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

Abstract

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

Technical Field

[0001] The present invention relates to the field of free radical detection technology, and in particular to a method for semi-quantitatively detecting sulfate free radicals using aryl propionic acid drugs, and in particular to performance evaluation and reaction mechanism research of advanced oxidation technology based on sulfate free radicals. Background Art

[0002] Sulfate radical (SO4 ·- ) is an oxidant with strong oxidizing ability. Its redox potential (2.60~3.10V NHE ) is higher than hydroxyl radical (HO · )'s redox potential (1.90~2.70V NHE ). In addition, SO4 ·- The half-life (t 1 / 2 ≤30~40μs) is also higher than HO · The half-life (t 1 / 2 ≤1μs). SO4 ·- It is a typical electrophilic oxidant, which oxidizes organic pollutants in water by attacking electron donors in organic matter, such as amino, hydroxyl, alkoxy, π electrons on aromatic structures, and conjugated structures. ·- Advanced oxidation technology has developed rapidly and has become one of the most promising advanced oxidation technologies in the field of sewage deep treatment and groundwater remediation. Quantitative detection of SO4 ·- The concentration is the premise for evaluating the performance of advanced oxidation technology and studying its reaction mechanism. It can also be used for engineering practice based on SO4 ·- The optimization of advanced oxidation process parameters is provided. ·- The main methods are: complete capture method, competitive kinetics method, and chemiluminescence method. The complete capture method is to use excess capture agent and SO4 ·- The product yield of the reaction is used to characterize SO4 ·- The yield of the product can be divided into electron spin resonance method and high performance liquid chromatography according to the product determination method. These methods are cumbersome to operate, take a long time to detect, are costly, and may be affected by other coexisting free radicals. The competitive kinetic method is to add a kind of SO4 ·- The reaction rate constant of the capture agent is known, and the concentration change of the capture agent is used to characterize the SO4 in the system. ·- The yield of this method is cumbersome, the detection time is long, the accuracy is low, and the added capture agent may interfere with the reaction process and cause errors. In addition, neither the complete capture method nor the competitive kinetic method can achieve the SO4 ·- In-situ real-time detection is not possible, and thus it is unable to provide timely feedback for the adjustment of process parameters. ·-Semi-quantitative analysis of SO4 by chemiluminescence produced by oxidation of luminescent reagents ·- The concentration method has the advantages of simple instrumentation, convenient operation, fast detection speed, high sensitivity, low price, and convenience for in situ detection.

[0003] However, the current choice of luminescent reagent is chemiluminescence detection of SO4 ·- The difficulty of the method directly affects the accuracy, reproducibility, sensitivity, specificity, and applicable conditions of the method. At present, the luminescent reagents used in the chemiluminescence method are tobacco extracts or tea extracts. The preparation process of these luminescent reagents is cumbersome. The type of raw materials and preparation methods will affect the composition of these luminescent reagents, thereby affecting the chemiluminescence method for determining SO4 ·- It should be noted that tobacco extract can be used with both SO4 ·- The reaction produces chemiluminescence and can also react with HO · The reaction produces chemiluminescence, so the existing chemiluminescence method cannot specifically detect SO4 in a system where multiple free radicals coexist. ·- In view of the limitations of the above chemiluminescence methods, it is urgent to find a simple, easy-to-obtain, definite and highly specific luminescent reagent for semi-quantitative detection of SO4 ·- .

[0004] Arylpropionic acid drugs are non-steroidal anti-inflammatory drugs that came out in the early 1960s. They have antipyretic, analgesic, anti-inflammatory, and anti-rheumatic effects. They mainly include flurbiprofen, pranoprofen, ibuprofen, naproxen, loxoprofen, ketoprofen, etc. At present, there is no research on the use of arylpropionic acid drugs for the detection of SO4 ·- Therefore, it is necessary to develop new methods to detect and quantify SO4 using arylpropionic acid drugs. ·- method. Summary of the invention

[0005] For existing SO4 ·- The detection technology has the disadvantages of cumbersome operation, long detection time, low sensitivity, poor reproducibility, low specificity and high cost. The main purpose of the present invention is to propose a semi-quantitative SO4 ·- This method utilizes SO4 ·- Semi-quantitative determination of SO4 in water by the luminescence intensity of chemiluminescence produced during the oxidation of arylpropionic acid drugs ·- The specific steps include:

[0006] Step (1) produces SO4 ·- The reaction system is mixed with a solution containing an aryl propionic acid drug in a certain mixing manner to obtain a reaction solution;

[0007] Step (2), detecting the chemiluminescence generated by the reaction solution in step (1) using a chemiluminescence analyzer;

[0008] Step (3), determine the SO4 in the reaction system according to the intensity of chemiluminescence ·- concentration.

[0009] The method for semi-quantitatively detecting sulfate free radicals using aromatic propionic acid drugs is characterized in that: in step (1), the aromatic propionic acid drugs having the structure of formula 1 are used as luminescent reagents to react with sulfate free radicals to generate chemiluminescence, which can be used for semi-quantitative detection of sulfate free radicals in water.

[0010] The method for semi-quantitatively detecting sulfate free radicals using aromatic propionic acid drugs is 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 based on the intensity of the chemiluminescence.

[0011] The method for semi-quantitatively detecting sulfate free radicals using aryl propionic acid drugs is characterized in that: in step (1), the aryl propionic acid drugs react with sulfate free radicals to produce excited state molecules, thereby generating chemiluminescence.

[0012] The method for semi-quantitatively detecting sulfate free radicals using aryl propionic acid drugs is characterized in that the method can specifically identify sulfate free radicals in a reaction system where hydroxyl free radicals and sulfate free radicals coexist.

[0013] The method for semi-quantitatively detecting sulfate radicals using aryl propionic acid drugs is 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 .

[0014] The method for semi-quantitatively detecting sulfate radicals using aromatic propionic acid drugs is characterized in that: in step (1), the certain mixing method is one of static injection method, flow injection method and stopped flow method.

[0015] The method for semi-quantitatively detecting sulfate radicals using aromatic propionic acid drugs is characterized in that: in step (3), the pH of the reaction system is 0 to 14.

[0016] The method for semi-quantitatively detecting sulfate free radicals using aromatic propionic acid drugs is characterized in that the method is suitable for performance evaluation and reaction mechanism research of advanced oxidation technology based on sulfate free radicals.

[0017]

[0018]

[0019] The beneficial effects of the present invention are as follows:

[0020] (1) The present invention uses commercial aryl propionic acid drugs as chemiluminescent reagents to detect SO4 in water ·- It has the advantages of simple operation, low detection cost, good reproducibility, high sensitivity and short detection time.

[0021] (2) The aromatic propionic acid drugs in the present invention and HO · The reaction does not produce chemiluminescence, so the present invention can be used in HO · With SO4 ·- Specific detection of SO4 in coexisting reaction systems ·- .

[0022] (3) The present invention can be based on SO4 ·- In the advanced oxidation technology, chemiluminescence is used to directly oxidize SO4 in water. ·- Semi-quantitative determination of the content of , and study of the efficacy and mechanism of advanced oxidation technology;

[0023] (4) The present invention can detect SO4 in water in real time online ·- The content is based on SO4 ·- It provides data support for the timely adjustment of process parameters in advanced oxidation technology to ensure the efficient operation of sewage treatment plants. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The three representative aromatic propionic acid drugs and Fe in Example 1 2+ / PMS reaction system after mixing chemiluminescence kinetic curve;

[0025] Figure 2 The results of naproxen and Fe under different PMS concentration conditions in Example 2 are shown in Table 2. 2+ / PMS reaction system after mixing chemiluminescence kinetic curve;

[0026] Figure 3 The results of naproxen and Fe under different benzoic acid concentrations in Example 3 are shown in Table 3. 2+ / PMS reaction system after mixing chemiluminescence kinetic curve;

[0027] Figure 4 For naproxen and Fe in Example 4 3+ / SO3 2- Chemiluminescence kinetic curve after the reaction system is mixed;

[0028] Figure 5 For naproxen and Fe in Example 52+ Chemiluminescence kinetic curve of the mixed / H2O2 reaction system. DETAILED DESCRIPTION

[0029] Example 1

[0030] In acidic solution, ferrous iron (Fe 2+ ) can activate peroxymonosulfate (PMS) to produce SO4 ·- .

[0031] In this example, three representative aromatic propionic acid drugs were selected as luminescent reagents, and the method of the present invention was used to detect Fe 2+ SO4 in PMS reaction system ·- , the specific steps are as follows:

[0032] Step (1) produces SO4 ·- The reaction system is mixed with a solution containing an aryl propionic acid drug in a certain mixing manner to obtain a reaction solution;

[0033] Step (2), detecting the chemiluminescence generated by the reaction solution in step (1) using a chemiluminescence analyzer;

[0034] Step (3), determine the SO4 in the reaction system according to the intensity of chemiluminescence ·- concentration.

[0035] The aromatic propionic acid drug is one of naproxen, ibuprofen and ketoprofen; the reaction system is Fe 2+ / PMS reaction system; the mixing method is a stopped flow method; the reaction solution contains Fe 2+ The initial concentrations of PMS and arylpropionic acid drugs were 40 μmol·L -1 , 320μmol·L -1 , 10μmol·L -1 ; The reaction pH of the reaction solution is 3.0.

[0036] Figure 1 Shown are the reactions of three representative arylpropionic acid drugs with Fe 2+ / PMS reaction system after mixing. When the concentration of aryl propionic acid drugs in the reaction solution is 0, Fe 2+ / PMS reaction system will not produce chemiluminescent signal; when the concentration of aryl propionic acid drugs in the reaction solution is 10μmol·L -1 When Fe 2+ / PMS reaction system will produce a strong chemiluminescent signal. This example shows that the three representative aromatic propionic acid drugs can be used as luminescent reagents in water SO4 ·- The chemical method can be used to detect Fe in real time.2+ SO4 in PMS reaction system ·- The concentration variation law is impossible to achieve by the complete capture method and the competitive kinetics method.

[0037] Example 2

[0038] With the increase of PMS concentration, Fe 2+ SO4 in PMS reaction system ·- By changing the initial concentration of PMS, the Fe 2+ SO4 in PMS reaction system ·- Naproxen was selected as the luminescent reagent to detect Fe 2+ SO4 in PMS reaction system ·- The concentration of was analyzed semi-quantitatively. The specific steps are as follows:

[0039] Step (1) produces SO4 ·- The reaction system is mixed with a solution containing an aryl propionic acid drug in a certain mixing manner to obtain a reaction solution;

[0040] Step (2), detecting the chemiluminescence generated by the reaction solution in step (1) using a chemiluminescence analyzer;

[0041] Step (3), determine the SO4 in the reaction system according to the intensity of chemiluminescence ·- concentration.

[0042] The arylpropionic acid drug is naproxen;

[0043] The reaction system is Fe 2+ / PMS reaction system;

[0044] The mixing method is a stopped flow method;

[0045] The Fe 2+ , PMS, and arylpropionic acid drugs had initial concentrations of 40 μmol / L, 40-800 μmol / L, and 10 μmol / L, respectively;

[0046] The pH of the reaction solution is 3.0.

[0047] Figure 2 The results show that the relationship between naproxen and Fe under different PMS concentrations 2+ / PMS reaction system after mixing. With the increase of PMS concentration, the chemiluminescence signal increased significantly, indicating that the increase of PMS concentration increased the Fe 2+ SO4 in PMS reaction system ·- This embodiment shows that the present invention can be used in the reaction system SO4 ·-The semi-quantitative analysis provides a basis for the optimization of operating parameters in the reaction system.

[0048] Example 3

[0049] Fe 2+ / Add SO4 to PMS reaction system ·- The quencher will reduce the SO4 ·- The concentration of benzoic acid and SO4 ·- The reaction rate is faster, toward Fe 2+ Adding benzoic acid to the PMS reaction system can reduce the SO4 ·- concentration, naproxen was selected as the luminescent reagent to react with SO4 ·- The concentration of was analyzed semi-quantitatively. The specific steps are as follows:

[0050] Step (1) produces SO4 ·- The reaction system is mixed with a solution containing an aryl propionic acid drug in a certain mixing manner to obtain a reaction solution;

[0051] Step (2), detecting the chemiluminescence generated by the reaction solution in step (1) using a chemiluminescence analyzer;

[0052] Step (3), determine the SO4 in the reaction system according to the intensity of chemiluminescence ·- concentration.

[0053] The arylpropionic acid drug is naproxen;

[0054] The reaction system is Fe 2+ / PMS reaction system;

[0055] The mixing method is a stopped flow method;

[0056] The Fe 2+ , PMS, arylpropionic acid drugs, and benzoic acid had initial concentrations of 40 μmol / L, 40 μmol / L, 10 μmol / L, and 0-1000 μmol / L, respectively;

[0057] The pH of the reaction solution is 3.0.

[0058] Figure 3 The results show that the relationship between naproxen and Fe under different benzoic acid concentrations 2+ / PMS reaction system after mixing. 2+ As the concentration of benzoic acid in the / PMS reaction system increased, the chemiluminescence signal intensity gradually weakened, indicating that Fe 2+ SO4 in PMS reaction system ·-The concentration of benzoic acid decreases with the increase of benzoic acid concentration, which is consistent with the facts.

[0059] Example 4

[0060] Ferric ions (Fe 3+ ) and sulfite ion (SO3 2- ) reaction can generate SO4 ·- , so Fe 3+ / SO3 2- The reaction system is also a typical SO4-based ·- Naproxen was selected as the luminescent reagent to oxidize Fe 3+ / SO3 2- SO4 in the reaction system ·- The concentration of was analyzed semi-quantitatively. The specific steps are as follows:

[0061] Step (1) produces SO4 ·- The reaction system is mixed with a solution containing an aryl propionic acid drug in a certain mixing manner to obtain a reaction solution;

[0062] Step (2), detecting the chemiluminescence generated by the reaction solution in step (1) using a chemiluminescence analyzer;

[0063] Step (3), determine the SO4 in the reaction system according to the intensity of chemiluminescence ·- concentration.

[0064] The aromatic propionic acid drug is naproxen; the reaction system is Fe 3+ / SO3 2- Reaction system; the mixing method is static injection method; the reaction solution Fe 3+ 、SO3 2- The initial concentrations of the arylpropionic acid drugs were 40 μmol / L, 40 μmol / L, and 5 μmol / L, respectively; and the pH of the reaction solution was 3.0.

[0065] Figure 4 Shows naproxen and Fe 3+ / SO3 2- The chemiluminescence kinetic curve of the reaction system after mixing. 3+ / SO3 2- SO4 is produced in the reaction system ·- The rate is relatively slow and the duration is nearly 3 minutes. This embodiment further illustrates that the present invention can be used to study the reaction mechanism of advanced oxidation technology.

[0066] Example 5

[0067] Ferrous ion / hydrogen peroxide (Fe 2+ / H2O2) reaction system is a typical HO-based · Advanced oxidation technology. Therefore, Fe 2+ / H2O2 reaction system as the object, verify the method of the present invention to detect SO4 ·- The specific steps are as follows:

[0068] Step (1), Fe 2+ The / H2O2 reaction system and the naproxen solution are mixed in a certain mixing manner to obtain a reaction solution;

[0069] Step (2), using a chemiluminescence analyzer to detect the chemiluminescence generated by the reaction solution in step (1).

[0070] The mixing method is a stopped flow method;

[0071] The Fe 2+ The initial concentrations of H2O2 and aromatic propionic acid drugs were 40 μmol / L, 40 μmol / L and 10 μmol / L, respectively; and the pH of the reaction solution was 3.0.

[0072] Figure 5 Naproxen and Fe 2+ / H2O2 reaction system after mixing. 2+ After the / H2O2 reaction system was mixed, no chemiluminescent signal was generated, indicating that HO · There is no chemiluminescence phenomenon when reacting with naproxen, which further illustrates that the present invention can be used in HO · With SO4 ·- Specific detection of SO4 in a coexisting system ·- The content.

Claims

1. A method for semi-quantitative detection of sulfate free radicals using aryl propionic acid drugs, characterized in that: The following steps are involved: Step (1), mixing the reaction system that generates sulfate free radicals with a solution containing an aryl propionic acid drug 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; Step (2), detecting the chemiluminescence generated by the reaction solution in step (1) using a chemiluminescence analyzer; Step (3), determining the concentration of sulfate radicals in the reaction system according to the intensity of chemiluminescence.

2. The method for semi-quantitative detection of sulfate radicals using arylpropionic acid drugs according to claim 1, characterized in that: In step (1), Formula 1 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. The method for semi-quantitative detection of sulfate radicals using arylpropionic 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 radicals in the reaction system, and the concentration of sulfate radicals in the reaction system is determined based on the intensity of the chemiluminescence.

4. The method for semi-quantitative detection of sulfate radicals using arylpropionic acid drugs according to claim 1, characterized in that: In step (1), the aromatic propionic acid drug reacts with sulfate radicals to generate excited state molecules, thereby generating chemiluminescence.

5. The method for semi-quantitative detection of sulfate radicals using arylpropionic acid drugs according to claim 1, characterized in that: The method can specifically identify sulfate radicals in a reaction system where hydroxyl radicals and sulfate radicals coexist.

6. The method for semi-quantitative detection of sulfate radicals using arylpropionic acid drugs according to claim 1, characterized in that: In step (1), the concentration of the arylpropionic acid drug in the reaction solution should be greater than 0.5 μmol•L −1 .

7. The method for semi-quantitative detection of sulfate radicals using arylpropionic acid drugs according to claim 1, characterized in that: In step (3), the pH of the reaction system is 0-14.

8. The method for semi-quantitative detection of sulfate radicals using arylpropionic acid drugs according to claim 1, characterized in that: The method is suitable for the performance evaluation and reaction mechanism research of advanced oxidation technology based on sulfate free radicals.

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