CN103558271B - Electrochemical biosensor for detecting penicillin and preparation method and application thereof - Google Patents
Electrochemical biosensor for detecting penicillin and preparation method and application thereof Download PDFInfo
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- 229940049954 penicillin Drugs 0.000 title claims abstract description 72
- 229930182555 Penicillin Natural products 0.000 title claims abstract description 68
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 34
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 14
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
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- 230000000694 effects Effects 0.000 claims description 5
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- 230000021523 carboxylation Effects 0.000 abstract 2
- 238000006473 carboxylation reaction Methods 0.000 abstract 2
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- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
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- RXZBMPWDPOLZGW-XMRMVWPWSA-N (E)-roxithromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=N/OCOCCOC)/[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 RXZBMPWDPOLZGW-XMRMVWPWSA-N 0.000 description 1
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- 229930182566 Gentamicin Natural products 0.000 description 1
- CEAZRRDELHUEMR-URQXQFDESA-N Gentamicin Chemical compound O1[C@H](C(C)NC)CC[C@@H](N)[C@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](NC)[C@@](C)(O)CO2)O)[C@H](N)C[C@@H]1N CEAZRRDELHUEMR-URQXQFDESA-N 0.000 description 1
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- AVKUERGKIZMTKX-NJBDSQKTSA-N ampicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=CC=C1 AVKUERGKIZMTKX-NJBDSQKTSA-N 0.000 description 1
- 229960000723 ampicillin Drugs 0.000 description 1
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- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
The invention discloses an electrochemical biosensor for detecting penicillin and a preparation method and application thereof. The electrochemical biosensor is characterized in that a working electrode is a magnetic glassy carbon electrode immobilized with MWCNTs-Fe3O4/Au-HRP-Ab. The preparation method comprises the following steps: carrying out carboxylation on a multi-walled carbon nanotube, preparing Fe3O4/Au composite nano particles, preparing a Fe3O4/Au magnetic nano particle-HRP-penicillin antibody, sequentially modifying the carbon nanotube subjected to carboxylation and Fe3O4/Au-HRP-Ab to the surface of the glassy carbon electrode of the carbon nanotube, forming the electrochemical biosensor by taking a platinum electrode as a counter electrode and taking a saturated calomel electrode as a reference electrode, immersing the electrochemical biosensor into a sample to be detected, and determining the concentration of the penicillin in the sample to be detected according to a quantitative relation between a corresponding current value and the concentration of the penicillin. The electrochemical biosensor has the advantages of high sensitivity, high selectivity, high accuracy and high detection speed.
Description
Technical field
The present invention relates to penicillin detection technique, especially relate to a kind of based on MWCNTs-Fe
3o
4/ Au for electrochemica biological sensor detecting penicillin and its preparation method and application.
Background technology
Penicillin is a kind of beta-lactam antibiotic; be widely used in treatment bovine mastitis and prevention bacteriological infection; but due to the unreasonable use of the mankind, often can cause a large amount of residual of penicillin in biological tissue, particularly can cause potential harm to the mankind in food.First, Penicillin Content exceeds standard and can develop immunity to drugs to the microorganism of people and animals' enteron aisle, causes flora imbalance, thus causes a series of diseases such as allergic reaction.Secondly, in employing penicillin prevention and therapy milk cow after disease, microbiotic accumulation can in its body, be produced.The long-term edible milk containing excessive penicillin, brings irreversible infringement will to the internal organs of people, therefore, extremely important for the detection of penicillin in food.
At present, about the detection means of penicillin mainly concentrates on microbial method, high performance liquid chromatography, mass spectroscopy, immunofluorescence technique, conductance method, these methods well can carry out quantitative and qualitative analysis to penicillin in sensitivity and selectivity, but also there is the operations such as derivatization, extraction and purifying, it is taken time and effort, complex steps thus be not suitable for practical application.Therefore, electrochemica biological sensor arises at the historic moment, and it had both combined the specificity of traditional antigen-antibody, combines again electrochemical low cost, high sensitivity and fast-response thereof, thus in food, medical science etc., have its huge using value.Wherein, differential pulse voltammetry has higher sensitivity, is therefore commonly used for highly sensitive detection.
Carbon nano-tube, particularly multi-walled carbon nano-tubes (MWCNTs) have good chemical property and large specific surface area and stronger characterization of adsorption because of it, are used widely in the development of electrochemica biological sensor.Carbon nano-tube is applied to overpotential, promotion electron transmission, the increase response current that electrochemical sensor preparation can not only reduce substrate, can also produce distinctive absorption and catalytic effect to after its acidification to Cucumber.Fe
3o
4nano particle, except having the character of general nano particle, also has unique superparamagnetism, can play the effect of magnetic resolution and enrich target biomolecule.Golden nanometer particle has the stability strong and synthetic operation point such as simply.Fe
3o
4/ Au nano particle can improve the charge capacity of horseradish peroxidase (HRP), and then increases catalytic current, improves the sensitivity of immune detection; Antibody and Fe simultaneously
3o
4after the reaction of/Au composite nanoparticle, can be separated with its free antibody by magnetic field, avoid centrifuging operation steps.But, also do not disclose any about utilizing carbon nano-tube and Fe at present both at home and abroad
3o
4/ Au nano composite material is reported as the correlative study of electrochemical sensing interface material for the preparation of the electrochemica biological sensor detecting penicillin.
Summary of the invention
Technical matters to be solved by this invention is to provide that a kind of detection speed is fast, accuracy and highly sensitive and be easy to operate for electrochemica biological sensor detecting penicillin and its preparation method and application.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of electrochemica biological sensor for detecting penicillin, comprise electrode, contrast electrode and working electrode, described is platinum electrode to electrode, described contrast electrode is saturated calomel electrode, the described working electrode MWCNTs-Fe that has been immobilized
3o
4the magnetic glassy carbon electrode of/Au-HRP-Ab.
For detecting a preparation method for the electrochemica biological sensor of penicillin, concrete steps are as follows:
(1) carbon nano-tube is carboxylated
Ultrasonic 7-9h after multi-walled carbon nano-tubes is mixed in the ratio of mass volume ratio 15mg:20ml with the mixed liquor be made up of sulfuric acid and nitric acid, then be the Kynoar micropore filtering film vacuum filtration of 0.22 μm by aperture, get filtrate ultrapure water repeatedly to wash until filtrate is neutral, namely obtain carboxylated carbon nano-tube aqueous solutions;
(2) Fe
3o
4prepared by/Au composite nanoparticle
By Fe
3o
4after magnetic nano-particle ultrapure water repeatedly washs, adopt tetramethyl azanol as spreading agent constant volume, obtain the Fe that concentration is 1 mg/mL
3o
4nano suspending liquid; Then, by Fe
3o
4after the ratio of the sodium citrate aqueous solution of nano suspending liquid and 0.01wt% 1:20 by volume mixes, be heated under agitation boil, then add 3/5Fe rapidly
3o
4the concentration of nano suspending liquid volume is the chlorauric acid solution of 1.0mg/mL, and sustained response 20-30min, until solution colour becomes claret, obtains Fe
3o
4/ Au composite nanoparticle, abandoning supernatant after magnetic resolution, uses milli-Q water again, is mixed with the Fe of 1mg/mL
3o
4/ Au composite nanoparticle solution, in 4 DEG C of stored refrigerated;
(3) Fe
3o
4prepared by/Au-HRP-Ab
By Fe
3o
4/ Au nano suspending liquid Na
2cO
3adjust pH to 8.0, add volume and be respectively Fe
3o
4the 1.0mg/mL horseradish peroxidase of/Au nano suspending liquid 1/5 and 10 μ g/mL penicillin antibody (Pen-Ab), stir and spend the night, after magnetic resolution, be dispersed in and Fe by potpourri at 4 DEG C
3o
4the isopyknic pH7.4 of/Au nano suspending liquid closes nonspecific activity site containing in the phosphate buffer of 1wt% bovine serum albumin, then after cleaning up with PBS phosphate buffer, to be ultrasonicly dispersed in and Fe
3o
4in the isopyknic phosphate buffer of/Au nano suspending liquid, obtain Fe
3o
4/ Au-HRP-Ab solution;
(4) electrode pre-service
By bare electrode successively with deionized water, absolute ethyl alcohol and deionized water ultrasonic 5min respectively, repeatedly polish to minute surface with the alumina powder that particle diameter is 1 μm, 0.3 μm, 0.05 μm successively again, then be placed in ethanol, deionized water for ultrasonic cleaning 5min respectively, finally dry up with nitrogen for subsequent use;
(5) working electrode is modified and sensor preparation
The carboxylated carbon nano-tube solution 5 μ L of preparation in step (1) is dripped in glassy carbon electrode surface, dry under room temperature, obtain carbon nano tube modified glass-carbon electrode (MWCNTs/GCE); By the Fe of preparation in step (3)
3o
4/ Au-HRP-Ab solution 5 μ L drips in carbon nano tube modified glassy carbon electrode surface, dry under room temperature, obtains Fe
3o
4the glass-carbon electrode that/Au-HRP-Ab-MWCNTs modifies; Fe will be secured
3o
4/ Au-HRP-Ab-MWCNTs glass-carbon electrode is as working electrode, and adopt platinum electrode as to electrode, saturated calomel electrode forms the electrochemica biological sensor for detecting penicillin of three-electrode system as contrast electrode.
In step (1), the volume ratio of sulfuric acid and nitric acid is 3:1.
Apply the method that above-mentioned electrochemica biological sensor detects penicillin concn, by Fe
3o
4/ Au-HRP-Ab-MWCNTs modifies naked glassy carbon electrode surface as working electrode, adopt platinum electrode as to electrode, saturated calomel electrode forms the electrochemica biological sensor of three-electrode system as contrast electrode, electrochemica biological sensor is immersed in testing sample, according to the quantitative relationship of corresponding current value and penicillin concn, determine the concentration of penicillin in testing sample.
Compared with prior art, the invention has the advantages that: the present invention is a kind of for electrochemica biological sensor detecting penicillin and its preparation method and application, based on MWCNTs-Fe
3o
4the detection penicillin of/Au-HRP-Ab immunosensor, first arrives naked glassy carbon electrode surface by carbon nano tube modified, secondly passes through strong suction-operated of magnet by Fe
3o
4/ Au-HRP-Ab compound is fixed to electrode surface, forms electroactive immune magnetic Nano probe.When there is target analytes penicillin in detection system, object and the antibody generation specific immune response being fixed on electrode surface, along with the increase of target concentration, more immune complexs will hinder the oxidation of p-dihydroxy-benzene in chem workstation, the transmission effects of impeded electrode surface electronic, reduces redox current, thus realizes detecting penicillin standard items, Criterion curve, to reach the object to carrying out containing penicillin sample quantitatively detecting.
The present invention passes through at glassy carbon electrode surface modifying multiwall nanotube (MWCNTs), Fe
3o
4/ Au, HRP (horseradish peroxidase) and penicillin antibody (Pen-Ab), construct the high-sensitive biosensor being applicable to penicillin and detecting fast.This Fe
3o
4the interfacial energy that/Au/MWCNTs composite materials is modified provides larger active area and less interface resistance, and Fe
3o
4in/Au, nanogold particle has very strong catalytic, the dual catalytic effect of nanotube and golden nanometer particle strengthens catalytic efficiency, than independent glass-carbon electrode directly modify hydroxylation carbon nano-tube assembling sensor (detectability 1.05 ng/mL) or directly modify Fe at glass-carbon electrode
3o
4immunosensor (the detectability 1.00 ng/mL) detectability of/Au-HRP-Ab improves about 10 times, thus greatly strengthens the sensitivity (detectability 0.1050 ng/mL) of prepared modified electrode, stability and reappearance; Tested by current time, recording the response time of this sensor to penicillin is less than 20s, than the response time 30min of traditional high effective liquid chromatography for measuring, the minute 2h of enzyme immunization (ELISA) wants much less, substantially reduce the current-responsive time, greatly improving detection speed, again demonstrating the huge applications of this sensor when measuring micro-penicillin.
In sum, the present invention for electrochemica biological sensor detecting penicillin and its preparation method and application, for being fixed on Fe
3o
4penicillin antibody capable on/Au successfully realizes the response of its Direct Electrochemistry, reaches object that is quick to penicillin, Sensitive Detection, thus for supervising food security and ensureing that people's interests provide the support of trace residue detection technique.
Accompanying drawing explanation
Fig. 1 is based on Fe
3o
4/ Au-HRP-Ab-CNTs/GCE electrochemical sensor detects the schematic diagram of penicillin;
Fig. 2 is the Fe of preparation
3o
4transmission electron microscope picture;
Fig. 3 is the Fe of preparation
3o
4the transmission electron microscope picture of/Au compound;
Fig. 4 is the Fe of preparation
3o
4the grain size distribution of/Au compound;
Fig. 5 is preparation Fe
3o
4the phenogram of/Au-HRP-Ab compound; A: the Fe of preparation
3o
4ultraviolet-visible absorption spectroscopy; B: the Fe of preparation
3o
4the ultraviolet-visible absorption spectroscopy of/Au compound; C: the Fe of preparation
3o
4the ultraviolet-visible absorption spectroscopy of/Au-HRP-Ab compound;
Fig. 6 is the ac impedance spectroscopy of different modifying electrode;
Fig. 7 is the canonical plotting that object penicillin current signal and penicillin concn are set up.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Specific embodiment one
A kind of electrochemica biological sensor for detecting penicillin, this electrochemical sensor is three-electrode system, comprise electrode, contrast electrode and working electrode, be wherein platinum electrode to electrode, contrast electrode is saturated calomel electrode, working electrode multi-walled carbon nano-tubes (the MWCNTs)-Fe that has been immobilized
3o
4the glass-carbon electrode of/Au magnetic nano-particle-HRP-penicillin antibody (Pen-Ab).
Specific embodiment two
For detecting a preparation method for the electrochemica biological sensor of penicillin, electrochemical sensor detects the principle of penicillin as shown in Figure 1, and concrete steps are as follows:
(1) carbon nano-tube is carboxylated
By multi-walled carbon nano-tubes (MWCNTs) and by sulfuric acid and nitric acid (3:1, v/v) mixed liquor formed is in ultrasonic 7-9h after the ratio mixing of mass volume ratio 15mg:20ml, then by Kynoar micropore filtering film (aperture is 0.22 μm) vacuum filtration, get filtrate ultrapure water repeatedly to wash until filtrate is neutral, namely obtain carboxylated carbon nano-tube aqueous solutions;
(2) Fe
3o
4prepared by/Au composite nanoparticle
By Fe
3o
4magnetic nano-particle (by coprecipitation and thermal decomposition method preparation or directly can be bought in Xi'an Goldmag Nanobiotech Co., Ltd., the Fe that the present invention adopts
3o
4transmission electron microscope picture as shown in Figure 2, visible Fe
3o
4granular composite is even, and particle diameter is roughly 20nm) repeatedly wash with ultrapure water after, adopt tetramethyl azanol as spreading agent constant volume, obtain the Fe that concentration is 1 mg/mL
3o
4nano suspending liquid; Then, by Fe
3o
4after the ratio of the sodium citrate aqueous solution of nano suspending liquid and 0.01wt% 1:20 by volume mixes, be heated under agitation boil, then add 3/5Fe rapidly
3o
4the concentration of nano suspending liquid volume is the chlorauric acid solution of 1.0mg/mL, and sustained response 20-30min, until solution colour becomes claret, obtains Fe
3o
4/ Au composite nanoparticle is (by the Fe of Fig. 3
3o
4the transmission electron microscope picture of/Au compound illustrates Fe
3o
4the particle diameter of/Au is roughly about 35nm, and this is than simple Fe
3o
4large about the 15nm of particle diameter, also illustrate that Au nano particle is successfully coated on Fe
3o
4surface.Fig. 4 grain size distribution illustrates the Fe of preparation
3o
4/ Au Granular composite is even, agglomeration does not occur), abandoning supernatant after magnetic resolution, uses milli-Q water again, is mixed with the Fe of 1mg/mL
3o
4/ Au composite nanoparticle solution, in 4 DEG C of stored refrigerated; (Fig. 5 is preparation Fe
3o
4the phenogram of/Au-HRP-Ab compound; A: the Fe of preparation
3o
4ultraviolet-visible absorption spectroscopy; B: the Fe of preparation
3o
4the ultraviolet-visible absorption spectroscopy of/Au compound; C: the Fe of preparation
3o
4the ultraviolet-visible absorption spectroscopy of/Au-HRP-Ab compound, Fe simple as seen
3o
4a () does not have characteristic absorption peak, and Fe
3o
4there is obvious characteristic absorption peak at 540nm in/Au compound (b), this is the characteristic absorption peak of Au, and Fe
3o
4also having there is the characteristic absorption peak of horseradish peroxidase at 280nm in/Au-HRP-Ab compound (c), illustrates that compound successfully synthesizes)
(4) electrode pre-service
By bare electrode successively with deionized water, absolute ethyl alcohol and deionized water ultrasonic 5min respectively, repeatedly polish to minute surface with the alumina powder that particle diameter is 1 μm, 0.3 μm, 0.05 μm successively again, then be placed in ethanol, deionized water for ultrasonic cleaning 5min respectively, finally dry up with nitrogen for subsequent use;
(5) working electrode is modified and sensor preparation
The carboxylated carbon nano-tube solution 5 μ L of preparation in step (1) is dripped in glassy carbon electrode surface, dry under room temperature, obtain carbon nano tube modified glass-carbon electrode (MWCNTs/GCE); By the Fe of preparation in step (3)
3o
4/ Au-HRP-Ab solution 5 μ L drips in carbon nano tube modified glassy carbon electrode surface, dry under room temperature, obtains Fe
3o
4the glass-carbon electrode that/Au-HRP-Ab-MWCNTs modifies; Fe will be secured
3o
4/ Au-HRP-Ab-MWCNTs glass-carbon electrode is as working electrode, and adopt platinum electrode as to electrode, saturated calomel electrode forms the electrochemica biological sensor for detecting penicillin of three-electrode system as contrast electrode.
The glass-carbon electrode of process in step (4) is measured containing 2 mM p-dihydroxy-benzene and 5 mM H on CHI660B electrochemical workstation
2 o
2 solution in AC impedance signal.Experimental result, as Fig. 6, is a straight line substantially under naked GCE low frequency, shows that naked GCE has lower AC impedance, be convenient to electrochemical sensing interface electron transmission; It is obviously less that MWCNTs/GCE compares current impedance than bare electrode (naked GCE), and be more conducive to electro transfer, current-responsive value may be larger.And Fe
3o
4/ Au-HRP-Ab-MWCNTs/GCE+2 ppm penicillin antigen compares Fe
3o
4/ Au-HRP-Ab-MWCNTs/GCE impedance is comparatively large, and this may be because antigen-antibody there occurs specific immunity recognition reaction and defines immune complex at electrode surface thus prevent the transmission of electronics.
Specific embodiment three
A kind of based on multi-walled carbon nano-tubes (MWCNTs)-Fe
3o
4the electrochemica biological sensor of the glass-carbon electrode of/Au magnetic nano-particle-HRP-penicillin antibody (Pen-Ab) detects the method for penicillin concn
By carboxylated carbon nano-tube, the Fe of preparation in above-mentioned specific embodiment two
3o
4/ Au-HRP-Ab modifies naked glassy carbon electrode surface successively as working electrode, and adopt platinum electrode as to electrode, saturated calomel electrode forms the electrochemica biological sensor of three-electrode system as contrast electrode.When there is target analytes penicillin in detection system, object and the antibody generation specific immune response being fixed on electrode surface, along with the increase of target concentration, more immune complexs will hinder the oxidation of p-dihydroxy-benzene, the transmission effects of impeded electrode surface electronic, reduce redox current, thus realize detecting penicillin standard items, Criterion curve, electrochemica biological sensor is immersed in testing sample, according to the quantitative relationship of corresponding current value and penicillin concn, determine the concentration of penicillin in testing sample, thus the object (as shown in Figure 1) reached carrying out containing penicillin sample quantitatively detecting.
Specific embodiment four
Fe of the present invention
3o
4the electrochemica biological sensor of/Au-HRP-Ab-MWCNTs is to the sensitivity of penicillin and the range of linearity
By the Fe utilizing specific embodiment two method to prepare
3o
4/ Au-HRP-Ab-MWCNTs sensor is placed in penicillin standard solution and reacts, standard solution concentration is followed successively by: 0 ng/mL, 0.005 ng/mL, 0.02 ng/mL, 0.08 ng/mL, 0.2 ng/mL, 0 .6 ng/mL, 2 ng/mL, 5 ng/mL, 10 ng/mL, 50 ng/mL(standard items solvents are PBS buffer solution), operating voltage 0 ~ 1V, working buffer system is NaH
2pO
4-Na
2hPO
4(pH=7.4), differential pulse method (DPV) gained response current is recorded, Criterion curve: y=4.5716LogC+18.244, R
2=0.9985 (as shown in Figure 7), obtaining this electrochemica biological sensor to the range of linearity of penicillin is 0.005-50 ng/mL, detects and is limited to 0.1050 ng/mL; This electrode favorable reproducibility, stable performance, makes simply and easily upgrades.
From measuring, glass-carbon electrode is directly modified the sensor of hydroxylation carbon nano-tube assembling, 1.05 ng/mL is limited to the detection of penicillin, directly modifies Fe at glass-carbon electrode
3o
4the immunosensor of/Au-HRP-Ab is 1.00 ng/mL to the detectability of penicillin.But this method is by multi-walled carbon nano-tubes and Fe
3o
4the detectability of the co-modified galvanochemistry magnetic immuno sensor in glassy carbon electrode surface composition of/Au nano material is 0.1050 ng/mL, improve about 10 times than modifying single material tests limit, absolutely prove that this sensor has and modified stronger advantage than independent material, there is larger using value.
Specific embodiment five
High selectivity confirmatory experiment
Other microbiotic of same concentrations are added respectively in PBS solution, be respectively ampicillin, streptomysin, Roxithromycin, neomycin, kanamycins, gentamicin, contrast with penicillin, its impact is respectively 9%, 5.0%, 6.0%, 3.5%, 4.5% and 2.5% of penicillin current-responsive, the detection impact of other materials on penicillin that result shows above-mentioned interpolation is smaller, illustrates that sensor has high selectivity thus.
Specific embodiment six
Get commercially available milk sample some, in milk sample, add the penicillin of known quantity, then add moderate amount of sulfuric acid ammonium (6g/20 mL milk), in 4 DEG C with centrifugal 30 min of 8000 r/min.The PBS buffer solution of its supernatant of leaching preparation variable concentrations.Voltage 0 ~ 1V, working buffer system is NaH
2pO
4-Na
2hPO
4(pH=7.4), by the Fe of preparation in above-mentioned specific embodiment two
3o
4the electrochemica biological sensor that/Au-HRP-Ab-CNTs/GCE modifies is placed in the PBS buffer solution containing appropriate extract, and differential pulse method (DPV) records the electrochemical properties of sample, and result is as shown in table 1.
The testing result of table 1 Penicillin in Milk
| Milk sample | Spiked levels/ng/mL | Measure concentration/ng/mL | The recovery/% |
| 1 | 3 | 3.40 | 113.3 |
| 2 | 5 | 4.79 | 98.6 |
From table 1 testing result, Fe
3o
4the average recovery rate that the electrochemica biological sensor that/Au-HRP-Ab-MWCNTs modifies detects the method for penicillin is 98.6 ~ 113.3%, shows prepared by the present invention, Fe
3o
4/ Au-HRP-Ab-MWCNTs electrochemica biological sensor is high for the detection precision of penicillin, and result accurately and reliably.
Specific embodiment seven
The chicken of the some equivalent of precise and pork sample, load centrifuge tube, add appropriate penicillin respectively, after ultrasonic 3min, 1:5 adds the phosphate buffer solution of 0.2 mol/L pH=7.4 in test tube by volume, sonic oscillation 15min, then centrifugal 5min at 4 DEG C, get supernatant, the ratio of chicken 1:2 by volume adds saturated ammonium sulfate, pork is by volume for the ratio of 1:0.5 adds trichloroacetic acid, the centrifugal 25min of centrifuge tube is loaded after mixing, now solution presents 3 layers, get middle layer clear liquid, 1:1 adds saturated ammonium sulfate (it is 1:1 trichloroacetic acid that pork adds volume ratio) by volume, secondary centrifuging in an identical manner.Chicken and pork get respectively supernatant by volume 1:1 add normal hexane and extract 1 time, leave standstill 5min, obtain final processing sample.Voltage 0 ~ 1V, working buffer system is NaH
2pO
4-Na
2hPO
4(pH=7.4), by the Fe of preparation in above-mentioned specific embodiment two
3o
4the electrochemica biological sensor that/Au-HRP-Ab-CNTs/GCE modifies is placed in the PBS buffer solution containing appropriate extract, and differential pulse method (DPV) records the electrochemical properties of sample, and result is as shown in table 2.
The testing result of penicillin in table 2 chicken and pork
From table 2 testing result, Fe
3o
4the average recovery rate that the electrochemica biological sensor that/Au-HRP-Ab-MWCNTs modifies detects the method for penicillin is 92.8 ~ 109%, shows Fe prepared by the present invention
3o
4the electrochemica biological sensor that/Au-HRP-Ab-MWCNTs modifies is high for the detection precision of penicillin, and result accurately and reliably.
Certainly, above-mentioned explanation is not limitation of the present invention, and the present invention is also not limited to above-mentioned citing.Those skilled in the art are in essential scope of the present invention, and the change made, remodeling, interpolation or replacement, also should belong to protection scope of the present invention.
Claims (2)
1., for detecting a preparation method for the electrochemica biological sensor of penicillin, it is characterized in that concrete steps are as follows:
(1) carbon nano-tube is carboxylated
Ultrasonic 7-9h after multi-walled carbon nano-tubes is mixed in the ratio of mass volume ratio 15mg:20ml with the mixed liquor be made up of sulfuric acid and nitric acid, then be the Kynoar micropore filtering film vacuum filtration of 0.22 μm by aperture, get filtrate ultrapure water repeatedly to wash until filtrate is neutral, namely obtain carboxylated carbon nano-tube aqueous solutions;
(2) Fe
3o
4prepared by/Au composite nanoparticle
By Fe
3o
4after magnetic nano-particle ultrapure water repeatedly washs, adopt tetramethyl azanol as spreading agent constant volume, obtain the Fe that concentration is 1mg/mL
3o
4nano suspending liquid; Then, by Fe
3o
4after the ratio of the sodium citrate aqueous solution of nano suspending liquid and 0.01wt% 1:20 by volume mixes, be heated under agitation boil, then add 3/5Fe rapidly
3o
4the concentration of nano suspending liquid volume is the chlorauric acid solution of 1.0mg/mL, and sustained response 20-30min, until solution colour becomes claret, obtains Fe
3o
4/ Au composite nanoparticle, abandoning supernatant after magnetic resolution, uses milli-Q water again, is mixed with the Fe of 1mg/mL
3o
4/ Au composite nanoparticle solution, in 4 DEG C of stored refrigerated;
(3) Fe
3o
4prepared by/Au-HRP-Ab
By Fe
3o
4/ Au nano suspending liquid Na
2cO
3adjust pH to 8.0, add volume and be respectively Fe
3o
4the 1.0mg/mL horseradish peroxidase of/Au nano suspending liquid 1/5 and 10 μ g/mL penicillin antibody (Pen-Ab), stir and spend the night, after magnetic resolution, be dispersed in and Fe by potpourri at 4 DEG C
3o
4the isopyknic pH7.4 of/Au nano suspending liquid closes nonspecific activity site containing in the phosphate buffer of 1wt% bovine serum albumin, then after cleaning up with PBS phosphate buffer, to be ultrasonicly dispersed in and Fe
3o
4in the isopyknic phosphate buffer of/Au nano suspending liquid, obtain Fe
3o
4/ Au-HRP-Ab solution;
(4) electrode pre-service
By bare electrode successively with deionized water, absolute ethyl alcohol and deionized water ultrasonic 5min respectively, repeatedly polish to minute surface with the alumina powder that particle diameter is 1 μm, 0.3 μm, 0.05 μm successively again, then be placed in ethanol, deionized water for ultrasonic cleaning 5min respectively, finally dry up with nitrogen for subsequent use;
(5) working electrode is modified and sensor preparation
The carboxylated carbon nano-tube solution 5 μ L of preparation in step (1) is dripped in glassy carbon electrode surface, dry under room temperature, obtain carbon nano tube modified glass-carbon electrode (MWCNTs/GCE); By the Fe of preparation in step (3)
3o
4/ Au-HRP-Ab solution 5 μ L drips in carbon nano tube modified glassy carbon electrode surface, dry under room temperature, obtains Fe
3o
4the glass-carbon electrode that/Au-HRP-Ab-MWCNTs modifies; Fe will be secured
3o
4/ Au-HRP-Ab-MWCNTs glass-carbon electrode is as working electrode, and adopt platinum electrode as to electrode, saturated calomel electrode forms the electrochemica biological sensor for detecting penicillin of three-electrode system as contrast electrode.
2. the preparation method of the electrochemica biological sensor for detecting penicillin according to claim 1, is characterized in that: in step (1), the volume ratio of sulfuric acid and nitric acid is 3:1.
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| CN104483363B (en) * | 2015-01-05 | 2016-09-28 | 天津商业大学 | A kind of preparation method of the electrochemica biological sensor for measuring antibiotic |
| CN104931693B (en) * | 2015-06-11 | 2017-05-17 | 上海海洋大学 | Electrochemical immunosensor and preparation method thereof |
| CN105158453B (en) * | 2015-07-09 | 2017-01-25 | 济南大学 | Preparation method of label-free electrochemical immunosensor for nonyl phenol detection |
| CN108375623A (en) * | 2018-01-12 | 2018-08-07 | 宁波大学 | The preparation method and applications of the electrochemical immunosensor of food-borne pathogens are detected based on quick scan anode Stripping Voltammetry technology |
| CN110646483B (en) * | 2018-06-27 | 2020-11-24 | 华中科技大学 | Nano immunosensor for detecting penicillin G residue of dairy products and preparation method thereof |
| CN109722481B (en) * | 2018-12-18 | 2022-04-15 | 山东师范大学 | Method for detecting microRNA in lung cancer cells based on substrate-free and non-labeled electrocatalytic amplification biosensor |
| CN111781342B (en) * | 2019-04-04 | 2023-07-07 | 中国医学科学院药用植物研究所 | Sensitization type SPR immunosensor constructed by gold-magnetic composite nano-meter detects carbendazim |
| CN110865116A (en) * | 2019-11-25 | 2020-03-06 | 江西科技师范大学 | Electrochemical nano enzyme sensor for detecting 5-nitroguaiacol sodium |
| CN110887883B (en) * | 2019-12-05 | 2021-06-01 | 吉林大学 | Electrochemical method for rapidly detecting penicillin sodium based on magnetic material |
| CN111007123B (en) * | 2019-12-20 | 2022-09-20 | 云南大学 | Fe 3 O 4 @PDA@MnO 2 Preparation of core-shell nano particles, enrichment of heavy metal ions and electrochemical detection |
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