CN102621216A - Method for detecting trace terramycin with double-amplification-effect molecular imprinting electrochemical sensor - Google Patents

Method for detecting trace terramycin with double-amplification-effect molecular imprinting electrochemical sensor Download PDF

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CN102621216A
CN102621216A CN2012101072879A CN201210107287A CN102621216A CN 102621216 A CN102621216 A CN 102621216A CN 2012101072879 A CN2012101072879 A CN 2012101072879A CN 201210107287 A CN201210107287 A CN 201210107287A CN 102621216 A CN102621216 A CN 102621216A
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terramycin
electrochemical sensor
molecular engram
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oxytetracycline
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李建平
李玉平
魏小平
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Guilin University of Technology
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Guilin University of Technology
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Abstract

The invention discloses a method for detecting trace terramycin with a double-amplification-effect molecular imprinting electrochemical sensor. When to-be-detected molecule oxytetracycline and oxytetracycline of glucose oxidase labeling on an oxytetracycline molecular imprinting membrane of the electrode surface compete for replacement, electrochemical signals of prussian blue catalytic hydrogen peroxide on a platinum electrode are changed, and accordingly, an electrochemical analysis method for detecting trace terramycin is set up. To-be-detected liquid is scanned with the differential pulse voltammetry method, scanning voltage is 0.5v to -0.3v. Within the concentration range of 0-1 x 10 - 7 mol/ L and 1 x 10 - 7 - 1 x 10 - 6 mol/ L, oxytetracycline and peak current decrease value delta i are in good linear relation. The method for detecting trace terramycin with the double-amplification-effect molecular imprinting electrochemical sensor overcomes the defects of being too complex in detection and the like in the prior art, better improves sensitivity and selectivity, and is easy to automate for detection of low-concentration oxytetracycline.

Description

Detect the method for trace terramycin with two enlarge-effect molecular engram electrochemical sensors
Technical field
The present invention relates to a kind of method of utilizing two enlarge-effects (film amplifies and enzyme amplifies) molecular imprinting and electrochemical sensor coupling fast measuring trace terramycin.
Background technology
Because its super quality and competitive price, broad spectrum antibiotic activity, the application of Tetracyclines veterinary drug in aquaculture is very extensive.Terramycin is a TCs, promptly is one of broad spectrum antibiotic of widespread use in the livestock and poultry.In environment such as feces of livestock and poultry, soil and waste water, often can detect residue of veterinary drug, and higher with the recall rate of terramycin in Tetracyclines veterinary drug microbiotic.Terramycin is as one of clinical practice microbiotic at most in addition, if the long-term edible resistance to the action of a drug that can increase human body produces toxic and side effect to human body, can enrichment in hepatic tissue, and cause hepatic injury.Therefore be necessary on the basis that preceding has, to improve sensitivity and study a kind of detection method that terramycin is had high selectivity.Molecular engram is that a kind of that developed recently gets up has high selectivity and highly sensitive technology to template molecule.Though the trace sensor of having reported has been introduced relevant enzyme amplifying technique, still sensitive inadequately to the detection of trace terramycin, and need electron mediator, make the detection complex steps.
Summary of the invention
The purpose of this invention is to provide the method that the two enlarge-effect molecular engram electrochemical sensors of a kind of usefulness detect trace terramycin.
Conceive as follows: Prussian blue (prussian blue PB) because its electroreduction to hydrogen peroxide has good catalytic activity and selectivity, therefore is referred to as " artificial peroxidase ".PB is because Fe to the reduction generation catalytic action of hydrogen peroxide 3+Reduzate Fe 2+With hydrogen peroxide chemical oxidation reaction has taken place, the Fe that reaction generates 3+Again reduction makes reductive agent Fe on electrode 2+Be able to regeneration, thereby catalytic current occurred.When the electrode surface electropolymerization obtains stable Prussian blue molecular engram film, just can directly detect through this film to the hydrogen peroxide in the liquid to be measured, do not need electron mediator, convenient mensuration.In addition, introduce the enzyme enlarge-effect, can improve the sensitivity of detection well.The change of electrochemical signals promptly is to compete the terramycin that replaces the glucose oxidase enzyme labeling of having hatched on the molecular engram film through the terramycin in the liquid to be measured to reach.Terramycin concentration in the liquid to be measured is big more; Competitiveness is strong more; Make the enzyme mark terramycin amount of electrode surface reduce, i.e. the amount of hydrogen peroxide that glucose oxidase enzymatic glucose produces reduces, thereby the electrochemical signals that detects Prussian blue catalyzing hydrogen peroxide generation weakens.Can reach the purpose that detects terramycin indirectly like this.
The present invention relates to the molecular engram enzyme mark enhanced sensitivity technology of two enlarge-effects.When the terramycin of glucose oxidase enzyme labeling on the terramycin molecular engram film of testing molecule terramycin and electrode surface is at war with replacement; The electrochemical signals of Prussian blue catalyzing hydrogen peroxide on platinum electrode changes, and the concentration of peak current and terramycin to be measured is 0～1 * 10 -7Mol/L and 1 * 10 -7～1 * 10 -6Be good linear relationship in the mol/L scope.
Concrete steps are following:
(1) processing of platinum electrode:
Platinum electrode being carried out surface finish with the alumina powder of 1.0～0.05 μ m successively handle, is washing by soaking in 50% nitric acid, absolute ethyl alcohol and the pure water at concentration of volume percent then successively, takes out back supersound washing 5min.
(2) preparation of terramycin molecular engram electrochemical sensor:
Step (1) is handled clean platinum electrode to be placed and contains 5.0mmol/L polypyrrole (PPY), 2.0mmol/LFeCl 3, 2.0mmol/L K 3[Fe (CN) 6], in the mixed solution of 0.3mmol/L terramycin (OTC), 0.1mol/L KCl and 0.1mol/L HCl, at 0.36V electro-deposition 30～50s, then between-0.1～0.4V in sweep speed scan round 10～30 circles of 50mV/s.With this platinum electrode of distilled water flushing, and place under the room temperature and dry; Again this platinum electrode is applied in the PBS (PBS) of the 0.02mol/L that contains 0.1mol/L KCl, pH=7.0-current potential 5～15min of 0.05V after; Between-0.05～0.36V, scan 5～20 circles; At room temperature dry after clean with distilled water flushing, terramycin molecular engram electrochemical sensor;
(3) detection method:
In the 15mL small beaker, add and contain the 0.02mol/L of 0.1mol/L potassium chloride, the PBS of pH=7.0 (PBS) 10mL as detection architecture; The terramycin molecular engram electrochemical sensor that step (2) is made places glucose oxidase enzyme labeling terramycin solution to hatch 15～20min; Take out terramycin molecular engram electrochemical sensor and wash its surface, obtain hatching terramycin molecular engram electrochemical sensor completely; To hatch completely then, terramycin molecular engram electrochemical sensor immerses 10mL 0～1.0 * 10 -7Mol/L and 1.0 * 10 -7～1.0 * 10 -6The absorption that is at war with in the terramycin standard solution in the mol/L concentration range inserts detection architecture behind the 10min, and select for use electrochemical workstation to carry out differential pulse voltammetry and scan, scanning voltage 0.5～-0.3V;
(4) drafting of standard working curve:
In the 15mL small beaker, add 10mL and contain the 0.02mol/L of 0.1mol/L potassium chloride, the PBS of pH=7.0 (PBS) as detection architecture; Competitive Adsorption in the 10mL terramycin standard solution is immersed in the hatching that step (3) is made terramycin molecular engram electrochemical sensor completely, inserts detection architecture behind the 10min, selects for use electrochemical workstation to carry out differential pulse voltammetry scanning; Terramycin is 0～1 * 10 -7Mol/L and 1 * 10 -7～1 * 10 -6Be good linear relationship with peak current minimizing value Δ i in the mol/L concentration range: Δ i (μ A)=-111.12C-0.4209, linearly dependent coefficient r=0.9972; Δ i (μ A)=-48.412C-6.977, linearly dependent coefficient r=0.9985.
(5) terramycin Determination on content in the testing sample:
In the 15mL small beaker, add and contain the 0.02mol/L of 0.1mol/L potassium chloride, the PBS of pH=7.0 (PBS) 10mL as detection architecture; Competitive Adsorption in the 10mL terramycin solution is immersed in the hatching that step (3) is made terramycin molecular engram electrochemical sensor completely; Insert detection architecture behind the 10min; Utilize electrochemical workstation to carry out differential pulse voltammetry scanning, scanning voltage 0.5～-0.3V, obtain peak point current i.Calculate the concentration C of terramycin according to calibration curve.
The present invention has overcome prior art and when detecting, has had too many shortcomings such as complicacy, has improved sensitivity and selectivity better, is easy to robotization for the detection of low concentration terramycin.
Description of drawings
Fig. 1 is the differential pulse voltammetry figure of terramycin molecular engram film in the PBS that contains 0.1mol/L potassium chloride on the embodiment of the invention platinum electrode.
Among the figure: a is naked platinum electrode; B is non-molecular engram electrochemical sensor; C is the molecular engram electrochemical sensor after hatching; D is the molecular engram electrochemical sensor after in the terramycin standard solution, having competed.
Fig. 2 is the graph of a relation of embodiment of the invention terramycin content and differential pulse voltammetry peak current.
Embodiment
Embodiment:
(1) processing of platinum electrode:
Platinum electrode being carried out surface finish with the alumina powder of 1.0 μ m, 0.3 μ m and 0.05 μ m successively handle, is washing by soaking in 50% nitric acid, absolute ethyl alcohol and the pure water at concentration of volume percent then successively, takes out back supersound washing 5min.
(2) preparation of terramycin molecular engram electrochemical sensor:
Step (1) is handled clean platinum electrode to be placed and contains 5.0mmol/L polypyrrole (PPY), 2.0mmol/L FeCl 3, 2.0mmol/L K 3[Fe (CN) 6], in the mixed solution of 0.3mmol/L terramycin (OTC), 0.1mol/L KCl and 0.1mol/L HCl, at 0.36V electro-deposition 40s, then between-0.1～0.4V in sweep speed scan round 20 circles of 50mV/s.With this electrode of distilled water flushing, and place under the room temperature and dry.Again this platinum electrode is applied in the PBS (PBS) of the 0.02mol/L that contains 0.1mol/L KCl, pH=7.0-the current potential 10min of 0.05V after; Scanning 10 circles between-0.05～0.36V; At room temperature dry after clean with distilled water flushing, terramycin molecular engram electrochemical sensor;
(3) detection method:
In the 15mL small beaker, add and contain the 0.02mol/L of 0.1mol/L potassium chloride, the PBS of pH=7.0 (PBS) 10mL as detection architecture; The terramycin molecular engram electrochemical sensor that step (2) is made places glucose oxidase enzyme labeling terramycin solution to hatch 18min; Take out terramycin molecular engram electrochemical sensor and wash its surface, obtain hatching terramycin molecular engram electrochemical sensor completely; To hatch completely then, terramycin molecular engram electrochemical sensor immerses 10mL 5.0 * 10 -7The absorption that is at war with in the mol/L terramycin standard solution inserts detection architecture behind the 10min, carry out differential pulse voltammetry scanning with electrochemical workstation, scanning voltage 0.5～-0.3V;
(4) drafting of standard working curve:
In the 15mL small beaker, add 10mL and contain the 0.02mol/L of 0.1mol/L potassium chloride, the PBS of pH=7.0 (PBS) as detection architecture; Competitive Adsorption in the 10mL terramycin standard solution is immersed in the hatching that step (3) is made terramycin molecular engram electrochemical sensor completely, inserts detection architecture behind the 10min, selects for use electrochemical workstation to carry out differential pulse voltammetry scanning.Terramycin is 0～1 * 10 -7Mol/L and 1 * 10 -7～1 * 10 -6Be good linear relationship with peak current changing value Δ i in the mol/L concentration range: Δ i (μ A)=-111.12C-0.4209, linearly dependent coefficient r=0.9972; Δ i (μ A)=-48.412C-6.977, linearly dependent coefficient r=0.9985.
(5) terramycin Determination on content in the milk sample
The milk that is used for sample detection is purchased in the supermarket, but does not detect terramycin, so adopt mark-on to reclaim experiment.In the 15mL small beaker, add and contain the 0.02mol/L of 0.1mol/L potassium chloride, the PBS of pH=7.0 (PBS) 10mL as detection architecture.Competitive Adsorption in the 10mL terramycin solution is immersed in the hatching that step (3) is made terramycin molecular engram electrochemical sensor completely; Insert detection architecture behind the 10min; Utilize electrochemical workstation to carry out differential pulse voltammetry scanning, scanning voltage 0.5～-0.3V, obtain peak point current i.Calculate the concentration C of terramycin according to calibration curve.Calculate recovery rate, the result is as shown in table 1.
Table 1 mark-on recovery test data
Figure BSA00000700360800041

Claims (1)

1. one kind is detected the method for trace terramycins with two enlarge-effect molecular engram electrochemical sensors, it is characterized in that concrete steps are following:
(1) processing of platinum electrode:
Platinum electrode being carried out surface finish with the alumina powder of 1.0～0.05 μ m successively handle, is washing by soaking in 50% nitric acid, absolute ethyl alcohol and the pure water at concentration of volume percent then successively, takes out back supersound washing 5min;
(2) preparation of terramycin molecular engram electrochemical sensor:
Step (1) is handled clean platinum electrode to be placed and contains 5.0mmol/L polypyrrole, 2.0mmol/L FeCl 3, 2.0mmol/L K 3[Fe (CN) 6], in the mixed solution of 0.3mmol/L terramycin, 0.1mol/L KCl and 0.1mol/L HCl, at 0.36V electro-deposition 30～50s, then between-0.1～0.4V in sweep speed scan round 10～30 circles of 50mV/s; With this platinum electrode of distilled water flushing, and place under the room temperature and dry; Again this platinum electrode is applied in the PBS of the 0.02mol/L that contains 0.1mol/L KCl, pH=7.0-current potential 5～15min of 0.05V after; Between-0.05～0.36V, scan 5～20 circles; At room temperature dry after clean with distilled water flushing, terramycin molecular engram electrochemical sensor;
(3) detection method:
The PBS 10mL that in the 15mL small beaker, adds the 0.02mol/L contain 0.1mol/L potassium chloride, pH=7.0 is as detection architecture; The terramycin molecular engram electrochemical sensor that step (2) is made places glucose oxidase enzyme labeling terramycin solution to hatch 15～20min; Take out terramycin molecular engram electrochemical sensor and wash its surface, obtain hatching terramycin molecular engram electrochemical sensor completely; To hatch completely then, terramycin molecular engram electrochemical sensor immerses 10mL 0～1.0 * 10 -7Mol/L and 1.0 * 10 -7～1.0 * 10 -6The absorption that is at war with in the terramycin standard solution in the mol/L concentration range inserts detection architecture behind the 10min, and select for use electrochemical workstation to carry out differential pulse voltammetry and scan, scanning voltage 0.5～-0.3V;
(4) drafting of standard working curve:
In the 15mL small beaker, add 10mL and contain the 0.02mol/L of 0.1mol/L potassium chloride, the PBS of pH=7.0; Competitive Adsorption in the 10mL terramycin standard solution is immersed in the hatching that step (3) is made terramycin molecular engram electrochemical sensor completely, inserts detection architecture behind the 10min, selects for use electrochemical workstation to carry out differential pulse voltammetry scanning; Terramycin is 0～1 * 10 -7Mol/L and 1 * 10 -7～1 * 10 -6Be good linear relationship with peak current minimizing value Δ i in the mol/L concentration range: Δ i (μ A)=-111.12C-0.4209, linearly dependent coefficient r=0.9972; Δ i (μ A)=-48.412C-6.977, linearly dependent coefficient r=0.9985;
(5) terramycin Determination on content in the testing sample:
In the 15mL small beaker, add and contain the 0.02mol/L of 0.1mol/L potassium chloride, the PBS 10mL of pH=7.0; Competitive Adsorption in the 10mL terramycin solution is immersed in the hatching that step (3) is made terramycin molecular engram electrochemical sensor completely; Insert detection architecture behind the 10min; Utilize electrochemical workstation that liquid to be measured is carried out differential pulse voltammetry scanning, scanning voltage 0.5～-0.3V, obtain peak point current i; Calculate the concentration C of terramycin according to calibration curve.
CN2012101072879A 2012-04-11 2012-04-11 Method for detecting trace terramycin with double-amplification-effect molecular imprinting electrochemical sensor Pending CN102621216A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103995103A (en) * 2014-06-11 2014-08-20 中国农业科学院农业质量标准与检测技术研究所 Method for detecting small molecule compound based on prussian blue bionic marker
CN104931689A (en) * 2015-05-14 2015-09-23 桂林理工大学 Molecularly imprinted test paper strip and preparation method as well as application thereof
CN109959684A (en) * 2019-03-25 2019-07-02 扬州工业职业技术学院 Preparation, the remaining method of the detection dead tick of vegetable poisoning and the detection device of double identification type chlopyrifos sensors

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CN101710116A (en) * 2009-11-10 2010-05-19 桂林理工大学 Method for determining trace terramycin by utilizing molecularly imprinted immunosensor

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103995103A (en) * 2014-06-11 2014-08-20 中国农业科学院农业质量标准与检测技术研究所 Method for detecting small molecule compound based on prussian blue bionic marker
CN104931689A (en) * 2015-05-14 2015-09-23 桂林理工大学 Molecularly imprinted test paper strip and preparation method as well as application thereof
CN109959684A (en) * 2019-03-25 2019-07-02 扬州工业职业技术学院 Preparation, the remaining method of the detection dead tick of vegetable poisoning and the detection device of double identification type chlopyrifos sensors
CN109959684B (en) * 2019-03-25 2021-07-13 扬州工业职业技术学院 Preparation of double-identification type chlorpyrifos sensor, method for detecting chlorpyrifos residues in vegetables and detection device

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Application publication date: 20120801