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CN114674813B - A method for semi-quantitative detection of sulfate free radicals using aryl propionic acid drugs - Google Patents

A method for semi-quantitative detection of sulfate free radicals using aryl propionic acid drugs Download PDF

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CN114674813B
CN114674813B CN202210278499.7A CN202210278499A CN114674813B CN 114674813 B CN114674813 B CN 114674813B CN 202210278499 A CN202210278499 A CN 202210278499A CN 114674813 B CN114674813 B CN 114674813B
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sulfate
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CN114674813A (en
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关小红
邵荟芯
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Tongji University
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Abstract

本发明公开了一种利用芳基丙酸类药物半定量检测硫酸根自由基的方法,涉及自由基检测技术领域。本发明的核心技术为:以芳基丙酸类药物作为发光试剂,根据硫酸根自由基氧化芳基丙酸类药物时产生的化学发光信号,半定量检测水中硫酸根自由基的含量。该检测方法可实时在线检测水中的硫酸根自由基,具有重现性好、灵敏度高、不受反应体系pH影响、特异性强、检测成本低等优点,在水污染防治领域具有广泛的应用前景,特别适用于基于硫酸根自由基的高级氧化工艺的性能评价和反应机理研究。

The present invention discloses a method for semi-quantitatively detecting sulfate free radicals using aryl propionic acid drugs, and relates to the field of free radical detection technology. The core technology of the present invention is: using aryl propionic acid drugs as luminescent reagents, semi-quantitatively detecting the content of sulfate free radicals in water according to the chemiluminescent signal generated when sulfate free radicals oxidize aryl propionic acid drugs. The detection method can detect sulfate free radicals in water in real time online, and has the advantages of good reproducibility, high sensitivity, no influence of pH value of the reaction system, strong specificity, low detection cost, etc. It has broad application prospects in the field of water pollution prevention and control, and is particularly suitable for performance evaluation and reaction mechanism research of advanced oxidation processes based on sulfate free radicals.

Description

Method for semi-quantitatively detecting sulfate radical by using aryl propionic acid drug
Technical Field
The invention relates to the technical field of free radical detection, in particular to a method for semi-quantitatively detecting sulfate radical by utilizing aryl propionic acid medicaments, which is particularly used for performance evaluation and reaction mechanism research of advanced oxidation technology based on the sulfate radical.
Background
The sulfate radical (SO 4 ·-) is an oxidant with strong oxidizing capability, and the oxidation-reduction potential (2.60-3.10V NHE) of the oxidant is higher than that of the hydroxyl radical (HO ·) (1.90-2.70V NHE). In addition, the half-life of SO 4 ·- (t 1/2.ltoreq.30 to 40. Mu.s) is also higher than that of HO · (t 1/2≤1μs).SO4 ·- is a typical electrophilic oxidant by attacking electron donors in organic matter, such as amino groups, Hydroxyl, alkoxy, pi electrons on aromatic structure, conjugated structure to oxidize organic pollutants in water. In recent years, advanced oxidation technology based on SO 4 ·- has been rapidly developed, and is one of the most promising advanced oxidation technologies in the fields of sewage deep treatment and groundwater remediation. The quantitative detection of the concentration of SO 4 ·- is a precondition for evaluating the efficiency of advanced oxidation technology and researching the reaction mechanism of the advanced oxidation technology, and can provide a basis for optimizing advanced oxidation process parameters based on SO 4 ·- in engineering practice. The main methods for detecting SO 4 ·- at present are a complete capture method, a competition dynamics method and a chemiluminescence method. The full capture method is characterized by utilizing the yield of the product of the reaction of the excessive capture agent and SO 4 ·- to characterize the yield of SO 4 ·-, and is classified into an electron spin resonance method and a high performance liquid chromatography method according to a product determination method, and the methods have the defects of complicated operation, long detection time, high cost and possibility of being influenced by other coexisting free radicals. The competitive kinetics method is to add a capturing agent with a known reaction rate constant with SO 4 ·- into a high-grade oxidation system, and the yield of SO 4 ·- in the system is represented by the concentration change of the capturing agent. In addition, the full capture method and the competitive dynamics method cannot realize in-situ real-time detection of SO 4 ·-, and further cannot provide timely feedback for adjustment of process parameters. The chemiluminescence method is a method for semi-quantitatively analyzing the concentration of SO 4 ·- by utilizing the chemiluminescence phenomenon generated when SO 4 ·- oxidizes a luminescent reagent, and has the advantages of simple instrument, Convenient operation, high detection speed, high sensitivity, low price, convenient in-situ detection and the like.
However, the selection of luminescent reagents is currently a difficulty in detecting SO 4 ·- by chemiluminescence, which directly affects the accuracy, reproducibility, sensitivity, specificity, applicable conditions, etc. of the method. The luminescent reagent selected in the chemiluminescence method is tobacco extract or tea extract, the preparation process of the luminescent reagent is complicated, and the raw material types and the preparation method can influence the composition components of the luminescent reagent, SO that the accuracy and the reproducibility of the determination of SO 4 ·- by the chemiluminescence method are influenced. It should be noted that the existing chemiluminescence method cannot specifically detect SO 4 ·- in a system where multiple free radicals coexist, because the tobacco extract can react with SO 4 ·- to produce chemiluminescence, or can react with HO · to produce chemiluminescence. In view of the limitations of the above chemiluminescence methods, it is highly desirable to find a simple and readily available luminescent reagent with a defined composition and a high specificity for semi-quantitatively detecting SO 4 ·-.
The aryl propionic acid medicine is a nonsteroidal anti-inflammatory medicine which is originally developed in the sixty of twentieth century, has the effects of relieving fever, easing pain, resisting inflammation, resisting rheumatism and the like, and mainly comprises flurbiprofen, pranoprofen, ibuprofen, naproxen, loxoprofen, ketoprofen and the like. At present, no report on the use of aryl propionic acid medicines for detecting SO 4 ·- exists. Thus, there is a need to develop new methods for detecting and quantifying SO 4 ·- using aryl propionic acid drugs.
Disclosure of Invention
Aiming at the defects of complicated operation, long detection time, low sensitivity, poor reproducibility, low specificity, high cost and the like of the existing SO 4 ·- detection technology, the invention mainly aims to provide a method for semi-quantifying SO 4 ·- by using aryl propionic acid medicaments. The method utilizes the luminous intensity of chemiluminescence generated by SO 4 ·- in oxidizing aryl propionic acid medicaments to semi-quantitatively determine SO 4 ·- in water. The method specifically comprises the following steps:
Step (1), mixing a reaction system for generating SO 4 ·- with a solution containing aryl propionic acid medicines in a certain mixing mode SO as to obtain a reaction solution;
Step (2), detecting chemiluminescence generated by the reaction solution in the step (1) by using a chemiluminescence analyzer;
And (3) determining the concentration of SO 4 ·- in the reaction system according to the intensity of chemiluminescence.
The method for semi-quantitatively detecting sulfate radical by using the aryl propionic acid medicine is characterized in that in the step (1), the aryl propionic acid medicine with the structure shown in the formula 1 is taken as a luminescent reagent to react with the sulfate radical to generate chemiluminescence, and the method can be used for semi-quantitatively detecting the sulfate radical in water.
The method for semi-quantitatively detecting sulfate radical by using aryl propionic acid medicines is characterized in that in the step (2), the intensity of chemiluminescence is positively correlated with the concentration of the sulfate radical in a reaction system, and the concentration of the sulfate radical in the reaction system is judged according to the intensity of the chemiluminescence.
The method for semi-quantitatively detecting sulfate radical by using aryl propionic acid medicine is characterized in that in the step (1), the aryl propionic acid medicine reacts with the sulfate radical to generate excited state molecules so as to generate chemiluminescence.
The method for semi-quantitatively detecting sulfate radical by utilizing aryl propionic acid medicaments is characterized by specifically identifying the sulfate radical in a reaction system in which hydroxyl radical and sulfate radical coexist.
The method for semi-quantitatively detecting sulfate radical by using aryl propionic acid medicines is characterized in that in the step (1), the concentration of the aryl propionic acid medicines in the reaction liquid is larger than 0.5 mu mol.L -1.
The method for semi-quantitatively detecting sulfate radical by using aryl propionic acid medicines is characterized in that in the step (1), the certain mixing mode is one of a static injection method, a flow injection method and a flow stopping method.
The method for semi-quantitatively detecting sulfate radical by using aryl propionic acid medicines is characterized in that in the step (3), the pH of a reaction system is 0-14.
The method for semi-quantitatively detecting sulfate radical by using aryl propionic acid medicaments is characterized by being suitable for performance evaluation and reaction mechanism research of advanced oxidation technology based on sulfate radical.
The beneficial effects of the invention are as follows:
(1) The invention uses the commercial aryl propionic acid medicine as the chemiluminescent reagent to detect the content of SO 4 ·- in water, and has the advantages of simple operation, low detection cost, good reproducibility, high sensitivity, short detection time and the like.
(2) The aryl propionic acid medicine does not generate chemiluminescence when reacting with HO ·, SO that the invention can specifically detect SO 4 ·- in a reaction system where HO · and SO 4 ·- coexist.
(3) The invention can directly carry out semi-quantitative determination on the content of SO 4 ·- in water by using chemiluminescence in the advanced oxidation technology based on SO 4 ·-, and research on the efficiency and mechanism of the advanced oxidation technology;
(4) The invention can detect the content of SO 4 ·- in water on line in real time, provide data support for the timely adjustment of process parameters in the advanced oxidation technology based on SO 4 ·-, and ensure the efficient operation of sewage treatment plants.
Drawings
FIG. 1 is a graph showing the chemiluminescent kinetics of three representative aryl propionic acids of example 1 mixed with a Fe 2+/PMS reaction system;
FIG. 2 is a graph showing the chemiluminescent kinetics of naproxen mixed with a Fe 2+/PMS reaction system at different PMS concentrations in example 2;
FIG. 3 is a graph showing the chemiluminescent kinetics of naproxen mixed with a Fe 2+/PMS reaction system at different benzoic acid concentrations in example 3;
FIG. 4 is a graph showing the chemiluminescent kinetics of naproxen in example 4 after mixing with a Fe 3+/SO3 2- reaction system;
FIG. 5 is a graph showing the chemiluminescent kinetics of naproxen in example 5 after mixing with a Fe 2+/H2O2 reaction system.
Detailed Description
Example 1
In an acidic solution, ferrous iron (Fe 2+) can activate Peroxymonosulfate (PMS) to produce SO 4 ·-.
In the embodiment, three representative aryl propionic acid medicines are selected as luminous reagents, and the method for detecting SO 4 ·- in a Fe 2+/PMS reaction system comprises the following specific steps:
Step (1), mixing a reaction system for generating SO 4 ·- with a solution containing aryl propionic acid medicines in a certain mixing mode SO as to obtain a reaction solution;
Step (2), detecting chemiluminescence generated by the reaction solution in the step (1) by using a chemiluminescence analyzer;
And (3) determining the concentration of SO 4 ·- in the reaction system according to the intensity of chemiluminescence.
The aryl propionic acid medicine is one of naproxen, ibuprofen and ketoprofen, the reaction system is a Fe 2+/PMS reaction system, the mixing mode is a stop flow method, the initial concentration of Fe 2+, PMS and aryl propionic acid medicine in the reaction liquid is 40 mu mol L -1、320μmol·L-1、10μmol·L-1 respectively, and the reaction pH of the reaction liquid is 3.0.
FIG. 1 shows chemiluminescent kinetics curves of three representative aryl propionic acids mixed with a Fe 2+/PMS reaction system. When the concentration of the aryl propionic acid medicine in the reaction liquid is 0, the Fe 2+/PMS reaction system can not generate a chemiluminescent signal, and when the concentration of the aryl propionic acid medicine in the reaction liquid is 10 mu mol.L -1, the Fe 2+/PMS reaction system can generate a strong chemiluminescent signal. This example illustrates that three representative aryl propionic acids can be used as luminescent agents in the detection of SO 4 ·- in water. The chemical method can be adopted to master the change rule of the concentration of SO 4 ·- in the Fe 2+/PMS reaction system in real time, which cannot be realized by a complete capturing method and a competition dynamics method.
Example 2
As the concentration of PMS increases, the concentration of SO 4 ·- in the Fe 2+/PMS reaction system increases, and the concentration of SO 4 ·- in the Fe 2+/PMS reaction system can be controlled by changing the initial concentration of PMS. The method selects naproxen as a luminescent reagent to perform semi-quantitative analysis on the concentration of SO 4 ·- in a Fe 2+/PMS reaction system, and specifically comprises the following steps:
Step (1), mixing a reaction system for generating SO 4 ·- with a solution containing aryl propionic acid medicines in a certain mixing mode SO as to obtain a reaction solution;
Step (2), detecting chemiluminescence generated by the reaction solution in the step (1) by using a chemiluminescence analyzer;
And (3) determining the concentration of SO 4 ·- in the reaction system according to the intensity of chemiluminescence.
The aryl propionic acid medicine is naproxen;
The reaction system is a Fe 2+/PMS reaction system;
The mixing mode is a stop flow method;
The initial concentration of Fe 2+, PMS and aryl propionic acid in the reaction solution is 40 mu mol/L, 40-800 mu mol/L and 10 mu mol/L respectively;
The pH of the reaction solution was 3.0.
FIG. 2 shows the chemiluminescent kinetics of naproxen mixed with a Fe 2+/PMS reaction system at different PMS concentrations. As the PMS concentration increases, the chemiluminescent signal obviously increases, which indicates that increasing the PMS concentration increases the concentration of SO 4 ·- in the Fe 2+/PMS reaction system, and the embodiment indicates that the invention can be used for semi-quantitative analysis of SO 4 ·- in the reaction system and provides basis for optimizing operation parameters in the reaction system.
Example 3
The addition of a quencher for SO 4 ·- to the Fe 2+/PMS reaction system reduces the concentration of SO 4 ·- in the reaction system. The reaction rate of the benzoic acid and SO 4 ·- is high, the concentration of SO 4 ·- in the reaction system can be reduced by adding the benzoic acid into the Fe 2+/PMS reaction system, naproxen is selected as a luminescent reagent to perform semi-quantitative analysis on the concentration of SO 4 ·- in the reaction system, and the specific steps are as follows:
Step (1), mixing a reaction system for generating SO 4 ·- with a solution containing aryl propionic acid medicines in a certain mixing mode SO as to obtain a reaction solution;
Step (2), detecting chemiluminescence generated by the reaction solution in the step (1) by using a chemiluminescence analyzer;
And (3) determining the concentration of SO 4 ·- in the reaction system according to the intensity of chemiluminescence.
The aryl propionic acid medicine is naproxen;
The reaction system is a Fe 2+/PMS reaction system;
The mixing mode is a stop flow method;
The initial concentration of Fe 2+, PMS, aryl propionic acid medicine and benzoic acid in the reaction solution is 40 mu mol/L, 10 mu mol/L and 0-1000 mu mol/L respectively;
The pH of the reaction solution was 3.0.
FIG. 3 shows the chemiluminescent kinetics of naproxen mixed with a Fe 2+/PMS reaction system at different benzoic acid concentrations. As the concentration of benzoic acid in the Fe 2+/PMS reaction system increases, the chemiluminescent signal intensity gradually decreases, indicating that the concentration of SO 4 ·- in the Fe 2+/PMS reaction system decreases with the increase of the concentration of benzoic acid, which is consistent with the fact.
Example 4
Ferric ion (Fe 3+) reacts with sulfite ion (SO 3 2-) to form SO 4 ·-, and thus Fe 3+/SO3 2- reaction system is also a typical advanced oxidation technology based on SO 4 ·-. The method selects naproxen as a luminescent reagent to perform semi-quantitative analysis on the concentration of SO 4 ·- in a Fe 3+/SO3 2- reaction system, and specifically comprises the following steps:
Step (1), mixing a reaction system for generating SO 4 ·- with a solution containing aryl propionic acid medicines in a certain mixing mode SO as to obtain a reaction solution;
Step (2), detecting chemiluminescence generated by the reaction solution in the step (1) by using a chemiluminescence analyzer;
And (3) determining the concentration of SO 4 ·- in the reaction system according to the intensity of chemiluminescence.
The aryl propionic acid medicine is naproxen, the reaction system is an Fe 3+/SO3 2- reaction system, the mixing mode is a static injection method, the initial concentration of Fe 3+、SO3 2- and the initial concentration of the aryl propionic acid medicine in the reaction solution are 40 mu mol/L, 40 mu mol/L and 5 mu mol/L respectively, and the pH value of the reaction solution is 3.0.
FIG. 4 shows the chemiluminescent kinetics of naproxen after mixing with a Fe 3+/SO3 2- reaction system. The rate of SO 4 ·- production in the Fe 3+/SO3 2- reaction system was slow, lasting approximately 3 minutes. This example further illustrates the reaction mechanism by which the present invention can be used to study advanced oxidation techniques.
Example 5
The ferrous ion/hydrogen peroxide (Fe 2+/H2O2) reaction system is a typical advanced oxidation technology based on HO ·. Therefore, the Fe 2+/H2O2 reaction system is selected as an object, and the specificity of SO 4 ·- detected by the method is verified. The method comprises the following specific steps:
Step (1), mixing a Fe 2+/H2O2 reaction system and a naproxen solution in a certain mixing mode to obtain a reaction solution;
And (2) detecting chemiluminescence generated by the reaction solution in the step (1) by using a chemiluminescence analyzer.
The mixing mode is a stop flow method;
The initial concentration of Fe 2+、H2O2 and aryl propionic acid medicines in the reaction solution is 40 mu mol/L, 40 mu mol/L and 10 mu mol/L respectively, and the pH value of the reaction solution is 3.0.
FIG. 5 is a graph showing the chemiluminescent kinetics of naproxen after mixing with a Fe 2+/H2O2 reaction system. After the naproxen and the Fe 2+/H2O2 reaction system are mixed, no chemiluminescent signal is generated, which indicates that no chemiluminescent phenomenon exists when HO · reacts with naproxen, and further indicates that the invention can specifically detect the content of SO 4 ·- in a system where HO · and SO 4 ·- coexist.

Claims (8)

1.一种利用芳基丙酸类药物半定量检测硫酸根自由基的方法,其特征在于,包括以下步骤:步骤(1)、将产生硫酸根自由基的反应体系与含有芳基丙酸类药物的溶液以某种混合方式混合,从而得到反应液;所述芳基丙酸类药物为萘普生、布洛芬、酮基布洛芬中的一种;所述的某种混合方式是静态注射法、流动注射法、停流法中的一种;1. A method for semi-quantitatively detecting sulfate free radicals using aryl propionic acid drugs, characterized in that it comprises the following steps: step (1), mixing a reaction system that generates sulfate free radicals with a solution containing aryl propionic acid drugs in a certain mixing manner to obtain a reaction solution; the aryl propionic acid drug is one of naproxen, ibuprofen, and ketoprofen; the certain mixing manner is one of a static injection method, a flow injection method, and a stopped flow method; 步骤(2)、用化学发光分析仪检测步骤(1)中反应液所产生的化学发光;Step (2), detecting the chemiluminescence generated by the reaction solution in step (1) using a chemiluminescence analyzer; 步骤(3)、根据化学发光的强度确定反应体系中硫酸根自由基的浓度。Step (3), determining the concentration of sulfate radicals in the reaction system according to the intensity of chemiluminescence. 2.根据权利要求1所述的一种利用芳基丙酸类药物半定量检测硫酸根自由基的方法,其特征在于:步骤(1)中,2. The method for semi-quantitative detection of sulfate radicals using aryl propionic acid drugs according to claim 1, characterized in that: in step (1), 式1Formula 1 具有式1结构的芳基丙酸类药物作为发光试剂与硫酸根自由基反应后产生的化学发光,可用于半定量检测水中的硫酸根自由基。The chemiluminescence generated by the reaction of the aromatic propionic acid drugs having the structure of Formula 1 with sulfate free radicals as luminescent reagents can be used for semi-quantitative detection of sulfate free radicals in water. 3.根据权利要求1所述的一种利用芳基丙酸类药物半定量检测硫酸根自由基的方法,其特征在于:步骤(2)中,所述的化学发光的强度与反应体系中硫酸根自由基的浓度正相关,根据化学发光的强度判断反应体系中硫酸根自由基的浓度。3. A method for semi-quantitative detection of sulfate free radicals using aromatic propionic acid drugs according to claim 1, characterized in that: in step (2), the intensity of the chemiluminescence is positively correlated with the concentration of sulfate free radicals in the reaction system, and the concentration of sulfate free radicals in the reaction system is judged according to the intensity of the chemiluminescence. 4.根据权利要求1所述的一种利用芳基丙酸类药物半定量检测硫酸根自由基的方法,其特征在于:步骤(1)中,所述的芳基丙酸类药物与硫酸根自由基反应,产生激发态分子,从而产生化学发光。4. A method for semi-quantitative detection of sulfate free radicals using aromatic propionic acid drugs according to claim 1, characterized in that: in step (1), the aromatic propionic acid drugs react with sulfate free radicals to produce excited state molecules, thereby generating chemiluminescence. 5.根据权利要求1所述的一种利用芳基丙酸类药物半定量检测硫酸根自由基的方法,其特征在于:所述的方法可特异性地在羟基自由基与硫酸根自由基共存的反应体系中识别硫酸根自由基。5. A method for semi-quantitatively detecting sulfate free radicals using aryl propionic acid drugs according to claim 1, characterized in that the method can specifically identify sulfate free radicals in a reaction system where hydroxyl free radicals and sulfate free radicals coexist. 6.根据权利要求1所述的一种利用芳基丙酸类药物半定量检测硫酸根自由基的方法,其特征在于:步骤(1)中,所述的反应液中芳基丙酸类药物的浓度应大于0.5 μmol•L−16. A method for semi-quantitative detection of sulfate radicals using aryl propionic acid drugs according to claim 1, characterized in that: in step (1), the concentration of the aryl propionic acid drugs in the reaction solution should be greater than 0.5 μmol•L −1 . 7.根据权利要求1所述的一种利用芳基丙酸类药物半定量检测硫酸根自由基的方法,其特征在于:步骤(3)中,所述的反应体系的pH为0~14。7. A method for semi-quantitative detection of sulfate radicals using aromatic propionic acid drugs according to claim 1, characterized in that: in step (3), the pH of the reaction system is 0-14. 8.根据权利要求1所述的一种利用芳基丙酸类药物半定量检测硫酸根自由基的方法,其特征在于:所述的方法适用于基于硫酸根自由基的高级氧化技术的性能评价和反应机理的研究。8. A method for semi-quantitative detection of sulfate free radicals using aromatic propionic acid drugs according to claim 1, characterized in that the method is suitable for performance evaluation and reaction mechanism research of advanced oxidation technology based on sulfate free radicals.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011057818A (en) * 2009-09-09 2011-03-24 Metawater Co Ltd New chemiluminescent reagent and new chemiluminescent method, measurement method of material to be detected using the same, and kit used for measurement method
TW201718576A (en) * 2015-09-02 2017-06-01 林伯士拉克許米公司 TYK2 inhibitors and uses thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011057818A (en) * 2009-09-09 2011-03-24 Metawater Co Ltd New chemiluminescent reagent and new chemiluminescent method, measurement method of material to be detected using the same, and kit used for measurement method
TW201718576A (en) * 2015-09-02 2017-06-01 林伯士拉克許米公司 TYK2 inhibitors and uses thereof

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