CN111272717A - One-step hydrothermal synthesis based on novel ionic liquid fluorescent carbon dots and application of one-step hydrothermal synthesis to detection of sulfathiazole - Google Patents

One-step hydrothermal synthesis based on novel ionic liquid fluorescent carbon dots and application of one-step hydrothermal synthesis to detection of sulfathiazole Download PDF

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CN111272717A
CN111272717A CN202010083740.1A CN202010083740A CN111272717A CN 111272717 A CN111272717 A CN 111272717A CN 202010083740 A CN202010083740 A CN 202010083740A CN 111272717 A CN111272717 A CN 111272717A
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fluorescent carbon
sulfathiazole
carbon dots
ionic liquid
hydrothermal synthesis
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CN111272717B (en
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朱桂芬
陈乐田
刘永丽
樊泽罡
何帅龙
苑靳钰
樊静
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Henan Normal University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6402Atomic fluorescence; Laser induced fluorescence
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • CCHEMISTRY; METALLURGY
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    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/65Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432Quenching

Abstract

The invention discloses one-step hydrothermal synthesis based on novel ionic liquid fluorescent carbon dots and detection application of the novel ionic liquid fluorescent carbon dots to sulfathiazole. The novel sulfathiazole fluorescent probe synthesized by the invention has the advantages of simple preparation process, low cost and high selectivity, has high sensitivity and accuracy for detecting trace amount of sulfathiazole remained in an environmental sample, and has wide application prospect in the field of analysis and detection of sulfathiazole.

Description

One-step hydrothermal synthesis based on novel ionic liquid fluorescent carbon dots and application of one-step hydrothermal synthesis to detection of sulfathiazole
Technical Field
The invention belongs to the technical field of synthesis of fluorescent carbon dot nano materials and detection and identification of sulfonamides antibiotics, and particularly relates to one-step hydrothermal synthesis based on novel ionic liquid fluorescent carbon dots and detection application of the one-step hydrothermal synthesis to sulfathiazole.
Background
The sulfathiazole is a sulfanilamide antibiotic with a sulfanilamide structure, is widely applied to livestock and poultry production, and is mainly used for preventing and treating infection of pathogenic bacteria such as meningococcus, hemolytic streptococcus, pneumococcus and the like. Because the sulfathiazole is difficult to metabolize in organisms and can enter the environment through biological excretion and other modes, the sulfathiazole is detected in surface water, soil and other environment media. Researches show that the sulfathiazole can harm the immune system of a human body, influence the hematopoietic function and have potential carcinogenicity, so that the development of a simple and efficient method capable of quickly detecting the trace amount of the sulfathiazole remained in the environment is very important.
At present, the commonly used detection methods such as immunoassay, liquid chromatography, capillary electrophoresis, liquid chromatography-mass spectrometry and the like have the defects of complex operation, high detection cost, long detection time consumption, poor sensitivity and specific identification and the like, and are difficult to directly carry out on-site real-time rapid detection on the sulfathiazole remained in the environment. The fluorescent carbon dots serving as a novel fluorescent carbon nano material have high stability, good biocompatibility and environmental friendliness, can be used as a high-performance nano fluorescent probe, quickly realize high-sensitivity detection and analysis on a target object, and can accurately detect the residual sulfathiazole in the environment.
However, some of the existing nano fluorescent probes have the problems of complex synthesis process, high synthesis cost, low selectivity and sensitivity, and the like, and how to realize the preparation of the high-performance fluorescent probe by a simple synthesis method has become a hot point of research.
Disclosure of Invention
The invention solves the technical problem of providing a method for preparing nano fluorescent carbon dots by a one-step hydrothermal method by taking ionic liquid as a carbon source, which is simple in synthesis and low in cost, wherein the optimal excitation/emission wavelengths of the prepared fluorescent carbon dots are 284nm and 385 nm respectively, the stability is good, the detection rate is high, the sensitivity is high, and the performance of high-selectivity identification on sulfathiazole is realized.
The invention adopts the following technical scheme for solving the technical problems, and is based on one-step hydrothermal synthesis of novel ionic liquid fluorescent carbon dots and detection application of the fluorescent carbon dots to sulfathiazole, and the method is characterized by comprising the following specific processes: the novel fluorescent carbon dots are synthesized by one-step hydrothermal reaction at 140-220 ℃ by taking 1-allyl-3-vinylimidazole tetrafluoroborate as a carbon source, malonic acid as a passivating agent and water as a solvent, have the effect of specifically identifying the sulfathiazole as a fluorescent probe, and can be used for identifying the trace sulfathiazole in an environmental sample with high sensitivity.
The invention relates to one-step hydrothermal synthesis based on novel ionic liquid fluorescent carbon dots and detection application of the novel ionic liquid fluorescent carbon dots to sulphathiazole, which are characterized by comprising the following specific steps of: respectively adding 1-allyl-3-vinyl imidazole tetrafluoroborate, malonic acid and water into a high-temperature reaction kettle, reacting at 140-220 ℃ for 3-12 h, separating and purifying the obtained product by a 0.22 mu m filter membrane, and collecting supernatant to be stored in a brown bottle at low temperature of 4 ℃.
Further preferably, the feeding molar ratio of the 1-allyl-3-vinyl imidazole tetrafluoroborate to the malonic acid is 0.2-1.8: 0.5-3.
The invention relates to one-step hydrothermal synthesis based on novel ionic liquid fluorescent carbon dots and detection application of the novel ionic liquid fluorescent carbon dots to sulphathiazole, which are characterized by comprising the following specific steps of: respectively adding 1.6650 g of 1-allyl-3-vinylimidazole tetrafluoroborate, 0.7805 g of malonic acid and 10 mL of pure water into a high-temperature reaction kettle, carrying out hydrothermal reaction for 12 h at 220 ℃, separating and purifying the obtained product by a 0.22 mu m filter membrane, diluting the product by 50 times to obtain fluorescent carbon dots for later use, placing 80 mu L of fluorescent carbon dots and sulfanilamide thiazole aqueous solution with different concentration gradients in a centrifuge tube, diluting the fluorescent carbon dots and the sulfanilamide thiazole aqueous solution to 2 mL, mixing and reacting for 2min at room temperature, placing the mixed solution in a fluorescence spectrophotometer, measuring the fluorescence intensity of the mixed solution under the condition of an excitation wavelength of 284nm, calculating the corresponding fluorescence intensity, and then calculating the correspondingQuenching effect, and obtaining the linear range of 0.008-10 mg L-1And 10-45 mg L-1Detection limit of 5 μ g L-1
Compared with the prior art, the invention has the following advantages:
1. the invention firstly provides one-step hydrothermal synthesis based on novel ionic liquid fluorescent carbon dots and detection application thereof to sulfathiazole, and the preparation process is simple, the cost is low and the operation is convenient;
2. the prepared fluorescent carbon dots have good stability, high detection rate and high sensitivity, and have high selective identification performance on sulfathiazole;
3. the method adopts 1-allyl-3-vinyl imidazole tetrafluoroborate as a carbon source to prepare the fluorescent carbon dots, and can be used for detecting and analyzing trace sulfathiazole in an actual environment sample.
Drawings
FIG. 1 is a graph of fluorescence intensity of fluorescent carbon dots prepared in example 1 at different pH;
FIG. 2 is a graph showing the fluorescence quenching effect of the carbon fluorescent dots prepared in example 1 on sulfathiazole at different pH values;
FIG. 3 is a linear curve of the fluorescence response of the fluorescent carbon dots prepared in example 1 to sulfathiazole at room temperature;
FIG. 4 is a selective recognition test chart of the fluorescent carbon dots prepared in example 1 for sulfathiazole in sulfanilamide antibiotics.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
1.11 g of 1-allyl-3-vinyl imidazole tetrafluoroborate, 0.2602 g of malonic acid and 10 mL of pure water are respectively added into a high-temperature reaction kettle, the mixture undergoes a hydrothermal reaction at 220 ℃ for 12 hours, and the obtained product is separated and purified by a 0.22 mu m filter membrane and then diluted by 50 times for later use.
Example 2
1.11 g of 1-allyl-3-vinyl imidazole tetrafluoroborate, 0.5215 g of malonic acid and 10 mL of pure water are respectively added into a high-temperature reaction kettle, the hydrothermal reaction is carried out for 12 hours at the high temperature of 180 ℃, and the obtained product is separated and purified by a filter membrane of 0.22 mu m and then diluted by 50 times for standby.
Example 3
1.6650 g of 1-allyl-3-vinylimidazole tetrafluoroborate, 0.7805 g of malonic acid and 10 mL of pure water are respectively added into a high-temperature reaction kettle, the hydrothermal reaction is carried out for 3 hours at the high temperature of 220 ℃, and the obtained product is separated and purified by a 0.22 mu m filter membrane and then diluted by 50 times for later use.
Example 4
1.11 g of 1-allyl-3-vinyl imidazole tetrafluoroborate, 1.0406 g of malonic acid and 20 mL of pure water are respectively added into a high-temperature reaction kettle, the hydrothermal reaction is carried out for 12 hours at the high temperature of 220 ℃, and the obtained product is separated and purified by a filter membrane of 0.22 mu m and then diluted by 50 times for standby.
Example 5
1.11 g of 1-allyl-3-vinyl imidazole tetrafluoroborate, 0.5215 g of malonic acid and 10 mL of pure water are respectively added into a high-temperature reaction kettle, the hydrothermal reaction is carried out for 12 hours at the high temperature of 220 ℃, and the obtained product is separated and purified by a filter membrane of 0.22 mu m and then diluted by 50 times for standby.
Example 6
0.2220 g of 1-allyl-3-vinylimidazole tetrafluoroborate, 0.7805 g of malonic acid and 10 mL of pure water are respectively added into a high-temperature reaction kettle, the hydrothermal reaction is carried out for 12 hours at the high temperature of 220 ℃, and the obtained product is separated and purified by a 0.22 mu m filter membrane and then diluted by 50 times for later use.
Example 7
1.6650 g of 1-allyl-3-vinylimidazole tetrafluoroborate, 0.7805 g of malonic acid and 10 mL of pure water are respectively added into a high-temperature reaction kettle, the hydrothermal reaction is carried out for 12 hours at the high temperature of 220 ℃, and the obtained product is separated and purified by a 0.22 mu m filter membrane and then diluted by 50 times for later use.
Example 8
1.11 g of 1-allyl-3-vinyl imidazole tetrafluoroborate, 0.5215 g of malonic acid and 10 mL of pure water are respectively added into a high-temperature reaction kettle, the hydrothermal reaction is carried out for 12 hours at the high temperature of 140 ℃, and the obtained product is separated and purified by a 0.22 mu m filter membrane and then diluted by 50 times for standby.
Example 9
1.6650 g of 1-allyl-3-vinylimidazole tetrafluoroborate, 0.7805 g of malonic acid and 10 mL of pure water are respectively added into a high-temperature reaction kettle, the hydrothermal reaction is carried out for 6 hours at the high temperature of 220 ℃, and the obtained product is separated and purified by a 0.22 mu m filter membrane and then diluted by 50 times for later use.
Example 10
80 μ L of each of the fluorescent carbon dot materials prepared in examples 1 to 9 was added to 60 μ L of 100 mg L molar concentration-1Mixing the sulfathiazole aqueous solution at room temperature, reacting for 2min, 5min, 10 min, 20 min, and 30min, measuring fluorescence intensity with fluorescence spectrophotometer, and calculating fluorescence quenching rate (F)0-F)/F (wherein F0Carbon spot initial fluorescence intensity, F carbon spot fluorescence intensity after adding sulfathiazole). Fluorescence quenching rate of nanocarbon points to sulfathiazole prepared in examples 1 to 9 (F)0-F)/F are each: 0.420, 0.384, 0.393, 0.406, 0.409, 0.410, 0.460, 0.358 and 0.398, and the analysis result shows that the fluorescent carbon dots prepared in example 7 have high sensitivity and accuracy on the identification and detection of the sulfathiazole.
Example 11
80 μ L of the fluorescent carbon dot material prepared in example 7 was added to an aqueous solution having a pH of 1 to 14, mixed and reacted at room temperature for 2min, and measured by a fluorescence spectrophotometer. As shown in FIG. 1, the fluorescence intensity of the carbon spot remained substantially constant between pH 3 and pH 11, indicating that the carbon spot has a certain acid-base resistance.
Example 12
80 mu L of the fluorescent carbon dot material prepared in the example 1 is taken and then respectively added into the sulfathiazole aqueous solution with the pH value of 3-11, and the mixture is fully mixed and reacted for 2min at room temperature and is measured by a fluorescence spectrophotometer. As shown in FIG. 2, the quenching rate of the carbon dot on the sulfathiazole fluorescence remains unchanged between pH 3 and pH 11, and the carbon dot has better stability.
Example 13
80 μ L of the fluorescent carbon dot material prepared in example 1 was taken and added to 0.008 mg L of the fluorescent carbon dot material-1、0.01 mg L-1、0.05 mg L-1、0.1 mg L-1、0.5 mg L-1、1 mg L-1、3 mg L-1、5 mg L-1、10 mg L-1、12.5 mg L-1、15 mg L-1、20 mg L-1、25 mg L-1、30 mg L-1、35 mg L-1、40 mg L-1、45 mg L-1The sulfathiazole aqueous solution is fully mixed and reacted for 2min at room temperature, and the reaction is measured by a fluorescence spectrophotometer. As a result, as shown in FIG. 3, the quenching rate (F) of the carbon spot fluorescence0the-F)/F becomes larger with the increase of the concentration of the sulfathiazole.
Example 14
80 μ L of the fluorescent carbon dot material prepared in example 1 was taken, and then added to the fluorescent carbon dot material at a concentration of 0.01 mg L-1Sulphathiazole, 0.03 mg L-1Sulfadiazine, 0.05 mg L-1Sulfapyridine, 0.03 mg L-1Sulfadimidine, 0.03 mg L-1Sulfamonomethoxine, 0.05 mg L-1Sulfamethoxazole and 0.05 mg L-1Mixing the aqueous solution of metronidazole at room temperature for 2min, measuring fluorescence intensity with fluorescence spectrophotometer, and calculating fluorescence quenching rate (F)0-F)/F. The result shows that the fluorescence quenching rate of the nano carbon dot material to the sulfathiazole is 0.027, but the nano carbon dot material has no obvious quenching effect to other structural analogues, and the result is shown in fig. 4, which shows that the prepared fluorescent carbon dot material has strong specific recognition capability.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.

Claims (4)

1. One-step hydrothermal synthesis based on novel ionic liquid fluorescent carbon dots and detection application of the ionic liquid fluorescent carbon dots to sulfathiazole are characterized by comprising the following specific steps: the novel fluorescent carbon dots are synthesized by one-step hydrothermal reaction at 140-220 ℃ by taking 1-allyl-3-vinylimidazole tetrafluoroborate as a carbon source, malonic acid as a passivating agent and water as a solvent, have the specific identification effect on the sulfathiazole by taking the novel fluorescent carbon dots as a fluorescent probe, and can be used for identifying the trace sulfathiazole in an environmental sample with high sensitivity.
2. The one-step hydrothermal synthesis and detection application of sulfanilamide thiazole based on the novel ionic liquid fluorescent carbon dot as claimed in claim 1, which is characterized by comprising the following specific steps: respectively adding 1-allyl-3-vinyl imidazole tetrafluoroborate, malonic acid and water into a high-temperature reaction kettle, reacting at 140-220 ℃ for 3-12 h, separating and purifying the obtained product by a 0.22 mu m filter membrane, and collecting supernatant to be stored in a brown bottle at low temperature of 4 ℃.
3. The one-step hydrothermal synthesis and detection application of sulfanilamide thiazole based on the ionic liquid novel fluorescent carbon dot as claimed in claim 1 or 2, characterized in that: the feeding molar ratio of the 1-allyl-3-vinyl imidazole tetrafluoroborate to the malonic acid is 0.2-1.8: 0.5-3.
4. The one-step hydrothermal synthesis and detection application of sulfanilamide thiazole based on the novel ionic liquid fluorescent carbon dot as claimed in claim 1 or 2, which is characterized by comprising the following specific steps: respectively adding 1.6650 g of 1-allyl-3-vinyl imidazole tetrafluoroborate, 0.7805 g of malonic acid and 10 mL of pure water into a high-temperature reaction kettle, carrying out a high-temperature hydrothermal reaction for 12 h at 220 ℃, separating and purifying the obtained product by a 0.22 mu m filter membrane, diluting the product by 50 times to obtain fluorescent carbon dots for later use, placing 80 mu L of the fluorescent carbon dots and sulfanilamide thiazole aqueous solution with different concentration gradients in a centrifuge tube, diluting the fluorescent carbon dots and the sulfanilamide thiazole aqueous solution to 2 mL, mixing and reacting for 2min at room temperature, placing the mixed solution in a fluorescence spectrophotometer, measuring the fluorescence intensity of the mixed solution under the condition of an excitation wavelength of 284nm, calculating the corresponding fluorescence quenching effect, and obtaining the linear range of the fluorescence quenching effect which is 0.008-1And 10-45 mg L-1Detection limit of 5 μ g L-1
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CN116515481A (en) * 2023-05-06 2023-08-01 河南工学院 Ratio fluorescent probe based on carbon point, construction and application of ratio fluorescent probe to detection of quercetin
CN116515481B (en) * 2023-05-06 2024-04-09 河南工学院 Ratio fluorescent probe based on carbon point, construction and application of ratio fluorescent probe to detection of quercetin

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