CN104730127A - Identification method of aliphatic chain isomer alpha-oxoglutarate and 1, 3-acetone dicarboxylic acid - Google Patents
Identification method of aliphatic chain isomer alpha-oxoglutarate and 1, 3-acetone dicarboxylic acid Download PDFInfo
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Abstract
The invention discloses an identification method of aliphatic chain isomer alpha-oxoglutarate and 1,3-acetone dicarboxylic acid. The identification method is characterized by comprising the following steps that with an H<2>SO<4>-KIO<3>-[NiL](ClO<4>)<2>-MA-H<2>O<2> nonlinear chemical oscillation system as an identification solution, differential identification of the aliphatic chain isomer is realized according to an oscillation response of the system generated by the aliphatic chain isomer; L in [NiL](ClO<4>)<2> is 5, 7, 7, 12, 14, 14-hexamethyl-1, 4, 8, 11-tetraaza tetradecyl-4, 11-diene. An oscillation map provided by the identification method is relatively high in intuition; moreover, the aliphatic chain isomer alpha-oxoglutarate and 1,3-acetone dicarboxylic acid can be conveniently and quickly identified, and the method can also be widely used in other isomers; in addition, identification equipment is simple, high in accuracy and easy to operate and observe.
Description
Technical field
The present invention relates to a kind of differentiation discrimination method, specifically a kind of four azepine 14 cyclic diolefine nickel complex [NiL] (ClO
4)
2the nonlinear chemical system of catalysis is to the discrimination method of aliphatics chain isomers α-ketoglutaric acid and 1,3-acetone dicarboxylic acid.
Technical background
α-ketoglutaric acid and 1,3-acetone dicarboxylic acid have identical molecular formula, belong to the isomers of aliphatics chain together, play very important role each other in respective field.α-ketoglutaric acid is as one of the intermediate product of tricarboxylic acid cycle in life entity, not only be widely used for measuring the substrate of aminotransferase and dehydrogenasa and measuring the matched reagent of liver function, also can be used as organic synthesis intermediate, in addition, it is also the important additives of medicine, health products and food; And 1,3-acetone dicarboxylic acid is then one of important medicine intermediate, also can be used for the anticholinergic agent such as atropine, anisodamine simultaneously.
Because α-ketoglutaric acid is identical with 1,3-acetone dicarboxylic acid molecular formula, structure is close, make some physics and chemistry character also similar, and both outward appearances are also very similar, cause both to be difficult to distinguish.Usually use the instrumental method such as reversed-phase high-performance liquid chromatography (RP-HPLC) and reverse-phase paired ion chromatography (IPC) to carry out assay to α-ketoglutaric acid at present, or adopt paper chromatographic analysis (PC) to carry out Analysis and Identification to it; And for the mensuration of 1,3-acetone dicarboxylic acid or discrimination method and the rare report of the differentiation discrimination method between α-ketoglutaric acid and 1,3-acetone dicarboxylic acid.Therefore, need to invent a kind of identification result especially good, and easy and simple to handle fast, the method that easily judges of result to be to differentiate this two kinds of materials.
Summary of the invention
The present invention is intended to provide a kind of novelty for aliphatics chain isomers α-ketoglutaric acid and 1,3-acetone dicarboxylic acid and conveniently distinguish discrimination method, namely with four azepine 14 cyclic diolefine nickel complex [NiL] (ClO
4)
2the nonlinear chemical system of catalysis is to α-ketoglutaric acid and 1, the discrimination method of 3-acetone dicarboxylic acid, this discrimination method is a kind of electrochemical oscillation system method developed the acumen response of aliphatics chain isomers based on this complex-catalyzed nonlinear chemical system (i.e. oscillation system).Specifically sample to be identified for same concentrations is joined in oscillation system, according to the oscillatory response (change of the collection of illustrative plates that namely vibrates) that sample to be identified produces oscillation system, realize the qualitative analysis to sample to be identified.
Technical solution problem of the present invention, adopts following technical scheme:
The discrimination method of aliphatics chain isomers α-ketoglutaric acid of the present invention and 1,3-acetone dicarboxylic acid, its feature is:
Be solvent with redistilled water, prepare the solution of sample to be identified;
Application " H
2sO
4-KIO
3-[NiL] (ClO
4)
2-MA-H
2o
2" nonlinear chemical oscillation system as discriminating solution; record oscillation system vibration collection of illustrative plates; any one stable current potential minimum point place; add the solution of sample to be identified in oscillation system; according to the oscillatory response that sample to be identified produces oscillation system, realize the qualitative analysis to sample to be identified;
Described sample to be identified is α-ketoglutaric acid or 1,3-acetone dicarboxylic acid;
After the solution adding sample to be identified in oscillation system, reduce again if sample to be identified makes the amplitude of oscillation of oscillation system first increase, then described sample to be identified is 1,3-acetone dicarboxylic acid, if and sample to be identified does not almost affect oscillation system, then described sample to be identified is α-ketoglutaric acid.
Wherein vibrate produce any one stable current potential minimum point refer to vibration produce 3rd ~ 25 current potential minimum points in any one.
Four azepine 14 cyclic diolefine nickel complexes alleged by the present invention are 5,7,7,12,14,14-vegolysen, 4,8,11-tetra-azepine ten four-4,11-diene is four major esters nickel (II) complex of part, and structural formula such as formula shown in (1), and is denoted as [NiL] (ClO
4)
2, L is 5,7,7,12,14,14-vegolysen, 4,8,11-tetra-azepine ten four-4,11-diene;
The structure of this complex is very similar to the key structure porphyrin ring of myoglobins, haemoglobin, chlorophyll and some metalloenzyme in life entity, this with [NiL] (ClO
4)
2the chemical oscillating reaction of catalysis and the intracellular biochemical oscillation of plant and animal similar.So this system has stable amplitude, longer vibration life-span and the acumen to α-ketoglutaric acid and 1,3-acetone dicarboxylic acid and responds.
[NiL] (ClO
4)
2preparation in two steps: 1) prepare L2HClO
4; 2) by L2HClO
4preparation [NiL] (ClO
4)
2.
1) L2HClO is prepared
4:
98.5mL ethylenediamine is loaded in a 500mL three-necked bottle, under condition of ice bath, in 120 minutes, stir lower slowly dropping 126mL70% perchloric acid.Initial reaction is violent and produce with white cigarette, thus rate of addition control every 5 second l drip.Along with reaction is carried out suitably to accelerate rate of addition, until drip, obtain transparent solution.Still under the condition of ice-water bath, add 224mL anhydrous propanone and vigorous stirring to this clear solution, solution becomes muddiness very soon and forms very viscous mixture simultaneously.Still under the condition of ice-water bath, 2-3 hour is kept fully to react.Products therefrom is transferred to Buchner funnel and carry out suction filtration separation, and fully wash with acetone, can pure white solid be obtained.By this pure in the methanol-water solution of look solid in heat recrystallization, use silica-gel desiccant vacuum drying, obtain 80g white crystal, this white crystal is L2HClO
4.
List of references:
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 PhD dissertation, p25-27, Hefei, 2005.
2) by L2HClO
4preparation [NiL] (ClO
4)
2:
By 11g Ni (AC)
24H
2the L2HClO of O and 21g
4be placed in 500mL three-necked bottle, make it be dissolved in 250mL methyl alcohol, hot bath adds hot reflux 3 hours, finally occurs yellow mercury oxide, and filter, filtrate is concentrated into original volume l/2 in hot bath, placement is spent the night, sufficient crystallising, obtains yellow crystals.Yellow crystals be transferred to Buchner funnel and use methanol wash, recrystallization in the ethanol-water solution of heat, vacuum drying, can obtain 8g [NiL] (ClO
4)
2glassy yellow crystal.
List of references:
1.N.F.Curtis,J.Chem.Soc.Dolton Tran.,1972,Vol.13,1357.
2. Hu Gang, China Science & Technology University's PhD dissertation, p42-43, Hefei, 2005.
This authentication method difference with the prior art is to apply " H
2sO
4-KIO
3-[NiL] (ClO
4)
2-MA-H
2o
2" nonlinear chemical oscillation system as discriminating solution; according to aliphatics chain isomers α-ketoglutaric acid and 1; 3-acetone dicarboxylic acid to the difference of the sharp oscillatory response that this reaction system produces, and then realize the differentiation of aliphatics chain isomers is differentiated.Aliphatics chain isomers α-ketoglutaric acid and 1,3-acetone dicarboxylic acid are differentiating that the concentration range differentiated in solution is 5.0 × 10
-6-6.0 × 10
-4mol/L, this can differentiate that concentration range is that the response that 1,3-acetone dicarboxylic acid produces vibration in this concentration range is very obviously clear through testing the optimal concentration scope determined, is easy to can realize differentiating; Differentiate that in solution, each concentration of component is as shown in table 1, the optium concentration determined through test of many times is as shown in table 2:
Table 1: the concentration range of each component in oscillation system
Table 2: the optium concentration of each component in oscillation system
Concrete operations are as follows:
1, solution is differentiated in the concentration range preparation specified by table 1, insert in solution by ready working electrode (platinum electrode) and contrast electrode (mercurous chloride electrode), the other end of working electrode is connected to data acquisition unit (Go! by amplifier (Instrument Amplifier) LINK) computer is connected to again, open after in computer, logger lite program is arranged acquisition time and sample rate, rapid click starts key thus carries out potential monitoring to solution, obtain gathered E-t curve (the time dependent curve of potential value) i.e. chemical potential vibration collection of illustrative plates (now not yet adding sample to be tested), to make blank.The differentiation that each concentration of component in testing to two groups with blank is identical is differentiated in solution, at any one stable current potential minimum point place that vibration produces, add rapidly the solution of sample to be identified respectively, according to the oscillatory response that sample to be identified produces oscillation system, realize the qualitative analysis to sample to be identified.That is: after the solution adding sample to be identified in oscillation system, if the amplitude of oscillation of oscillation system first increases and reduces, then described sample to be identified is 1,3-acetone dicarboxylic acid, if and oscillation system is not almost affected, then described sample to be identified is α-ketoglutaric acid.
The basic parameter of vibration collection of illustrative plates comprises:
Induction time: time required before adding last a kind of material to solution starting of oscillation;
Amplitude of oscillation: in oscillatory process from a current potential minimum point to next current potential peak current potential; Oscillation period: from minimum (height) current potential to next minimum (height) current potential required time in oscillatory process;
Maximum potential: the current potential peak that during stable oscillation stationary vibration, system occurs;
Potential minimum: the current potential minimum point that during stable oscillation stationary vibration, system occurs;
The vibration life-span: time of playing needed for self-oscillation starts to terminate to vibration;
Equilibrium potential: system reaches current potential during thermodynamic equilibrium state, and current potential does not change over time this moment.
The vibration collection of illustrative plates that this authentication method provides has more intuitive, not only can identify aliphatics chain isomers α-ketoglutaric acid and 1 quickly and easily, 3-acetone dicarboxylic acid, can also be widely used in other isomerss, and equipment is simple, accuracy is high, be easy to operation and observation.
Accompanying drawing explanation
Fig. 1 is in embodiment 1, when not adding sample to be identified, differentiates the vibration collection of illustrative plates of solution (oscillation system).
Fig. 2, Fig. 3 are in embodiment 1, add 1.0 × 10 respectively
-4after mol/L α-ketoglutaric acid and 1,3-acetone dicarboxylic acid, the oscillatory response collection of illustrative plates that oscillation system obtains.
Fig. 4 is in embodiment 2, when not adding sample to be identified, differentiates the vibration collection of illustrative plates of solution (oscillation system).
Fig. 5, Fig. 6 are in embodiment 2, add 2.4 × 10 respectively
-4after mol/L α-ketoglutaric acid and 1,3-acetone dicarboxylic acid, the oscillatory response collection of illustrative plates that oscillation system obtains.
Fig. 7 is in embodiment 3, when not adding sample to be identified, differentiates the vibration collection of illustrative plates of solution (oscillation system).
Fig. 8, Fig. 9 are in embodiment 3, add 6.0 × 10 respectively
-5after mol/L α-ketoglutaric acid and 1,3-acetone dicarboxylic acid, the oscillatory response collection of illustrative plates that oscillation system obtains.
Figure 10 is in embodiment 4, when not adding sample to be identified, differentiates the vibration collection of illustrative plates of solution (oscillation system).
Figure 11, Figure 12 are in embodiment 4, add 1.2 × 10 respectively
-6after mol/L α-ketoglutaric acid and 1,3-acetone dicarboxylic acid, the oscillatory response collection of illustrative plates that oscillation system obtains.
Embodiment
Embodiment 1:
The present embodiment verifies the feasibility of the discrimination method of aliphatics chain isomers α-ketoglutaric acid of the present invention and 1,3-acetone dicarboxylic acid as follows:
(1) obtain solution
First with 98% the concentrated sulphuric acid and distilled water preparation 0.025mol/L sulfuric acid as storing solution, then prepare the potassium iodate solution of 0.14mol/L, [NiL] (ClO of 0.0173mol/L respectively with the sulfuric acid solution of 0.025mol/L
4)
2the malonic acid solution of solution, 2mol/L, the superoxol of 4mol/L; 14.5mL 0.025mol/L sulfuric acid solution, 6.5mL 0.14mol/L potassium iodate solution, 1.5mL 0.0173mol/L [NiL] (ClO is added successively in 50mL small beaker
4)
2solution, 3.5mL 2mol/L malonic acid solution and 14mL 4mol/L superoxol, to ensure " H
2sO
4-KIO
3-[NiL] (ClO
4)
2-MA-H
2o
2" concentration of each component is sulfuric acid 0.025mol/L, Potassiumiodate 0.02275mol/L, [NiL] (ClO in nonlinear chemical oscillation system
4)
26.4875 × 10
-4mol/L, malonic acid 0.175mol/L, hydrogen peroxide 1.4mol/L;
Simultaneously with second distillation water as solvent, prepare α-ketoglutaric acid and 1, the 3-acetone dicarboxylic acid solution of 0.1mol/L respectively.
(2) vibrate collection of illustrative plates
The vibration collection of illustrative plates of oscillation system is by the computer recording that logger lite program is housed, and Fig. 1 is (sulfuric acid 0.025mol/L, Potassiumiodate 0.02275mol/L, [NiL] (ClO under typical concentration
4)
26.4875 × 10
-4mol/L, malonic acid 0.175mol/L, hydrogen peroxide 1.4mol/L), above-mentioned discriminating solution does not add the vibration collection of illustrative plates of sample to be tested, to make blank.To in the discriminating solution of two groups of above-mentioned typical concentration, add α-ketoglutaric acid and 1, the 3-acetone dicarboxylic acid solution of 40 μ L 0.1mol/L respectively, make it differentiate that the concentration in solution is 1.0 × 10
-4mol/L, the time at every turn added is all at the 5th current potential minimum point place of vibration collection of illustrative plates, and the oscillatory response collection of illustrative plates obtained respectively as shown in Figure 2 and Figure 3.
(3) discriminating is distinguished
As α-ketoglutaric acid and the difference of 1,3-acetone dicarboxylic acid because molecular structure difference to reaction system generation oscillatory response of aliphatics chain isomers.As shown in Figure 2, compared to Figure 1, adding of α-ketoglutaric acid vibration collection of illustrative plates and basic parameter thereof are not almost affected; And in Fig. 3,1 of same concentrations, adding of 3-acetone dicarboxylic acid affects larger on vibration collection of illustrative plates and basic parameter thereof: current potential declines instantaneously, maximal value is risen to immediately again after dropping to a minimum value, the maximal value that this value is once vibrated before will being far longer than, namely makes the amplitude of oscillation first increases and then decreases of oscillation system; From above-mentioned test, can realize differentiating the differentiation of α-ketoglutaric acid and 1,3-acetone dicarboxylic acid according to the difference of oscillatory response collection of illustrative plates.
(one of them is α-ketoglutaric acid solution to get the solution of the sample to be identified of two 0.1mol/L of in advance preparation, another is 1,3-acetone dicarboxylic acid solution, but both not yet distinguish), one of them is labeled as sample 1, another is labeled as sample 2;
Prepare the discriminating solution of two groups of above-mentioned typical concentration, gather the collection of illustrative plates that vibrates accordingly respectively, and add sample 1 and the sample 2 of 40 μ l 0.1mol/L respectively at the 5th current potential minimum point place, make them differentiate that the concentration in solution is 1.0 × 10
-4mol/L.
Com-parison and analysis is known: the vibration collection of illustrative plates of sample 1 is corresponding with Fig. 2, not corresponding with Fig. 3, and the vibration collection of illustrative plates of sample 2 is corresponding with Fig. 3, not corresponding with Fig. 2.Therefore, sample 1 is α-ketoglutaric acid solution, sample 2 is 1,3-acetone dicarboxylic acid solution, thus achieves the differentiation to isomers α-ketoglutaric acid and 1,3-acetone dicarboxylic acid.
Embodiment 2:
The present embodiment verifies the feasibility of the discrimination method of aliphatics chain isomers α-ketoglutaric acid of the present invention and 1,3-acetone dicarboxylic acid as follows:
(1) obtain solution
First prepare the sulfuric acid of 0.025mol/L as storing solution with the concentrated sulphuric acid of 98%, then prepare the potassium iodate solution of 0.14mol/L, [NiL] (ClO of 0.0173mol/L respectively with the sulfuric acid solution of 0.025mol/L
4)
2the malonic acid solution of solution, 2mol/L, the superoxol of 4mol/L; 13.5mL 0.025mol/L sulfuric acid solution, 6.5mL0.14mol/L potassium iodate solution, 2mL 0.0173mol/L [NiL] (ClO is added successively in 50mL small beaker
4)
2solution, 3.5mL 2mol/L malonic acid solution and 14.5mL 4mol/L superoxol, to ensure " H
2sO
4-KIO
3-[NiL] (ClO
4)
2-MA-H
2o
2" concentration of each component is sulfuric acid 0.025mol/L, Potassiumiodate 0.02275mol/L, [NiL] (ClO in nonlinear chemical oscillation system
4)
28.65 × 10
-4mol/L, malonic acid 0.175mol/L, hydrogen peroxide 1.45mol/L; Simultaneously with second distillation water as solvent, prepare α-ketoglutaric acid and 1, the 3-acetone dicarboxylic acid solution of 0.24mol/L respectively.
(2) vibrate collection of illustrative plates
The vibration collection of illustrative plates of above-mentioned oscillation system, by the computer recording that logger lite program is housed, investigates the difference between oscillatory response that high concentration α-ketoglutaric acid and 1,3-acetone dicarboxylic acid produce.Fig. 4 is vibration collection of illustrative plates when differentiating that solution does not add sample to be tested, to make blank.Be in the discriminating solution of above-mentioned concentration to two groups of each concentration of component, add α-ketoglutaric acid and 1, the 3-acetone dicarboxylic acid solution of 40 μ l 0.24mol/L respectively, make it differentiate that the concentration in solution is 2.4 × 10
-4mol/L, the time at every turn added is all at the 5th current potential minimum point place of vibration collection of illustrative plates, and the oscillatory response collection of illustrative plates obtained respectively as shown in Figure 5, Figure 6.
(3) discriminating is distinguished
As α-ketoglutaric acid and the difference of 1,3-acetone dicarboxylic acid because molecular structure difference to reaction system generation oscillatory response of aliphatics chain isomers.As shown in Figure 5, adding of α-ketoglutaric acid does not almost affect vibration collection of illustrative plates and basic parameter thereof compared with Fig. 4; And in Fig. 6 same concentrations 1, adding of 3-acetone dicarboxylic acid affects larger on vibration collection of illustrative plates and basic parameter thereof: current potential declines instantaneously, maximal value is risen to immediately again after dropping to a minimum value, the maximal value that this value is once vibrated before will being far longer than, namely makes the amplitude of oscillation first increases and then decreases of oscillation system; From above-mentioned test, can realize differentiating the differentiation of α-ketoglutaric acid and 1,3-acetone dicarboxylic acid according to the difference of oscillatory response collection of illustrative plates.
(one of them is α-ketoglutaric acid solution to get the solution of the sample to be identified of two 0.24mol/L of in advance preparation, another is 1,3-acetone dicarboxylic acid solution, but both not yet distinguish), one of them is labeled as sample 1, another is labeled as sample 2;
Prepare the discriminating solution that two groups of each concentration of component are above-mentioned concentration, gather corresponding oscillatory response collection of illustrative plates respectively, and sample 1 and the sample 2 of 40 μ l 0.24mol/L is added respectively at the 5th current potential minimum point place, make them differentiate that the concentration in solution is 2.4 × 10
-4mol/L.Com-parison and analysis is known: the vibration collection of illustrative plates of sample 1 is corresponding with Fig. 5, not corresponding with Fig. 6, and the vibration collection of illustrative plates of sample 2 is corresponding with Fig. 6, not corresponding with Fig. 5.Therefore, sample 1 is α-ketoglutaric acid solution, sample 2 is 1,3-acetone dicarboxylic acid solution, thus achieves the differentiation to isomers α-ketoglutaric acid and 1,3-acetone dicarboxylic acid.
Embodiment 3:
The present embodiment verifies the feasibility of the discrimination method of aliphatics chain isomers α-ketoglutaric acid of the present invention and 1,3-acetone dicarboxylic acid as follows:
(1) obtain solution
First prepare the sulfuric acid of 0.025mol/L as storing solution with the concentrated sulphuric acid of 98%, then prepare the potassium iodate solution of 0.14mol/L, [NiL] (ClO of 0.0173mol/L respectively with the sulfuric acid solution of 0.025mol/L
4)
2the malonic acid solution of solution, 2mol/L, the superoxol of 4mol/L; 15.5mL 0.025mol/L sulfuric acid solution, 6mL0.14mol/L potassium iodate solution, 1.5mL 0.0173mol/L [NiL] (ClO is added successively in 50mL small beaker
4)
2solution, 3mL 2mol/L malonic acid solution and 14mL4mol/L superoxol, to ensure " H
2sO
4-KIO
3-[NiL] (ClO
4)
2-MA-H
2o
2" concentration of each component is sulfuric acid 0.025mol/L, Potassiumiodate 0.021mol/L, [NiL] (ClO in nonlinear chemical oscillation system
4)
26.4875 × 10
-4mol/L, malonic acid 0.15mol/L, hydrogen peroxide 1.4mol/L; Simultaneously with second distillation water as solvent, prepare α-ketoglutaric acid and 1, the 3-acetone dicarboxylic acid solution of 0.06mol/L respectively.
(2) vibrate collection of illustrative plates
The vibration collection of illustrative plates of above-mentioned oscillation system, by the computer recording that logger lite program is housed, investigates the difference between oscillatory response that low concentration α-ketoglutaric acid and 1,3-acetone dicarboxylic acid produce.Fig. 7 is vibration collection of illustrative plates when differentiating that solution does not add sample to be tested, to make blank.Prepare the discriminating solution that two groups of each concentration of component are above-mentioned concentration, add α-ketoglutaric acid and 1, the 3-acetone dicarboxylic acid solution of 40 μ l 0.06mol/L respectively, make it differentiate that the concentration in solution is 6.0 × 10
-5mol/L, the time at every turn added is all at the 5th current potential minimum point place of vibration collection of illustrative plates, and the oscillatory response collection of illustrative plates obtained respectively as shown in Figure 8, Figure 9.
(3) discriminating is distinguished
As α-ketoglutaric acid and the difference of 1,3-acetone dicarboxylic acid because molecular structure difference to reaction system generation oscillatory response of aliphatics chain isomers.As shown in Figure 8, adding of α-ketoglutaric acid does not almost affect vibration collection of illustrative plates and basic parameter thereof compared with Fig. 7; And in Fig. 9 same concentrations 1, adding of 3-acetone dicarboxylic acid affects larger on vibration collection of illustrative plates and basic parameter thereof: current potential declines instantaneously, maximal value is risen to immediately again after dropping to a minimum value, the maximal value that this value is once vibrated before will being far longer than, namely makes the amplitude of oscillation first increases and then decreases of oscillation system; From above-mentioned test, can realize differentiating the differentiation of α-ketoglutaric acid and 1,3-acetone dicarboxylic acid according to the difference of oscillatory response collection of illustrative plates.
(one of them is α-ketoglutaric acid solution to get the solution of the sample to be identified of two 0.06mol/L of in advance preparation, another is 1,3-acetone dicarboxylic acid solution, but both not yet distinguish), one of them is labeled as sample 1, another is labeled as sample 2;
Prepare the discriminating solution that two groups of each concentration of component are above-mentioned concentration, gather corresponding oscillatory response collection of illustrative plates, and add sample 1 and the sample 2 of 40 μ l 0.06mol/L respectively at the 5th current potential minimum point place, make them differentiate that the concentration in solution is 6.0 × 10
-5mol/L.Com-parison and analysis is known: the vibration collection of illustrative plates of sample 1 is corresponding with Fig. 8, not corresponding with Fig. 9, and the vibration collection of illustrative plates of sample 2 is corresponding with Fig. 9, not corresponding with Fig. 8.Therefore, sample 1 is α-ketoglutaric acid solution, sample 2 is 1,3-acetone dicarboxylic acid solution, thus achieves the differentiation to isomers α-ketoglutaric acid and 1,3-acetone dicarboxylic acid.
Embodiment 4:
The present embodiment verifies the feasibility of the discrimination method of aliphatics chain isomers α-ketoglutaric acid of the present invention and 1,3-acetone dicarboxylic acid as follows:
(1) obtain solution
First prepare the sulfuric acid of 0.025mol/L as storing solution with the concentrated sulphuric acid of 98%, then prepare the potassium iodate solution of 0.14mol/L, [NiL] (ClO of 0.0173mol/L respectively with the sulfuric acid solution of 0.025mol/L
4)
2the malonic acid solution of solution, 2mol/L, the superoxol of 4mol/L; 14.5mL 0.025mol/L sulfuric acid solution, 6mL0.14mol/L potassium iodate solution, 2mL 0.0173mol/L [NiL] (ClO is added successively in 50mL small beaker
4)
2solution, 3.5mL 2mol/L malonic acid solution and 14mL4mol/L superoxol, to ensure " H
2sO
4-KIO
3-[NiL] (ClO
4)
2-MA-H
2o
2" concentration of each component is sulfuric acid 0.025mol/L, Potassiumiodate 0.021mol/L, [NiL] (ClO in nonlinear chemical oscillation system
4)
28.65 × 10
-4mol/L, malonic acid 0.175mol/L, hydrogen peroxide 1.4mol/L;
Simultaneously with second distillation water as solvent, prepare α-ketoglutaric acid and 1, the 3-acetone dicarboxylic acid solution of 0.0012mol/L respectively.
(2) vibrate collection of illustrative plates
The vibration collection of illustrative plates of above-mentioned oscillation system, by the computer recording that logger lite program is housed, investigates the difference between oscillatory response that lower concentration α-ketoglutaric acid and 1,3-acetone dicarboxylic acid produce.Figure 10 is vibration collection of illustrative plates when differentiating that solution does not add sample to be tested, to make blank.Be in the discriminating solution of above-mentioned concentration to two groups of each concentration of component, add α-ketoglutaric acid and 1, the 3-acetone dicarboxylic acid solution of 40 μ l 0.0012mol/L respectively, make it differentiate that the concentration in solution is 1.2 × 10
-6mol/L, the time at every turn added is all that the oscillatory response collection of illustrative plates obtained is respectively as shown in Figure 11, Figure 12 at the 5th current potential minimum point place of vibration collection of illustrative plates.
(3) discriminating is distinguished
As α-ketoglutaric acid and the difference of 1,3-acetone dicarboxylic acid because molecular structure difference to reaction system generation oscillatory response of aliphatics chain isomers.As shown in Figure 11, compared with Figure 10, adding of α-ketoglutaric acid does not almost affect vibration collection of illustrative plates and basic parameter thereof; And in Figure 12,1 of same concentrations, adding of 3-acetone dicarboxylic acid affects larger on vibration collection of illustrative plates and basic parameter thereof: current potential declines instantaneously, maximal value is risen to immediately again after dropping to a minimum value, the maximal value that this value is once vibrated before will being far longer than, namely makes the amplitude of oscillation first increases and then decreases of oscillation system; From above-mentioned test, can realize differentiating the differentiation of α-ketoglutaric acid and 1,3-acetone dicarboxylic acid according to the difference of oscillatory response collection of illustrative plates.
(one of them is α-ketoglutaric acid solution to get the solution of the sample to be identified of two 0.0012mol/L of in advance preparation, another is 1,3-acetone dicarboxylic acid solution, but both not yet distinguish), one of them is labeled as sample 1, another is labeled as sample 2;
Prepare the discriminating solution that two groups of each concentration of component are above-mentioned concentration, gather corresponding oscillatory response collection of illustrative plates, and add sample 1 and the sample 2 of 40 μ l 0.0012mol/L respectively at the 5th current potential minimum point place, make them differentiate that the concentration in solution is 1.2 × 10
-6mol/L.
Com-parison and analysis is known: the vibration collection of illustrative plates of sample 1 is corresponding with Figure 11, not corresponding with Figure 12, and the vibration collection of illustrative plates of sample 2 is corresponding with Figure 12, not corresponding with Figure 11.Therefore, sample 1 is α-ketoglutaric acid solution, sample 2 is 1,3-acetone dicarboxylic acid solution, thus achieves the differentiation to isomers α-ketoglutaric acid and 1,3-acetone dicarboxylic acid.
As can be seen from the present embodiment, more the α-ketoglutaric acid of small concentration and 1,3-acetone dicarboxylic acid also can be differentiated by the inventive method.
Claims (5)
1. the discrimination method of an aliphatics chain isomers α-ketoglutaric acid and 1,3-acetone dicarboxylic acid, is characterized in that:
Be solvent with redistilled water, prepare the solution of sample to be identified;
Application " H
2sO
4-KIO
3-[NiL] (ClO
4)
2-MA-H
2o
2" nonlinear chemical oscillation system as discriminating solution; record oscillation system vibration collection of illustrative plates; vibration produce any one stable current potential minimum point place; in oscillation system, add the solution of sample to be identified; according to the oscillatory response that sample to be identified produces oscillation system, realize the qualitative analysis to sample to be identified;
[NiL] (ClO
4)
2middle L is 5,7,7,12,14,14-vegolysen, 4,8,11-tetra-azepine ten four-4,11-diene;
Differentiate that the volumetric molar concentration of each component in solution is: sulfuric acid 0.00125-0.045mol/L, Potassiumiodate 0.01-0.028mol/L, [NiL] (ClO
4)
22.16 × 10
-4-1.51 × 10
-3mol/L, malonic acid 0.03-0.25mol/L, hydrogen peroxidase 10 .8-1.8mol/L;
Described sample to be identified is α-ketoglutaric acid or 1,3-acetone dicarboxylic acid.
2. differentiation discrimination method according to claim 1, is characterized in that:
After the solution adding sample to be identified in oscillation system, reduce if the amplitude of oscillation of oscillation system first increases, then described sample to be identified is 1,3-acetone dicarboxylic acid again; If do not affect oscillation system, then described sample to be identified is α-ketoglutaric acid.
3. differentiation discrimination method according to claim 1 and 2, is characterized in that: any one stable current potential minimum point that described vibration produces refers to any one in 3rd ~ 25 current potential minimum points that vibration produces.
4. discrimination method according to claim 1 and 2, is characterized in that: differentiate that the volumetric molar concentration of each component in solution is: sulfuric acid 0.025mol/L, Potassiumiodate 0.02275mol/L, [NiL] (ClO
4)
26.4875 × 10
-4mol/L, malonic acid 0.175mol/L, hydrogen peroxide 1.4mol/L.
5. discrimination method according to claim 1 and 2, is characterized in that: sample to be identified is differentiating that the concentration range differentiated in solution is 5.0 × 10
-6-6.0 × 10
-4mol/L.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105954332A (en) * | 2016-07-04 | 2016-09-21 | 安徽大学 | Identification method for amino acid (tyrosine) isomerides |
| CN106908491A (en) * | 2017-02-26 | 2017-06-30 | 安徽大学 | A kind of method for differentiating vanillic aldehyde and its methoxybenzaldehyde of 2 hydroxyl of isomer 3 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102818827A (en) * | 2012-08-24 | 2012-12-12 | 安徽大学 | Natural antioxidant detecting method |
| CN103675046A (en) * | 2012-09-10 | 2014-03-26 | 安徽大学 | Detection method of protocatechuic acid |
| CN104049005A (en) * | 2013-03-11 | 2014-09-17 | 安徽大学 | Detection method of phenol |
-
2015
- 2015-03-31 CN CN201510149369.3A patent/CN104730127B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102818827A (en) * | 2012-08-24 | 2012-12-12 | 安徽大学 | Natural antioxidant detecting method |
| CN103675046A (en) * | 2012-09-10 | 2014-03-26 | 安徽大学 | Detection method of protocatechuic acid |
| CN104049005A (en) * | 2013-03-11 | 2014-09-17 | 安徽大学 | Detection method of phenol |
Non-Patent Citations (3)
| Title |
|---|
| STANLEY D. FURROW: "Iodine-Production Subsystem of the Briggs-Rauscher Oscillating Reaction. Effect of Crotonic Acid", 《J. PHYS. CHEM》 * |
| 孟敏等: "BZ化学振荡法测定对氨基水杨酸钠", 《化学试剂》 * |
| 李梦硕等: "大环铜配合物催化的B－Z振荡化学体系检测苯酚", 《安徽大学学报( 自然科学版)》 * |
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