CN108535347B - Method for distinguishing 6-hydroxyquinoline and isomer 3-hydroxyquinoline thereof - Google Patents
Method for distinguishing 6-hydroxyquinoline and isomer 3-hydroxyquinoline thereof Download PDFInfo
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Abstract
A method for distinguishing 6-hydroxyquinoline and an isomer thereof, namely 3-hydroxyquinoline, is characterized by comprising the following steps: application of "H2SO4‑KIO3‑[NiL](ClO4)2-malonic acid-H2O2The nonlinear chemical oscillation system is used as a distinguishing solution, and 6-hydroxyquinoline and an isomer 3-hydroxyquinoline thereof are distinguished according to different influences of the 6-hydroxyquinoline and the isomer 3-hydroxyquinoline on the system. The potential oscillation spectrum provided by the distinguishing method has intuition, can conveniently and quickly distinguish the 6-hydroxyquinoline and the isomer 3-hydroxyquinoline thereof, and has the advantages of simple equipment, high accuracy and easy operation and observation.
Description
Technical Field
The invention relates to a distinguishing method, in particular to a tetraazadecatetracyclodiennickel complex [ NiL](ClO4)2A method for distinguishing 6-hydroxyquinoline and an isomer 3-hydroxyquinoline thereof by a catalytic nonlinear chemical system belongs to the field of qualitative analytical chemistry.
Background
6-hydroxyquinoline and its isomer 3-hydroxyquinoline have the same molecular formula, belong to the same isomers of compounds, and play a very important role in each field. The 6-hydroxyquinoline is light yellow powder, is widely used for synthesizing dyes, medicine and pesticide intermediates and various chemical auxiliaries, and is one of important quinoline compounds. 3-hydroxyquinoline is a basic raw material for synthesizing medicaments, is commonly used as a medical intermediate and is mainly applied to the synthesis of antimalarial medicaments.
Because 6-hydroxyquinoline and 3-hydroxyquinoline isomer have the same molecular formula and similar structure, some physical and chemical properties of the 6-hydroxyquinoline and the 3-hydroxyquinoline isomer are similar, and the appearances of the 6-hydroxyquinoline and the 3-hydroxyquinoline are extremely similar, so that the 6-hydroxyquinoline and the 3-hydroxyquinoline are difficult to distinguish, and the structures of the 6-hydroxyquinoline and the isomers are shown in the following figures. Since the two kinds of hydroxyquinolines belong to positional isomers, the chemical properties and physical properties of the functional groups of the hydroxyquinolines are very close to each other, and the appearances of the hydroxyquinolines and the functional groups of the hydroxyquinolines are very similar, the hydroxyquinolines and the functional groups of the hydroxyquinolines are difficult to distinguish, which brings difficulty to qualitative analysis of the hydroxyquinolines, and the structures of the hydroxyquinolines are shown in the following figures. The methods for detecting 6-hydroxyquinoline and the isomer 3-hydroxyquinoline thereof reported at present mainly comprise thin layer chromatography, gas chromatography, spectrophotometry and high performance liquid chromatography. However, the identification method for distinguishing the two has not been reported, so that it is necessary to find a qualitative analysis method with good distinguishing effect, simple and fast operation and easily judged result. Both structural formulas are shown as formula (1)
Disclosure of Invention
The invention aims to provide a novel, convenient and quick distinguishing method for 6-hydroxyquinoline and 3-hydroxyquinoline isomer thereof, namely application of [ NiL](ClO4)2The method for distinguishing 6-hydroxyquinoline and 3-hydroxyquinoline isomer thereof by a catalytic nonlinear chemical oscillation system is an electrochemical oscillation system method developed based on the sharp response of the nonlinear chemical oscillation system catalyzed by the complex to 6-hydroxyquinoline and 3-hydroxyquinoline isomer thereof. Specifically, samples to be distinguished (6-hydroxyquinoline and 3-hydroxyquinoline) with the same concentration are respectively added into two groups of oscillation systems, and qualitative analysis of the samples to be distinguished is realized according to different influences of the samples to be distinguished on the oscillation systems: if the oscillation of the system is suppressed, a suppression period (t) is passedin) The post-oscillation is recovered, the oscillation period of the recovered oscillation is increased, and the oscillation frequency is increasedThe phenomenon of reduction is that the added sample to be distinguished is 6-hydroxyquinoline; if the oscillation system is not influenced, the added sample to be distinguished is 3-hydroxyquinoline, and the method has the advantages of short sample processing time, simple and easily controlled determination conditions, and convenient popularization and application.
The invention solves the technical problem and adopts the following technical scheme:
the invention provides a distinguishing method for 6-hydroxyquinoline and 3-hydroxyquinoline isomer thereof, which is characterized in that:
preparing a solution of a sample to be distinguished by using ethanol as a solvent;
application of "H2SO4- KIO3- [NiL](ClO4)2-malonic acid-H2O2The nonlinear chemical oscillation system is used as a distinguishing solution, an oscillation spectrum of the oscillation system is recorded, a solution of a sample to be distinguished is added into the oscillation system at any stable potential lowest point, and qualitative analysis of the sample to be distinguished is realized according to different influences of the sample to be distinguished on the oscillation system;
the samples to be distinguished are 6-hydroxyquinoline and 3-hydroxyquinoline;
to the two sets of discrimination solutions (non-linear system), solutions of the samples to be discriminated (6-hydroxyquinoline and 3-hydroxyquinoline) were added, respectively. If the samples to be distinguished are such that the oscillation of the system is suppressed, a suppression period (t) is passedin) The post-oscillation is recovered, and if the oscillation period of the recovered oscillation is increased and the oscillation frequency is reduced, the sample to be distinguished is 6-hydroxyquinoline; and if the sample to be distinguished has no influence on the oscillation system, the sample to be distinguished is 3-hydroxyquinoline.
The stable potential lowest point generated by oscillation is any one of the 3 rd to 25 th potential lowest points generated by oscillation.
The tetraazatetradecadienylnickel complex is tetraazamacrocyclic nickel (nickel) (with 5,7,7,12,14, 14-hexamethyl-1, 4,8, 11-tetraazatetradecyl-4, 11-diene as ligand
) Complexes, complexes and complexesThe formula is shown as formula (2) and is denoted as [ NiL](ClO4)2L is 5,7,7,12,14, 14-hexamethyl-1, 4,8, 11-tetraazatetradec-4, 11-diene;
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 6-hydroxyquinoline and 3-hydroxyquinoline.
[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. Still under ice-water bath conditions, to the clear solution was added 224mL of anhydrous acetone and stirred vigorously, the solution quickly becoming 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 discrimination method differs from the prior art in that the present invention employs "H2SO4-KIO3-[NiL](ClO4)2-malonic acid-H2O2The nonlinear chemical oscillation system is used as a distinguishing solution, and 6-hydroxyquinoline and an isomer 3-hydroxyquinoline thereof have different influences on an oscillation spectrum of the distinguishing solution, so that the 6-hydroxyquinoline and the isomer 3-hydroxyquinoline are distinguished.
6-hydroxyquinoline and 3-hydroxyquinoline in a detectable concentration range of 5.0X 10 in a discriminating solution (non-linear oscillatory system)-5-2.0×10-4mol/L。
The concentration ranges that can be distinguished by the solutions to be distinguished are the optimum concentration ranges determined experimentally. In the concentration range, the influence difference of the 6-hydroxyquinoline and the 3-hydroxyquinoline on the distinguishing solution is very obvious, and the distinguishing solution is easy to observe and analyze and realize distinguishing. 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) |
| 0.024375-0.025 | 0.01925-0.02275 | 6.4875×10-4-8.65×10-4 | 0.15-0.175 | 1.4-1.55 |
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 | 0.01925 | 8.65×10-4 | 0.15 | 1.55 |
The specific experimental steps are as follows:
1. preparing a distinguishing 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 contrast. And (3) respectively and rapidly adding the solutions of the samples to be distinguished into the two groups of distinguishing solutions with the same component concentration as the components in the blank control experiment at any stable potential lowest point generated by oscillation, and realizing qualitative analysis of the samples to be distinguished according to different influences of the samples to be distinguished on an oscillation system. Namely: after the solution of the sample to be distinguished is added into the oscillation system, the qualitative analysis of the sample to be distinguished is realized according to whether the sample to be distinguished can inhibit the system and has an inhibition period, and the phenomena of increased oscillation period and reduced oscillation frequency occur after the oscillation is recovered.
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.
Inhibition period (t)in): the time is required from the moment when the oscillation of the liquid to be tested is suppressed to the moment when the oscillation is recovered.
Drawings
FIG. 1 is a vibration pattern of a discrimination solution (vibration system) in example 1 when a sample to be discriminated is not added.
FIG. 2 is a graph of example 1, to which 5.00X 10 of-5After mol/L of 6-hydroxyquinoline, oscillating a response spectrum obtained by the system.
FIG. 3 is a graph of example 1, with 5.00X 10-5After mol/L of 3-hydroxyquinoline, oscillating a response spectrum obtained by the system.
FIG. 4 is a vibration pattern of the discrimination solution (vibration system) in example 2 when the sample to be discriminated is not added.
FIG. 5 is a graph of example 2, with 1.0X 10-4After mol/L of 6-hydroxyquinoline, oscillating a response spectrum obtained by the system.
FIG. 6 shows the addition of 1.0X 10 in example 2-4After mol/L of 3-hydroxyquinoline, oscillating a response spectrum obtained by the system.
FIG. 7 is a vibration pattern of the discrimination solution (vibration system) in example 3 when the sample to be discriminated is not added.
FIG. 8 is a graph of example 3, with the addition of 2.0X 10-4After mol/L of 6-hydroxyquinoline, oscillating a response spectrum obtained by the system.
FIG. 9 is a graph of example 3, with the addition of 2.0X 10-4Oscillation response spectrum obtained by oscillating system after mol/L3-hydroxyquinoline。
Detailed Description
Example 1:
this example verifies the feasibility of the method for distinguishing 6-hydroxyquinoline and its isomer 3-hydroxyquinoline of the present invention according to the following steps:
(1) preparing solution
Firstly, 98% concentrated sulfuric acid and distilled water are used to prepare 0.025mol/L sulfuric acid as stock solution, then 0.025mol/L sulfuric acid solution is used to prepare 0.14mol/L potassium iodate solution and 0.0173mol/L [ NiL ] solution](ClO4)2The solution, 2mol/L malonic acid solution and 4mol/L hydrogen peroxide solution. To a 50mL small beaker were added 14mL of a 0.025mol/L sulfuric acid solution, 5.5mL of a 0.14mol/L potassium iodate solution, and 2.0mL of 0.0173mol/L [ NiL ] in this order](ClO4)2Solution, 3mL of 2mol/L malonic acid solution and 15.5mL of 4mol/L hydrogen peroxide solution to ensure "H2SO4- KIO3- [NiL](ClO4)2-malonic acid-H2O2The concentrations of each component in the nonlinear chemical oscillation system are 0.025mol/L sulfuric acid, 0.01925mol/L potassium iodate and [ NiL ]](ClO4)28.65×10-4mol/L, 0.15mol/L of malonic acid and 1.55mol/L of hydrogen peroxide;
simultaneously, ethanol is used as a solvent to prepare 0.05mol/L of 6-hydroxyquinoline solution and 3-hydroxyquinoline solution respectively.
(2) Oscillation atlas
The oscillation pattern of the oscillating system was recorded by a computer equipped with the logger lite program, FIG. 1 showing the oscillation pattern at typical concentrations (0.025 mol/L sulfuric acid, 0.01925mol/L potassium iodate, [ NiL ] in](ClO4)28.65×10-4mol/L, 0.15mol/L of malonic acid and 1.55mol/L of hydrogen peroxide), and the above distinguishing solution is not added with the oscillation spectrum of the sample to be tested to be used as a blank control. Adding 40 mu L of 0.05 mol/L6-hydroxyquinoline and 3-hydroxyquinoline into two groups of distinguishing solutions with the same component concentration as the concentration so that the concentrations of the 6-hydroxyquinoline and the 3-hydroxyquinoline in the distinguishing solutions are 5.0 x 10-5mol/L, the time of each addition is at the lowest point of the 5 th potential of the oscillation map, and the obtained oscillation response maps are respectively shown in figure 2 and figure3, respectively.
(3) Distinguishing isomers
The 6-hydroxyquinoline and the isomer 3-hydroxyquinoline have different influences on an oscillation system due to different molecular space structures. As can be seen from FIG. 2, the addition of 6-hydroxyquinoline inhibits the oscillation of the system for a period of inhibition (t)in) The post-oscillation is recovered, and the phenomenon that the oscillation period is increased and the oscillation frequency is reduced occurs in the recovered oscillation; as can be seen from FIG. 3, the addition of 3-hydroxyquinoline has no effect on the oscillation system. As can be seen from the above experiments, the discrimination of 6-hydroxyquinoline and its isomer 3-hydroxyquinoline can be realized by comparing the changes of the oscillation spectrum.
Taking two 0.05mol/L solutions of samples to be distinguished (one is a 6-hydroxyquinoline solution, the other is 3-hydroxyquinoline, but the two are not distinguished) prepared in advance, and marking one of the 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 component concentration, respectively collecting corresponding oscillation maps, and respectively adding 40 mu L of 0.05mol/L of sample 1 and sample 2 at the 5 th potential lowest point to ensure that the concentrations of the two groups of oscillation solutions in the distinguishing solutions are 5.0 x 10-5mol/L。
The analysis and comparison can show that: sample 1 was added so that oscillation of the system was suppressed for a period of suppression (t)in) The post-oscillation is recovered, the oscillation cycle of the recovered oscillation is increased, and the oscillation frequency is reduced (the spectrum of the oscillation is corresponding to fig. 2 and is not corresponding to fig. 3), while the sample 2 has no influence on the oscillation spectrum (the spectrum of the oscillation is corresponding to fig. 3 and is not corresponding to fig. 2). Therefore, the sample 1 is the 6-hydroxyquinoline solution, and the sample 2 is the 3-hydroxyquinoline solution, so that the 6-hydroxyquinoline solution and the isomer 3-hydroxyquinoline solution thereof are distinguished.
Example 2:
this example verifies the feasibility of the method for distinguishing 6-hydroxyquinoline and its isomer 3-hydroxyquinoline of the present invention according to the following steps:
(1) preparing solution
Firstly, using 98% concentrated sulfuric acid to preparePreparing 0.025mol/L sulfuric acid as stock solution, and preparing 0.14mol/L potassium iodate solution and 0.0173mol/L [ NiL ] with 0.025mol/L sulfuric acid solution](ClO4)2The solution, 2mol/L malonic acid solution and 4mol/L hydrogen peroxide solution; to a 50mL beaker were added 14.5mL of a 0.025mol/L sulfuric acid solution, 6.5mL of a 0.14mol/L potassium iodate solution, and 1.5mL of 0.0173mol/L [ NiL ] in that order](ClO4)2Solution, 3.5mL of 2mol/L malonic acid solution, 14mL of 4mol/L hydrogen peroxide solution and so as to ensure "H2SO4- KIO3- [NiL](ClO4)2-malonic acid-H2O2The concentrations of each component in the nonlinear chemical oscillation system are 0.025mol/L sulfuric acid, 0.02275mol/L potassium iodate and [ NiL ]](ClO4)26.4875×10-4mol/L, 0.175mol/L of malonic acid and 1.4mol/L of hydrogen peroxide;
simultaneously, ethanol is used as a solvent to prepare 0.05mol/L of 6-hydroxyquinoline solution and 3-hydroxyquinoline solution respectively.
(2) Oscillation atlas
The oscillation spectrum of the above oscillation system was recorded by a computer equipped with a logger lite program, and the difference between the oscillation responses produced by high concentrations of 6-hydroxyquinoline and 3-hydroxyquinoline was examined. FIG. 4 is a graph of the oscillation spectrum of a discrimination solution without adding a test sample as a blank. Adding 80 mu L of 0.05mol/L6-hydroxyquinoline solution and 3-hydroxyquinoline solution into two groups of distinguishing solutions with the same component concentration as the above concentration respectively, so that the concentrations of the two groups of distinguishing solutions are 1.0 multiplied by 10-4mol/L, the time of each addition is at the lowest point of the 5 th potential of the oscillation map, and the obtained oscillation response maps are respectively shown in figures 5 and 6.
(3) Distinguishing isomers
The 6-hydroxyquinoline and the isomer 3-hydroxyquinoline have different influences on an oscillation system due to different molecular space structures. As can be seen from FIG. 5, the addition of 6-hydroxyquinoline inhibits the oscillation of the system for a period of inhibition (t)in) The post-oscillation is recovered, and the phenomenon that the oscillation period is increased and the oscillation frequency is reduced occurs in the recovered oscillation; as can be seen from FIG. 6, 3-The addition of the hydroxyquinoline has no influence on an oscillation system. As can be seen from the above experiments, the discrimination of 6-hydroxyquinoline and its isomer 3-hydroxyquinoline can be realized by comparing the changes of the oscillation spectrum.
Taking two 0.05mol/L solutions of samples to be distinguished (one is a 6-hydroxyquinoline solution, the other is 3-hydroxyquinoline, but the two are not distinguished) prepared in advance, and marking one of the 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 component concentration, respectively collecting corresponding oscillation maps, and respectively adding 80 mu L of 0.05mol/L of sample 1 and sample 2 at the 5 th potential lowest point to ensure that the concentrations of the two groups of oscillation solutions in the distinguishing solutions are 1.0 x 10-4mol/L。
The analysis and comparison can show that: sample 1 was added so that oscillation of the system was suppressed for a period of suppression (t)in) The post-oscillation recovers, and the oscillation cycle of the recovered oscillation increases and the oscillation frequency decreases (the map thereof corresponds to fig. 5 and does not correspond to fig. 6), while the sample 2 has no influence on the oscillation system (the map thereof corresponds to fig. 6 and does not correspond to fig. 5). Therefore, the sample 1 is the 6-hydroxyquinoline solution, and the sample 2 is the 3-hydroxyquinoline solution, so that the 6-hydroxyquinoline solution and the isomer 3-hydroxyquinoline solution thereof are distinguished.
Example 3:
this example verifies the feasibility of the method for distinguishing 6-hydroxyquinoline and its isomer 3-hydroxyquinoline of the present invention according to the following steps:
(1) preparing solution
Firstly, 98% concentrated sulfuric acid and distilled water are used to prepare 0.025mol/L sulfuric acid as stock solution, then 0.025mol/L sulfuric acid solution is used to prepare 0.14mol/L potassium iodate solution and 0.0173mol/L [ NiL ] solution](ClO4)2The solution, 2mol/L malonic acid solution and 4mol/L hydrogen peroxide solution. To a 50mL small beaker were added 14.2mL of a 0.025mol/L sulfuric acid solution, 6mL of a 0.14mol/L potassium iodate solution, and 1.8mL of 0.0173mol/L [ NiL ] in this order](ClO4)2Solution, 3mL of 2mol/L malonic acid solution, 14mL of 4mol/L hydrogen peroxide and 1 mL of steamDistilling the aqueous solution to ensure "H2SO4- KIO3-[NiL](ClO4)2-malonic acid-H2O2The concentrations of each component in the nonlinear chemical oscillation system are 0.024375mol/L sulfuric acid, 0.021mol/L potassium iodate and [ NiL](ClO4)27.785×10-4mol/L, 0.15mol/L of malonic acid and 1.4mol/L of hydrogen peroxide;
simultaneously, ethanol is used as a solvent to prepare 0.1 mol/L6-hydroxyquinoline solution and 3-hydroxyquinoline solution respectively.
(2) Oscillation atlas
The oscillation pattern of the oscillation system was recorded by a computer equipped with the logger lite program, and fig. 1 shows the oscillation pattern at high concentration without adding the sample to be measured to the above discrimination solution, as a blank control. Adding 80 mu L of 0.1 mol/L6-hydroxyquinoline and 3-hydroxyquinoline into two groups of distinguishing solutions with the same component concentration as the concentration so that the concentrations of the 6-hydroxyquinoline and the 3-hydroxyquinoline in the distinguishing solutions are 2.0 x 10-4mol/L, the time of each addition is at the lowest point of the 5 th potential of the oscillation map, and the obtained oscillation response maps are respectively shown in FIG. 8 and FIG. 9.
(3) Distinguishing isomers
The 6-hydroxyquinoline and the isomer 3-hydroxyquinoline have different influences on an oscillation system due to different molecular space structures. As can be seen from FIG. 8, the addition of 6-hydroxyquinoline inhibits the oscillation of the system for a period of inhibition (t)in) The post-oscillation is recovered, and the phenomenon that the oscillation period is increased and the oscillation frequency is reduced occurs in the recovered oscillation; as can be seen from FIG. 9, the addition of 3-hydroxyquinoline has no effect on the oscillation system. As can be seen from the above experiments, the discrimination of 6-hydroxyquinoline and its isomer 3-hydroxyquinoline can be realized by comparing the changes of the oscillation spectrum.
Taking two 0.1mol/L solutions of samples to be distinguished (one is a 6-hydroxyquinoline solution, the other is 3-hydroxyquinoline, but the two are not distinguished) prepared in advance, and marking one of the solutions as a sample 1 and the other as a sample 2;
preparing two groups of concentrations of each component and the concentrationsRespectively collecting corresponding oscillation maps of the same oscillation solution, and respectively adding 80 mu L of sample 1 and sample 2 of 0.1mol/L at the 5 th potential lowest point to ensure that the concentration of the samples in the discrimination solution is 2.0 x 10-4mol/L。
The analysis and comparison can show that: sample 1 was added so that oscillation of the system was suppressed for a period of suppression (t)in) The post-oscillation recovers, and the oscillation cycle of the recovered oscillation increases and the oscillation frequency decreases (the pattern thereof corresponds to fig. 8 and does not correspond to fig. 9), while the sample 2 has no influence on the oscillation pattern (the pattern thereof corresponds to fig. 9 and does not correspond to fig. 8). Therefore, the sample 1 is the 6-hydroxyquinoline solution, and the sample 2 is the 3-hydroxyquinoline solution, so that the 6-hydroxyquinoline solution and the isomer 3-hydroxyquinoline solution thereof are distinguished.
As can be seen from the above examples, solutions of 6-hydroxyquinoline and its isomer, 3-hydroxyquinoline, in smaller or larger concentrations can also be distinguished by the process of the present invention.
Claims (4)
1. A method for distinguishing 6-hydroxyquinoline and an isomer thereof, namely 3-hydroxyquinoline, is characterized by comprising the following steps:
preparing a solution of a sample to be distinguished by using ethanol as a solvent;
application of "H2SO4- KIO3- [NiL](ClO4)2-malonic acid-H2O2The nonlinear chemical oscillation system is used as a distinguishing solution, a potential oscillation spectrum of the potential variation of the oscillation system along with time is recorded, solutions of samples to be distinguished are respectively added into the two groups of distinguishing solutions at any stable potential lowest point in 3-25 times of oscillation, and the distinguishing of the samples to be distinguished is realized according to different influences of the samples to be distinguished on the oscillation system;
[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: 0.024375-0.025mol/L sulfuric acid, 0.01925-0.02275mol/L potassium iodate and [ NiL](ClO4)26.4875×10-4-8.65×10-4mol/L, 0.15-0.175mol/L of malonic acid and 1.4-1.55mol/L of hydrogen peroxide;
the sample to be distinguished is 6-hydroxyquinoline or 3-hydroxyquinoline.
2. The discrimination method according to claim 1, characterized in that:
respectively adding samples to be distinguished with the same concentration into the two groups of nonlinear oscillation systems, wherein if the solution to be distinguished is added, the oscillation of the systems is inhibited, the oscillation is recovered after a period of inhibition period, and the recovered oscillation has the phenomena of increased oscillation period and reduced oscillation frequency, so that the added samples to be distinguished are 6-hydroxyquinoline; if the oscillation system is not affected after the solution to be distinguished is added, the added sample to be distinguished is 3-hydroxyquinoline.
3. The distinguishing method according to claim 1 or 2, characterized in that: the molar concentrations of the components in the detection solution are 0.025mol/L sulfuric acid, 0.01925mol/L potassium iodate and [ NiL ]](ClO4)26.4875×10-4mol/L, 0.15mol/L of malonic acid and 1.55mol/L of hydrogen peroxide.
4. The distinguishing method according to claim 1 or 2, characterized in that: the detectable concentration range of the sample to be distinguished in the distinguishing solution is 5.0X 10-5-2.0×10-4mol/L。
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| CN110186983A (en) * | 2019-06-06 | 2019-08-30 | 安徽大学 | A kind of identification metal ion Cu2+And Ag+Method |
| CN111781255B (en) * | 2020-07-07 | 2024-04-09 | 安徽大学 | Method for distinguishing halogen anions Cl & lt- & gt and I & lt- & gt |
| CN112557478B (en) * | 2020-10-10 | 2024-04-09 | 安徽大学 | Method for distinguishing sodium phosphite and sodium hypophosphite of oxygen acid salts with different valence states of phosphorus |
| CN112557479B (en) * | 2020-11-22 | 2024-04-09 | 安徽大学 | Method for distinguishing alpha-naphthol and isomer beta-naphthol thereof |
| CN112557480A (en) * | 2020-11-22 | 2021-03-26 | 安徽大学 | Method for distinguishing tetracycline and doxycycline as isomer thereof |
| CN115032256B (en) * | 2022-05-17 | 2024-04-02 | 安徽大学 | Method for distinguishing chrysin and isomer 3,4' -dihydroxyflavone thereof |
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