CN105092671A - OAP-MIP multiple binding site affinity membrane chlortetracycline (CTC) sensor and preparation method thereof - Google Patents
OAP-MIP multiple binding site affinity membrane chlortetracycline (CTC) sensor and preparation method thereof Download PDFInfo
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- CN105092671A CN105092671A CN201410759072.4A CN201410759072A CN105092671A CN 105092671 A CN105092671 A CN 105092671A CN 201410759072 A CN201410759072 A CN 201410759072A CN 105092671 A CN105092671 A CN 105092671A
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Abstract
The invention relates to a chlortetracycline (CTC) molecularly imprinted (MIP) affinity membrane sensor and a preparation method thereof. The specific affinity membrane is formed based on an electropolymerization method, and CTC as a template molecule and o-aminophenol (OAP) as a functional monomer form a molecularly imprinted polymer membrane on the surface of a glassy carbon electrode by an electrochemistry method. CTC contains a phenolic hydroxyl group, an enol group and a dimethylamino group and the hydroxyl group in the OAP structure can be used as a latent coordination site so that OAP amino group, and phenolic hydroxyl group and enol group of CTC undergo intermolecular hydrogen bond interaction. OAP hydroxyl group and CTC dimethylamino group undergo a reaction so that multiple binding sites between OAP and CTC exist and the prepared molecularly imprinted polymer has very high CTC selectivity and bonding capability. The sensor can be used for on-site fast detection, does not need specimen pre-treatment, and has a low cost, simple processes and high sensitivity. The sensor has a detection linear range of 20-610nM and sensitivity of 15nM.
Description
Technical field
The invention belongs to the electrochemical analysis field of antibiotic residue, relate to molecular imprinting, especially a kind of aureomycin molecular engram sensor and preparation method thereof.
Background technology
Aureomycin (Chlortetracyline, CTC) the antibiotic one of Tetracyclines spectrum is belonged to, can by extracting in streptomycete nutrient solution or producing with semisynthesis, can effectively suppress gram positive bacteria, negative bacterium, rickettsia etc., antibacterial range is wider.Can be widely used in fish, the prevention of diseases of bird and livestock and treatment, make an addition in feed and can increase poultry daily gain and feed conversion rate.But due to drug abuse, the aureomycin residued in animal food constitutes potential harm to health.Most countries has made strict restriction to the residual of aureomycin in animal food, in animal food, most high residue amount is respectively muscle to No. 235 file " animal food herbal medicine maximum residue limit(MRL) " the regulation aureomycin hydrochloride that the Ministry of Agriculture of China 2002 issues is 100mg/kg, liver is 300mg/kg, and kidney is 600mg/kg; In ox or sheep class, milk is 100mg/kg; In bird, be 200mg/kg in egg; In fish or shrimps, meat is 100mg/kg.
In recent years, the common method of the detection aureomycin reported both at home and abroad comprises high performance liquid chromatography (HPLC), immunoassay, capillary electrophoresis, thin-layered chromatography (TLC), culture of microorganism, wherein, although HPLC method is most widely used, testing result is precisely reliable, but require higher to sample purity, the needs of sample rapid screening in enormous quantities cannot be met.Immunoassay is less demanding to sample purity, but testing result poor reproducibility.Capillary electrophoresis and TLC method analysis speed are fast, but sensitivity is low.Culture of microorganism is applicable to the screening of a large amount of sample, but can not do quantitative test by the impact of antibacterial activity impurity.
Molecularly imprinted polymer (MIPs) is a kind of novel high polymer biomimetic material with stronger specific molecular recognition capability, there is preparation simple, usable range be wide, high temperature resistant, high pressure, acid and alkali corrosion and can repeatedly reclaim the advantage repeating to be used.The preparation method that MIPs is traditional mainly contains molecular self-assembling method, original position initiated polymerization method, surperficial cladding process, in recent years, the electropolymerization method developed rapidly is successfully applied to preparation MIPs, has and reaches the ultrathin membrane of nanometer grade thickness, good rigidity and reappearance by controlling the quantity of electric charge and can operate under water environment.
Summary of the invention
The object of the present invention is to provide a kind of respond fast, selectivity is high, highly sensitive, the field fast detection method of favorable reproducibility.
The object of the invention is to be achieved through the following technical solutions:
The preparation of aureomycin molecular engram sensor
(1) pre-service of glass-carbon electrode: α-Al glass-carbon electrode being used successively 1.0,0.30,0.05 μm of granularities
2o
3burnishing powder grinding and polishing, then uses 1: 1HNO successively
3, absolute ethyl alcohol and redistilled water ultrasonic cleaning 2 ~ 3min respectively, then electrode is placed in 0.5mol/LH
2sO
4with cyclic voltammetry activation in solution, sweep limit is-0.1 ~ 1.0V, and scanning is till obtaining symmetrical and stable cyclic voltammetric (CV) figure in cathode and anode peak repeatedly.Reach after stablizing, spike potential difference at below 80mV, then takes out electrode stand-by.
(2) molecular self-assembling mode prepares blotting membrane electrode: be dissolved in 0.1M perchloric acid by 0.1g o-aminophenol (OAP), and add 0.4M NaOH and pH value is adjusted to faintly acid (pH5.5), being settled to 250mL concentration is 3.67mM, therefrom pipettes the NaClO that 9mL has prepared 3.67mMOAP
4solution, then aureomycin (CTC) mixed dissolution adding 1mL1mM wherein.Because of the polyreaction initial stage, oxygen attack radical cation, then need logical N
2except O
2about 15min, immerses the three-electrode system handled well containing 3.67mMOAP, 0.1mMCTC and 0.1MNaClO
4in solution (pH5.5), enclose at the potential region Inner eycle voltammetric scan 30 of-0.2 ~ 1.2V, sweep velocity is 50mV/s, and prepared polymeric membrane is fixed on glassy carbon electrode surface through chemical modification effect deposition.Owing to containing phenolic hydroxyl group, enol base and dimethylamino in aureomycin (CTC) molecule.And select o-aminophenol (OAP) as function monomer, the hydroxyl existed in its structure also can be used as potential coordination site, not only can there is intermolecular ydrogen bonding and interact in the phenolic hydroxyl group of the amino of OAP and CTC, enol base, and also can have an effect between the hydroxyl of OAP and the dimethylamino of CTC, therefore there is more binding site between OAP and CTC, make prepared molecularly imprinted polymer have high selectivity and binding ability to aureomycin.And along with scanning the increase of the number of turns, electrode surface covers the non-conductive polymeric membrane of one deck densification gradually, prevent the further oxidation of OAP, voltammetric current is responded and is suppressed, just obtain dielectric blotting membrane electrode (CTC-MIP-OAP/GCE) thus.
(3) wash-out of template molecule: adopt CTC-MIP-OAP/GCE prepared by above-mentioned steps (2), being inserted volume ratio is in the methanol/sulfuric acid solution of 1: 4 after wash-out 24h, the blotting membrane electrode (MIP-POAP/GCE) with the recognition site that can match with aureomycin can be obtained, i.e. aureomycin molecular imprinted membrane sensor.At present, the research of aureomycin molecular imprinted membrane sensor is not yet reported, the present invention is that to adopt first with OAP be function monomer, and CTC is template molecule, utilize electropolymerization mode construct a kind of can indirectly by electrochemical techniques to measure the molecular imprinted membrane sensor of aureomycin.
A kind of aureomycin molecular engram sensor according to claim 1 and preparation thereof, is characterized in that:
The electrochemical response of blotting membrane electrode and typical curve
Differential pulse voltammetry is utilized to contain 5mMK
3[Fe (CN)
6] 100mMKClPBS in characterize the current-responsive of blotting membrane sensor.Prepared trace Sensitive membrane electrode is immersed and carries out differential pulse voltammetry detection containing after staticaccelerator adsorption in finite concentration aureomycin solution, when the adsorption time of each concentration is 20min, reach balance.Each test repetition 3 times, according to the current-responsive change occurred after blotting membrane electrode adsorption aureomycin, draws the typical curve of chlortetracycline concentration and response current difference.
Advantage of the present invention and beneficial effect are:
1, the present invention is based on electropolymerization method, utilize that cyclic voltammetry take aureomycin hydrochloride as template molecule, o-aminophenol prepared molecular imprinting electrochemical sensor for function monomer, application differential pulse voltammetry have studied the response performance of this sensor.The response of this sensor is fast, and cost is low, and selectivity is good, meets the requirement of aureomycin hydrochloride trace analysis, is expected to better be applied in food inspection.
What 2, the present invention adopted is o-aminophenol is as function monomer, and can form fine and close rigid insulation polymeric membrane in the polymerization of Different electrodes surface electrical, thickness can be controlled in 10-100nm, and hydroxyl is as potential coordination site, can further improve the performance of sensor.Therefore in the present invention, choose [Fe (CN)
6]
3-.The potassium ferricyanide has good electrochemical stability, can ensure the reliability of analysis result.From Fig. 2-1, K
3[Fe (CN)
6] non-blotting membrane surface after wash-out process is almost without response (curve d), and blotting membrane peak current (curve b) after wash-out process is comparatively large, but with bare electrode surface peak current (curve a) compared with little.
3, the present invention adopts differential pulse voltammetry to measure the aureomycin hydrochloride of same concentration and chaff interference solution.Select the larger chloromycetin of tetracycline, terramycin and the textural difference similar to aureomycin hydrochloride structure, penicillin compares checking as chaff interference, fully can reflect the selectivity of this sensor.As shown in Figure 4, chloromycetin and penicillin almost noiseless to aureomycin hydrochloride, terramycin and tetracycline create atomic weak current-responsive, illustrate that this sensor has specific selectivity to aureomycin hydrochloride.
4, the sensor that prepared by the present invention meets the requirement of aureomycin hydrochloride trace analysis and response is fast, and cost is low, and selectivity is good.As known in Fig. 5-1, the differential pulse voltammetry current-responsive under different aureomycin hydrochloride concentration; According to the current-responsive change occurred after blotting membrane electrode adsorption aureomycin, draw the typical curve of chlortetracycline concentration and response current difference, as known in Fig. 5-2, it detects the range of linearity and can reach to 20-610nM.
5, sensor ultrasonic cleaning 5min in elute soln of preparing of the present invention, and with electrode can be made after second distillation water wash substantially to return to the state before response.Therefore use same blotting membrane electrode pair 0.2 μM of CTC replicate determination 5 times, RSD is 1.9%, shows good reappearance.By this blotting membrane electrode storage in 4 DEG C of refrigerators, after two weeks, under equal ambient, 90.3% is down to the response of 0.2 μM of CTC.After surrounding, response is down to 82.7%.There are preferably long-time stability.
Accompanying drawing explanation
Fig. 1-1 and Fig. 1-2 is cyclic voltammetric electropolymerization curve of the present invention: wherein, Fig. 1-1 is o-aminophenol monomer polymerization; Fig. 1-2 is o-aminophenol and aureomycin hydrochloride polymerization;
Fig. 2-1 and Fig. 2-2 is for Different electrodes of the present invention is at K
3[Fe (CN)
6] and KCl solution in differential pulse voltammetry curve and cyclic voltammetry curve: (a) GCE; (b) MIP-POAP/GCE; (c) CTC
ad-MIP-POAP/GCE; (d) POAP/GCE;
Fig. 3 is that the present invention's difference polymerization number of turns is on the impact of peak current difference before and after wash-out;
The Relative Peak current changing rate that Fig. 4 produces for the different measured object of the present invention: (a) aureomycin hydrochloride; (b) tetracycline; (c) terramycin; (d) chloromycetin; (e) penicillin;
Fig. 5-1 and Fig. 5-2 is differential pulse voltammetry curve under different aureomycin hydrochloride concentration of the present invention and typical curve;
Embodiment
The present invention is based on the detection method that the Determination of trace gold mycin of molecular imprinted membrane sensor is residual, comprise the preparation of aureomycin molecular imprinted membrane sensor and the drafting of electrochemical response and typical curve.
1, the preparation of aureomycin molecular imprinted membrane sensor
(1) pre-service of glass-carbon electrode: d-Al glass-carbon electrode being used successively 1.0,0.30,0.05 μm of granularities
2o
3burnishing powder grinding and polishing, then use 1: 1HNO3 successively, absolute ethyl alcohol and redistilled water ultrasonic cleaning 2 ~ 3min respectively, again electrode is placed in 0.5mol/LH2SO4 solution cyclic voltammetry to activate, sweep limit is-0.1 ~ 1.0V, and scanning is till obtaining symmetrical and stable cyclic voltammetric (CV) figure in cathode and anode peak repeatedly.Reach after stablizing, spike potential difference at below 80mV, then takes out electrode stand-by.
(2) molecular self-assembling mode prepares blotting membrane electrode: be dissolved in 0.1M perchloric acid by 0.1g o-aminophenol (OAP), and add 0.4M NaOH and pH value is adjusted to faintly acid (pH5.5), being settled to 250mL concentration is 3.67mM, therefrom pipettes the NaClO that 9mL has prepared 3.67mMOAP
4solution, then aureomycin (CTC) mixed dissolution adding 1mL1mM wherein.Because of the polyreaction initial stage, oxygen attack radical cation, then need logical N
2except O
2about 15min, immerses the three-electrode system handled well containing 3.67mMOAP, 0.1mMCTC and 0.1MNaClO
4in solution (pH5.5), enclose at the potential region Inner eycle voltammetric scan 30 of-0.2 ~ 1.2V, sweep velocity is 50mV/s, and prepared polymeric membrane is fixed on glassy carbon electrode surface through chemical modification effect deposition.Owing to containing phenolic hydroxyl group, enol base and dimethylamino in aureomycin (CTC) molecule.And select o-aminophenol (OAP) as function monomer, the hydroxyl existed in its structure also can be used as potential coordination site, not only can there is intermolecular ydrogen bonding and interact in the phenolic hydroxyl group of the amino of OAP and CTC, enol base, and also can have an effect between the hydroxyl of OAP and the dimethylamino of CTC, therefore there is more binding site between OAP and CTC, make prepared molecularly imprinted polymer have high selectivity and binding ability to aureomycin.And along with scanning the increase of the number of turns, electrode surface covers the non-conductive polymeric membrane of one deck densification gradually, prevent the further oxidation of OAP, voltammetric current is responded and is suppressed, just obtain dielectric blotting membrane electrode (CTC-MIP-OAP/GCE) thus.
(3) wash-out of template molecule: adopt CTC-MIP-OAP/GCE prepared by above-mentioned steps (2), being inserted volume ratio is in the methanol/sulfuric acid solution of 1: 4 after wash-out 24h, the blotting membrane electrode (MIP-POAP/GCE) with the recognition site that can match with aureomycin can be obtained, i.e. aureomycin molecular imprinted membrane sensor.At present, the research of aureomycin molecular imprinted membrane sensor is not yet reported, the present invention is that to adopt first with OAP be function monomer, and CTC is template molecule, utilize electropolymerization mode construct a kind of can indirectly by electrochemical techniques to measure the molecular imprinted membrane sensor of aureomycin.
2, electrochemical response and Specification Curve of Increasing
Adopt differential pulse voltammetry to characterize blotting membrane electrode (MIP-POAP/GCE) characteristic in 5mM potassium ferricyanide solution in the present invention.By the change (Δ I) of potassium ferricyanide differential pulse peak current before and after blotting membrane electrode adsorption aureomycin, calculate the relation between differential pulse peak current reduction and aureomycin hydrochloride solution concentration, drawing standard curve, and then the content that indirectly can record aureomycin hydrochloride.
Testing result is as follows:
1, molecular engram electropolymerization
Fig. 1-1 is the CV curve under the existence of template molecule CTC on glass-carbon electrode in OAP electropolymerization process.From CV curve, the electrochemical polymerization of OAP is an irreversible process.From the second circle of scanning, just there is obvious rapid drawdown in electric current, and increasing along with the CV scanning number of turns, electric current slowly drops to background value, this demonstrate and electrode surface covers gradually and defines fine and close non-conductive polymeric membrane, prevent the further oxidation of OAP, voltammetric current is responded and is suppressed.And Fig. 1-2 is the CV curve of the OAP electropolymerization not adding CTC, there is no significant difference compared with Fig. 1-1, this shows that the electropolymerization of OAP is not disturbed in the existence of CTC, and CTC structure does not also change.
2, molecular engram effect
Adopt CV and DPV method to characterize bare electrode (GCE), blotting membrane electrode (MIP-POAP/GCE), adsorb the blotting membrane electrode (CTC of CTC through wash-out again
ad-MIP-POAP/GCE) and non-blotting membrane electrode (POAP/GCE) containing 5mMK
3[Fe (CN)
6] 100mMKClPBS (pH6.4) in characteristic.The curve (Fig. 2-1) characterized from DPV method, a has higher reduction peak current to occur, probe ion Fe (CN) is described
6 -3there occurs electrochemical reaction on GCE surface, thus create electric current.And d is compared to pole a, almost do not have reduction peak to occur, this is because the POAP/GCE electrode not containing CTC be covered on electrode is non-conductive, hinders Fe (CN)
6 -3diffusion transmission.B is for d, and reduction peak value has had and significantly increases substantially, and this is the trace hole left after wash-out due to CTC-MIP-POAP/GCE film is [Fe (CN)
6]
-3provide mass transfer channel and there occurs electrochemical reaction.Then there is the decline of peak value compared to b in c, this then illustrates the hole that the CTC of 0.2 μM leaves through blotting membrane, is adsorbed on MIP-POAP/GCE electrode, a part of trace hole block by the CTC in absorption, make [Fe (CN)
6]
- 3mass transfer channel reduces.CV method is consistent with the characterization result of DPV method.
3, the optimization of the electropolymerization scanning number of turns
The number of times that electropolymerization CV scans can control the thickness of polymeric membrane.This experiment employing has been polymerized the obtained MIP-POAP/GCE membrane electrode of 20,25,30 and 35 number of turns respectively and has contained 5mMK
3[Fe (CN)
6] and 100mMKCl PBS in carry out the mensuration of DPV electrochemical response.The DPV reduction peak value difference of the polymeric membrane electrode prepared by the more different polymerization number of turns before and after wash-out, can be learnt from Fig. 3, when the polymerization number of turns is 30 circle, and electroactive the best of membrane electrode.The polymerization number of turns can form film time less, be unfavorable for the attachment of CTC, and then the formation in trace hole also reduces thereupon.And be polymerized the number of turns higher time, film is too thick, and the activation of sensor response needs the longer time, to Fe (CN)
6 -3process close to trace hole creates certain obstruction, makes electrode response value on the low side equally and when aggregation number is too high, has the phenomenon generation that template molecule elution is not fallen.
4, adsorption time detects the impact of aureomycin on blotting membrane
Response time is the important parameter characterizing sensor performance, is immersed by MIP-POAP/GCE membrane electrode in finite concentration aureomycin solution and carries out standing adsorption, take out every 2min, and clean with second distillation water wash, is containing 5mMK
3[Fe (CN)
6] 100mMKClPBS in detect by DPV method.Result shows, along with the increase of adsorption time, imprinted sites is gradually occupied by aureomycin molecule, and peak current declines gradually, and after adsorption time is more than 20min, peak current reaches balance substantially.Therefore 20min is selected to be the optimal adsorption time.
5, the selectivity of blotting membrane
Select tetracycline, terramycin, chloromycetin and penicillin as chaff interference and adopt DPV method to verify the MIP-POAP/GCE membrane electrode leaving trace hole to the selectivity of CTC.Determine modified membrane trace electrode pair respectively containing the aureomycin hydrochloride of 5,7.5,10,15,20,40 and 80 μMs and the response of chaff interference solution, and calculate Relative Peak current changing rate (Ai/i
0), wherein, Δ i be MIP-POAP/GCE membrane electrode to the peak current difference before and after various substance responds, i
0for the peak point current of blotting membrane after wash-out.In Fig. 4, chloromycetin and penicillin almost noiseless to aureomycin hydrochloride, terramycin and tetracycline create atomic weak current-responsive.These results suggest that the structural difference of chloromycetin and penicillin and CTC is larger, electrochemical response signal intensity is extremely faint, and terramycin is similar to the structure of CTC with tetracycline, this makes a small amount of terramycin and tetracycline can be adsorbed on the hole of microsphere modified electrode, thus cause faint electrochemical response, but significantly interference is not formed to CTC, this illustrates that the effect between blotting membrane modified electrode and template molecule is not singly determined by the functional group with its complementation, and the trace hole that spatial structure complementation is formed also creates larger impact.
6, the electrochemical response of blotting membrane electrode and typical curve
Application DPV method, makes this sensor contain 5mMK to after the absorption of finite concentration aureomycin
3[Fe (CN)
6] 100mMKClPBS (pH=6.4, V=10mL) in carry out DPV mensuration.By the CTC of peak current measured in background solution for MIP-POAP/GCE membrane electrode with absorption variable concentrations CTC
adpeak point current measured by-MIP-POAP/GCE membrane electrode carries out doing poor (Δ I), and is mapped by the relation of Δ I and CTC concentration, thus obtains the typical curve (Fig. 5-2) about CTC concentration.
7, the reappearance of blotting membrane electrode and stability
Used electrode is ultrasonic cleaning 5min in elute soln, and with electrode can be made after second distillation water wash substantially to return to the state before response.Therefore use same blotting membrane electrode pair 0.2 μM of CTC replicate determination 5 times, RSD is 1.9%, shows good reappearance.By this blotting membrane electrode storage in 4 DEG C of refrigerators, after two weeks, under equal ambient, 90.3% is down to the response of 0.2 μM of CTC.After surrounding, response is down to 82.7%.There are preferably long-time stability.
Claims (3)
1. OAP-MIP multiple binding sites affinity membrane aureomycin sensor and preparation method thereof, is characterized in that, what it was fixed wtih by glass-carbon electrode and surface thereof forms the molecular engram film of aureomycin by function of specific connecting.
2. sensor described in claim 1, it is characterized in that, the intermolecular ydrogen bonding effect that specificity affinity membrane has the phenolic hydroxyl group of the amino of OAP and CTC, enol base occurs on its surface, also the effect between the hydroxyl of OAP and the dimethylamino of CTC is had, under electrochemical conditions, form more binding site between OAP and CTC, make prepared molecularly imprinted polymer have high selectivity and binding ability to aureomycin.
The preparation method of 3.OAP-MIP multiple binding sites affinity membrane electrode
Be dissolved in by 0.1gOAP in 0.1M perchloric acid, and add 0.4M NaOH and pH value is adjusted to faintly acid (pH5.5), being settled to 250mL concentration is 3.67mM, therefrom pipettes the NaClO that 9mL has prepared 3.67mMOAP
4solution, then aureomycin (CTC) mixed dissolution adding 1mL1mM wherein.Because of the polyreaction initial stage, oxygen attack radical cation, then need logical N
2except O
2about 15min, immerses the three-electrode system handled well containing 3.67mMOAP, 0.1mMCTC and 0.1MNaClO
4in solution (pH5.5), enclose at the potential region Inner eycle voltammetric scan 30 of-0.2 ~ 1.2V, sweep velocity is 50mV/s, and prepared polymeric membrane is fixed on glassy carbon electrode surface through chemical modification effect deposition.Along with the increase of the scanning number of turns, electrode surface covers the non-conductive polymeric membrane of one deck densification gradually, prevent the further oxidation of OAP, voltammetric current is responded and is suppressed, just obtain dielectric blotting membrane electrode (CTC-MIP-OAP/GCE) thus.
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| CN113295740A (en) * | 2021-05-10 | 2021-08-24 | 中国地质大学（武汉） | Thrombin electrochemical sensor based on multi-binding site aptamer |
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| CN105973958A (en) * | 2016-05-05 | 2016-09-28 | 济南大学 | Preparation method of fluorouracil molecularly imprinted electrochemical sensor |
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| CN106198695A (en) * | 2016-07-01 | 2016-12-07 | 湖北师范大学 | A kind of electrochemical aptamer sensor of quick detection chloromycetin |
| CN106198695B (en) * | 2016-07-01 | 2018-10-30 | 湖北师范大学 | A kind of electrochemical aptamer sensor of quick detection chloramphenicol |
| CN113295740A (en) * | 2021-05-10 | 2021-08-24 | 中国地质大学（武汉） | Thrombin electrochemical sensor based on multi-binding site aptamer |
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