CN102706927B - Method for measuring gibberellin in fruits by aid of molecularly imprinted electrochemically modified electrode - Google Patents
Method for measuring gibberellin in fruits by aid of molecularly imprinted electrochemically modified electrode Download PDFInfo
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- CN102706927B CN102706927B CN201210107283.0A CN201210107283A CN102706927B CN 102706927 B CN102706927 B CN 102706927B CN 201210107283 A CN201210107283 A CN 201210107283A CN 102706927 B CN102706927 B CN 102706927B
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Abstract
The invention discloses a method for measuring gibberellin in fruits by the aid of a molecularly imprinted electrochemically modified electrode. The gibberellin and methylene blue are mixed and are electrochemically polymerized to form a membrane on the surface of a glassy carbon electrode, and a molecularly imprinted electrochemical sensor is prepared after the gibberellin is eluted. Along with the increase of the quantity of the gibberellin which is marked by dopamine on various recognition sites on the molecular imprinted membrane and is eluted, current of oxidation peaks is greatly reduced, and accordingly the electrochemical analysis method for measuring the trace gibberellin is built. Good linear relation between peak current I and the gibberellin within the concentration range from 2.5X10-8 to 1.05X10-6mol/L is good. The method overcomes various shortcomings such as excessive complexity in the prior art, is high in measuring sensitivity, wide in measuring linear range and low in detection limit, and has an excellent effect in detecting the gibberellin with the concentration of 10-8mol/L in the fruits.
Description
Technical field
The present invention relates to a kind of method of measuring gibberellin in fruit with molecular imprinting electrochemical modified electrode.
Background technology
Molecular imprinting electrochemical sensor combines the advantage of molecularly imprinted polymer and electrochemical sensor, both shown the specificity of height, there is again low cost, be easy to miniaturization, robotization, detect limit for height and longer serviceable life, and the features such as preparation process is simple, thereby be used widely.Gibberellin is a large class plant hormone, and as macrolide antibiotic, in state's regulation fruit, the vegetables such as the U.S., Japan, gibberellin (GA) maximum residue limit(MRL) is 0.2 μ g/g.The mensuration of gibberellin is people's concern extremely.At present, the mensuration of gibberellin mainly adopts high performance liquid chromatography, square wave voltammetry, fluorimetry, Folin reagent photometry and phosphorus molybdenum blue spectrophotometry etc.These method complex operations, and need to use a large amount of organic solvents.Therefore study that residual to have method for quick highly sensitive, high selectivity significant to gibberellin.
Summary of the invention
A kind of method of measuring gibberellin in fruit with molecular imprinting electrochemical modified electrode that provides is provided.
Conceive as follows: (1) carrys out mark gibberellin (GA) with excessive dopamine (DA), obtain the gibberellin (DA-GA) of dopamine mark; (2) by electropolymerization at electrode face finish molecular engram film, wash-out obtains molecular engram hole that can specific recognition; (3) when hatching, DA-GA enters into the molecular engram hole on blotting membrane with specific recognition.The GA standard solution that the modified electrode of having hatched DA-GA is put into the variable concentrations reaction that is at war with, by measuring mark DA on the modified electrode electrocatalytic oxidation galvanic current on methylene blue modified electrode, can indirect determination GA content.
Concrete steps are:
(1) dopamine mark gibberellin:
Get 5.0 × 10
-4gibberellin standard solution 0.4～0.6mL of mol/L, in color-comparison tube, adds N-hydroxy-succinamide (NHS) 1～3mL of 0.01mol/L, shakes up, and standing 5～15min, then add 2.5 × 10
-3dopamine (DA) 1～3mL of mol/L, adds 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) 1～3mL of 0.01mol/L to make gibberellin (GA) and dopamine (DA) carry out dehydration as dehydrating condensation agent after shaking up; After reaction 15～25min, obtaining concentration is 2.0 × 10
-5～3.0 × 10
-5dopamine mark gibberellin (DA-GA) standard solution of mol/L;
(2) preparation of molecular imprinting modification electrode:
It is 5.0 × 10 that processed clean working electrode is placed in containing volumetric molar concentration
-4the methylene blue monomer of mol/L, volumetric molar concentration are 2.5 × 10
-4the gibberellin of mol/L and volumetric molar concentration are to carry out electrochemical polymerization in the borax buffer solution of 0.2mol/L, pH=9.2, using 0.2mol/LKCl as supporting electrolyte, and sweep velocity 100mV/s; After within the scope of+1.4～-0.6V, scan round 20～40 is enclosed, electrode is taken out from polymer fluid, after intermediate water rinses, foam washing 10～50min in the pure methanol acetic acid solution of analysis, with the template molecule gibberellin in wash-out molecular engram film and other some adsorbates, make molecular engram Polymethylene blue modified electrode;
(3) detection method:
Under room temperature (25 ℃), it is 2.0 × 10 that the molecular engram Polymethylene blue modified electrode that step (2) is made is placed in the concentration that step (1) makes
-5～3.0 × 10
-5in mol/L dopamine mark gibberellin standard solution, hatch 10～15min, then use distilled water flushing electrode surface; During detection, first the electrode after cleaning being placed in containing concentration is 2.5 × 10
-8～1.05 × 10
-6in the 0.2mol/L of the gibberellin of mol/L, the borate buffer of pH=7.0, be at war with and react 5～15min, the measurement of being correlated with cyclic voltammetry and differential pulse voltammetry subsequently;
(4) mensuration of GA content:
Along with the gibberellin that the dopamine mark on increasing recognition site on molecular engram film is crossed is out replaced, the electric current of oxidation peak declines gradually; Gibberellin concentration is 2.5 × 10
-8～1.05 × 10
-6within the scope of mol/L, be good linear relationship with peak current I: I=-0.0412C+6.4786, its linearly dependent coefficient r=0.9992; By relational expression DL=3 δ b/K, record this molecular engram sensor detecting of gibberellin is limited to 7.348 × 10
-9mol/L.
Electrode life of the present invention is long, cost of manufacture is low, highly sensitive, the mensuration range of linearity is wide and detectability is low, for the detection of low content gibberellin in fruit, is easy to robotization.
Accompanying drawing explanation
Accompanying drawing is the graph of a relation of embodiment of the present invention GA content and cyclic voltammetry peak current.
Embodiment
Embodiment:
(1) dopamine mark gibberellin:
Get 5.0 × 10
-4the gibberellin standard solution 0.5mL of mol/L, in color-comparison tube, adds N-hydroxy-succinamide (NHS) 2mL of 0.01mol/L, shakes up, and standing 10min, then add 2.5 × 10
-3dopamine (DA) 2mL of mol/L, adds 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) 2mL of 0.01mol/L to make gibberellin (GA) and dopamine (DA) carry out dehydration as dehydrating condensation agent after shaking up; After reaction 20min, obtaining concentration is 2.5 × 10
-5dopamine mark gibberellin (DA-GA) standard solution of mol/L;
(2) preparation of molecular imprinting modification electrode:
It is 5.0 × 10 that processed clean working electrode is placed in containing volumetric molar concentration
-4the methylene blue monomer of mol/L, volumetric molar concentration are 2.5 × 10
-4the gibberellin of mol/L and volumetric molar concentration are to carry out electrochemical polymerization in the borax buffer solution of 0.2mol/L, pH=9.2, using 0.2mol/L KCl as supporting electrolyte, and sweep velocity 100mV/s; After within the scope of+1.4～-0.6V, scan round 30 is enclosed, electrode is taken out from polymer fluid, after intermediate water rinses, foam washing 30min in the pure methanol acetic acid solution of analysis, with the template molecule gibberellin in wash-out molecular engram film and other some adsorbates, make molecular engram Polymethylene blue modified electrode;
(3) detection method:
Under room temperature (25 ℃), it is 2.5 × 10 that the molecular engram Polymethylene blue modified electrode that step (2) is made is placed in the concentration that step (1) makes
-5in mol/L dopamine mark gibberellin standard solution, hatch 12min, then use distilled water flushing electrode surface; During detection, first the electrode after cleaning being placed in containing concentration is 2.5 × 10
-8reaction 10min is at war with in the 0.2mol/L of the gibberellin of mol/L, the borate buffer of pH=7.0, select subsequently differential pulse voltammetry or cyclic voltammetry in CHI660 type electrochemical workstation to scan solution to be measured, scanning voltage-0.2～0.6V;
(4) mensuration of GA content:
Along with the gibberellin that the dopamine mark on increasing recognition site on molecular engram film is crossed is out replaced, the electric current of oxidation peak declines gradually; Gibberellin concentration is 2.5 × 10
-8～1.05 × 10
-6within the scope of mol/L, be good linear relationship with peak current I: I=-0.0412C+6.4786, its linearly dependent coefficient r=0.9992; By relational expression DL=3 δ b/K, record this molecular engram sensor detecting of gibberellin is limited to 7.348 × 10
-9mol/L, GA content and peak current relation are shown in Figure of description;
(5) mensuration of GA content in strawberry sample:
Utilize this sensor to carry out analyzing to the gibberellin in the strawberry sample purchased from supermarket and measure, but do not detect gibberellin, therefore adopt standard addition method to carry out recovery testu.Select the cyclic voltammetry of CHI660 type electrochemical workstation to carry out sweep measuring, scanning voltage-0.2～0.6V to solution to be measured.Read peak point current I, and by its substitution I=-0.0412C+6.4786, calculate C.Replicate determination three times, calculate recovery rate is 95.8～103.6%.
Claims (1)
1. a method of measuring gibberellin in fruit with molecular imprinting electrochemical modified electrode, is characterized in that concrete steps are:
(1) dopamine mark gibberellin:
Get 5.0 × 10
-4gibberellin standard solution 0.4 ~ 0.6 mL of mol/L, in color-comparison tube, adds N-hydroxy-succinamide 1 ~ 3 mL of 0.01 mol/L, shakes up, and standing 5 ~ 15 min, then add 2.5 × 10
-3dopamine 1 ~ 3 mL of mol/L, adds 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride 1 ~ 3 mL of 0.01 mol/L to make gibberellin and dopamine carry out dehydration as dehydrating condensation agent after shaking up; After reaction 15 ~ 25 min, obtaining concentration is 2.0 × 10
-5~ 3.0 × 10
-5the dopamine mark gibberellin standard solution of mol/L;
(2) preparation of molecular imprinting modification electrode:
It is 5.0 × 10 that processed clean working electrode is placed in containing volumetric molar concentration
-4the methylene blue monomer of mol/L, volumetric molar concentration are 2.5 × 10
-4the gibberellin of mol/L and volumetric molar concentration are to carry out electrochemical polymerization in the borax buffer solution of 0.2 mol/L, pH=9.2, using 0.2 mol/L KCl as supporting electrolyte, and sweep velocity 100 mV/s; After within the scope of+1.4～-0.6 V, scan round 20 ~ 40 is enclosed, electrode is taken out from polymer fluid, after intermediate water rinses, foam washing 10 ~ 50 min in the pure methanol acetic acid solution of analysis, with the template molecule gibberellin in wash-out molecular engram film and other some adsorbates, make molecular engram Polymethylene blue modified electrode;
(3) detection method:
In room temperature at 25 ℃, it is 2.0 × 10 that the molecular engram Polymethylene blue modified electrode that step (2) is made is placed in the concentration that step (1) makes
-5~ 3.0 × 10
-5in mol/L dopamine mark gibberellin standard solution, hatch 10 ~ 15 min, then use distilled water flushing electrode surface; During detection, first the electrode after cleaning being placed in containing concentration is 2.5 × 10
-8～1.05 × 10
-6reaction 5 ~ 15 min are at war with in the borate buffer of 0.2 mol/L, the pH=7.0 of the gibberellin of mol/L, with the differential pulse voltammetry in CHI660 type electrochemical workstation or cyclic voltammetry, solution to be measured is scanned subsequently scanning voltage-0.2～0.6 V;
(4) mensuration of GA content:
Along with the gibberellin that the dopamine mark on increasing recognition site on molecular engram film is crossed is out replaced, the electric current of oxidation peak declines gradually; Gibberellin concentration is 2.5 × 10
-8～1.05 × 10
-6within the scope of mol/L and peak current
ibe good linear relationship:
i=-0.0412
c+ 6.4786, its linearly dependent coefficient
r=0.9992; By relational expression DL=3 δ b/K, record this molecular engram sensor detecting of gibberellin is limited to 7.348 × 10
-9mol/L.
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| CN103163124A (en) * | 2013-03-18 | 2013-06-19 | 桂林理工大学 | Method for detecting trace amount of gibberellin A3 by molecular imprinting electrochemical luminescence sensor |
| CN103149268B (en) * | 2013-03-18 | 2014-09-24 | 桂林理工大学 | Method for utilizing molecularly imprinted electrochemical sensor to detect trace gibberellin A3 |
| CN103399052B (en) * | 2013-08-02 | 2016-07-06 | 嘉兴学院 | Molecular imprinting electrochemical sensor and preparation method thereof |
| CN105548151B (en) * | 2015-12-14 | 2019-02-12 | 江南大学 | Based on ionic type iridium complex electrogenerated chemiluminescence-electropolymerization molecular engram recognition detection codeine novel method |
| CN106124462B (en) * | 2016-06-12 | 2018-11-27 | 青岛大学 | A kind of preparation method of artemisinin molecularly imprinted optical electro-chemistry sensor |
| CN106404507A (en) * | 2016-08-31 | 2017-02-15 | 广东省农业科学院农产品公共监测中心 | Leaf vegetable gibberellins residue detection sample pretreatment method and detection method |
| CN106404868B (en) * | 2016-11-04 | 2018-07-06 | 北京农业信息技术研究中心 | A kind of microelectrode biosensor of live body on-line checking plant gibberellin and its application |
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Non-Patent Citations (2)
| Title |
|---|
| 《Molecularly Imprinted Electrochemical Luminescence Sensor Based On Signal Amplification for Selective Determination of Trace Gibberellin A3》;Jianping Li 等;《Analytical Chemistry》;20121026(第84期);全文 * |
| Jianping Li 等.《Molecularly Imprinted Electrochemical Luminescence Sensor Based On Signal Amplification for Selective Determination of Trace Gibberellin A3》.《Analytical Chemistry》.2012,(第84期), |
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