for purification to remove unreacted precursor substances; centrifuging the purified mixture to remove insoluble large-particle solutes, and taking supernatant as purified CNQDs solution, wherein the concentration of the CNQDs solution is 30-50 mg/mL;
(2) Mixing penicillamine with the CNQDs solution obtained in the step (1) to obtain penicillamine mixed solution, mixing and stirring the obtained penicillamine mixed solution and copper nitrate trihydrate solution at 20-25 ℃ to generate white precipitate, collecting the precipitate, centrifugally washing the precipitate with methanol for a plurality of times, and freeze-drying the centrifuged product to obtain a final product, namely CuNCs/CNQDs; the concentration of the CNQDs solution is 0.25-1mg/mL; the concentration of the penicillamine in the penicillamine mixed solution is 10mM; the volume ratio of the penicillamine mixed solution to the copper nitrate trihydrate solution is 100:1, and the concentration of the copper nitrate trihydrate solution is 100mM;
(3) Dissolving the CuNCs/CNQDs obtained in the step (2) in a methanol solution to obtain a CuCNs/CNQDs solution; then dripping CuNCs/CNQDs solution onto filter paper every 1cm 2 The filter paper of (2) was dried and supported on the filter paper by nitrogen blowing using 50. Mu.l of CuNCs/CNQDs solution to obtain a ratio-type fluorescent paper-based sensor.
2. The use according to claim 1, wherein the dialysis membrane in step (1) has a molecular weight of 1000Da and the dialysis fluid is ultrapure water, distilled water or deionized water; the standing time is 24 hours; the centrifugation conditions are 8000rpm, 5-10min.
3. The use according to claim 1, wherein in step (2), the mixing and stirring time is 25 to 30 minutes.
4. The use according to claim 1, wherein the nitrogen blowing time in step (3) is 5-10min.
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