CN113866244A - Method for distinguishing galangin and baicalein isomer thereof - Google Patents
Method for distinguishing galangin and baicalein isomer thereof Download PDFInfo
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- VCCRNZQBSJXYJD-UHFFFAOYSA-N galangin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=CC=C1 VCCRNZQBSJXYJD-UHFFFAOYSA-N 0.000 title claims abstract description 148
- UDFLTIRFTXWNJO-UHFFFAOYSA-N baicalein Chemical class O1C2=CC(=O)C(O)=C(O)C2=C(O)C=C1C1=CC=CC=C1 UDFLTIRFTXWNJO-UHFFFAOYSA-N 0.000 title claims abstract description 74
- CIPSYTVGZURWPT-UHFFFAOYSA-N galangin Natural products OC1=C(Oc2cc(O)c(O)cc2C1=O)c3ccccc3 CIPSYTVGZURWPT-UHFFFAOYSA-N 0.000 title claims abstract description 74
- SUYJZKRQHBQNCA-UHFFFAOYSA-N pinobanksin Natural products O1C2=CC(O)=CC(O)=C2C(=O)C(O)C1C1=CC=CC=C1 SUYJZKRQHBQNCA-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000010355 oscillation Effects 0.000 claims abstract description 86
- FXNFHKRTJBSTCS-UHFFFAOYSA-N Baicalein Natural products C=1C(=O)C=2C(O)=C(O)C(O)=CC=2OC=1C1=CC=CC=C1 FXNFHKRTJBSTCS-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229940015301 baicalein Drugs 0.000 claims abstract description 48
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims abstract description 32
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 32
- 238000001228 spectrum Methods 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 47
- 239000000523 sample Substances 0.000 claims description 37
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 32
- 230000005764 inhibitory process Effects 0.000 claims description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000012488 sample solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 5
- KXUFHWRWAGAWEW-UHFFFAOYSA-N 4-(2-aminoethylimino)-2-methyl-N-[2-(4-methylpentan-2-ylideneamino)ethyl]pentan-2-amine Chemical compound CC(=NCCN)CC(NCCN=C(CC(C)C)C)(C)C KXUFHWRWAGAWEW-UHFFFAOYSA-N 0.000 claims description 3
- 238000012850 discrimination method Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 119
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 12
- 239000001230 potassium iodate Substances 0.000 description 12
- 229940093930 potassium iodate Drugs 0.000 description 12
- 235000006666 potassium iodate Nutrition 0.000 description 12
- 230000001629 suppression Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000004451 qualitative analysis Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 244000062241 Kaempferia galanga Species 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 235000013421 Kaempferia galanga Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 208000026106 cerebrovascular disease Diseases 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 229930003935 flavonoid Natural products 0.000 description 2
- -1 flavonoid compounds Chemical class 0.000 description 2
- 235000017173 flavonoids Nutrition 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
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- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 102000036675 Myoglobin Human genes 0.000 description 1
- 108010062374 Myoglobin Proteins 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 240000004534 Scutellaria baicalensis Species 0.000 description 1
- 235000017089 Scutellaria baicalensis Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GAMYVSCDDLXAQW-AOIWZFSPSA-N Thermopsosid Natural products O(C)c1c(O)ccc(C=2Oc3c(c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O4)c3)C(=O)C=2)c1 GAMYVSCDDLXAQW-AOIWZFSPSA-N 0.000 description 1
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- 229940075397 calomel Drugs 0.000 description 1
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- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
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- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
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- 235000019633 pungent taste Nutrition 0.000 description 1
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- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/10—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using catalysis
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Abstract
A method for distinguishing galangin and baicalein isomer thereof is characterized in that: application of "H2SO4–KIO3‑[NiL](ClO4)2-malonic acid-H2O2The nonlinear chemical oscillation system is used as a distinguishing solution, and galangin and baicalein isomers are distinguished according to different influences of galangin and baicalein on the oscillation spectrum peak shapes of the oscillation system. The potential oscillation spectrum provided by the invention has intuition, can conveniently and quickly distinguish galangin and baicalein isomer 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 galangin from baicalein by a catalytic nonlinear chemical system belongs to the field of qualitative analytical chemistry.
Background
Galangin and its isomer baicalein are natural flavonoids. The antioxidant effect of the natural flavonoid compounds is widely applied to delaying senility and treating cardiovascular and cerebrovascular diseases. Galangin is a natural flavone compound extracted from the rhizome of galangal and is an important medicinal component in galangal. The natural plant galangal is used as a traditional Chinese medicine, collected in the Chinese pharmacopoeia of the calendar edition, has pungent and hot taste, can warm the stomach and dispel cold, regulate qi and alleviate pain, and is commonly used for treating abdominal psychroalgia, stomach cold and vomiting, improving microcirculation and the like. The galangal is reported to have the effects of resisting oxidation, resisting thrombus and the like. In vitro tumor cell simulation experiments prove that the compound has an inhibiting effect on the proliferation of various tumor cells. Baicalein is mainly present in Baikal skullcap root, and has effects of reducing vascular resistance, improving cerebral blood circulation, increasing cerebral blood flow and resisting platelet aggregation. The traditional Chinese medicine composition is clinically used for treating paralysis caused by cerebrovascular diseases. Because the galangin and the isomer baicalein thereof have the same molecular formula and similar structure, some physical and chemical properties of the galangin and the isomer baicalein are similar, and the appearances of the galangin and the isomer baicalein are extremely similar, so that the galangin and the isomer baicalein are difficult to distinguish, and difficulty is brought to qualitative analysis of the galangin and the baicalein. The structure is shown in formula (I). The reported methods for quantitatively detecting galangin and baicalein isomer thereof mainly comprise thin-layer chromatography, gas chromatography, spectrophotometry and high-performance liquid chromatography. However, a distinguishing method for distinguishing the two is not reported, so that it is necessary to find a qualitative analysis method which has a good distinguishing effect, is simple, convenient and quick to operate and has an easily-judged result.
Galangin baicalein
The structure of galangin and baicalein in formula 1.
Disclosure of Invention
The invention aims to provide a novel, convenient and quick distinguishing method for galangin and baicalein isomer thereof, namely application of [ NiL](ClO4)2The method for distinguishing galangin and baicalein isomer thereof by a catalytic nonlinear chemical oscillation system is an electrochemical oscillation system method developed based on the sharp response of the complex-catalyzed nonlinear chemical oscillation system to galangin and baicalein isomer thereof. Specifically, samples to be distinguished (solutions of galangin and baicalein) with the same concentration are respectively added into two groups of oscillation systems, and the qualitative determination of the samples to be distinguished is realized according to different influences of the samples to be distinguished on the peak shapes of oscillation spectra of the oscillation systemsAnd (3) analysis: if the inhibition phenomenon occurs after the solution to be distinguished is added, and the potential is continuously increased in the inhibition period, the added sample solution to be distinguished is galangin; if the inhibition phenomenon occurs after the solution to be distinguished is added, the potential increase process is not continuous in the inhibition period, a platform with unchanged potential is formed in the middle, or a concave platform caused by the slightly reduced potential and then increased potential is formed, the added sample solution to be distinguished is baicalein. 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 a distinguishing method for galangin and baicalein isomer thereof, which is characterized by comprising the following steps:
preparing a solution of galangin and baicalein to be distinguished samples by using distilled water 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 (a solution of galangin and baicalein) of a sample to be distinguished is added into two groups of distinguishing solutions (nonlinear systems) 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 peak shape of the oscillation spectrum of the oscillation system: if the inhibition phenomenon occurs after the solution to be distinguished is added, and the potential is continuously increased in the inhibition period, the added sample solution to be distinguished is galangin; if the inhibition phenomenon occurs after the solution to be distinguished is added, the potential increase process is not continuous in the inhibition period, a platform with unchanged potential is formed in the middle, or a concave platform caused by the slightly reduced potential and then increased potential is formed, the added sample solution to be distinguished is baicalein.
The stable potential lowest point generated by oscillation is any potential lowest point from 6 th to 21 th generated by oscillation.
Tetraazatetradecadiene as defined in the present inventionThe nickel complex is tetraazamacrocyclic nickel (5, 7,7,12,14, 14-hexamethyl-1, 4,8, 11-tetraazatetradec-4, 11-diene as ligand: (
) The structural formula of the complex is shown as the formula (
) Shown and described 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. The system has stable oscillation amplitude, long oscillation life and sharp response to galangin and baicalein.
[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 maintained under the conditions of the ice-water bath2-3 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 non-linear chemical oscillation system is used as the distinguishing solution, and galangin and its isomer baicalein are used in the peak shape of oscillation spectrum of the distinguishing solutionDifferent influences are achieved, and galangin and baicalein isomers thereof are distinguished.
Galangin and its isomer baicalein, and its detectable concentration range in solution (nonlinear oscillation system) is 1.0 × 10-5-2.75×10-5mol/L。
The concentration ranges that can be distinguished by the solutions to be distinguished are the optimum concentration ranges determined experimentally. Within the concentration range, the sample solution of galangin and the isomer baicalein thereof has obvious influence difference on the distinguishing solution, is easy to observe and analyze and is easy to distinguish. 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) | KIO3 (mol/L) | [NiL](ClO4)2 (mol/L) | Malonic acid (mol/L) | H2O2(mol/L) |
| 0.0074375-0.007465 | 0.02812-0.02825 | 0.002-0.003 | 0.13175-0.131875 | 1.5369-1.5375 |
Table 2: optimum concentration of each component in the oscillating system
| Sulfuric acid (mol/L) | KIO3 (mol/L) | [NiL](ClO4)2 (mol/) | Malonic acid (mol/L) | H2O2(mol/L) |
| 0.0074375 | 0.028125 | 0.0027 | 0.13175 | 1.5375 |
The specific experimental steps are as follows:
the reference electrode (calomel electrode) and the working electrode (Pt electrode) are inserted into a distinguishing solution (oscillation system), and are connected to a data acquisition unit through an Amplifier (Instrument Amplifier) and then connected to a computer, after a loader lite program in the computer is opened to set acquisition time and sampling speed, a start key is quickly clicked to monitor the potential of the solution, and an acquired E-t curve (a curve of the potential value changing along with the time), namely a chemical potential oscillation spectrum (at the moment, a sample to be detected is not added) is obtained to be used as blank contrast. And (3) respectively and rapidly adding the solution of the sample to be distinguished to any one stable potential lowest point generated by oscillation in two groups of distinguishing solutions with the same component concentration as that in the blank control experiment, and realizing qualitative analysis of the sample to be distinguished according to different influences of the sample to be distinguished on the oscillation spectrum peak shape of the 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 potential of the sample solution to be distinguished is continuously increased in the inhibition period.
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) potential 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 shows the addition of 1.0X 10 in example 1-5Oscillating the oscillation response spectrum obtained by the system after the galangin solution is mol/L.
FIG. 3 is a graph of example 1, with 1.0X 10-5Oscillating the oscillation response spectrum obtained by the system after the baicalein solution is mol/L.
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 2.0X 10-5 After the galangin solution is in mol/L, the oscillation spectrum of the solution (oscillation system) is distinguished.
FIG. 6 shows the result of example 2, with the addition of 2.0X 10-5 After the baicalein solution is in mol/L, distinguishing the oscillation spectrum of the solution (oscillation system).
FIG. 7 is a vibration pattern of the discrimination solution (vibration system) in example 3 without adding the sample to be discriminated.
FIG. 8 is a graph of example 3, with the addition of 2.75X 10-5After the galangin solution is in mol/L, the oscillation spectrum of the solution (oscillation system) is distinguished.
FIG. 9 is a graph of example 3, with the addition of 2.75X 10-5After the baicalein solution is in mol/L, distinguishing the oscillation spectrum of the solution (oscillation system).
Detailed Description
Example 1:
the feasibility of the method for distinguishing galangin and baicalein isomers thereof is verified according to the following steps:
(1) preparing solution
Firstly, 98% concentrated sulfuric acid and distilled water are used for preparing 0.025mol/L sulfuric acid as stock solution, and then 0.025mol/L sulfuric acid is used for dissolvingThe solution is respectively prepared into 0.15mol/L potassium iodate solution and 0.03mol/L [ NiL ]](ClO4)2The solution, 1.70mol/L malonic acid solution and 4.5mol/L hydrogen peroxide solution. Into a 50mL beaker were added 11.9mL of a 0.025mol/L sulfuric acid solution, 7.5mL of a 0.15mol/L potassium iodate solution, and 3.6mL of a 0.03mol/L [ NiL ] solution in that order](ClO4)2Solution, 3.1mL of 1.70mol/L malonic acid solution and 13.9mL of 4.5mol/L hydrogen peroxide solution to ensure "H2SO4 - KIO3 - [NiL](ClO4)2 -malonic acid-H2O2The concentrations of the components in the nonlinear chemical oscillation system are 0.0074375mol/L sulfuric acid, 0.028125mol/L potassium iodate and [ NiL ]](ClO4)2 0.0027mol/L, 0.13175mol/L malonic acid, 1.5375mol/L hydrogen peroxide;
meanwhile, distilled water is used as a solvent to prepare 0.01mol/L galangin solution and baicalein 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 (0.0074375 mol/L sulfuric acid, 0.028125mol/L potassium iodate, [ NiL ]](ClO4)2 0.0027mol/L, 0.13175mol/L malonic acid, 1.5375mol/L hydrogen peroxide), and the above discrimination solution is not added with the oscillation spectrum of the sample to be tested to be used as blank control. Adding 40 μ L of 0.01mol/L galangin solution and baicalein isomer thereof into two groups of discrimination solutions with the same component concentration as the above concentration, so that the concentration of galangin and baicalein isomer thereof in the discrimination solutions is 1.0 × 10-5mol/L, when the time is at the 6 th potential lowest point, the obtained oscillation response maps are respectively shown in FIG. 2 and FIG. 3.
(3) Distinguishing isomers
Due to the different properties of galangin and its isomer baicalein, galangin and its isomer baicalein have different effects on the oscillation system. Comparing fig. 2 and fig. 3 with fig. 1, respectively, it can be seen that the galangin solution shows an inhibition phenomenon, and the potential is continuously increased in the inhibition period; the baicalein solution is added, the inhibition phenomenon appears, the potential increase process is not continuous in the inhibition period, and a 'platform' with unchanged potential is formed in the middle. The experiments show that the galangin and the isomer baicalein thereof are distinguished by different influences on the map compared with the galangin and the isomer baicalein thereof.
Taking two 0.01mol/L solutions of galangin to be distinguished and baicalein isomers thereof (which are not distinguished yet) prepared in advance, and respectively marking the solutions as a sample 1 and 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 0.01mol/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 10-5mol/L。
The analysis and comparison can show that: with the addition of sample 1, a suppression phenomenon occurs, and the potential continues to increase during the suppression period (the oscillation pattern corresponds to fig. 2, and does not correspond to fig. 3); the addition of sample 2 resulted in the suppression phenomenon, and the potential increase process did not continue during the suppression period, and a "plateau" with unchanged potential was formed in the middle (the oscillation pattern corresponds to fig. 3, and does not correspond to fig. 2). Therefore, the sample 1 is a galangin solution, and the sample 2 is a baicalein solution, so that the galangin and an isomer thereof, namely the baicalein solution, can be distinguished.
Example 2:
the feasibility of the method for distinguishing galangin and baicalein isomers thereof is verified 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 0.15mol/L potassium iodate solution and 0.03mol/L [ NiL ] solution](ClO4)2The solution, 1.70mol/L malonic acid solution and 4.5mol/L hydrogen peroxide solution. Into a 50mL beaker were added 11.9mL of a 0.025mol/L sulfuric acid solution, 7.5mL of a 0.15mol/L potassium iodate solution, and 3.6mL of a 0.03mol/L [ NiL ] solution in that order](ClO4)2Solution, 3.1mL of 1.70mol/L malonic acid solution and 13.9mL of 4.5mol/L hydrogen peroxide solution to ensure "H2SO4 - KIO3 - [NiL](ClO4)2 -malonic acid-H2O2The concentrations of the components in the nonlinear chemical oscillation system are 0.0074375mol/L sulfuric acid, 0.028125mol/L potassium iodate and [ NiL ]](ClO4)2 0.0027mol/L, 0.13175mol/L malonic acid and 1.5375mol/L hydrogen peroxide.
Meanwhile, distilled water is used as a solvent to prepare 0.01mol/L galangin solution and baicalein solution respectively.
(2) Oscillation atlas
The oscillation pattern of the oscillating system was recorded by a computer equipped with the logger lite program, FIG. 4 is a graph of the oscillation pattern at typical concentrations (0.0074375 mol/L sulfuric acid, 0.028125mol/L potassium iodate, [ NiL ] N](ClO4)2 0.0027mol/L, 0.13175mol/L malonic acid, 1.5375mol/L hydrogen peroxide), and the above discrimination solution is not added with the oscillation spectrum of the sample to be tested to be used as blank control. Adding 0.01mol/L galangin solution and baicalein isomer solution into two groups of discrimination solutions with the same component concentration as the above concentration, respectively, so that the concentration of galangin and baicalein isomer in the discrimination solutions is 2.0 × 10-5mol/L, when the time is at the 6 th potential lowest point, the obtained oscillation response maps are respectively shown in FIG. 5 and FIG. 6.
(3) Distinguishing isomers
Due to the different properties of galangin and its isomer baicalein, galangin and its isomer baicalein have different effects on the oscillation system. As can be seen from comparison of fig. 5 and fig. 6 with fig. 4, respectively, the galangin solution shows an inhibition phenomenon, and the potential continues to increase during the inhibition period; the baicalein solution is added, the inhibition phenomenon appears, the potential increase process is not continuous in the inhibition period, and a 'platform' with unchanged potential is formed in the middle. The experiments show that the galangin and the isomer baicalein thereof are distinguished by different influences on the map compared with the galangin and the isomer baicalein thereof.
Taking two 0.01mol/L solutions of galangin to be distinguished and baicalein isomers thereof (which are not distinguished yet) prepared in advance, and respectively marking the solutions as a sample 3 and a sample 4;
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 0.01mol/L of samples 3 and 4 at the 6 th potential lowest point to ensure that the concentrations of the samples in the solution are 2.0 x 10-5mol/L。
The analysis and comparison can show that: with the addition of sample 3, a suppression phenomenon occurs, and the potential continues to increase during the suppression period (the oscillation pattern corresponds to fig. 5, and does not correspond to fig. 6); the addition of sample 4 resulted in a suppression phenomenon, and the potential increase process did not continue during the suppression period, forming a "plateau" with a constant potential (the oscillation pattern corresponds to fig. 6, and does not correspond to fig. 5). Therefore, the sample 3 is galangin solution, and the sample 4 is baicalein solution, so that the galangin and the isomer thereof baicalein solution are distinguished.
Example 3:
the feasibility of the method for distinguishing galangin and baicalein isomers thereof is verified 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 0.15mol/L potassium iodate solution and 0.03mol/L [ NiL ] solution](ClO4)2The solution, 1.70mol/L malonic acid solution and 4.5mol/L hydrogen peroxide solution. Into a 50mL beaker were added 11.9mL of a 0.025mol/L sulfuric acid solution, 7.5mL of a 0.15mol/L potassium iodate solution, and 3.6mL of a 0.03mol/L [ NiL ] solution in that order](ClO4)2Solution, 3.1mL of 1.70mol/L malonic acid solution and 13.9mL of 4.5mol/L hydrogen peroxide solution to ensure "H2SO4 - KIO3 - [NiL](ClO4)2 -malonic acid-H2O2The concentrations of the components in the nonlinear chemical oscillation system are 0.0074375mol/L sulfuric acid, 0.028125mol/L potassium iodate and [ NiL ]](ClO4)2 0.0027mol/L, 0.13175mol/L malonic acid and 1.5375mol/L hydrogen peroxide.
Meanwhile, distilled water is used as a solvent to prepare 0.01mol/L galangin solution and baicalein solution respectively.
(2) Oscillation atlas
The oscillating pattern of the oscillating system is recorded by a computer equipped with the logger lite program, FIG. 7 is the plot of the concentrations at typical concentrations (0.0084375 mol/L sulfuric acid, 0.0245mol/L potassium iodate, [ NiL ]](ClO4)2 0.000865mol/L, 0.15mol/L malonic acid, 1.45mol/L hydrogen peroxide), and the above discrimination solution is not added with the oscillation spectrum of the sample to be tested to be used as a blank control. Adding 110 μ L of 0.01mol/L galangin solution and baicalein isomer thereof into two groups of discrimination solutions with the same component concentration as the above concentration, so that the concentration of galangin and baicalein isomer thereof in the discrimination solutions is 2.75 × 10-5mol/L, when the time is at the 6 th potential lowest point, the obtained oscillation response maps are respectively shown in FIG. 8 and FIG. 9.
(3) Distinguishing isomers
Due to the different properties of galangin and its isomer baicalein, galangin and its isomer baicalein have different effects on the oscillation system. As can be seen from comparison of fig. 8 and 9 with fig. 7, respectively, the galangin solution shows an inhibition phenomenon, and the potential continues to increase during the inhibition period; the addition of the baicalein solution causes inhibition phenomenon, and the potential increase process is not continuous in the inhibition period, and a concave platform caused by slight potential decrease and then increase is formed in the middle. The experiments show that the effect of galangin and the isomer baicalein thereof on the map is different than that of galangin and the isomer baicalein thereof-The differentiation of (1).
Taking two 0.01mol/L solutions of galangin to be distinguished and baicalein isomers thereof (which are not distinguished yet) prepared in advance, and respectively marking the solutions as a sample 5 and a sample 6;
preparing two groups of oscillation solutions with the same component concentration as the concentration, respectively collecting corresponding oscillation maps, and respectively adding 110 mu L of 0.01mol/L samples 5 and 6 at the 6 th potential lowest point to ensure that the concentration of the samples in the solution is 2.75 multiplied by 10-5mol/L。
The analysis and comparison can show that: the addition of sample 5 resulted in a suppression phenomenon and the potential continued to increase during the suppression period (the oscillation pattern corresponds to fig. 8 and does not correspond to fig. 9), and the addition of sample 6 resulted in a suppression phenomenon and the potential increase did not continue during the suppression period, with the formation of a "pit" in the middle due to a slight decrease in potential and then an increase (the oscillation pattern corresponds to fig. 9 and does not correspond to fig. 8). Therefore, the sample 5 is a galangin solution, and the sample 6 is a baicalein solution, so that the galangin and an isomer thereof, namely the baicalein solution, can be distinguished.
Claims (3)
1. A method for distinguishing galangin and baicalein isomer thereof is characterized in that:
respectively preparing solutions of samples to be distinguished, which contain galangin and baicalein isomers thereof, by using distilled water 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 a distinguishing solution, recording a potential oscillation spectrum of the potential of the oscillation system along with the change of time, adding solutions respectively containing galangin and baicalein isomers thereof into two groups of distinguishing solutions at any stable potential lowest point of 6-21 potential lowest points generated by oscillation, and distinguishing samples according to different influences of the samples to be distinguished on the peak shape of the oscillation spectrum of the oscillation system: if the inhibition phenomenon occurs after the solution to be distinguished is added, and the potential is continuously increased in the inhibition period, the added sample solution to be distinguished is galangin; if the inhibition phenomenon occurs after the solution to be distinguished is added, the potential increase process is not continuous in the inhibition period, a platform with unchanged potential is formed in the middle, or a concave platform caused by the slightly reduced potential and then increased potential is formed, the added sample solution to be distinguished is baicalein;
[NiL](ClO4)2wherein L is 5,7,7,12,14, 14-hexamethyl-1, 4,8, 11-tetraazatetradec-4, 11-diene; the molar concentration of each component in the distinguishing solution is as follows: 0.0074375-0.007465mol/L, KIO sulfuric acid3 0.02812-0.02825mol/L、[NiL](ClO4)2 0.002-0.003mol/L, and malonic acid 0.13175-0.131875mol/L, H2O2 1.5369-1.5375mol/L。
2. The discrimination method according to claim 1, characterized in that: the molar concentration of each component in the solution is distinguished to be 0.0074375mol/L, KIO sulfuric acid3 0.028125mol/L、[NiL](ClO4)2 0.0027mol/L, malonic acid 0.13175mol/L, H mol2O2 1.5375mol/L。
3. The discrimination method according to claim 1, characterized in that: the detectable concentration range of the sample to be distinguished in the distinguishing solution is 1.0X 10-5-2.75×10-5mol/L。
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