CN108445068B - Method for identifying 2-hydroxy-1, 4-naphthoquinone and isomer 5-hydroxy-naphthoquinone thereof - Google Patents
Method for identifying 2-hydroxy-1, 4-naphthoquinone and isomer 5-hydroxy-naphthoquinone thereof Download PDFInfo
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Abstract
A method for identifying 2-hydroxy-1, 4-naphthoquinone and its isomer 5-hydroxy-naphthoquinone is characterized in that: application of "H2SO4‑KIO3‑[NiL](ClO4)2-malonic acid-H2O2"non-linearisationThe chemical oscillation system is used as an identification solution, and the identification of the 2-hydroxy-1, 4-naphthoquinone and the isomer thereof, namely 5-hydroxy-naphthoquinone, is realized according to different degrees of potential reduction caused by the 2-hydroxy-1, 4-naphthoquinone and the isomer thereof, namely 5-hydroxy-naphthoquinone, to the identification solution; [ NiL ]](ClO4)2Wherein L is 5,7,7,12,14, 14-hexamethyl-1, 4,8, 11-tetraazatetradec-4, 11-diene. The oscillation spectrum provided by the identification method has intuition, can conveniently and quickly identify the 2-hydroxy-1, 4-naphthoquinone and the isomer 5-hydroxy-naphthoquinone thereof, and has the advantages of simple equipment, high accuracy and easy operation and observation.
Description
Technical Field
The invention relates to a distinguishing and identifying method, in particular to a tetraazadecatetracyclodiennickel complex [ NiL](ClO4)2A method for identifying 2-hydroxy-1, 4-naphthoquinone and isomer thereof, namely 5-hydroxy-naphthoquinone by a catalytic nonlinear chemical oscillation system belongs to the field of qualitative analytical chemistry.
Background
2-hydroxy-1, 4-naphthoquinone and 5-hydroxy para-naphthoquinone have the same molecular formula, belong to isomers of aromatic compounds, and have the structure shown in formula (1), and play important roles in each field. 2-hydroxy-1, 4-naphthoquinone is a dye present in plants, and is used in the form of cream and lotion formulated with 1, 3-dihydroxyacetone, as a highly effective chemical sunscreen for the treatment and prevention of linear skin diseases due to its broad UV screening spectrum. In recent years, compounds having a 2-hydroxy-1, 4-naphthoquinone structure have been used as agricultural chemical intermediates, raw materials for herbicides, wood, kapok fibers, preservatives for rubbers, reducing cocatalysts, raw materials for dye intermediates, and the like. The 2-hydroxy 1, 4-naphthoquinone can be used as an intermediate and a raw material in the synthesis of the medicine, and can also be used as an important intermediate of a feed additive. The 5-hydroxy naphthoquinone is also called juglone, and is present in the green pericarp of juglans mandshurica maxim. Chinese medicinal composition comprising Chinese olive peel of Juglans mandshuricaIt is often used as an anticancer drug. Juglone extracted from Juglans mandshurica Maxim, S180The solid tumor, mouse ascites type liver cancer and spontaneous breast cancer have obvious anticancer activity. Juglone has also been used in treating digestive system tumor, especially esophagus cancer and stomach cancer. The juglone can also be added into cosmetics and toothpaste to be used as bactericide. Obviously, juglone has wide application and is more and more valued by people. Juglone also has hemostatic and antibacterial activity, and has been used as pH indicator for treating eczema, psoriasis and psoriasis, dye, pigment, perfume material, pH indicator, medicinal hemostatic, and psoriasis.
Because 2-hydroxy-1, 4-naphthoquinone and 5-hydroxy-p-naphthoquinone have the same molecular formula and similar structure, some physical and chemical properties of the two naphthoquinones are similar, and the appearances of the two naphthoquinones are very similar, so that the two naphthoquinones are difficult to distinguish. The high performance liquid chromatography is established at present to simultaneously determine the content of 2-hydroxy-1, 4-naphthoquinone and 5-hydroxy-naphthoquinone, the method has the advantages of simple and rapid operation and the like, and a satisfactory effect is obtained in the application of practical samples. The method has important significance for research and development of 2-hydroxy-1, 4-naphthoquinone and 5-hydroxy-naphthoquinone and quality control in the production process, and few reports are made on a distinguishing and identifying method between 2-hydroxy-1, 4-naphthoquinone and 5-hydroxy-naphthoquinone. Therefore, it is particularly necessary to invent a method for identifying the two substances with good identification effect, simple and fast operation and easily judged result.
Disclosure of Invention
The invention aims to provide a novel, convenient and rapid distinguishing and identifying method for 2-hydroxy-1, 4-naphthoquinone and 5-hydroxy-naphthoquinone, namely application of [ NiL ]](ClO4)2The identification method of 2-hydroxy-1, 4-naphthoquinone and 5-hydroxy-naphthoquinone by using catalytic nonlinear chemical oscillation system is based on the sharp response of the complex-catalyzed nonlinear chemical oscillation system to 2-hydroxy-1, 4-naphthoquinone and its isomer 5-hydroxy-naphthoquinoneAn electrochemical oscillation system method has been developed. Specifically, samples to be identified (2-hydroxy-1, 4-naphthoquinone and 5-hydroxy-naphthoquinone) with the same concentration are respectively added into two groups of oscillation systems, and qualitative analysis of the samples to be identified is realized according to different degrees of potential reduction caused by the samples to be identified to the oscillation systems: if the potential of the oscillation system rapidly decreases and then rapidly rises after the sample to be identified is added, then the oscillation is rapidly recovered, and a downward line is added on the oscillation map, the added sample to be identified is 2-hydroxy-1, 4-naphthoquinone; if the potential of the oscillation system is hardly reduced and the oscillation is hardly affected after the sample to be identified is added, the added sample to be identified is 5-hydroxy-naphthoquinone. The invention has short sample processing time, simple and easily controlled measuring conditions and convenient popularization and application.
The invention solves the technical problem and adopts the following technical scheme:
the invention provides an identification method for 2-hydroxy-1, 4-naphthoquinone and isomer thereof, namely 5-hydroxy-naphthoquinone, which is characterized by comprising the following steps:
preparing a solution of a sample to be identified by using ethanol as a solvent;
application of "H2SO4- KIO3- [NiL](ClO4)2-malonic acid-H2O2The method comprises the following steps of taking a nonlinear chemical oscillation system as an identification solution, recording an oscillation spectrum of the oscillation system, adding a solution of a sample to be identified into the oscillation system when oscillation is at any one stable potential lowest point, and realizing qualitative analysis of the sample to be identified according to different potential reduction degrees of the sample to be identified to the oscillation system;
the samples to be identified are 2-hydroxy-1, 4-naphthoquinone and 5-hydroxy-p-naphthoquinone;
the degree of potential reduction caused by the solution to be identified to the oscillation system can be found to be different by adding the solutions of the samples to be identified (2-hydroxy-1, 4-naphthoquinone and 5-hydroxy-naphthoquinone, but the two are not distinguished) to the two groups of identification solutions (nonlinear system). If the potential of the oscillation system rapidly decreases and then rapidly rises after the sample to be identified is added, then the oscillation is rapidly recovered, and a downward line is added on the oscillation map, the added sample to be identified is 2-hydroxy-1, 4-naphthoquinone; if the potential of the oscillation system is hardly reduced and the oscillation is hardly affected after the sample to be identified is added, the added sample to be identified is 5-hydroxy-naphthoquinone.
When the oscillation is at any stable potential lowest point, the oscillation is at any 3 rd to 25 th potential lowest points.
The tetraazatetradecadiene nickel complex is a tetraazamacrocyclic nickel (II) complex taking 5,7,7,12,14, 14-hexamethyl-1, 4,8, 11-tetraazatetradecane-4, 11-diene as a ligand, and is marked as [ NiL](ClO4)2L is 5,7,7,12,14, 14-hexamethyl-1, 4,8, 11-tetraazatetradec-4, 11-diene; [ NiL ]](ClO4)2The structure is shown as formula (2).
The structure of the complex is very similar to that of key structure porphyrin ring of myoglobin, hemoglobin, chlorophyll and some metalloenzymes in a living body, and the structure is expressed by [ NiL](ClO4)2The catalyzed chemical oscillatory reaction is similar to biochemical oscillations within plant and animal cells. Therefore, the system has stable amplitude, long oscillation life and sharp response to 2-hydroxy-1, 4-naphthoquinone and isomer 5-hydroxy naphthoquinone.
[NiL](ClO4)2The preparation method comprises the following two steps: 1) preparation of L.2 HClO4(ii) a 2) From L.2 HClO4Preparation of [ NiL](ClO4)2。
1) Preparation of L.2 HClO4：
98.5mL of ethylenediamine were placed in a 500mL three-necked flask and 126mL of 70% perchloric acid were slowly added dropwise with stirring over 120 minutes under ice-bath conditions. The initial reaction was vigorous with white smoke generation, so the dropping rate was controlled to be one drop per 5 seconds. The dropping speed can be increased appropriately as the reaction proceeds until the dropping is completed, and a transparent solution is obtained. Adding the clear solution under ice-water bath224mL of anhydrous acetone and vigorous stirring, the solution quickly became cloudy and a very viscous mixture formed. Still under ice-water bath conditions for 2-3 hours for adequate reaction. And transferring the obtained product to a Buchner funnel for suction filtration and separation, and fully washing the product with acetone to obtain a pure white solid. Recrystallizing the self-color solid in hot methanol-water solution, and vacuum drying with silica gel desiccant to obtain 80g white crystal of L.2 HClO4。
Reference documents:
1.Curtis, N. F. and Hay, R. W. , J. Chem. Soc. , Chem. Commun. ,1966, p. 534.
2.Gang Hu, Panpan Chen, Wei Wang, Lin Hu, Jimei Song, Lingguang Qiu,Juan Song, E1ectrochimica Acta, 2007, Vol. 52, pp. 7996-8002.
3. Lin Hu, Gang Hu, Han-Hong Xu, J. Ana1. Chem. , 2006, Vol. 61, NO.10, pp. 1021-1025.
4. hugang, doctor's paper of Chinese university of science and technology, p25-27, fertilizer combination, 2005.
2) From L.2 HClO4Preparation of [ NiL](ClO4)2：
Mix 11g Ni (AC)24H2O and 21g of L.2 HClO4Placing in a 500mL three-necked bottle, dissolving in 250mL methanol, heating and refluxing in a hot water bath for 3 hours, finally generating yellow precipitate, filtering, concentrating the filtrate in the hot water bath to the original volume l/2, standing overnight, and fully crystallizing to obtain yellow crystals. The yellow crystals were transferred to a Buchner funnel and washed with methanol, recrystallized from hot ethanol-water solution, and dried under vacuum to give 8g of [ NiL ]](ClO4)2Bright yellow crystals.
Reference documents:
1. N. F. Curtis, J. Chem. Soc. Dolton Tran. , 1972, Vol. 13, 1357.
2. hugang, doctor's paper of Chinese university of science and technology, p42-43, fertilizer combination, 2005.
The present identification method is different from the prior art in that the present invention employs "H2SO4-KIO3-[NiL](ClO4)2-malonic acid-H2O2The non-linear chemical oscillation system is used as a discrimination solution, and the discrimination of 2-hydroxy-1, 4-naphthoquinone and 5-hydroxy-naphthoquinone isomers is realized by using 2-hydroxy-1, 4-naphthoquinone and isomers of 5-hydroxy-naphthoquinone in different degrees of potential reduction caused by the 2-hydroxy-1, 4-naphthoquinone and isomers of 5-hydroxy-naphthoquinone, wherein the detectable concentration range of 2-hydroxy-1, 4-naphthoquinone and 5-hydroxy-naphthoquinone in the discrimination solution (the non-linear oscillation system) is 1.75 × 10-5-1×10-4mol/L。
The concentration range identifiable by the solution to be identified is an optimum concentration range determined experimentally. In the concentration range, the potential change phenomena of the 2-hydroxy-1, 4-naphthoquinone and the 5-hydroxy-naphthoquinone to the identification solution are very obvious, and the identification solution is easy to observe and analyze and realize identification. In addition, the concentration ranges of the respective components in the discrimination solution (oscillation system) are shown in table 1, and the optimum solutions of the discrimination solution (oscillation system) obtained through a plurality of experiments are shown in table 2:
table 1: concentration range of each component in oscillating system
| Sulfuric acid (mol/L) | Potassium iodate (mol/L) | [NiL](ClO4)2 (mol/L) | Malonic acid (mol/L) | Hydrogen peroxide (mol/L) |
| 0.0246875-0.025 | 0.021-0.02275 | 6.4875×10-4-8.65×10-4 | 0.15-0.175 | 1.35-1.45 |
Table 2: optimum concentration of each component in the oscillating system
| Sulfuric acid (mol/L) | Potassium iodate (mol/L) | [NiL](ClO4)2 (mol/L) | Malonic acid (mol/L) | Hydrogen peroxide (mol/L) |
| 0.025 | 0.021 | 8.65×10-4 | 0.165 | 1.4 |
The specific experimental steps are as follows:
1. preparing an identification solution according to the concentration range specified in table 1, inserting a prepared working electrode (platinum electrode) and a reference electrode (calomel electrode) into the solution, connecting the other end of the working electrode to a data collector (Go | LINK) through an Amplifier (Instrument Amplifier), connecting the other end of the working electrode to a computer, starting a loader lite program in the computer to set the collection time and the sampling speed, quickly clicking a start key to monitor the potential of the solution, and obtaining an acquired E-t curve (the curve of the potential value changing along with the time), namely a chemical potential oscillation map (at the moment, a sample to be detected is not added) to be used as a blank control. And (3) respectively and rapidly adding the solution of the sample to be identified into two groups of distinguishing and identifying solutions with the same component concentration as those in the blank control experiment at any stable potential lowest point generated by oscillation, and realizing qualitative analysis of the sample to be identified according to different potential reduction degrees of the sample to be identified to the distinguishing solutions.
The basic parameters of the chemical potential oscillation spectrum include:
oscillation amplitude: the potential difference from one lowest potential to the next highest potential during oscillation.
Oscillation period: the time required from one lowest (high) point to the next lowest (high) potential during oscillation.
The highest potential: the highest potential point of the system appears when the system oscillates stably.
Lowest potential: the lowest point of potential of the system appears when the system oscillates stably.
Drawings
FIG. 1 is a vibration pattern of the discrimination solution (vibration system) in example 1 without adding the sample to be discriminated.
FIG. 2 is a graph of example 1, with 1.75 × 10 added-5And (3) oscillating the oscillation response spectrum obtained by the system after mol/L of 2-hydroxy-1, 4-naphthoquinone.
FIG. 3 is a graph of example 1, with 1.75 × 10 added-5And (3) oscillating the oscillation response spectrum obtained by the system after the mol/L of 5-hydroxy naphthoquinone is reacted.
FIG. 4 is a vibration pattern of the discrimination solution (vibration system) in example 2 without adding the sample to be discriminated.
FIG. 5 is a schematic representation of example 2, with addition of 5 × 10-5And (3) oscillating the oscillation response spectrum obtained by the system after mol/L of 2-hydroxy-1, 4-naphthoquinone.
FIG. 6 shows example 2 with 5 × 10 added-5And (3) oscillating the oscillation response spectrum obtained by the system after the naphthoquinone is subjected to mol/L5-hydroxyl.
FIG. 7 is a vibration pattern of the discrimination solution (vibration system) in example 3 without adding the sample to be discriminated.
FIG. 8 shows example 3 with 1 × 10 added-4And (3) oscillating the oscillation response spectrum obtained by the system after mol/L of 2-hydroxy-1, 4-naphthoquinone.
FIG. 9 is a schematic representation of example 3, with the addition of 1 × 10-4And (3) oscillating the oscillation response spectrum obtained by the system after the mol/L of 5-hydroxy naphthoquinone is reacted.
Detailed Description
Example 1:
this example verifies the feasibility of the method for identifying 2-hydroxy-1, 4-naphthoquinone and its isomer 5-hydroxy-naphthoquinone of the present invention according to the following steps:
(1) preparing solution
Firstly, preparing a 0.025mol/L sulfuric acid solution by using 98% concentrated sulfuric acid as a solvent; then 0.14mol/L potassium iodate solution, 2.0mol/L malonic acid solution, 4.0mol/L hydrogen peroxide solution and 0.0173mol/L [ NiL ] are respectively prepared by using 0.025mol/L sulfuric acid solvent](ClO4)2Then, 14.7ml of a 0.025mol/L sulfuric acid solution, 6ml of a 0.14mol/L potassium iodate solution, 2ml of a 0.0173mol/L catalyst, 3.3ml of a 2.0mol/L malonic acid solution, 14ml of a 4.0mol/L hydrogen peroxide solution were successively added to an open system of a 50ml beaker, and the above solution was used as an identification solution, and finally, the concentration of sulfuric acid in the identification solution (shaking system) was 0.025mol/L, the concentration of potassium iodate was 0.021mol/L, and the concentration of the catalyst was 8.65 × 10-4The mol/L, the concentration of malonic acid is 0.165mol/L, and the concentration of hydrogen peroxide is 1.4 mol/L.
Simultaneously, ethanol is used as a solvent to prepare 0.01 mol/L2-hydroxy-1, 4-naphthoquinone solution and 5-hydroxy-naphthoquinone solution respectively.
(2) Oscillation atlas
The oscillation spectrum of the oscillating system is recorded by a computer equipped with the logger lite program, FIG. 1 shows the oscillation spectrum at typical concentrations (0.025 mol/L sulfuric acid, 0.021mol/L potassium iodate, [ NiL ]](ClO4)28.65×10-4mol/L, 0.165mol/L malonic acid, 1.4mol/L hydrogen peroxide), and the above identification solution is not added with the oscillation spectrum of the sample to be tested to be used as a blank control. Adding into two groups of identification solutions with the same concentration as above70 μ L of 0.01 mol/L2-hydroxy-1, 4-naphthoquinone and 5-hydroxy-p-naphthoquinone were added so that the concentrations thereof in the discrimination solutions were each 1.75 × 10-5mol/L, the time of each addition is at the 6 th potential lowest point of the oscillation map, and the obtained oscillation response maps are respectively shown in FIG. 2 and FIG. 3.
(3) Distinguishing authentication
2-hydroxy-1, 4-naphthoquinone and its isomer 5-hydroxy paranaphthoquinone have different molecular spatial structures, and they have different degrees of potential reduction caused by identification solution. Comparing fig. 2 and fig. 3, it can be seen that the addition of 2-hydroxy-1, 4-naphthoquinone causes the electric potential of the oscillation system to rapidly decrease and then rapidly increase, and then the oscillation is rapidly resumed, and a downward line is added on the oscillation spectrum; the potential of the system is hardly reduced by adding the 5-hydroxyl to the naphthoquinone, the oscillation is hardly influenced, and the map is basically consistent with that of a blank experiment. From the above experiments, it can be known that identification of 2-hydroxy-1, 4-naphthoquinone and its isomer 5-hydroxy-naphthoquinone can be achieved by comparing the degree of potential drop or whether the map has one more downward line.
Taking two 0.01mol/L solutions of samples to be identified (one of which is a 2-hydroxy-1, 4-naphthoquinone solution and the other is a 5-hydroxy-naphthoquinone solution, but the two solutions are not distinguished) prepared in advance, marking one of the two solutions as a sample 1 and the other as a sample 2;
preparing two groups of oscillation solutions with the same component concentration as the concentration, respectively collecting corresponding oscillation maps, and respectively adding 70 mu L of 0.01mol/L sample 1 and sample 2 at the 6 th potential lowest point to enable the concentration of the two groups of oscillation solutions in the identification solution to be 1.75 × 10-5mol/L。
The analysis and comparison can show that: the addition of sample 1 caused a rapid decrease in potential followed by a rapid increase, followed by a rapid recovery of oscillation, with an additional downward line on the oscillation pattern (the oscillation pattern corresponds to fig. 2 and does not correspond to fig. 3). And the potential is hardly reduced and the oscillation is hardly influenced by adding the sample 2, and the spectrum is basically consistent with the blank experiment spectrum (the oscillation spectrum of the sample is corresponding to the graph 3 and is not corresponding to the graph 2). Therefore, the sample 1 is the 2-hydroxy-1, 4-naphthoquinone solution, and the sample 2 is the 5-hydroxy-naphthoquinone solution, so that the identification of the 2-hydroxy-1, 4-naphthoquinone solution and the isomer thereof, namely the 5-hydroxy-naphthoquinone solution, is realized.
Example 2:
this example verifies the feasibility of the method for identifying 2-hydroxy-1, 4-naphthoquinone and its isomer 5-hydroxy-naphthoquinone of the present invention according to the following steps:
(1) preparing solution
Firstly, preparing a 0.025mol/L sulfuric acid solution by using 98% concentrated sulfuric acid as a solvent; then 0.14mol/L potassium iodate solution, 2.0mol/L malonic acid solution, 4.0mol/L hydrogen peroxide solution and 0.0173mol/L [ NiL ] are respectively prepared by using 0.025mol/L sulfuric acid solvent](ClO4)2Then, 14ml of a 0.025mol/L sulfuric acid solution, 0.5ml of distilled water, 6.5ml of a 0.14mol/L potassium iodate solution, 1.5ml of a 0.0173mol/L catalyst, 3ml of a 2.0mol/L malonic acid solution, 14.5ml of a 4.0mol/L hydrogen peroxide solution were successively added to an open system of a 50ml beaker, and finally, the concentration of sulfuric acid in the identifying solution (shaking system) was 0.0246875mol/L, the concentration of potassium iodate was 0.02275mol/L, and the concentration of the catalyst was 6.4875 × 10 mol/L-4The mol/L, the concentration of malonic acid is 0.15mol/L, and the concentration of hydrogen peroxide is 1.45 mol/L.
Simultaneously, ethanol is used as a solvent to prepare 0.05 mol/L2-hydroxy-1, 4-naphthoquinone solution and 5-hydroxy-naphthoquinone solution respectively.
(2) Oscillation atlas
The difference between the oscillation responses generated by the high-concentration 2-hydroxy-1, 4-naphthoquinone and the 5-hydroxy-naphthoquinone is examined by recording the oscillation map of the oscillation system by a computer provided with a logger lite program, and the figure 4 is the oscillation map when the identification solution is not added to a sample to be tested to be used as a blank control-5mol/L, the time of each addition is at the 6 th potential lowest point of the oscillation map, and the obtained oscillation response maps are respectively shown in FIG. 5 and FIG. 6.
(3) Distinguishing authentication
The 2-hydroxy-1, 4-naphthoquinone and the isomer 5-hydroxy thereof have different influences on an oscillation system due to different molecular space structures. Comparing fig. 5 and fig. 6, it can be seen that the addition of 2-hydroxy-1, 4-naphthoquinone causes the electric potential of the oscillation system to rapidly decrease and then rapidly increase, and then the oscillation is rapidly resumed, and a downward line is added on the oscillation spectrum; the potential of the system is hardly reduced by adding the 5-hydroxyl to the naphthoquinone, the oscillation is hardly influenced, and the map is basically consistent with that of a blank experiment. From the above experiments, it can be known that identification of 2-hydroxy-1, 4-naphthoquinone and its isomer 5-hydroxy-naphthoquinone can be achieved by comparing the degree of potential drop or whether the map has one more downward line.
Taking two 0.05mol/L solutions of samples to be identified (one of which is a 2-hydroxy-1, 4-naphthoquinone solution and the other is a 5-hydroxy-naphthoquinone solution, but the two solutions are not distinguished) prepared in advance, marking one of the two solutions as a sample 1 and the other as a sample 2;
preparing two groups of oscillation solutions with the same component concentration as the concentration, respectively collecting corresponding oscillation response maps, and respectively adding 40 mu L of sample 1 and sample 2 with the concentration of 0.05mol/L at the 6 th potential lowest point to enable the concentration of the two groups of oscillation solutions to be 5 × 10 in the identification solution-5mol/L。
The analysis and comparison can show that: the addition of sample 1 caused a rapid decrease in potential followed by a rapid increase, followed by a rapid recovery of oscillation, with an additional downward line on the oscillation pattern (the oscillation pattern corresponds to fig. 5 and does not correspond to fig. 6). And the potential is hardly reduced and the oscillation is hardly influenced by adding the sample 2, and the spectrum is basically consistent with the blank experiment spectrum (the oscillation spectrum of the sample is corresponding to the graph 6 and is not corresponding to the graph 5). Therefore, the sample 1 is the 2-hydroxy-1, 4-naphthoquinone solution, and the sample 2 is the 5-hydroxy-naphthoquinone solution, so that the identification of the 2-hydroxy-1, 4-naphthoquinone solution and the isomer thereof, namely the 5-hydroxy-naphthoquinone solution, is realized.
Example 3:
this example verifies the feasibility of the method for identifying 2-hydroxy-1, 4-naphthoquinone and its isomer 5-hydroxy-naphthoquinone of the present invention according to the following steps:
(1) preparing solution
Firstly, preparing a 0.025mol/L sulfuric acid solution by using 98% concentrated sulfuric acid as a solvent; then 0.14mol/L potassium iodate solution, 2.0mol/L malonic acid solution, 4.0mol/L hydrogen peroxide solution and 0.0173mol/L [ NiL ] are respectively prepared by using 0.025mol/L sulfuric acid solvent](ClO4)2Then, 15ml of a 0.025mol/L sulfuric acid solution, 6ml of a 0.14mol/L potassium iodate solution, 2ml of a 0.0173mol/L catalyst, 3.5ml of a 2.0mol/L malonic acid solution, 13.5ml of a 4.0mol/L hydrogen peroxide solution were successively added to an open system of a 50ml beaker, and the above-mentioned solution was used as an identification solution, and finally, the concentration of sulfuric acid in the identification solution (shaking system) was 0.025mol/L, the concentration of potassium iodate was 0.021mol/L, and the concentration of the catalyst was 8.65 × 10-4The mol/L, the concentration of malonic acid is 0.175mol/L, and the concentration of hydrogen peroxide is 1.35 mol/L.
Simultaneously, ethanol is used as a solvent to prepare 0.05 mol/L2-hydroxy-1, 4-naphthoquinone solution and 5-hydroxy-naphthoquinone solution respectively.
(2) Oscillation atlas
The difference between the oscillation responses of the high-concentration 2-hydroxy-1, 4-naphthoquinone and 5-hydroxy-naphthoquinone was examined by recording the oscillation pattern of the above oscillation system with a computer equipped with a logger lite program, and fig. 7 is an oscillation pattern of the discrimination solution without adding a sample to be tested as a blank control, and 80 μ L of 0.05 mol/L2-hydroxy-1, 4-naphthoquinone solution and 5-hydroxy-naphthoquinone (4-hydroxy-3-methoxybenzaldehyde) solution were added to the two groups of discrimination solutions having the same component concentration as the above concentration, respectively, so that the concentrations thereof in the discrimination solutions were all 1 × 10-4mol/L, the time of each addition is at the 6 th potential lowest point of the oscillation map, and the obtained oscillation response maps are respectively shown in figures 8 and 9.
(3) Distinguishing authentication
The 2-hydroxy-1, 4-naphthoquinone and the isomer 5-hydroxy thereof have different influences on an oscillation system due to different molecular space structures. Comparing fig. 8 and fig. 9, it can be seen that the addition of 2-hydroxy-1, 4-naphthoquinone causes the electric potential of the oscillation system to rapidly decrease and then rapidly increase, and then the oscillation is rapidly resumed, and a downward line is added on the oscillation spectrum; the potential of the system is hardly reduced by adding the 5-hydroxyl to the naphthoquinone, the oscillation is hardly influenced, and the map is basically consistent with that of a blank experiment. From the above experiments, it can be known that identification of 2-hydroxy-1, 4-naphthoquinone and its isomer 5-hydroxy-naphthoquinone can be achieved by comparing the degree of potential drop or whether the map has one more downward line.
Taking two 0.05mol/L solutions of samples to be identified (one of which is a 2-hydroxy-1, 4-naphthoquinone solution and the other is a 5-hydroxy-naphthoquinone solution, but the two solutions are not distinguished) prepared in advance, marking one of the two solutions as a sample 1 and the other as a sample 2;
preparing two groups of oscillation solutions with the same component concentration as the concentration, collecting corresponding oscillation response maps, and respectively adding 80 mu L of sample 1 and sample 2 with the concentration of 0.05mol/L at the 6 th potential lowest point to enable the concentration of the two groups of oscillation solutions to be 1 × 10 in the identification solution-4mol/L。
The analysis and comparison can show that: the addition of sample 1 caused a rapid decrease in potential followed by a rapid increase, followed by a rapid recovery of oscillation, with an additional downward line on the oscillation pattern (the oscillation pattern corresponds to fig. 8 and does not correspond to fig. 9). And the potential is hardly reduced and the oscillation is hardly influenced by adding the sample 2, and the spectrum is basically consistent with the blank experiment spectrum (the oscillation spectrum of the sample is corresponding to the graph 9 and is not corresponding to the graph 8). Therefore, the sample 1 is the 2-hydroxy-1, 4-naphthoquinone solution, and the sample 2 is the 5-hydroxy-naphthoquinone solution, so that the identification of the 2-hydroxy-1, 4-naphthoquinone solution and the isomer thereof, namely the 5-hydroxy-naphthoquinone solution, is realized.
As can be seen from the above examples, smaller or larger concentrations of 2-hydroxy-1, 4-naphthoquinone and its isomer 5-hydroxy para-naphthoquinone can also be identified by the method of the present invention.
Claims (4)
1. A method for identifying 2-hydroxy-1, 4-naphthoquinone and its isomer 5-hydroxy-naphthoquinone is characterized in that:
taking 0.025mol/L sulfuric acid as a solvent to prepare a solution of 2-hydroxy-1, 4-naphthoquinone or 5-hydroxy-naphthoquinone of a sample to be identified;
application of "H2SO4- KIO3-[NiL](ClO4)2-malonic acid-H2O2The non-linear chemical oscillation system is used as an identification solution, a change map of the potential of the oscillation system along with time is recorded, when the oscillation is at the lowest point of any stable potential, the solutions of samples to be identified are respectively added into two groups of identification solutions, and the identification of the samples to be identified is realized according to the difference of the potential reduction degrees of the samples to be identified to the identification solutions: if the potential of the oscillation system rapidly decreases and then rapidly rises after the sample to be identified is added, then the oscillation is rapidly recovered, and a downward line is added on the oscillation map, the added sample to be identified is 2-hydroxy-1, 4-naphthoquinone; if the potential of the oscillation system is hardly reduced and the oscillation is hardly affected after the sample to be identified is added, the added sample to be identified is 5-hydroxy-naphthoquinone;
[NiL](ClO4)2wherein L is 5,7,7,12,14, 14-hexamethyl-1, 4,8, 11-tetraazatetradec-4, 11-diene; identifying the molar concentrations of the components in the solution as follows: 0.0246875-0.025mol/L sulfuric acid, 0.021-0.02275mol/L potassium iodate and [ NiL](ClO4)26.4875×10-4-8.65×10-4mol/L, 0.15-0.175mol/L of malonic acid and 1.35-1.45 mol/L of hydrogen peroxide.
2. The method of claim 1, wherein: the molar concentrations of the components in the detection solution are 0.025mol/L sulfuric acid, 0.021mol/L potassium iodate and [ NiL](ClO4)28 .65×10-4mol/L, 0.165mol/L of malonic acid and 1.4mol/L of hydrogen peroxide.
3. The method according to claim 1 or 2, characterized in that: the stable potential lowest point generated by oscillation is any one of the 3 rd to 25 th potential lowest points generated by oscillation.
4. Method according to claim 1 or 2, characterized in thatThe detectable concentration range of the sample to be identified in the identification solution is 1.75 × 10-5-1×10-4mol/L。
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