CN112945925B - Method for detecting permanganate acid radicals by coumarin-based probe - Google Patents
Method for detecting permanganate acid radicals by coumarin-based probe Download PDFInfo
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Abstract
The invention provides a method for detecting permanganate acid radicals by using a coumarin-based probe, wherein the coumarin-based probe is 2-oxo-2H-benzopyran-7-R basic acid ester and is obtained by condensing 7-hydroxy benzopyran-2-ketone and acyl chloride, and a response group of the coumarin-based probe to the permanganate acid radicals is a double bond. The single probe has no fluorescence in the mixed solution of the organic solvent and the water, shows obvious fluorescent lighting response when being used for detecting the high manganese acid radicals, has response time less than 3s, and can realize the real-time detection of the high manganese acid radicals; the detection sensitivity is high, and the detection limit is as low as 0.95 nmol/L; has higher selectivity to permanganate, and can accurately determine the content of the permanganate in a water sample and a nonstandard explosive raw material in the environment by utilizing a standard curve. The method has excellent selectivity and sensitivity, can be used for rapidly detecting the permanganate acid radicals on site, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of environmental and non-standard explosive detection, and provides a method for detecting permanganate acid radicals by using a coumarin-based probe. The probe has low detection limit, strong anti-interference performance and short reaction time, and can realize the purpose of detecting the high manganese acid radical by fluorescence in real time at low cost.
Background
Owing to the strong oxidizing property of permanganate radical, it is widely used as oxidant in chemical production, antiseptic, disinfectant, deodorant and antidote in medicine, water treating agent in water purification and waste water treatment, bleaching agent for special fabric, wax, oil and resin, adsorbent for gas mask, coloring agent for wood and copper, etc. Research shows that the KMnO has high concentration4The release into the water body can cause water body pollution, and the ingestion of the permanganate can cause blood coagulation necrosis and damage, thereby causing local or systemic toxicity in the body. Excessive intake of permanganate acid causes hypoxia and upper respiratory obstruction, and severe causes acute hepatotoxicity and coagulopathy, resulting in irreversible functional organ necrosis. In the book of easy-to-explode chemicals published by the ministry of public security in 2017, permanganate acid radicals and sodium permanganate are ninth (other) type oxidizing solids, and belong to controlled articles. Therefore, the detection of the permanganate in the water sample and the nonstandard explosive raw material in the environment is high in sensitivity, rapidness and specificity, and is very important.
At present, scientists at home and abroad mainly take biological health and environmental sanitation into consideration and adopt a plurality of methods to detect permanganate in organisms, drinking water and environmental water. Common permanganate detection means mainly comprise a spectrophotometric method, a chemiluminescence analysis method, an electrochemical method, an atomic absorption spectrometry method and the like. However, these analysis methods require expensive instruments and specialized operators, and are difficult to realize rapid field visual identification. Therefore, the development of a rapid, inexpensive, accurate, and real-time permanganate detection means has become a major research point.
Compared with the existing detection method, the fluorescence detection method is widely applied due to the advantages of high sensitivity, high selectivity, simple operation, real-time analysis and the like, the molecular structure of the probe is mainly characterized in that an active site capable of specifically reacting with permanganate is connected to a fluorophore, such as electron-deficient olefin, ester group and the like, and commonly used fluorophores include rhodamine, fluorescein, boron-dipyrromethene (BODIPY), cyanine dye, naphthone, coumarin, iridium (III) complex, naphthalimide, benzothiazole derivatives, benzoxazole and the like. However, most fluorescent probes still have the defects of poor detection limit, low quantum yield, low molar absorption coefficient, delayed oxidation reaction time, poor anti-interference performance and the like.
According to the invention, a probe which takes coumarin as a fluorophore and takes acrylate or methacrylate as a permanganate reaction site is designed and prepared from the structural analysis of a probe molecule per se, so that the on-site, rapid, specific, trace and visual fluorescence lighting detection of permanganate is realized.
Disclosure of Invention
The invention aims to provide a method for detecting permanganate radicals by using a coumarin-based probe, aiming at the defects in the prior art, wherein the response group of the coumarin-based probe to the permanganate radicals is a carbon-carbon double bond. The single probe has no fluorescence in the mixed solution of the organic solvent and the water, and shows obvious fluorescent lighting response when being used for detecting the high manganese acid radicals, the response time is less than 3s, and the real-time detection of the high manganese acid radicals can be realized; the detection sensitivity is high, and the detection limit is as low as 0.95 nmol/L; the catalyst has higher selectivity to permanganate, and other common oxidizing substances do not interfere; by utilizing the standard curve, the content of permanganate in a water sample and a non-standard explosive raw material in the environment can be accurately measured.
The invention relates to a method for detecting permanganate acid radicals by using a coumarin-based probe, which comprises the following steps: 2-oxo-2 hydro-benzopyran-7-R acid ester obtained by condensing 7-hydroxy benzopyran-2-one with acyl chloride, and having the chemical structural formula (I):
wherein: r is propylene or methyl propylene.
The invention relates to a method for detecting permanganate acid radicals by using a coumarin-based probe, which comprises the following steps:
a. respectively dissolving 7-hydroxy benzopyran-2-one and an acid-binding agent triethylamine or pyridine into an organic solvent tetrahydrofuran or chloroform according to a molar ratio of 1:1-5, controlling the reaction temperature to be 0 ℃ under the protection of nitrogen atmosphere, slowly adding acyl chloride into the mixture to be acryloyl chloride or methacryloyl chloride, carrying out ice bath for 2 hours, and then carrying out reaction for 1-24 hours at room temperature; the mol ratio of the acyl chloride to the 7-hydroxy benzopyran-2-ketone is 1-5: 1;
b. after the reaction is finished, washing the product with deionized water to be neutral, then extracting the product with dichloromethane, washing the product with sodium chloride, drying the product with anhydrous magnesium sulfate, carrying out suction filtration and spin drying to obtain a crude product;
c. and d, separating and purifying the crude product obtained in the step b by using a forward silica gel chromatographic column to obtain a white solid probe.
The invention relates to a method for detecting permanganate acid radicals by using a coumarin-based probe, which has the detection principle that: the probe molecules do not have fluorescence, and in a neutral environment, an oxidation reaction is generated between the permanganate acid radicals and the acryloyl groups, and the double bonds of the acryloyl groups are oxidized into two hydroxyl groups. In addition, permanganate radicals generate a large number of hydroxyl radicals in aqueous solution, which attack carbonyl groups of ester bonds, resulting in the cleavage of the ester bonds, releasing 7-hydroxychroman-2-one with intense blue fluorescence; the change of the fluorescence intensity after the reaction and the concentration of the permanganate form a linear relation, so that the quantitative detection of the permanganate radical can be realized according to the change of the fluorescence intensity.
The method for detecting the permanganate acid radicals by using the coumarin-based probe has the advantages that the probe in the method can be used for quickly and specifically detecting the permanganate acid radicals in the environment and the explosion case site; the specific method comprises the following steps: the probe molecules are dissolved in acetonitrile or dimethyl sulfoxide (DMSO) organic solvent, or dissolved in 10mL of mixed solvent with the volume ratio of water to organic solvent being 1:1, to prepare a probe solution.
For the purpose of permanganate radical detection, according to an embodiment of the present invention, the probe molecule of the present invention detects permanganate radicals by the following steps:
(1) dissolving the probe molecule 2-oxo-2H-benzopyran-7 radical R acid ester in a mixed system of acetonitrile or DMSO and water, wherein the mixed solution is uniform and colorless and has no fluorescence;
(2) uniformly dripping the probe molecule solution obtained in the step (1) on slow qualitative filter paper or adding the probe molecule solution into a fluorescent cuvette to obtain detection test paper and a reagent for detecting the permanganate acid radicals;
(3) preparing a permanganate radical standard solution, reacting the permanganate radical standard solution with the probe of the detection test paper or the reagent obtained in the step (2), and measuring fluorescence intensity, wherein the fluorescence intensity corresponds to the content of permanganate radicals and is used for making a calibration curve for quantitative analysis;
(4) fully contacting and reacting a sample to be detected with the detection test paper obtained in the step (2), and then taking a fluorescence picture;
(5) calculating to obtain the content of permanganate in the sample to be detected according to the correction curve obtained in the step (3);
the optimal excitation wavelength was chosen to be 342nm and the maximum emission wavelength was 458 nm.
The method for detecting the high manganese acid radical by using the coumarin-based probe has the detection limit of 0.95nmol/L in the high manganese acid radical in a field sample of a detection environment and an explosion case. The fluorescence intensity of the detected molecules and the concentration of the permanganate radical present a good linear relationship under the concentration of 1-25 mu mol/L of the permanganate radical standard solution, and the detection time is less than 3 s. Compared with the prior permanganate detection technology, the invention has the beneficial effects that: under the neutral condition, the probe molecule has high sensitivity, rapidness and specificity to selectively identify permanganate, generates corresponding 7-hydroxy benzopyran-2-ketone with high fluorescence efficiency, and realizes quantitative fluorescence detection of the permanganate through the change of the fluorescence property after the probe molecule reacts with the permanganate.
The method has no special limitation when in use, can quickly finish qualitative detection at room temperature, is simple, efficient, economical, practical, stable and environment-friendly. The kit has the advantages of quick response, obvious signal, high sensitivity, strong specificity, simple manufacture, low cost, stable and repeatable result and the like, is easy to realize detection without pretreatment of an object to be detected, and is extremely easy to be practically applied and popularized in the field of on-site instant detection.
Drawings
Fig. 1 is a diagram for selectively detecting and identifying permanganate radicals by probe molecules in example 9 of the present invention, wherein the horizontal coordinate represents different compound interferents, and the vertical coordinate represents fluorescence intensity.
FIG. 2 is a graph showing fluorescence intensity and permanganate concentration in a probe of example 11 of the present invention in which the abscissa is wavelength and the ordinate is fluorescence intensity;
FIG. 3 is a graph showing the linear relationship between the fluorescence intensity and the permanganate radical concentration of the probe of example 14 of the present invention, in which the abscissa represents the permanganate radical concentration and the ordinate represents the fluorescence intensity;
fig. 4 is a graph showing the fluorescence intensity and reaction time variation when potassium permanganate with different concentrations is added into a 10 μmol/L probe solution in example 15 of the present invention, wherein the horizontal coordinate is the response time, and the vertical coordinate is the fluorescence intensity.
Detailed Description
The present invention will be further illustrated by the following specific examples, but the present invention is not limited to these examples.
Example 1
Synthesis of probe molecule 2-oxo-2H-benzopyran-7-acrylate:
a. dissolving 7-hydroxy benzopyran-2-one (5mmol, 0.81g) in 50mL tetrahydrofuran, adding into a 200mL three-neck round-bottom flask, adding organic base pyridine (5mmol, 0.402mL) and stirring, introducing nitrogen for protection, slowly dropwise adding acryloyl chloride (5mmol, 0.398mL) to react for 2h when the temperature is raised to 0 ℃, heating to room temperature and reacting for 1h, and stopping the reaction;
b. after the reaction is finished, washing the product with deionized water to be neutral, then extracting water with dichloromethane, washing with sodium chloride, drying with anhydrous magnesium sulfate, carrying out suction filtration, and carrying out spin drying to obtain a crude product;
c. and (3) carrying out gradient elution on the obtained crude product by using a forward silica gel chromatographic column, wherein an eluent is ethyl acetate/petroleum ether, and the ratio of the eluent is from 0: 7 is gradually increased to 2: 7, obtaining a white solid after separation and purification, namely the probe molecule 2-oxo-2H-benzopyran-7-acrylate for detecting the permanganate radical, wherein the yield is 62.3%.
Example 2
Synthesis of probe molecule 2-oxo-2H-benzopyran-7-acrylate:
a. 7-Hydroxybenzopyran-2-one (5mmol, 0.81g) was dissolved in 50mL of chloroform, added to a 200mL three-necked round bottom flask, and added triethylamine (25.5mmol, 3.55mL) as an organic base with stirring. Introducing nitrogen for protection, carrying out ice bath to 0 ℃, slowly dropwise adding acryloyl chloride (25mmol, 1.99mL) for reaction for 2h, heating to room temperature for reaction for 24h, and stopping reaction;
b. after the reaction is finished, washing the product with deionized water to be neutral, then extracting water with dichloromethane, washing with sodium chloride, drying with anhydrous magnesium sulfate, carrying out suction filtration, and carrying out spin drying to obtain a crude product;
c. and (3) carrying out gradient elution on the obtained crude product by using a forward silica gel chromatographic column, wherein an eluent is ethyl acetate/petroleum ether, and the ratio of the eluent is from 0: 7 is gradually increased to 2: and 7, separating and purifying to obtain a white solid, namely the probe molecule 2-oxo-2H-benzopyran-7-acrylate for detecting the permanganate radical, wherein the yield is 68.9%.
Example 3
Synthesis of probe molecule 2-oxo-2H-benzopyran-7-methacrylate:
a. dissolving 7-hydroxy benzopyran-2-one (5mmol, 0.81g) in 50mL tetrahydrofuran, adding into a 200mL three-neck round-bottom flask, adding organic base pyridine (5mmol, 0.402mL) and stirring, introducing nitrogen for protection, slowly adding methacryloyl chloride (5mmol, 0.484mL) dropwise to react for 2h when the temperature is raised to 0 ℃, heating to room temperature and reacting for 1h, and stopping the reaction;
b. after the reaction is finished, washing the product with deionized water to be neutral, then extracting water with dichloromethane, washing with sodium chloride, drying with anhydrous magnesium sulfate, carrying out suction filtration, and carrying out spin drying to obtain a crude product;
c. and (3) carrying out gradient elution on the obtained crude product by using a forward silica gel chromatographic column, wherein an eluent is ethyl acetate/petroleum ether, and the ratio of the eluent is from 0: 7 is gradually increased to 2: and 7, separating and purifying to obtain a white solid, namely the probe molecule 2-oxo-2H-benzopyran-7-methacrylate for detecting the permanganate radical, wherein the yield is 59.9%.
Example 4
Synthesis of probe molecule 2-oxo-2H-benzopyran-7-methacrylate:
a. 7-Hydroxybenzopyran-2-one (5mmol, 0.81g) was dissolved in 50mL of chloroform, added to a 200mL three-necked round bottom flask, and added triethylamine (25.5mmol, 3.55mL) as an organic base with stirring. Introducing nitrogen for protection, carrying out ice bath to 0 ℃, slowly dropwise adding methacryloyl chloride (25mmol, 2.42mL) for reaction for 2h, heating to room temperature for reaction for 24h, and stopping the reaction;
b. after the reaction is finished, washing the product with deionized water to be neutral, then extracting water with dichloromethane, washing with sodium chloride, drying with anhydrous magnesium sulfate, carrying out suction filtration, and carrying out spin drying to obtain a crude product;
c. and (3) carrying out gradient elution on the obtained crude product by using a forward silica gel chromatographic column, wherein an eluent is ethyl acetate/petroleum ether, and the ratio of the eluent is from 0: 7 is gradually increased to 2: and 7, separating and purifying to obtain a white solid, namely the probe molecule 2-oxo-2H-benzopyran-7-methacrylate for detecting the permanganate acid radicals, wherein the yield is 65.7%.
Example 5
Detection of coumarin-based probe molecules on potassium permanganate:
a. dissolving the coumarin-based probe prepared in example 1 in a mixed system of acetonitrile and water to prepare a coumarin-based probe solution with the concentration of 10 mu mol/L;
b. uniformly dropwise adding the coumarin-based probe solution obtained in the step a onto slow qualitative filter paper to obtain detection test paper;
c. b, preparing a potassium permanganate standard solution, taking water as a solvent, preparing the potassium permanganate standard solution with the concentration of 5, 10, 20, 40, 60, 80, 100, 120, 140, 160, 180 and 200 mu mol/L, dropwise adding the potassium permanganate standard solution onto the detection test paper obtained in the step b, fully contacting and reacting, selecting the excitation wavelength of 342nm and the maximum emission wavelength of 458nm to determine the fluorescence intensity, taking a fluorescence photo, and making a correction curve corresponding to the potassium permanganate content in the fluorescence intensity for quantitative analysis; and calculating to obtain the potassium permanganate content in the sample to be detected.
Example 6
Detection of the coumarin-based probe molecule on potassium permanganate:
a. dissolving the coumarin-based probe prepared in example 3 in a mixed system of dimethyl sulfoxide and water to prepare a coumarin-based probe solution with the concentration of 10 mu mol/L;
b. uniformly adding the coumarin-based probe solution obtained in the step a into a fluorescent cuvette to obtain a detection reagent;
c. b, preparing a potassium permanganate standard solution, taking water as a solvent, preparing the potassium permanganate standard solution with the concentration of 5, 10, 20, 40, 60, 80, 100, 120, 140, 160, 180 and 200 mu mol/L, dropwise adding the potassium permanganate standard solution into the detection reagent obtained in the step b, fully contacting and reacting, selecting the excitation wavelength of 342nm and the maximum emission wavelength of 458nm to determine fluorescence intensity, taking a fluorescence photo, and making a correction curve corresponding to the potassium permanganate content in the fluorescence intensity for quantitative analysis; and calculating to obtain the potassium permanganate content in the sample to be detected.
Example 7
Detection of sodium permanganate by coumarin-based probe molecules:
a. dissolving the coumarin-based probe prepared in example 1 in a mixed system of acetonitrile and water to prepare a coumarin-based probe solution with the concentration of 10 mu mol/L;
b. uniformly dripping the coumarin-based probe solution obtained in the step a on slow qualitative filter paper to obtain detection test paper;
c. b, preparing a sodium permanganate standard solution, taking water as a solvent, preparing the sodium permanganate standard solution with the concentration of 5, 10, 20, 40, 60, 80, 100, 120, 140, 160, 180 and 200 mu mol/L, dropwise adding the sodium permanganate standard solution onto the detection test paper obtained in the step b, fully contacting and reacting, selecting the excitation wavelength of 342nm and the maximum emission wavelength of 458nm to measure the fluorescence intensity, taking a fluorescence photo, and making a correction curve corresponding to the sodium permanganate content in the fluorescence intensity for quantitative analysis; and calculating to obtain the content of the high manganese and sodium in the sample to be detected.
Example 8
Detection of sodium permanganate by coumarin-based probe molecules:
a. dissolving the coumarin-based probe prepared in example 3 in a mixed system of dimethyl sulfoxide and water to prepare a coumarin-based probe solution with the concentration of 10 mu mol/L;
b. uniformly adding the coumarin-based probe solution obtained in the step a into a fluorescent cuvette to obtain a detection reagent;
c. b, preparing a sodium permanganate standard solution, taking water as a solvent, preparing the sodium permanganate standard solution with the concentration of 5, 10, 20, 40, 60, 80, 100, 120, 140, 160, 180 and 200 mu mol/L, dropwise adding the sodium permanganate standard solution into the detection reagent obtained in the step b, fully contacting and reacting, selecting the excitation wavelength of 342nm and the maximum emission wavelength of 458nm to measure the fluorescence intensity, taking a fluorescence photo, and making a correction curve corresponding to the sodium permanganate content in the fluorescence intensity for quantitative analysis; and calculating to obtain the content of the sodium permanganate in the sample to be detected.
Example 9
The coumarin-based probe molecule is used for specific detection and identification of potassium permanganate:
as shown in FIG. 1, the coumarin-based probe prepared in example 1 was dissolved in acetonitrile/water and various common interferents orWhen oxidizing agents, e.g. NH4NO3,Urea,K2SO3,Na2S,CaCl2,Na2SO4,KI,H2O2,NaClO4,KClO3,NaIO4,NaCl,AgNO3,Cd(AcO)2,KNO3,NaBr,NaBrO3Sodium Dodecyl Sulfate (SDS), NaNO2The fluorescence intensity did not change; when potassium permanganate is added into the probe solution, the fluorescence intensity of the probe solution is increased dramatically, and when various common interfering species are added, the fluorescence intensity of the probe is almost unchanged, so that the probe molecule has a good specific recognition function on potassium permanganate;
example 10
The coumarin-based probe molecule is used for detecting and identifying the specificity of the sodium permanganate:
the coumarin-based probe prepared in example 1 was dissolved in acetonitrile/water solution when various common interferents or oxidants, such as NH, were added4NO3,Urea,K2SO3,Na2S,CaCl2,Na2SO4,KI,H2O2,NaClO4,KClO3,NaIO4,NaCl,AgNO3,Cd(AcO)2,KNO3,NaBr,NaBrO3,SDS,NaNO2The fluorescence intensity did not change; when sodium permanganate is added into the probe solution, the fluorescence intensity of the probe solution is increased dramatically, and when various common interfering species are added, the fluorescence intensity of the probe is almost unchanged, so that the probe molecule has a good specific recognition function on the sodium permanganate;
example 11
Linear relationship between change in molecular strength of coumarin-based probe and potassium permanganate concentration:
the coumarin-based probe molecule prepared in example 1 is used for evaluating the linear relationship between the fluorescence intensity of the probe molecule and the concentration of potassium permanganate ions, fig. 2 is a curve of the change relationship between the fluorescence intensity of the emission center wavelength of the probe molecule at 458nm and the concentration of potassium permanganate ions, and the results show that: the fluorescence intensity change of the probe molecule solution and the concentration change of potassium permanganate present a good linear relationship in the range of 1-25 mu mol/L, so the probe molecules have excellent capability of detecting potassium permanganate and present good detection performance;
example 12
Linear relationship between change in strength of coumarin-based probe molecule and concentration of sodium permanganate:
the coumarin-based probe molecules prepared in the example 1 are used for evaluating the linear relation between the fluorescence intensity of the probe molecules and the concentration of sodium permanganate ions, and the change relation curve result of the fluorescence intensity of the emission center wavelength of the probe molecules at 458nm along with the concentration of the sodium permanganate ions shows that: the change of the fluorescence intensity of the probe molecule solution and the change of the concentration of the sodium permanganate present a good linear relationship in the range of 1-25 mu mol/L, so the probe molecules have excellent capability of detecting the sodium permanganate and present good detection performance;
example 13
The detection result of the paper-based loaded coumarin-based probe molecule detection potassium permanganate solution is as follows:
dissolving the coumarin-based probe molecule prepared in example 1 in acetonitrile/water solution to prepare 10 mu mol/L coumarin-based probe solution;
uniformly dripping the obtained coumarin-based probe solution on slow qualitative filter paper to obtain detection test paper;
preparing a potassium permanganate standard solution, taking water as a solvent, preparing the potassium permanganate standard solution with the concentration of 5, 10, 20, 40, 60, 80, 100, 120, 140, 160, 180 and 200 mu mol/L, dropwise adding the potassium permanganate standard solution into the obtained detection reagent for full contact, and obtaining detection test paper for detecting potassium permanganate after reaction; the potassium permanganate solution is dripped through a pipettor, the fluorescence intensity change of probe molecules on the filter paper is observed under the irradiation of an ultraviolet lamp, and the test result shows that: the filter paper loaded with the probe molecules can efficiently detect the potassium permanganate solution, shows an obvious fluorescent lighting phenomenon and shows good potassium permanganate detection performance;
example 14
The linear relation between the fluorescence intensity change and the potassium permanganate concentration after the probe molecule reaction is as follows:
dissolving the coumarin-based probe molecule prepared in example 1 in a mixed solvent of acetonitrile and water in a volume ratio of 1:1, wherein the concentration of the probe molecule is 10 mu mol/L; taking 2mL of detection solution, adding 0.5mL of potassium permanganate aqueous solution with different concentrations, making a fluorescence spectrum standard graph (shown in figure 2) by using the fluorescence emission intensity of the solution at 458nM to the concentration of potassium permanganate, quantitatively detecting the content of potassium permanganate in the detection solution (shown in figure 3), and calculating the detection limit to be 0.95nM by using a formula LOD (0.009, 3);
example 15
Response time of probe molecules and potassium permanganate with different concentrations:
dissolving the coumarin-based probe molecule prepared in example 1 in a mixed solvent of acetonitrile and water in a volume ratio of 1:1, wherein the concentration of the probe molecule is 10 mu mol/L; taking 1.5mL of detection liquid, respectively adding 0.5mL of potassium permanganate aqueous solution with the concentrations of 200, 100, 60 and 40 mu M, and making a scatter diagram as shown in figure 4 by using the fluorescence emission intensity of the solution at 458nm to the reaction time, wherein the fluorescence intensity is changed immediately after the potassium permanganate is added, and the response time is less than 3 s;
example 16
Response time of probe molecules and sodium permanganate with different concentrations:
dissolving the coumarin-based probe molecule prepared in example 1 in a mixed solvent of acetonitrile and water in a volume ratio of 1:1, wherein the concentration of the probe molecule is 10 mu mol/L; taking 1.5mL of detection solution, respectively adding 0.5mL of sodium permanganate aqueous solution with the concentration of 200, 100, 60 and 40 mu M, respectively, making a scatter diagram of the fluorescence emission intensity of the solution at 458nm to the reaction time, wherein the fluorescence intensity is changed immediately after the sodium permanganate is added, and the response time is less than 3 s;
and (4) conclusion:
through the embodiment, the coumarin-based probe provided by the invention can realize detection of permanganate, the detection effect is fluorescence lightening, the response time is less than 3s, the detection limit is as low as 0.95nmol/L, and the coumarin-based probe has excellent anti-interference performance on more than 20 common interferents.
Claims (1)
1. A method for detecting permanganate acid radicals by using a coumarin-based probe is characterized in that the chemical name of the coumarin-based probe is as follows: 2-oxo-2 hydro-benzopyran-7-R acid ester, having the chemical formula (i):
wherein: the specific operation is carried out according to the following steps:
a. dissolving a coumarin-based probe in a mixed system of acetonitrile or dimethyl sulfoxide and water to prepare a coumarin-based probe solution with the concentration of 10 mu mol/L;
b. uniformly dropwise adding the coumarin-based probe solution obtained in the step a onto slow-speed qualitative filter paper or a fluorescent cuvette to obtain detection test paper or a detection reagent;
c. b, preparing a permanganate radical standard solution, taking water as a solvent, preparing the permanganate radical standard solution with the concentration of 5-200 mu mol/L, dropwise adding the permanganate radical standard solution onto the detection test paper or reagent obtained in the step b, fully contacting and reacting, selecting the excitation wavelength of 342nm and the maximum emission wavelength of 458nm to determine the fluorescence intensity, taking a fluorescence photo, and making a correction curve corresponding to the permanganate radical content to perform quantitative analysis; and calculating to obtain the content of the permanganate in the sample to be detected.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104812777A (en) * | 2012-10-24 | 2015-07-29 | 塞拉尼斯醋酸纤维有限公司 | Polysaccharide ester microspheres and methods and articles relating thereto |
| CN105885831A (en) * | 2016-05-18 | 2016-08-24 | 贵州大学 | Thiosemicarbazone 7-umbelliferone-8-aldehyde probe reagent as well as preparation and application thereof |
| CN110483461A (en) * | 2019-08-29 | 2019-11-22 | 浙江理工大学 | A kind of detection nitrite ion fluorescence probe and preparation method thereof and application method |
| CN111420055A (en) * | 2020-05-07 | 2020-07-17 | 吉林大学 | Magnetic target self-oxygen-supply nano particle and preparation method and application thereof |
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| CN105566270B (en) * | 2016-01-15 | 2017-08-29 | 河南工业大学 | 3 aryl-coumarin derivatives and preparation method thereof |
| US20200332028A1 (en) * | 2016-04-24 | 2020-10-22 | Waters Technologies Corporation | Charged surface reversed phase chromatographic materials method for analysis of glycans modified with amphipathic, strongly basic moieties |
| CN107382935B (en) * | 2017-09-05 | 2019-11-12 | 南京农业大学 | A kind of coumarin fluorescent probe C1 and its preparation method and application |
| CN110627756B (en) * | 2019-10-10 | 2023-03-17 | 中国科学院新疆理化技术研究所 | Colorimetric-fluorescent probe for detecting hypochlorite and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104812777A (en) * | 2012-10-24 | 2015-07-29 | 塞拉尼斯醋酸纤维有限公司 | Polysaccharide ester microspheres and methods and articles relating thereto |
| CN105885831A (en) * | 2016-05-18 | 2016-08-24 | 贵州大学 | Thiosemicarbazone 7-umbelliferone-8-aldehyde probe reagent as well as preparation and application thereof |
| CN110483461A (en) * | 2019-08-29 | 2019-11-22 | 浙江理工大学 | A kind of detection nitrite ion fluorescence probe and preparation method thereof and application method |
| CN111420055A (en) * | 2020-05-07 | 2020-07-17 | 吉林大学 | Magnetic target self-oxygen-supply nano particle and preparation method and application thereof |
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