CN108445068A - A method of differentiate 2 hydroxy 1,4 naphthoquinone (lawsone) and its isomer 5- hydroxyls to naphthoquinones - Google Patents
A method of differentiate 2 hydroxy 1,4 naphthoquinone (lawsone) and its isomer 5- hydroxyls to naphthoquinones Download PDFInfo
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Abstract
A method of differentiate 2 hydroxyl Isosorbide-5-Nitrae naphthoquinones and its 5 hydroxyl of isomer to naphthoquinones, it is characterised in that：Using " H2SO4 ‑ KIO3 ‑ [NiL](ClO4)2 Malonic acid H2O2" nonlinear chemical oscillation system is as differentiating solution; according to 2 hydroxyls 1; degree that 4 naphthoquinones and its 5 hydroxyl of isomer reduce current potential caused by the discriminating solution naphthoquinones is different, and then realizes the discriminating to 2 hydroxyl Isosorbide-5-Nitrae naphthoquinones and its 5 hydroxyl of isomer to naphthoquinones；[NiL](ClO4)2Middle L is 5,7,7,12,14,14 hexamethyl, 1,4,8,11 4 azepine, 14 diene.The oscillation collection of illustrative plates that identification method according to the present invention is provided has intuitive, can conveniently and efficiently identify 2 hydroxyl Isosorbide-5-Nitrae naphthoquinones and its 5 hydroxyl of isomer to naphthoquinones, and equipment is simple, accuracy is high, easily operated and observation.
Description
Technical field
The present invention relates to a kind of differentiation discrimination methods, specifically a kind of 14 cyclic diolefine nickel complex of four azepine
[NiL](ClO4)2 The nonlinear chemical oscillation system of catalysis is to 2 hydroxy 1,4 naphthoquinone (lawsone) and its isomer 5- hydroxyls to naphthalene
The discrimination method of quinone belongs to qualitative analysis chemical field.
Background technology
2-hydroxy-1,4-naphthoquinone and 5- hydroxyls belong to same point of aromatic compound to naphthoquinones molecular formula having the same
Isomers, structure such as formula（1）Shown, they play very important role in respective field each other.Hydroxyl -1 2-,
4- naphthoquinones is a kind of dyestuff being present in plant, external to prepare creme and lotion with it and 1,3-Dihydroxyacetone, due to it
Anti- screening ultraviolet spectrogram is wider, has been used as a kind of efficient chemical opacifier sick for treating and preventing linear skin.Have in recent years
There is the compound of 2 hydroxy 1,4 naphthoquinone (lawsone) structure to be often used as pesticide intermediate mouth, herbicide raw material, timber, bombax cotton, rubber
Preservative, reproducibility co-catalyst and dyestuff intermediate raw material of glue etc..2- hydroxyl 1,4- naphthoquinones not only can in pharmaceutical synthesis
As intermediate and raw material, and it can be used as the important intermediate of feed addictive.5- hydroxyls are called juglone to naphthoquinones, recklessly
Peach quinone is present in the Chinese olive skin of walnut Chinese catalpa.The Chinese olive skin of Juglans mandshurica, through frequently as a kind of anticancer in civil Chinese medicine prescription
Drug uses.The juglone isolated is extracted from Juglans mandshurica, for S180Solid tumor, morse ascites hepatoma clones with different metastatic ability and spontaneous breast
Gland cancer has apparent active anticancer.Juglone has also been applied to treat digestive system tumor, especially has to cancer of the esophagus, gastric cancer aobvious
Write curative effect.Juglone can also be added in cosmetics and toothpaste, be used as fungicide.Obviously, the application of juglone is very
Extensively, it is increasingly valued by people.Juglone also has hemostasis and antibacterial activity, is also once used to treat eczema, ox-hide
Make pH index agent dyestuff, pigment, spice material, pH indicator, pharmaceutical hemostat and treatment psoriasis drug with tinea capitis.
Since 2-hydroxy-1,4-naphthoquinone and 5- hydroxyls are identical to naphthoquinone molecule formula, structure is close, so that their one
A little physics and chemical property are also similar, and the appearance of the two is also very much like, and the two is caused to be difficult to differentiate between.Efficient liquid is established at present
Phase chromatography measures 2-hydroxy-1,4-naphthoquinone and 5- hydroxyls to naphthoquinones content simultaneously, this method have it is easy to operate, it is quickly etc. excellent
Point achieves promising result in actual sample application.Research of this method to 2 hydroxy 1,4 naphthoquinone (lawsone) and 5- hydroxyls to naphthoquinones
Quality control is of great significance in exploitation and production process, and for 2-hydroxy-1,4-naphthoquinone and 5- hydroxyls to naphthoquinones it
Between differentiation discrimination method rare report.It is accordingly required in particular to it is good to invent a kind of identification result, and it is easy to operate quickly, knot
The method that fruit easily determines differentiates both substances.
Invention content
The present invention is directed to provide a kind of novel to naphthoquinones for 2 hydroxy 1,4 naphthoquinone (lawsone) and 5- hydroxyls and conveniently distinguish
Discrimination method applies [NiL] (ClO4)2The nonlinear chemical oscillation system of catalysis is to 2 hydroxy 1,4 naphthoquinone (lawsone) and 5- hydroxyls pair
The discrimination method of naphthoquinones, this discrimination method are based on the complex-catalyzed nonlinear chemical oscillation system to 2- hydroxyls-Isosorbide-5-Nitrae-
A kind of electrochemical oscillation system method that naphthoquinones and its isomer 5- hydroxyls develop sharp respond of naphthoquinones.Specifically
It says, is by same concentrations sample to be identified（2 hydroxy 1,4 naphthoquinone (lawsone) and 5- hydroxyls are to naphthoquinones）It is added separately to two groups of oscillating bodies
In system, the degree reduced to the current potential caused by oscillation system according to sample to be identified is different, and sample to be identified is determined in realization
Property analysis：If after sample to be identified is added, rising rapidly after the rapid decline of current potential of oscillation system, then fast quick-recovery oscillation,
A downward line is had more on oscillation collection of illustrative plates, then the sample to be identified being added is 2-hydroxy-1,4-naphthoquinone；It waits reflecting if being added
After other style product, the current potential of oscillation system hardly reduces, and oscillation is barely affected, then the sample to be identified being added is 5- hydroxyls
Base is to naphthoquinones.And present invention processing sample time is short, determination condition is simple and easy to control to be easy to be extended and applied.
The present invention solves technical problem, adopts the following technical scheme that：
The present invention provides discrimination method for 2-hydroxy-1,4-naphthoquinone and its isomer 5- hydroxyls to naphthoquinones, and feature exists
In：
Using ethyl alcohol as solvent, the solution of sample to be identified is prepared；
Using " H2SO4 - KIO3 - [NiL](ClO4)2 Malonic acid-H2O2" the conduct discriminating of nonlinear chemical oscillation system
Solution records the oscillation collection of illustrative plates of oscillation system, when oscillation is in any one stable potential minimum point, adds into oscillation system
The solution for entering sample to be identified, the degree reduced to the current potential caused by oscillation system according to sample to be identified is different, realization pair
The qualitative analysis of sample to be identified；
The sample to be identified is 2 hydroxy 1,4 naphthoquinone (lawsone) and 5- hydroxyls to naphthoquinones；
To two groups of discriminating solution（Nonlinear system）In, it is separately added into sample to be identified（2 hydroxy 1,4 naphthoquinone (lawsone) and 5- hydroxyls pair
Naphthoquinones, but the two is not yet distinguished）Solution, it can be found that solution to be identified to caused by oscillation system current potential reduce degree
It is different.If after sample to be identified is added, rising rapidly after the rapid decline of current potential of oscillation system, then fast quick-recovery oscillation,
A downward line is had more on oscillation collection of illustrative plates, then the sample to be identified being added is 2-hydroxy-1,4-naphthoquinone；If being added to be identified
After sample, the current potential of oscillation system hardly reduces, and oscillation is barely affected, then the sample to be identified being added is 5- hydroxyls
To naphthoquinones.
It is described when oscillation in any one stable potential minimum point when, refer to when oscillation in the 3rd ~ 25 current potential it is minimum
Point when in any one.
So-called four azepines, the 14 cyclic diolefine nickel complex of the present invention is 5,7,7,12,14,14- vegolysens,
4,8,11- tetra- azepines 14-4,11- diene are four major esters nickel (II) complex of ligand, are denoted as [NiL] (ClO4)2,
L is 5,7,7,12,14,14- vegolysens, tetra- azepines of 4,8,11-, 14-4,11- diene；[NiL](ClO4)2Structure such as formula
（2）It is shown.
The key structure of myoglobins, hemoglobin, chlorophyll and some metalloenzyme in the structure and life entity of this complex
Porphyrin ring is much like, this with [NiL] (ClO4)2The chemical oscillating reaction of catalysis and the intracellular biochemical oscillation of plant and animal
It is similar.So the system has stable amplitude, longer oscillation service life and to 2-hydroxy-1,4-naphthoquinone and its isomerism
Body 5- hydroxyls have sharp response to naphthoquinones.
[NiL](ClO4)2Preparation in two steps：1) L2HClO is prepared4；2) by L2HClO4It prepares [NiL]
(ClO4)2。
1) L2HClO is prepared4：
98.5mL ethylenediamines are fitted into a 500mL three-necked bottle, under condition of ice bath, are slowly added dropwise under being stirred in 120 minutes
126mL70% perchloric acid.Initial reaction is violent and is generated with white cigarette, so rate of addition control is in every five seconds for example clock l drops.With
Reaction carries out suitably accelerating rate of addition, until dripping, obtains transparent solution.Still in the condition of ice-water bath
Under, 224mL anhydrous propanones are added to the clear solution and are vigorously stirred, solution becomes cloudy quickly is formed simultaneously very sticky mixing
Object.Still 2-3 hours are kept under conditions of ice-water bath fully to react.Products therefrom is transferred to Buchner funnel to take out
Filter separation, is used in combination acetone fully to wash, can obtain pure white solid.It will again be tied in this pure methanol-water solution in heat from color solid
Crystalline substance is dried in vacuo with silica-gel desiccant, obtains 80g white crystals, this white crystal is L2HClO4。
Bibliography：
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. Hu Gang, China Science ＆ Technology University's doctoral thesis, p25-27, Hefei, 2005.
2) by L2HClO4Prepare [NiL] (ClO4)2：
By 11g Ni (AC)24H2The L2HClO of O and 21g4It is placed in 500mL three-necked bottles, it is made to be dissolved in 250mL methanol, hot water
Bath is heated to reflux 3 hours, yellow mercury oxide finally occurs, and filtrate is concentrated into original volume l/2 by filtering in hot bath, is placed
Night, sufficient crystallising obtain yellow crystals.Yellow crystals are transferred to Buchner funnel and are washed with methanol, it is molten in the alcohol-water of heat
It is recrystallized in liquid, is dried in vacuo, 8g [NiL] (ClO can be obtained4)2Glassy yellow crystal.
Bibliography：
1. N. F. Curtis, J. Chem. Soc. Dolton Tran. , 1972, Vol. 13, 1357.
2. Hu Gang, China Science ＆ Technology University's doctoral thesis, p42-43, Hefei, 2005.
This identification method difference with the prior art is that the present invention applies " H2SO4 -KIO3-[NiL](ClO4)2- the third two
Acid-H2O2" nonlinear chemical oscillation system is as solution is differentiated, with 2-hydroxy-1,4-naphthoquinone and its isomer 5- hydroxyls pair
The degree that naphthoquinones reduces current potential caused by the discriminating solution is different, realizes to 2-hydroxy-1,4-naphthoquinone and 5- hydroxyls to naphthoquinones
The discriminating of isomer.2-hydroxy-1,4-naphthoquinone and 5- hydroxyls are differentiating solution to naphthoquinones（Non-Linear Ocsillation system）In
Detectable concentration range is 1.75 × 10-5-1×10-4mol/L。
The above-mentioned identifiable concentration range of solution to be identified is experimentally determined optimal concentration range.In the concentration range
Interior, 2-hydroxy-1,4-naphthoquinone and 5- hydroxyls are fairly obvious to potential change phenomenon caused by the discriminating solution to naphthoquinones, are easy to see
Examine analysis, discriminating easy to implement.In addition, differentiating solution（Oscillation system）The concentration range of middle each component is as shown in table 1, through excessive
It is secondary to test obtained discriminating solution（Oscillation system）Best solution it is as shown in table 2：
Table 1：The concentration range of each component in oscillation system
| Sulfuric acid (mol/L) | Potassiumiodate (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：The optium concentration of each component in oscillation system
| Sulfuric acid (mol/L) | Potassiumiodate (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 |
Steps are as follows for specific experiment：
1, it presses concentration range as defined in table 1 and prepares and differentiate solution, ready working electrode (platinum electrode) and reference electrode is (sweet
Mercury electrode) it is inserted into solution, the other end of working electrode is connected to data by amplifier (Instrument Amplifier)
Collector (Go!LINK) be then connected to computer, open in computer logger lite programs to acquisition time and sample rate into
After row setting, rapid start button of clicking obtains acquired E-t curves to carry out potential monitoring to solution（Potential value is at any time
Between the curve that changes）I.e. chemical potential vibrates collection of illustrative plates（Sample to be tested is not yet added at this time）, to make blank control.To two groups and sky
The identical differentiation of each component concentration in white control experiment differentiates in solution, is vibrating current potential of any one stabilization generated most
At low spot, it is rapidly added the solution of sample to be identified respectively, current potential caused by the discriminating solution is reduced according to sample to be identified
Degree it is different, realize the qualitative analysis to sample to be identified.
Chemical potential oscillation collection of illustrative plates basic parameter include：
Amplitude of oscillation：From a potential minimum to the potential difference next maximum potential in oscillatory process.
Cycle of oscillation：It is minimum from one in oscillatory process（It is high）Point is to next minimum（It is high）The time required to current potential.
Maximum potential：The current potential peak that system occurs when stable oscillation stationary vibration.
Potential minimum：The current potential minimum point that system occurs when stable oscillation stationary vibration.
Description of the drawings
Fig. 1 is when sample to be identified not being added, to differentiate solution in embodiment 1（Oscillation system）Oscillation collection of illustrative plates.
Fig. 2 is to be added 1.75 × 10 in embodiment 1-5After mol/L 2-hydroxy-1,4-naphthoquinone, what oscillation system was obtained
Oscillatory response collection of illustrative plates.
Fig. 3 is to be added 1.75 × 10 in embodiment 1-5After mol/L 5- hydroxyls are to naphthoquinones, what oscillation system was obtained shakes
Swing response collection of illustrative plates.
Fig. 4 is when sample to be identified not being added, to differentiate solution in embodiment 2（Oscillation system）Oscillation collection of illustrative plates.
Fig. 5 is to be added 5 × 10 in embodiment 2-5After mol/L 2-hydroxy-1,4-naphthoquinone, oscillation that oscillation system is obtained
Respond collection of illustrative plates.
Fig. 6 is to be added 5 × 10 in embodiment 2-5After mol/L5- hydroxyls are to naphthoquinones, oscillatory response that oscillation system is obtained
Collection of illustrative plates.
Fig. 7 is when sample to be identified not being added, to differentiate solution in embodiment 3（Oscillation system）Oscillation collection of illustrative plates.
Fig. 8 is to be added 1 × 10 in embodiment 3-4After mol/L 2-hydroxy-1,4-naphthoquinone, what oscillation system was obtained shakes
Swing response collection of illustrative plates.
Fig. 9 is to be added 1 × 10 in embodiment 3-4After mol/L 5- hydroxyls are to naphthoquinones, the oscillation that oscillation system is obtained is rung
Answer collection of illustrative plates.
Specific implementation mode
Embodiment 1：
The present embodiment verifies mirror of 2 hydroxy 1,4 naphthoquinone (lawsone) and its isomer the 5- hydroxyls of the present invention to naphthoquinones as follows
The feasibility of other method：
(1) solution is prepared
98% concentrated sulfuric acid is used to prepare the sulfuric acid solution of 0.025mol/L as solvent first；Then the sulfuric acid of 0.025mol/L is used
Solvent prepares the potassium iodate solution of 0.14mol/L, the malonic acid solution of 2.0mol/L, the hydrogenperoxide steam generator of 4.0mol/L respectively
With [NiL] (ClO of 0.0173mol/L4)2Solution.Then, 14.7ml is gradually added into the open system of 50ml beakers,
The sulfuric acid solution of 0.025mol/L;The potassium iodate solution of 6ml, 0.14mol/L；The catalyst of 2ml, 0.0173mol/L；3.3ml,
The malonic acid solution of 2.0mol/L；The hydrogenperoxide steam generator of 14ml, 4.0mol/L.Use above-mentioned solution as discriminating solution.Finally,
Differentiate solution（Oscillation system）A concentration of 0.025mol/L of middle sulfuric acid, a concentration of 0.021mol/L of Potassiumiodate, catalyst
A concentration of 8.65 × 10-4Mol/L, a concentration of 0.165mol/L of malonic acid, a concentration of 1.4mol/L of hydrogen peroxide.
Simultaneously with ethanol as solvent, the 2-hydroxy-1,4-naphthoquinone solution of preparation 0.01mol/L and 5- hydroxyls are to naphthalene respectively
Quinone solution.
(2) collection of illustrative plates is vibrated
The oscillation collection of illustrative plates of oscillation system is recorded by the computer equipped with logger lite programs, and Fig. 1 is under typical concentration（Sulphur
Sour 0.025mol/L, Potassiumiodate 0.021mol/L, [NiL] (ClO4)2 8.65×10-4Mol/L, malonic acid 0.165mol/L, mistake
Hydrogen oxide 1.4mol/L）, the oscillation collection of illustrative plates of sample to be tested is not added for above-mentioned discriminating solution, to make blank control.To two groups of each groups
Divide in concentration discriminating solution identical with above-mentioned concentration, is separately added into the 2-hydroxy-1,4-naphthoquinone and 5- of 70 μ L 0.01mol/L
Hydroxyl is to naphthoquinones so that its concentration in differentiating solution is 1.75 × 10-5Mol/L, the time being added every time are all to shake
It swings at the 6th current potential minimum point of collection of illustrative plates, the oscillatory response collection of illustrative plates difference obtained is as shown in Figure 2 and Figure 3.
(3) it distinguishes and differentiates
As 2-hydroxy-1,4-naphthoquinone and its isomer 5- hydroxyls to naphthoquinones because of spatial configuration of molecules difference, they are to mirror
The degree that current potential caused by other solution reduces is different.Compare Fig. 2 Fig. 3 it is found that 2-hydroxy-1,4-naphthoquinone addition so that oscillation
The current potential of system rises rapidly after declining rapidly, and then fast quick-recovery oscillation, a downward line is had more on oscillation collection of illustrative plates；5-
Addition of the hydroxyl to naphthoquinones, the current potential of system hardly reduce, and oscillation is barely affected, and collection of illustrative plates and blank assay collection of illustrative plates are basic
It coincide.By above-mentioned experiment it is found that whether having more a downward line by comparing current potential decline degree or collection of illustrative plates, may be implemented
Discriminating to 2 hydroxy 1,4 naphthoquinone (lawsone) and its isomer 5- hydroxyls to naphthoquinones.
Take the solution of the sample to be identified of two 0.01mol/L prepared in advance（One of them is 2 hydroxy 1,4 naphthoquinone (lawsone)
Solution, another is 5- hydroxyls to naphthoquinone solution, but the two is not yet distinguished）, it is 1 by one of label, another mark
It is denoted as sample 2；
Two groups of each component concentration oscillation solution identical with above-mentioned concentration is prepared, respectively the corresponding oscillation collection of illustrative plates of acquisition, and the 6th
The sample 1 and sample 2 of 70 μ l 0.01mol/L are separately added at a current potential minimum point so that their concentration in differentiating solution
It is 1.75 × 10-5mol/L。
Known to analysis relatively：The addition of sample 1 so that current potential rises rapidly after declining rapidly, then fast quick-recovery oscillation,
A downward line is had more on oscillation collection of illustrative plates (it is vibrated, and collection of illustrative plates is corresponding with Fig. 2, is not corresponded to Fig. 3).And sample 2 plus
Enter, current potential hardly reduces, and oscillation is barely affected, and collection of illustrative plates coincide substantially with blank assay collection of illustrative plates（It vibrates collection of illustrative plates and Fig. 3
It is corresponding, not corresponding with Fig. 2）.Therefore, it is 5- hydroxyls to naphthoquinone solution that sample 1, which is 2-hydroxy-1,4-naphthoquinone solution, sample 2,
To realize the discriminating to 2 hydroxy 1,4 naphthoquinone (lawsone) solution and its isomer 5- hydroxyls to naphthoquinone solution.
Embodiment 2：
The present embodiment verifies mirror of 2 hydroxy 1,4 naphthoquinone (lawsone) and its isomer the 5- hydroxyls of the present invention to naphthoquinones as follows
The feasibility of other method：
(1) solution is prepared
98% concentrated sulfuric acid is used to prepare the sulfuric acid solution of 0.025mol/L as solvent first；Then the sulfuric acid of 0.025mol/L is used
Solvent prepares the potassium iodate solution of 0.14mol/L, the malonic acid solution of 2.0mol/L, the hydrogenperoxide steam generator of 4.0mol/L respectively
With [NiL] (ClO of 0.0173mol/L4)2Solution.Then, 14ml is gradually added into the open system of 50ml beakers,
The sulfuric acid solution of 0.025mol/L;0.5ml distilled water;The potassium iodate solution of 6.5ml, 0.14mol/L；1.5ml,
The catalyst of 0.0173mol/L；The malonic acid solution of 3ml, 2.0mol/L；The hydrogenperoxide steam generator of 14.5ml, 4.0mol/L.With
Above-mentioned solution is as discriminating solution.Finally, differentiate solution（Oscillation system）A concentration of 0.0246875mol/L of middle sulfuric acid, acid iodide
A concentration of 0.02275mol/L of potassium, a concentration of the 6.4875 × 10 of catalyst-4Mol/L, a concentration of 0.15mol/ of malonic acid
L, a concentration of 1.45mol/L of hydrogen peroxide.
Simultaneously with ethanol as solvent, prepare respectively 0.05 mol/L 2-hydroxy-1,4-naphthoquinone solution and 5- hydroxyls to naphthalene
Quinone solution.
(2) collection of illustrative plates is vibrated
The oscillation collection of illustrative plates of above-mentioned oscillation system is recorded by the computer equipped with logger lite programs, investigates high concentration 2- hydroxyls-
The difference of 1,4- naphthoquinones and 5- hydroxyls between oscillatory response caused by naphthoquinones.Fig. 4 is when differentiating that sample to be tested is not added for solution
Oscillation collection of illustrative plates, to make blank control.Into two groups of each component concentration discriminating solution identical with above-mentioned concentration, it is separately added into 40
The 2-hydroxy-1,4-naphthoquinone solution and 5- hydroxyls of μ l 0.05mol/L is to naphthoquinone solution so that its concentration in differentiating solution
It is 5 × 10-5Mol/L, the time being added every time are all the oscillations that are obtained at the 6th current potential minimum point of oscillation collection of illustrative plates
It is as shown in Figure 5, Figure 6 to respond collection of illustrative plates difference.
(3) it distinguishes and differentiates
As 2-hydroxy-1,4-naphthoquinone and its isomer 5- hydroxyls to naphthoquinones because of spatial configuration of molecules difference, to oscillation
The influence that system generates also differs.Compare Fig. 5 Fig. 6 it is found that 2-hydroxy-1,4-naphthoquinone addition so that the electricity of oscillation system
Rise rapidly after the rapid decline in position, then fast quick-recovery oscillation, a downward line is had more on oscillation collection of illustrative plates；5- hydroxyls are to naphthalene
The current potential of the addition of quinone, system hardly reduces, and oscillation is barely affected, and collection of illustrative plates coincide substantially with blank assay collection of illustrative plates.By
Above-mentioned experiment may be implemented to 2- hydroxyls it is found that decline whether degree or collection of illustrative plates have more a downward line by comparing current potential
The discriminating of base -1,4- naphthoquinones and its isomer 5- hydroxyls to naphthoquinones.
Take the solution of the sample to be identified of two 0.05mol/L prepared in advance（One of them is 2 hydroxy 1,4 naphthoquinone (lawsone)
Solution, another is 5- hydroxyls to naphthoquinone solution, but the two is not yet distinguished）, it is 1 by one of label, another mark
It is denoted as sample 2；
Two groups of each component concentration oscillation solution identical with above-mentioned concentration is prepared, acquires corresponding oscillatory response collection of illustrative plates respectively, and
The sample 1 and sample 2 of 40 μ l 0.05mol/L are separately added at the 6th current potential minimum point so that they are in differentiating solution
A concentration of 5 × 10-5mol/L。
Known to analysis relatively：The addition of sample 1 so that current potential rises rapidly after declining rapidly, then fast quick-recovery oscillation,
A downward line is had more on oscillation collection of illustrative plates (it is vibrated, and collection of illustrative plates is corresponding with Fig. 5, is not corresponded to Fig. 6).And sample 2 plus
Enter, current potential hardly reduces, and oscillation is barely affected, and collection of illustrative plates coincide substantially with blank assay collection of illustrative plates（It vibrates collection of illustrative plates and Fig. 6
It is corresponding, not corresponding with Fig. 5）.Therefore, it is 5- hydroxyls to naphthoquinone solution that sample 1, which is 2-hydroxy-1,4-naphthoquinone solution, sample 2,
To realize the discriminating to 2 hydroxy 1,4 naphthoquinone (lawsone) solution and its isomer 5- hydroxyls to naphthoquinone solution.
Embodiment 3：
The present embodiment verifies mirror of 2 hydroxy 1,4 naphthoquinone (lawsone) and its isomer the 5- hydroxyls of the present invention to naphthoquinones as follows
The feasibility of other method：
(1) solution is prepared
98% concentrated sulfuric acid is used to prepare the sulfuric acid solution of 0.025mol/L as solvent first；Then the sulfuric acid of 0.025mol/L is used
Solvent prepares the potassium iodate solution of 0.14mol/L, the malonic acid solution of 2.0mol/L, the hydrogenperoxide steam generator of 4.0mol/L respectively
With [NiL] (ClO of 0.0173mol/L4)2Solution.Then, 15ml is gradually added into the open system of 50ml beakers,
The sulfuric acid solution of 0.025mol/L;The potassium iodate solution of 6ml, 0.14mol/L；The catalyst of 2ml, 0.0173mol/L；3.5ml,
The malonic acid solution of 2.0mol/L；The hydrogenperoxide steam generator of 13.5ml, 4.0mol/L.Use above-mentioned solution as discriminating solution.Most
Afterwards, differentiate solution（Oscillation system）A concentration of 0.025mol/L of middle sulfuric acid, a concentration of 0.021mol/L of Potassiumiodate, catalyst
A concentration of 8.65 × 10-4Mol/L, a concentration of 0.175mol/L of malonic acid, a concentration of 1.35mol/L of hydrogen peroxide.
Simultaneously with ethanol as solvent, the 2-hydroxy-1,4-naphthoquinone solution of preparation 0.05mol/L and 5- hydroxyls are to naphthoquinones respectively
Solution.
(2) collection of illustrative plates is vibrated
The oscillation collection of illustrative plates of above-mentioned oscillation system is recorded by the computer equipped with logger lite programs, investigates high concentration 2- hydroxyls-
The difference of 1,4- naphthoquinones and 5- hydroxyls between oscillatory response caused by naphthoquinones.Fig. 7 is when differentiating that sample to be tested is not added for solution
Oscillation collection of illustrative plates, to make blank control.To two groups of each component concentration discriminating solution identical with above-mentioned concentration, it is separately added into 80 μ l
The 2 hydroxy 1,4 naphthoquinone (lawsone) solution and 5- hydroxyls of 0.05mol/L is to naphthoquinones（3-methoxy-4-hydroxybenzaldehyde）Solution so that
Its concentration in differentiating solution is 1 × 10-4Mol/L, the time being added every time are all to vibrate the 6th current potential of collection of illustrative plates most
At low spot, the oscillatory response collection of illustrative plates difference obtained is as shown in Figure 8, Figure 9.
(3) it distinguishes and differentiates
As 2-hydroxy-1,4-naphthoquinone and its isomer 5- hydroxyls to naphthoquinones because of spatial configuration of molecules difference, to oscillation
The influence that system generates also differs.Compare Fig. 8 Fig. 9 it is found that 2-hydroxy-1,4-naphthoquinone addition so that the electricity of oscillation system
Rise rapidly after the rapid decline in position, then fast quick-recovery oscillation, a downward line is had more on oscillation collection of illustrative plates；5- hydroxyls are to naphthalene
The current potential of the addition of quinone, system hardly reduces, and oscillation is barely affected, and collection of illustrative plates coincide substantially with blank assay collection of illustrative plates.By
Above-mentioned experiment may be implemented to 2- hydroxyls it is found that decline whether degree or collection of illustrative plates have more a downward line by comparing current potential
The discriminating of base -1,4- naphthoquinones and its isomer 5- hydroxyls to naphthoquinones.
Take the solution of the sample to be identified of two 0.05mol/L prepared in advance（One of them is 2 hydroxy 1,4 naphthoquinone (lawsone)
Solution, another is 5- hydroxyls to naphthoquinone solution, but the two is not yet distinguished）, it is 1 by one of label, another mark
It is denoted as sample 2；
Two groups of each component concentration oscillation solution identical with above-mentioned concentration is prepared, acquires corresponding oscillatory response collection of illustrative plates, and the 6th
The sample 1 and sample 2 of 80 μ l 0.05mol/L are separately added at a current potential minimum point so that their concentration in differentiating solution
It is 1 × 10-4mol/L。
Known to analysis relatively：The addition of sample 1 so that current potential rises rapidly after declining rapidly, then fast quick-recovery oscillation,
A downward line is had more on oscillation collection of illustrative plates (it is vibrated, and collection of illustrative plates is corresponding with Fig. 8, is not corresponded to Fig. 9).And sample 2 plus
Enter, current potential hardly reduces, and oscillation is barely affected, and collection of illustrative plates coincide substantially with blank assay collection of illustrative plates（It vibrates collection of illustrative plates and Fig. 9
It is corresponding, not corresponding with Fig. 8）.Therefore, it is 5- hydroxyls to naphthoquinone solution that sample 1, which is 2-hydroxy-1,4-naphthoquinone solution, sample 2,
To realize the discriminating to 2 hydroxy 1,4 naphthoquinone (lawsone) solution and its isomer 5- hydroxyls to naphthoquinone solution.
By the above various embodiments as can be seen that the 2-hydroxy-1,4-naphthoquinone and its isomerism of smaller or larger concentration
Body 5- hydroxyls can also differentiate naphthoquinones by the method for the invention.
Claims (5)
1. a kind of differentiating the method for 2-hydroxy-1,4-naphthoquinone and its isomer 5- hydroxyls to naphthoquinones, it is characterised in that：
Using 0.025mol/L sulfuric acid as solvent, the solution of sample to be identified is prepared；
Using H2SO4 - KIO3 - [NiL](ClO4)2 Malonic acid-H2O2" nonlinear chemical oscillation system as differentiate it is molten
Liquid, the current potential for recording oscillation system change with time collection of illustrative plates, when oscillation is in any one stable potential minimum point, to two
Group differentiates solution（Non-Linear Ocsillation system）In be separately added into the solution of sample to be identified, it is molten to the discriminating according to sample to be identified
The degree that current potential caused by liquid reduces is different, realizes the discriminating to sample to be identified；
[NiL](ClO4)2Middle L is 5,7,7,12,14,14- vegolysens, tetra- azepines of 4,8,11-, 14-4,11-
Diene；Differentiate that the molar concentration of each component in solution is：Sulfuric acid 0.0246875-0.025mol/L, Potassiumiodate 0.021-
0.02275mol/L、[NiL](ClO4)26.4875×10-4-8.65×10-4Mol/L, malonic acid 0.15-0.175mol/L, mistake
Hydrogen oxide 1.35-1.45mol/L；
The sample to be identified is 2 hydroxy 1,4 naphthoquinone (lawsone) or 5- hydroxyls to naphthoquinones.
2. differentiation discrimination method according to claim 1, it is characterised in that：
When oscillation is in any one stable potential minimum point, to two groups of discriminating solution（Non-Linear Ocsillation system）It is middle to add respectively
Enter the sample to be identified of same concentrations（2-hydroxy-1,4-naphthoquinone or 5- hydroxyls are to naphthoquinones, but the two is not yet distinguished）If addition waits for
After differentiating sample, rise rapidly after the rapid decline of current potential of oscillation system, then fast quick-recovery oscillation, has more on oscillation collection of illustrative plates
One downward line, the then sample to be identified being added are 2-hydroxy-1,4-naphthoquinone；After if sample to be identified is added, oscillating body
The current potential of system hardly reduces, and oscillation is barely affected, then the sample to be identified being added is 5- hydroxyls to naphthoquinones.
3. detection method according to claim 1 or 2, it is characterised in that：The molar concentration of each component is in detection solution
Sulfuric acid 0.025mol/L, Potassiumiodate 0.021mol/L, [NiL] (ClO4)2 8.65×10-4Mol/L, malonic acid 0.165mol/L,
Hydrogen peroxide 1.4mol/L.
4. differentiation discrimination method according to claim 1 or 2, it is characterised in that：Any one of the oscillation generation is steady
Fixed current potential minimum point refers to any one in the 3rd ~ 25 current potential minimum point that oscillation generates.
5. discrimination method according to claim 1 or 2, it is characterised in that：Sample to be identified examining in differentiating solution
The concentration range of survey is 1.75 × 10-5-1×10-4mol/L。
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| CN110186982A (en) * | 2019-06-06 | 2019-08-30 | 安徽大学 | A kind of identification metal cations Fe3+And Ag+Method |
| CN110186983A (en) * | 2019-06-06 | 2019-08-30 | 安徽大学 | A kind of identification metal ion Cu2+And Ag+Method |
| CN112557479A (en) * | 2020-11-22 | 2021-03-26 | 安徽大学 | Method for distinguishing alpha-naphthol and beta-naphthol isomers thereof |
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