CN106053565A - Electrochemical sensor for detecting trace olaquindox - Google Patents
Electrochemical sensor for detecting trace olaquindox Download PDFInfo
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Abstract
The invention relates to an electrochemical sensor for detecting trace olaquindox. A gold electrode is modified by adopting nanosilver-loaded reduced graphite, and then electro-polymerization is performed in a phosphate buffered solution (pH=8.0) on the modified electrode by taking olaquindox as a template and dopamine as a functional monomer, thus preparing an olaquindox electrochemical sensor with high sensitivity and good selectivity and stability. When the concentration of olaquindox is 1*10<8>-6*10<6>mol/L, a good linear relationship is formed, the linear regression equation is delta I(mu A)=0.1989C (mu mol/L)+0.2381, the related coefficient is r=0.9978, and the detection limit is 1*10<9>mol/L(S/N=3).
Description
Technical field
The invention belongs to new function material, electrochemical sensing detection technique field, relate to a kind of electrochemical sensor, special
It it not a kind of electrochemical sensor for detecting trace olaquindox.
Background technology
Olaquindox (Olaquindox, OLA), also known as olaquindox, Olaquindox, quinoline phthalein amine alcohol, belongs to quinolines, nineteen sixty-five
By the Bayer company of Germany a kind of antivirus somatotropic agent with nitroaniline as Material synthesis, it is used primarily for preventing and treating piglet diarrhea,
Within 1976, European Community's approval is for additive for farm animal feed.Owing to it can be improved food conversion ratio, promote growth of animal and have
The antibacterial action of wide spectrum, Zeng Zuowei feed additive is widely used in aquaculture.
But, there are some researches show, olaquindox may be enriched with accumulation in human body after long-term use, causes chronic poisoning,
Even canceration, causes potential safety hazard to human health.At present, some developed countries are to the olaquindox of poultry and aquatic products
High residue limitation is made that strict regulations, China to forbid poultry and aquatic products and uses olaquindox.Therefore, find a kind of quick,
The method detecting trace olaquindox convenient, highly sensitive, low detection limit is significant.Measure at present in various complex matrices
The analysis method of olaquindox mainly has high performance liquid chromatography (HPLC), Liquid Chromatography-Tandem Mass Spectrometry (LC-MS-MS) etc., this
Although a little methods have the highest sensitivity and accuracy, but need instrument and equipment and the Sample Purification on Single system of complexity of Large expensive
Standby program, analyzes program complicated, and the detection cycle is long, and testing cost is high, and higher to detection technique level requirement, needs specialty
Technical staff complete, popularize difficulty in grass-roots unit big, it is difficult to poultry and the cultivation of aquatic products, process, circulate
Link carries out overall monitor.Therefore, developing easy, quick, economic, to be applicable to Site Detection method will be to solve current quinoline second
One of effective way of alcohol residual excessive problem.
Molecular engram is the molecular specificity identification technology of rising in recent years, by molecular imprinting and Electroanalytical Chemistry skill
Art combines, and can obtain high sensitivity, high selective biosensor, have relevant report, but applied
Detection in trace olaquindox does not has correlational study temporarily.
Summary of the invention
For solving the deficiencies in the prior art, the invention reside in a kind of electrochemical sensing for detecting trace olaquindox of offer
Device, this sensor utilizes Graphene and nanometer silver dual amplification effect, can high sensitivity, highly selective be used for detecting trace quinoline
Ethanol.
Electrochemical sensor for detecting trace olaquindox of the present invention, is prepared by the following method:
(1) gold electrode pretreatment
Gold electrode alumina powder is polished on flannelette, then distinguishes ultrasonic 30s with dehydrated alcohol, distilled water.
At 0.5mol/L H2SO4Solution being circulated voltammetric scan-0.2～1.4V, until obtaining stable electric current, taking out electrode
Totally dry standby with distilled water flushing.
(2) load silver reduced graphene (rGO@Ag) modified electrode
Weighing 3mg load silver reduced graphene, to be scattered in the N,N-dimethylformamide of the chitosan that 3mL contains 0.1mL molten
In liquid, ultrasonic disperse 5min.The dispersant liquid drop pipetting 3 μ L is coated on naked gold electrode, naturally dries.It is-0.2～0.6V at voltage
Between be circulated voltammetric scan multi-turn, until stable.
(3) preparation of olaquindox electrochemical sensor
Electropolymerization is used to prepare olaquindox electrochemical sensor.Accurately weigh a certain amount of olaquindox and dopamine is dissolved in
In phosphate buffer solution, ultrasonic 15min.Being scanned in current potential-0.2～1.4V by cyclic voltammetry, response time is 2s,
Scanning speed is 50mV/s, and molecular engram film is polymerized at electrode surface.With the HCl of 0.5mol/L: dehydrated alcohol=7:3 mixed liquor
Eluting 15min, removes template olaquindox, i.e. can obtain the electrochemical sensor with the hole of template molecule.
According to the further feature of electrochemical sensor of the present invention, in described step (3), the scanning number of turns is 20
Circle.
According to the further feature of electrochemical sensor of the present invention, in described step (3), olaquindox is 5mmol/
L, o-phenylenediamine is 10mmol/L.
According to the further feature of electrochemical sensor of the present invention, in described step (3), phosphate buffered solution
PH value be 8.0.
The present invention uses loading nano silvery reduction graphite modified gold electrode, with olaquindox on the electrode after then modifying at this
For template, dopamine is function monomer, electropolymerization in the phosphate buffered solution of pH=8.0, is prepared for one and has sensitive
Degree is high, selectivity is good and the olaquindox electrochemical sensor of good stability.When olaquindox concentration is 1 × 10-8～6 × 10-6mol/
Becoming good linear relationship in L, equation of linear regression is Δ I (μ A)=0.1989C (μm ol/L)+0.2381, and correlation coefficient is r
=0.9978, detection is limited to 1 × 10-9Mol/L (S/N=3).
Accompanying drawing explanation
Fig. 1 is that different modifying electrode is at K3Fe(CN)6Cyclic voltammetry curve, in figure, a: bare electrode；B:rGO electrode；C:
RGO@Ag electrode；D: non-eluting MIP/rGO@Ag；E: eluting MIP/rGO@Ag.
Fig. 2 is the scanning electron microscope diagram of different modifying electrode, in figure, a: the MIP electrode of non-eluting；B: after eluting
MIP electrode.
Fig. 3 is DPV curve (a) of the present invention and standard curve (b)
Detailed description of the invention
Embodiment 1: the structure of the electrochemical sensor for detecting trace olaquindox of the present invention
(1) gold electrode pretreatment
Gold electrode alumina powder is polished on flannelette, then distinguishes ultrasonic 30s with dehydrated alcohol, distilled water.
At 0.5mol/L H2SO4Solution being circulated voltammetric scan-0.2～1.4V, until obtaining stable electric current, taking out electrode
Totally dry standby with distilled water flushing.
(2) load silver reduced graphene (rGO@Ag) modified electrode
Weighing 3mg load silver reduced graphene, to be scattered in the N,N-dimethylformamide of the chitosan that 3mL contains 0.1mL molten
In liquid, ultrasonic disperse 5min.The dispersant liquid drop pipetting 3 μ L is coated on naked gold electrode, naturally dries.It is-0.2～0.6V at voltage
Between be circulated voltammetric scan multi-turn, until stable.
(3) preparation of olaquindox electrochemical sensor
Electropolymerization is used to prepare olaquindox electrochemical sensor.Accurately weigh a certain amount of olaquindox and dopamine is dissolved in
In phosphate buffer solution, ultrasonic 15min.Being scanned in current potential-0.2～1.4V by cyclic voltammetry, response time is 2s,
Scanning speed is 50mV/s, and molecular engram film is polymerized at electrode surface.With the HCl of 0.5mol/L: dehydrated alcohol=7:3 mixed liquor
Eluting 15min, removes template olaquindox, i.e. can obtain the electrochemical sensor with the hole of template molecule.
Embodiment 2: the differential pulse of the electrochemical sensor for detecting trace olaquindox of the present invention characterizes
Owing to the trace hole in film can use K as the passage of electron transmission3Fe(CN)6For probe, according to its electric current
Size characterize various electrodes surface nature.As it is shown in figure 1, Different electrodes 0.2mol/L [Fe (CN)6]3-/4-Difference in solution
Sectors rushes curve significant difference.[Fe (CN) in solution6]3-/4-Redox reaction occurs on bare electrode (a) surface, and electronics turns
Move fast, obtain a high current peak of comparison.After rGO modified electrode (b), peak current significantly increases, and shows that rGO improves electricity
The sensitivity of pole.After rGO@Ag modified electrode (c), peak current continues to raise, i.e. rGO@Ag modified electrode substantially increases detection
Sensitivity.Forming insulation film at electrode surface after the polymerization of molecular engram film, non-blotting membrane, electric current is close to 0.Non-after eluting
Molecular engram film electrode, because not having template removal current-responsive little, stays under many after the electrode eluted template of molecular engram film
Trace hole, makes [Fe (CN)6]3-/4-Can pass freely through, current-responsive is big, indicates and successfully gathers on rGO@Ag modified electrode
Close molecular engram film, and there is more imprinted sites.
Embodiment 3: the different modifying electrode of the electrochemical sensor for detecting trace olaquindox of the present invention
Scanning electron microscope characterizes
Using scanning electron microscope, the microstructure to different modifying electrode is characterized.As shown in Fig. 2 (a), molecular engram
Polymerization caudacoria surface smoother, does not has hole.When after eluted template (see Fig. 2 (b)), leave many holes on the surface of film,
Show olaquindox template molecule by success trace on film, stay after eluting and there is the hole that structure therewith matches.
Embodiment 4: the range of linearity is tested with detection limit
Prepare synthesis olaquindox molecular engram polymeric membrane with optimal conditions, by the blotting membrane electrode after eluted template molecule
Respectively 1 × 10-8、1×10-7、1×10-6、2×10-6、4×10-6、6×10-6The olaquindox standard solution of mol/L is hatched
15min, at 0.2mol/L [Fe (CN)6]3-/4-Solution carries out DPV scanning, after measuring, electrode is steeped 0.5mol/L's every time
Eluting 15min in hydrochloric acid and dehydrated alcohol=7:3 mixed liquor, to remove template molecule recovery electrode.Result such as Fig. 3, shows
Olaquindox concentration is 1 × 10-8～6 × 10-6In the range of mol/L, concentration and peak current are good linear relation, are linearly Δ I
(μ A)=0.1989C (μm ol/L)+0.2381, correlation coefficient is r=0.9978, and detection is limited to 1 × 10-9Mol/L (S/N=3).
Embodiment 5: repeatability and stability experiment
With same electrode, the olaquindox solution that concentration is 1 μm ol/L is carried out 5 parallel assays, its relative standard deviation
It is 3.1%, shows that this blotting membrane has good repeatability.The blotting membrane simultaneously prepared with another root electrode is within a week
Every day is placed on 0.2mol/L [Fe (CN) electrode6]3-/4-In carry out DPV sweep measuring, response current difference is little, and it is relative
Standard deviation is 8.5%, it was demonstrated that this blotting membrane has preferable stability.
Embodiment 6: actual sample measures
Piglet feed is soluble in water, it is made into sample solution, and carries out mark-on detection.By differential pulse method to each mark-on
Sample carries out 3 times and measures, and average results is as shown in table 1, and the response rate of method is 99%～102% as shown in Table 1, relatively marks
Quasi-deviation is 3.0%-3.5%.
Table 1: the testing result (n=3) of olaquindox in piglet feed
| Sample | Add scalar (μm ol/L) | Average recovery rate (%) | RSD (%) |
| 1 | 0.1 | 102 | 3.5 |
| 2 | 0.5 | 99.8 | 3.0 |
| 3 | 1.0 | 99 | 3.0 |
Claims (4)
1. the electrochemical sensor being used for detecting trace olaquindox, it is characterised in that described electrochemical sensor is to pass through
Prepared by following methods:
(1) gold electrode pretreatment:
Gold electrode alumina powder is polished on flannelette, then distinguishes ultrasonic 30s with dehydrated alcohol, distilled water；?
0.5mol/L H2SO4Solution is circulated voltammetric scan-0.2～1.4V, until obtaining stable electric current, taking out electrode and using
Distilled water flushing totally dries standby；
(2) load silver reduced graphene (rGO@Ag) modified electrode:
Weigh 3mg load silver reduced graphene and be scattered in the N,N-dimethylformamide solution of the chitosan that 3mL contains 0.1mL
In, ultrasonic disperse 5min；The dispersant liquid drop pipetting 3 μ L is coated on naked gold electrode, naturally dries；It is between-0.2～0.6V at voltage
It is circulated voltammetric scan multi-turn, until stable；
(3) preparation of olaquindox electrochemical sensor:
Accurately weigh a certain amount of olaquindox and dopamine is dissolved in phosphate buffer solution, ultrasonic 15min；Exist by cyclic voltammetry
Being scanned in current potential-0.2～1.4V, response time is 2s, and scanning speed is 50mV/s, and molecular engram film gathers at electrode surface
Close；With the HCl of 0.5mol/L: dehydrated alcohol=7:3 mixed liquor eluting 15min, remove template olaquindox, i.e. can obtain that there is mould
The electrochemical sensor in the hole of plate molecule.
Electrochemical sensor the most according to claim 1, it is characterised in that: in described step (3), the scanning number of turns is 20
Circle.
Electrochemical sensor the most according to claim 1, it is characterised in that: in described step (3), olaquindox is 5mmol/
L, o-phenylenediamine is 10mmol/L.
Electrochemical sensor the most according to claim 1, it is characterised in that: in described step (3), phosphate buffered solution
PH value be 8.0.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610495054.9A CN106053565A (en) | 2016-06-27 | 2016-06-27 | Electrochemical sensor for detecting trace olaquindox |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610495054.9A CN106053565A (en) | 2016-06-27 | 2016-06-27 | Electrochemical sensor for detecting trace olaquindox |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110057886A (en) * | 2019-04-23 | 2019-07-26 | 上海应用技术大学 | A kind of preparation method of disposable electrochemistry trace sensor |
Citations (2)
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| CN105675683A (en) * | 2015-12-31 | 2016-06-15 | 江苏大学 | Preparation method and application of electrochemical sensor for detecting sunset yellow |
| CN105699470A (en) * | 2016-03-31 | 2016-06-22 | 肇庆学院 | Magnetic molecular imprinting electrochemical sensor for detecting trace sulfadimidine |
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2016
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105675683A (en) * | 2015-12-31 | 2016-06-15 | 江苏大学 | Preparation method and application of electrochemical sensor for detecting sunset yellow |
| CN105699470A (en) * | 2016-03-31 | 2016-06-22 | 肇庆学院 | Magnetic molecular imprinting electrochemical sensor for detecting trace sulfadimidine |
Non-Patent Citations (3)
| Title |
|---|
| TIANCI XU 等: "Development of electrochemical method for the determination of olaquindox using multi-walled carbon nanotubes modified glassy carbon electrode", 《TALANTA》 * |
| 刘婷婷: "分子印迹聚合物电化学传感器的制备及其在药物分析中的应用_", 《中国优秀硕士学位论文全文数据库（电子期刊）医药卫生科技辑》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110057886A (en) * | 2019-04-23 | 2019-07-26 | 上海应用技术大学 | A kind of preparation method of disposable electrochemistry trace sensor |
| CN110057886B (en) * | 2019-04-23 | 2021-07-20 | 上海应用技术大学 | Preparation method of disposable electrochemical imprinting sensor |
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Application publication date: 20161026 |