CN107300582A - Antibiotic detection means and its manufacture method, detection method based on microsensor - Google Patents
Antibiotic detection means and its manufacture method, detection method based on microsensor Download PDFInfo
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- 230000003115 biocidal effect Effects 0.000 title claims abstract description 67
- 238000001514 detection method Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000011258 core-shell material Substances 0.000 claims abstract description 23
- 239000004005 microsphere Substances 0.000 claims abstract description 17
- 239000012528 membrane Substances 0.000 claims abstract description 9
- 239000007791 liquid phase Substances 0.000 claims abstract description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 94
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 64
- 229910052681 coesite Inorganic materials 0.000 claims description 60
- 229910052906 cristobalite Inorganic materials 0.000 claims description 60
- 229910052682 stishovite Inorganic materials 0.000 claims description 60
- 229910052905 tridymite Inorganic materials 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000003242 anti bacterial agent Substances 0.000 claims description 12
- 229940088710 antibiotic agent Drugs 0.000 claims description 12
- 229920001661 Chitosan Polymers 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
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- 238000005352 clarification Methods 0.000 claims description 6
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- 238000005406 washing Methods 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical class CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000557 Nafion® Polymers 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
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- 239000002105 nanoparticle Substances 0.000 claims description 3
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- 239000011550 stock solution Substances 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 2
- 239000006194 liquid suspension Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 19
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- QJGQUHMNIGDVPM-OUBTZVSYSA-N nitrogen-15 Chemical compound [15N] QJGQUHMNIGDVPM-OUBTZVSYSA-N 0.000 claims 1
- 238000012946 outsourcing Methods 0.000 claims 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims 1
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- 229960000479 ceftriaxone sodium Drugs 0.000 description 6
- FDRNWTJTHBSPMW-GNXCPKRQSA-L disodium;(6r,7r)-7-[[(2e)-2-(2-amino-1,3-thiazol-4-yl)-2-methoxyiminoacetyl]amino]-3-[(2-methyl-6-oxido-5-oxo-1,2,4-triazin-3-yl)sulfanylmethyl]-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate Chemical compound [Na+].[Na+].S([C@@H]1[C@@H](C(N1C=1C([O-])=O)=O)NC(=O)/C(=N/OC)C=2N=C(N)SC=2)CC=1CSC1=NC(=O)C([O-])=NN1C FDRNWTJTHBSPMW-GNXCPKRQSA-L 0.000 description 6
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- -1 Potassium ferricyanide Chemical compound 0.000 description 3
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-OUBTZVSYSA-N Ammonia-15N Chemical compound [15NH3] QGZKDVFQNNGYKY-OUBTZVSYSA-N 0.000 description 2
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- 229960004755 ceftriaxone Drugs 0.000 description 1
- VAAUVRVFOQPIGI-SPQHTLEESA-N ceftriaxone Chemical compound S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)\C(=N/OC)C=2N=C(N)SC=2)CC=1CSC1=NC(=O)C(=O)NN1C VAAUVRVFOQPIGI-SPQHTLEESA-N 0.000 description 1
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
Abstract
The invention discloses a kind of antibiotic detection means and its manufacture method, detection method based on microsensor, the antibiotic detection means based on microsensor includes microsensor and the picoammeter of output with voltage；The voltage output end of picoammeter connects the electrode interface of microsensor；PFSA polymeric membranes are coated with the working electrode of microsensor；Magnetic Nano core-shell microspheres are embedded with PFSA polymeric membranes.The present invention utilizes the good absorption property of magnetic Nano core-shell microspheres, and response quickly, amount of samples that microsensor itself has are few, strong antijamming capability the advantages of, it is possible to achieve effectively, it is easy, quickly and accurately the antibiotic concentration in liquid phase is detected.
Description
Technical field
The present invention relates to antibiotic detection technique field, more particularly to a kind of antibiotic detection means based on microsensor
And its manufacture method, antibiotic detection method.
Background technology
With developing rapidly and scientific and technological progress for global industry, the living standard of people has large increase,
Problem of environmental pollution is also increasingly paid close attention to by people, one of three big world sex chromosome mosaicisms faced as today's society.At present,
The residual of the mankind or veterinary antibiotic is all detected in a variety of matrix of the earth.The accumulation of antibiotic can to the ecological balance and
Human life causes harm, and causes the microorganism in water body to produce drug resistance, even the antibiotic of minor levels is long-term sudden and violent
Under dew, ecological environment and health can also be caused harm.Chinese infectious diseases accounts for whole diseases and always falls ill the 49% of number,
Wherein bacterial infection accounts for the 18% to 21% of whole diseases, i.e., more than 80% and belongs to abuse of antibiotics, has 80,000 people every year therefore
It is dead.Therefore antibiotic pollution problem oneself through being classified as important environmental problem, related wastewater recycle and processing by multiple countries
Technical research deploys rapidly.
In recent years, there is quick development for the antibiotic detection technique in water environment, have height what is commonly used on the market
Effect liquid phase chromatogram method (HPLC), SERS technology (SERS), immunoassay, electrochemica biological sensor method
Deng, in the presence of it is certain the problem of.For example, HPLC technologies have complex pretreatment, to be easily caused the rate of recovery relatively low, impracticable, time-consuming
Grow, flow velocity is low, cost is high, need the problems such as special messenger's measurement, equipment costliness；There is substrate uniformity and repeatability in SERS technologies
Bad the problems such as；Immunoassay has sample pre-treatments and cleaning, and time-consuming, quick detection is impracticable, expensive, non real-time inspection
The defects such as survey；Moreover, three of the above detection technique is highly professional, threshold is higher, it is desirable to have professional and technical personnel safeguards, difficult
To adapt to the growth requirement of antibiotic detection.
Although the electrochemica biological sensor method grown up in recent years has, simple to operate, sensitivity is high, high specificity
The advantages of, but it is poor for the life active compound physical and chemical stability for building sensor, easily by external worlds such as temperature, pH
The interference of factor, easily inactivates in actual production life application, limits the practical application of sensor.
Therefore, it is badly in need of a kind of quick simple to operate, detection, degree of accuracy height and the stable antibiotic detection device of performance at present
Or method.
The content of the invention
Based on this, the present invention proposes a kind of antibiotic detection means based on microsensor and its manufacture method, antibiosis
Plain detection method, using the good absorption property of magnetic Nano core-shell microspheres, response quickly that microsensor itself has, sample
Product consumption is few, strong antijamming capability the advantages of, it is possible to achieve effectively, it is easy, quickly and accurately to the antibiotic concentration in liquid phase
Detected.
The antibiotic detection means based on microsensor that the present invention is provided, including microsensor and the skin of output with voltage
Peace meter；
The voltage output end of the picoammeter connects the electrode interface of the microsensor；
PFSA polymeric membranes are coated with the working electrode of the microsensor；
Magnetic Nano core-shell microspheres are embedded with the PFSA polymeric membranes.
As a kind of embodiment, the core of the magnetic Nano core-shell microspheres is superparamagnetism Fe3O4, superparamagnetic
Property Fe3O4Outer wrap one layer of SiO2,SiO2The outer wrapping of layer one layer of chitosan；The surface of chitosan is by molecular engram
Polymer is constituted, for specifically binding the antibiotic in liquid phase.
As a kind of embodiment, the tip of the working electrode of the microsensor is provided with for preventing to be detected molten
Liquid flows into the glassivation of electrode interior.
The manufacture method for the antibiotic detection means based on microsensor that the present invention is provided, comprises the following steps：
Superparamagnetism Fe is prepared using polyol process3O4；
Superparamagnetism Fe based on preparation3O4, Fe is prepared using sol-gel process3O4@SiO2；
Fe based on preparation3O4@SiO2, Fe is prepared using inverted emulsion cross-linking method3O4@SiO2@CS；
Using molecular imprinting technology, to Fe3O4@SiO2@CS are modified, and obtain corresponding antibiotics molecular engram magnetic
Core-shell microspheres Fe3O4@SiO2@CS-MIP；
Fe based on preparation3O4@SiO2@CS-MIP, using drop-coating, by Fe3O4@SiO2@CS-MIP solution is coated in micro-
The surface of the working electrode of sensor；
Obtained antibiotics molecular engram microsensor is accessed to the voltage output end of picoammeter, antibiotic detection dress is obtained
Put.
As a kind of embodiment, the utilization polyol process prepares superparamagnetism Fe3O4, comprise the following steps：
By Fe (acac)3Mixed with triethylene glycol, obtain Fe (acac)3With the mixture of triethylene glycol；
By Fe (acac)3180 DEG C are heated to the mixture of triethylene glycol, and is kept for 30 minutes at such a temperature；Then it is fast
Speed is heated to reflux, and maintains the reflux for 30 minutes；
To Fe after heating (acac)3Carry out being cooled to room temperature with the mixture of triethylene glycol, obtain containing Fe3O4Black it is equal
Spin coating liquid suspension；
Ethanol and ethyl acetate are added into obtained suspension, nano particle is flocculated, and using magnetic field from solution
Isolated black flocculate；
Black flocculate is dispersed again in ethanol, precipitated again with ethyl acetate, magnetic separation three times is removed completely
Excessive triethylene glycol and accessory substance, by the way that precipitation is dried under vacuum, obtains solid product, as superparamagnetism Fe3O4。
As a kind of embodiment, the superparamagnetism Fe based on preparation3O4, prepared using sol-gel process
Fe3O4@SiO2, comprise the following steps：
By superparamagnetism Fe3O4It is dispersed in deionized water, magnetic fluid is obtained using ultrasonic disperse；
By magnetic fluid add absolute ethyl alcohol in, then add ammoniacal liquor, by mixed system under 30 degree of water bath condition it is even
Fast mechanical agitation；
After mixed system is stirred 30 minutes, tetraethyl orthosilicate is added dropwise into the system, stirring uses sample introduction after 45 minutes
3- aminopropyl trimethoxysilanes are added dropwise in pin dropwise, persistently stir 4 hours；
After reaction terminates, product is reclaimed using externally-applied magnetic field, is carried out washing straight successively with deionized water and absolute ethyl alcohol
To eluate clarification, it is finally putting into 60 degree of baking ovens and dries, obtain Fe3O4@SiO2。
It is used as a kind of embodiment, the Fe based on preparation3O4@SiO2, prepared using inverted emulsion cross-linking method
Fe3O4@SiO2@CS, comprise the following steps：
By Fe3O4@SiO2Then system is transferred in 50 degree of water bath with thermostatic control system by ultrasonic disperse into deionized water
Mechanical agitation is carried out, and 5%GLA solution is added dropwise, persistently stirs 1 hour, system is fully reacted；
After stirring terminates, the acetic acid solution of chitosan is added into system, stirs 30 minutes, is reacted；
After reaction terminates, 5%GLA solution is added dropwise into reaction system again, system natural cooling after reacting 1 hour
To room temperature；Then product is separated using externally-applied magnetic field, and washed with absolute ethyl alcohol to eluate clarification, be dried to obtain Fe3O4@
SiO2@CS。
As a kind of embodiment, using molecular imprinting technology, to Fe3O4@SiO2@CS are modified, and obtain corresponding
Antibiotics molecular engram magnetic core-shell microballoon Fe3O4@SiO2@CS-MIP, comprise the following steps：
Configuration contains a certain amount of target antibiotic, methanol, the solution of methacrylic acid, vibrates 5 minutes, secretly puts 12 hours,
Target antibiotic is set fully to be acted on function monomer；
By appropriate Fe3O4@SiO2@CS are dissolved in solution, add appropriate crosslinking agent ethylene glycol dimethacrylate and initiation
Agent azodiisobutyronitrile, ultrasonic disperse 5 minutes leads to nitrogen 15 minutes；Then 60 degree are heated in the case where nitrogen is protected, instead
Answer after 24 hours, obtain antibiotics molecular engram magnetic core-shell microballoon Fe3O4@SiO2@CS-MIP；
It is stripped using apparatus,Soxhlet's, repeated multiple times, until can't detect antibiotic molecule in solution, drying is standby
With.
It is used as a kind of embodiment, the Fe based on preparation3O4@SiO2@CS-MIP, using drop-coating, by Fe3O4@
SiO2@CS-MIP solution is coated in the surface of the working electrode of microsensor, comprises the following steps：
By Fe3O4@SiO2@CS-MIP are distributed in Nafion PFSA Polymer (perfluorinated sulfonic acid polymer), are fully stirred
Mixing makes it be uniformly dispersed, and obtains stock solution；
By stock solution drop coating in the working electrode surface of microsensor, stand to drying under normal temperature, use ultrapure water
Working electrode surface, nitrogen drying is stand-by.
The antibiotic detection method that the present invention is provided, antibiotic detection is carried out using above-mentioned antibiotic detection means, including
Following steps：
By reference electrode, the working electrode of microsensor and electrode is connected on electrochemical workstation, in a cell
Potassium ferricyanide solution is added, current-responsive is detected by cyclic voltammetry；
According to the relation between the concentration of standard solution of gained current-responsive and solution to be detected, drawing curve；
The concentration of solution to be detected is obtained, and according to the working curve drawn, calculates antibiotic in solution to be detected
Concentration.
The present invention is compared to the beneficial effect of prior art：
The antibiotic detection means and its manufacture method, antibiotic detection method based on microsensor that the present invention is provided,
Utilize the good absorption property of magnetic Nano core-shell microspheres, and response quickly, the amount of samples that microsensor itself has
Less, the advantages of strong antijamming capability, it is possible to achieve effectively, it is easy, quickly and accurately the antibiotic concentration in liquid phase is examined
Survey.
Brief description of the drawings
Fig. 1 is the structural representation for the antibiotic detection means based on microsensor that the embodiment of the present invention one is provided；
Fig. 2 is enlarged drawing at the A in Fig. 1, and it illustrates the structure of working electrode；
Fig. 3 is the magnetic Nano nucleocapsid in the antibiotic detection means based on microsensor that the embodiment of the present invention one is provided
The structural representation of type microballoon.
Embodiment
Below in conjunction with accompanying drawing, the technical characteristic above-mentioned and other to the present invention and advantage are clearly and completely described,
Obviously, described embodiment is only the section Example of the present invention, rather than whole embodiments.
Referring to Fig. 1, the embodiment of the present invention one provides a kind of antibiotic detection means based on microsensor, including micro- biography
Sensor 100 and the picoammeter of output with voltage 200.The present invention detects the telecommunications produced in course of reaction using microsensor 100
Number, shown by picoammeter 200, so as to obtain specific current value.Obtained current value and working curve are compared
It is right, you can to detect the actual concentrations of antibiotic.The voltage output end of picoammeter 200 connects the electrode interface of microsensor 100,
It is provided with PFSA polymeric membranes, PFSA polymeric membranes that to be embedded with magnetic Nano hud typed micro- on the working electrode of microsensor 100
Ball.The core of magnetic Nano core-shell microspheres is superparamagnetism Fe3O4, superparamagnetism Fe3O4Outer wrap one layer of SiO2,
SiO2The outer wrapping of layer one layer of chitosan；The surface of chitosan is made up of molecularly imprinted polymer, for specifically binding liquid
Antibiotic in phase.
As shown in Fig. 2 being wrapped up outside the sophisticated A of microsensor by glass, glassivation can in use
Effectively to prevent solution from flowing into electrode interior, its internal electrode silk 110 is protected.The wire electrode 110 of working electrode uses carbon fiber
Material, PFSA polymeric membranes are scribbled on the surface of carbon fiber wire, and substantial amounts of magnetic Nano core-shell microspheres 111 are embedded with film,
Adhesiveness and stability of the magnetic Nano core-shell microspheres on microsensor had so both been improved, has also enabled microsensor more
Uniform conduction electronics.
As shown in figure 3, the core of magnetic Nano core-shell microspheres 111 is by superparamagnetism Fe3O4Composition, has its microballoon
Good magnetic property and absorption property；Centre is wrapped in one layer of SiO2, to protect Fe3O4；Outer layer covers one layer of chitosan,
Absorption property to improve core-shell microspheres, and it is used as the carrier of molecularly imprinted polymer；On the surface of chitosan by dividing
Sub- imprinted polymer composition, for specifically binding the antibiotic in liquid phase.
The present invention is using the good absorption property of magnetic Nano core-shell microspheres, and obtains the sound that microsensor has in itself
Should quick, few sample size, strong antijamming capability the advantages of, it is possible to achieve effectively, it is easy, quickly and accurately to anti-in liquid phase
Raw element concentration is detected.
The embodiment of the present invention two provide a kind of manufacture method of the antibiotic detection means based on microsensor, including with
Lower step：
S100, polyol process is utilized to prepare superparamagnetism Fe3O4；
By a certain amount of Fe (acac)3Three-neck flask is added with triethylene glycol (TREG), logical nitrogen is protected and is stirred；Will
Mixture is slowly heated to 180 DEG C, and is kept for 30 minutes at such a temperature；Then quickly it is heated to reflux, and maintains the reflux for 30 points
Clock；It is cooled to after room temperature, obtains containing Fe3O4Black even soliquid；Ethanol and acetic acid second are added in reaction solution
Ester makes nano particle be flocculated, and flocculate is separated from solution using magnetic field.Then by black precipitate redisperse in ethanol,
Precipitated again with ethyl acetate, magnetic separation three times, excessive TREG and accessory substance is removed completely, it is heavy by being dried under vacuum
Form sediment and obtain solid product, as superparamagnetism Fe3O4。
S200, the superparamagnetism Fe based on preparation3O4, Fe is prepared using sol-gel process3O4@SiO2；
By Fe3O4It is dispersed in deionized water, carries out disperseing 15 minutes using ultrasound, obtain certain density magnetic fluid；Amount
Take the magnetic fluid 20mL of Fresh to be added to equipped with 150mL absolute ethyl alcohol three-neck flasks, be subsequently added appropriate ammoniacal liquor, finally will
Mixed system at the uniform velocity mechanical agitation under 30 degree of water bath condition；After mixed system is stirred 30 minutes, add dropwise into the system
Enter a certain amount of tetraethyl orthosilicate, appropriate 3- aminopropyl trimethoxysilanes are added dropwise with sample introduction needle after 45 minutes dropwise for stirring；
After the completion of sample introduction, persistently stir 4 hours；After reaction terminates, product is reclaimed using externally-applied magnetic field, with deionized water and anhydrous second
Alcohol carries out washing successively until eluate clarification, is finally putting into 60 degree of baking ovens and dries, obtain Fe3O4@SiO2。
S300, the Fe based on preparation3O4@SiO2, Fe is prepared using inverted emulsion cross-linking method3O4@SiO2@CS；
Weigh Fe3O4@SiO2System is transferred to 50 degree of water bath with thermostatic control system by ultrasonic disperse into deionized water, then
In；Under mechanical agitation, 5%GLA solution is added dropwise, persistently stirs 1 hour, fully reaction；Chitosan is added into system
Acetic acid solution, stirs 30min；After reaction terminates, 5%GLA solution is added dropwise into reaction system again；After reaction 1 hour,
System is naturally cooled into room temperature；Then product is separated using externally-applied magnetic field, and washed with absolute ethyl alcohol to eluate clarification,
It is dried to obtain Fe3O4@SiO2@CS。
S400, using molecular imprinting technology, to Fe3O4@SiO2@CS are modified, and obtain corresponding antibiotics molecular engram
Magnetic core-shell microballoon Fe3O4@SiO2@CS-MIP。
Exemplified by detecting Ceftriaxone Sodium：Configuration contains a certain amount of Ceftriaxone Sodium, methanol, the solution of methacrylic acid,
Vibration 5 minutes, secretly puts about 12 hours, Ceftriaxone Sodium is fully acted on function monomer；By appropriate Fe3O4@SiO2@CS are dissolved in
In solution, the appropriate crosslinking agent ethylene glycol dimethacrylate of addition and initiator azodiisobutyronitrile, ultrasonic disperse 5 minutes,
Logical nitrogen 15 minutes；60 degree are heated in the case where nitrogen is protected, after reacting 24 hours, antibiotics molecular engram magnetic is obtained
Core-shell microspheres Fe3O4@SiO2@CS-MIP.It is stripped using apparatus,Soxhlet's, it is repeated multiple times, until can't detect in solution
Antibiotic molecule, drying for standby.Preparing for the molecular engram microsensor of other antibiotic is substantially the same, is simply preparing
During add different template molecules.
S500, the Fe based on preparation3O4@SiO2@CS-MIP, using drop-coating, by Fe3O4@SiO2@CS-MIP solution is coated
On the surface of the working electrode of microsensor；
Take a small amount of Fe3O4@SiO2@CS-MIP are distributed in Nafion PFSA Polymer, are sufficiently stirred for making it scattered equal
It is even；Solution drop coating is stood to drying under carbon fiber microelectrodes with micro pipette tips surface, normal temperature, ultrapure water electrode surface is used, nitrogen blows
It is dry stand-by.
S600, the voltage output end by obtained antibiotics molecular engram microsensor access picoammeter, obtain antibiotic
Detection means.
The embodiment of the present invention three provides a kind of antibiotic detection method, is passed using what above-described embodiment one was provided based on micro-
The antibiotic detection means of sensor carries out antibiotic detection, comprises the following steps：
The first step, is connected to reference electrode, the working electrode of microsensor electrochemical workstation on and to electrode, in electricity
The potassium ferricyanide solution that 8mmol/L is added in groove is solved, current-responsive is detected by cyclic voltammetry；
Second step, according to the relation between the concentration of standard solution of gained current-responsive and solution to be detected, drawing
Curve；
3rd step, obtains the concentration of solution to be detected, and according to the working curve drawn, calculates in solution to be detected
The concentration of antibiotic.
Working curve refers to a kind of linear relationship that the electric current of microsensor changes with antibiotic concentration, is by many numbers
Value point is simultaneously obtained by Mathematical Fitting.The simply current value that microsensor detection sample is obtained, detects obtained electric current
Value compares the concentration that can obtain antibiotic with working curve.
By reference electrode, working electrode and electrode is connected on electrochemical workstation, 8mmol/L is added in a cell
Potassium ferricyanide solution, current-responsive is detected by cyclic voltammetry；After Ceftriaxone Sodium template molecule is washed away, electric current rings
It should significantly increase, because after template molecule is removed, electrode surface has the solid of much energy specific recognition Ceftriaxone Sodiums
Hole, [Fe (CN)6]3-/4-Electrode surface, which is reached, by these holes occurs redox reaction.According to gained current-responsive with
Relation between the concentration of standard solution of Ceftriaxone Sodium, drawing curve, for sample detection；Wardrobe are entered to testing sample
The measure of spore Qusong na concn, its testing result compares drawn Ceftriaxone Sodium working curve, calculates cephalo in sample
The concentration of Qusong sodium.
The present invention uses molecularly imprinted polymer structure-controllable, can prepare different molecules for different target molecules
Imprinted polymer, there is good specificity to different templates molecule.Magnetic Nano core-shell microspheres environmental resistance is good, can be with
Stable property is kept in various adverse circumstances such as high temperature, organic solvent and acid-base environment；It is easy to preserve, there is very long make
With the life-span, the problems such as traditional biological microsensor easy in inactivation, stability are poor is efficiently solved.Further, micro sensing is utilized
Device detects antibiotic, has the advantages that few amount of samples, response quickly, strong antijamming capability compared to traditional electrode.
Particular embodiments described above, has been carried out further to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail, it will be appreciated that the foregoing is only the specific embodiment of the present invention, the protection being not intended to limit the present invention
Scope.Particularly point out, to those skilled in the art, within the spirit and principles of the invention, that is done any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (10)
1. a kind of antibiotic detection means based on microsensor, it is characterised in that including microsensor and output with voltage
Picoammeter；
The voltage output end of the picoammeter connects the electrode interface of the microsensor；
PFSA polymeric membranes are coated with the working electrode of the microsensor；
Magnetic Nano core-shell microspheres are embedded with the PFSA polymeric membranes.
2. the antibiotic detection means according to claim 1 based on microsensor, it is characterised in that the magnetic Nano
The core of core-shell microspheres is superparamagnetism Fe3O4, superparamagnetism Fe3O4Outer wrap one layer of SiO2,SiO2The outsourcing of layer
Wrap up in one layer of chitosan；The surface of chitosan is made up of molecularly imprinted polymer, for specifically binding the antibiotic in liquid phase.
3. the antibiotic detection means according to claim 1 or 2 based on microsensor, it is characterised in that micro- biography
The tip of the working electrode of sensor is provided with for preventing solution to be detected from flowing into the glassivation of electrode interior.
4. a kind of manufacture method of such as antibiotic detection means based on microsensor of any one of claims 1 to 3,
It is characterised in that it includes following steps：
Superparamagnetism Fe is prepared using polyol process3O4；
Superparamagnetism Fe based on preparation3O4, Fe is prepared using sol-gel process3O4@SiO2；
Fe based on preparation3O4@SiO2, Fe is prepared using inverted emulsion cross-linking method3O4@SiO2@CS；
Using molecular imprinting technology, to Fe3O4@SiO2@CS are modified, and obtain corresponding antibiotics molecular engram magnetic core-shell
Type microballoon Fe3O4@SiO2@CS-MIP；
Fe based on preparation3O4@SiO2@CS-MIP, using drop-coating, by Fe3O4@SiO2@CS-MIP solution is coated in micro sensing
The surface of the working electrode of device；
Obtained antibiotics molecular engram microsensor is accessed to the voltage output end of picoammeter, antibiotic detection means is obtained.
5. the manufacture method of the antibiotic detection means according to claim 4 based on microsensor, it is characterised in that institute
State and prepare superparamagnetism Fe using polyol process3O4, comprise the following steps：
By Fe (acac)3Mixed with triethylene glycol, obtain Fe (acac)3With the mixture of triethylene glycol；
By Fe (acac)3180 DEG C are heated to the mixture of triethylene glycol, and is kept for 30 minutes at such a temperature；Then quick heating
Backflow, and maintain the reflux for 30 minutes；
To Fe after heating (acac)3Carry out being cooled to room temperature with the mixture of triethylene glycol, obtain containing Fe3O4Black even glue
Liquid suspension；
Ethanol and ethyl acetate are added into obtained suspension, nano particle is flocculated, and is separated using magnetic field from solution
Obtain black flocculate；
Black flocculate is dispersed again in ethanol, precipitated again with ethyl acetate, magnetic separation three times is removed excessive completely
Triethylene glycol and accessory substance, by being dried under vacuum precipitation, obtain solid product, as superparamagnetism Fe3O4。
6. the manufacture method of the antibiotic detection means according to claim 4 based on microsensor, it is characterised in that institute
State the superparamagnetism Fe based on preparation3O4, Fe is prepared using sol-gel process3O4@SiO2, comprise the following steps：
By superparamagnetism Fe3O4It is dispersed in deionized water, magnetic fluid is obtained using ultrasonic disperse；
Magnetic fluid is added in absolute ethyl alcohol, ammoniacal liquor is then added, by mixed system under 30 degree of water bath condition at the uniform velocity machine
Tool is stirred；
After mixed system is stirred 30 minutes, be added dropwise tetraethyl orthosilicate into the system, after stirring 45 minutes with sample introduction needle by
3- aminopropyl trimethoxysilanes are added dropwise in drop, persistently stir 4 hours；
After reaction terminates, product is reclaimed using externally-applied magnetic field, carries out washing successively with deionized water and absolute ethyl alcohol until washing
Go out liquid clarification, be finally putting into 60 degree of baking ovens and dry, obtain Fe3O4@SiO2。
7. the manufacture method of the antibiotic detection means according to claim 4 based on microsensor, it is characterised in that institute
State the Fe based on preparation3O4@SiO2, Fe is prepared using inverted emulsion cross-linking method3O4@SiO2@CS, comprise the following steps：
By Fe3O4@SiO2System is transferred in 50 degree of water bath with thermostatic control system and carried out by ultrasonic disperse into deionized water, then
Mechanical agitation, and 5%GLA solution is added dropwise, persistently stir 1 hour, system is fully reacted；
After stirring terminates, the acetic acid solution of chitosan is added into system, stirs 30 minutes, is reacted；
After reaction terminates, 5%GLA solution is added dropwise into reaction system again, system naturally cools to room after reacting 1 hour
Temperature；Then product is separated using externally-applied magnetic field, and washed with absolute ethyl alcohol to eluate clarification, be dried to obtain Fe3O4@SiO2@
CS。
8. the manufacture method of the antibiotic detection means according to claim 4 based on microsensor, it is characterised in that profit
With molecular imprinting technology, to Fe3O4@SiO2@CS are modified, and obtain corresponding antibiotics molecular engram magnetic core-shell microballoon
Fe3O4@SiO2@CS-MIP, comprise the following steps：
Configuration contains a certain amount of target antibiotic, methanol, the solution of methacrylic acid, vibrates 5 minutes, secretly puts 12 hours, make mesh
Mark antibiotic is fully acted on function monomer；
By appropriate Fe3O4@SiO2@CS are dissolved in solution, add appropriate crosslinking agent ethylene glycol dimethacrylate and initiator is even
Nitrogen bis-isobutyronitrile, ultrasonic disperse 5 minutes leads to nitrogen 15 minutes；Then 60 degree, reaction 24 are heated in the case where nitrogen is protected
After hour, antibiotics molecular engram magnetic core-shell microballoon Fe is obtained3O4@SiO2@CS-MIP；
It is stripped using apparatus,Soxhlet's, it is repeated multiple times, until can't detect antibiotic molecule, drying for standby in solution.
9. the manufacture method of the antibiotic detection means according to claim 4 based on microsensor, it is characterised in that institute
State the Fe based on preparation3O4@SiO2@CS-MIP, using drop-coating, by Fe3O4@SiO2@CS-MIP solution is coated in microsensor
Working electrode surface, comprise the following steps：
By Fe3O4@SiO2@CS-MIP are distributed in Nafion PFSA Polymer, are sufficiently stirred for making it be uniformly dispersed, and obtain standby
Use solution；
By stock solution drop coating in the working electrode surface of microsensor, stand to drying under normal temperature, worked with ultrapure water
Electrode surface, nitrogen drying is stand-by.
10. a kind of antibiotic detection method, it is characterised in that using described in any one of claims 1 to 33 based on microsensor
Antibiotic detection means carry out antibiotic detection, comprise the following steps：
By reference electrode, the working electrode of microsensor and electrode is connected on electrochemical workstation, iron is added in a cell
Potassium cyanide solution, current-responsive is detected by cyclic voltammetry；
According to the relation between the concentration of standard solution of gained current-responsive and solution to be detected, drawing curve；
The concentration of solution to be detected is obtained, and according to the working curve drawn, calculates the concentration of antibiotic in detection solution.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110346428A (en) * | 2019-06-24 | 2019-10-18 | 杭州电子科技大学 | The microsensor detection system and its detection method of real-time in-situ detection antibiotic |
| CN110398531A (en) * | 2019-07-02 | 2019-11-01 | 杭州电子科技大学 | Applied to trace detection heavy metal ion device and its detection method |
| CN110887883A (en) * | 2019-12-05 | 2020-03-17 | 吉林大学 | Electrochemical method for rapidly detecting penicillin sodium based on magnetic material |
| CN113418872A (en) * | 2021-06-17 | 2021-09-21 | 东莞市人民医院 | Drug resistance monitoring device for drug resistance bacterium culture and implementation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103243367A (en) * | 2013-05-17 | 2013-08-14 | 天津前方科技有限公司 | Producing method of streptomycin antibiotic molecular imprinting biosensor |
| CN103308675A (en) * | 2013-05-08 | 2013-09-18 | 北京工业大学 | Preparation and detection methods of screen-printed electrode immunosensor for rapidly detecting microcystin |
| CN103990443A (en) * | 2014-03-27 | 2014-08-20 | 华南师范大学 | Single-stranded DNA nucleic acid modified chitosan magnetic microsphere preparation method |
| CN104151764A (en) * | 2014-08-11 | 2014-11-19 | 四川大学 | Polymer-brush-modified magnetic composite microsphere as well as preparation method and application thereof |
| CN104587951A (en) * | 2015-01-21 | 2015-05-06 | 广西大学 | Preparation method for Fe-SiO2-Al molecular imprinting adsorbent |
| CN104592446A (en) * | 2015-01-15 | 2015-05-06 | 宁波大学 | Preparation method and application of nano fiber molecularly-imprinted polymer of tetracycline antibiotics |
| CN105713156A (en) * | 2015-06-11 | 2016-06-29 | 衡阳师范学院 | Preparation method and application of carbostyril nanometer molecularly imprinted polymer |
| CN106432577A (en) * | 2016-09-29 | 2017-02-22 | 湖北出入境检验检疫局检验检疫技术中心 | High selectivity tetracycline antibiotics molecularly imprinted polymer preparation method and application |
| CN106645363A (en) * | 2016-11-22 | 2017-05-10 | 信阳师范学院 | Molecularly imprinted electrochemical sensor for CYR trace rapid detection and preparation method and application thereof |
| CN106750316A (en) * | 2017-01-16 | 2017-05-31 | 南华大学 | A kind of preparation method of magnetic core-shell nanoparticle surface uranyl molecularly imprinted polymer |
-
2017
- 2017-08-16 CN CN201710702221.7A patent/CN107300582A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103308675A (en) * | 2013-05-08 | 2013-09-18 | 北京工业大学 | Preparation and detection methods of screen-printed electrode immunosensor for rapidly detecting microcystin |
| CN103243367A (en) * | 2013-05-17 | 2013-08-14 | 天津前方科技有限公司 | Producing method of streptomycin antibiotic molecular imprinting biosensor |
| CN103990443A (en) * | 2014-03-27 | 2014-08-20 | 华南师范大学 | Single-stranded DNA nucleic acid modified chitosan magnetic microsphere preparation method |
| CN104151764A (en) * | 2014-08-11 | 2014-11-19 | 四川大学 | Polymer-brush-modified magnetic composite microsphere as well as preparation method and application thereof |
| CN104592446A (en) * | 2015-01-15 | 2015-05-06 | 宁波大学 | Preparation method and application of nano fiber molecularly-imprinted polymer of tetracycline antibiotics |
| CN104587951A (en) * | 2015-01-21 | 2015-05-06 | 广西大学 | Preparation method for Fe-SiO2-Al molecular imprinting adsorbent |
| CN105713156A (en) * | 2015-06-11 | 2016-06-29 | 衡阳师范学院 | Preparation method and application of carbostyril nanometer molecularly imprinted polymer |
| CN106432577A (en) * | 2016-09-29 | 2017-02-22 | 湖北出入境检验检疫局检验检疫技术中心 | High selectivity tetracycline antibiotics molecularly imprinted polymer preparation method and application |
| CN106645363A (en) * | 2016-11-22 | 2017-05-10 | 信阳师范学院 | Molecularly imprinted electrochemical sensor for CYR trace rapid detection and preparation method and application thereof |
| CN106750316A (en) * | 2017-01-16 | 2017-05-31 | 南华大学 | A kind of preparation method of magnetic core-shell nanoparticle surface uranyl molecularly imprinted polymer |
Non-Patent Citations (4)
| Title |
|---|
| 叶跃雯 等: "《物理化学实验》", 合肥：合肥工业大学出版社, pages: 88 - 89 * |
| 尚宏周;张鑫;梁红玉;张小梅;孙晓然;韩利华;: "核壳型表面离子印迹聚合物的制备及其吸附性能研究", no. 11 * |
| 张明磊;张朝晖;罗丽娟;杨潇;刘玉楠;聂利华;: "磁性Fe_3O_4@SiO_2@CS镉离子印迹聚合物的制备及吸附性能", pages 3 * |
| 潘胜东;叶美君;金米聪;: "磁性固相萃取在食品安全检测中的应用进展", no. 03 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110346428A (en) * | 2019-06-24 | 2019-10-18 | 杭州电子科技大学 | The microsensor detection system and its detection method of real-time in-situ detection antibiotic |
| CN110398531A (en) * | 2019-07-02 | 2019-11-01 | 杭州电子科技大学 | Applied to trace detection heavy metal ion device and its detection method |
| CN110887883A (en) * | 2019-12-05 | 2020-03-17 | 吉林大学 | Electrochemical method for rapidly detecting penicillin sodium based on magnetic material |
| CN113418872A (en) * | 2021-06-17 | 2021-09-21 | 东莞市人民医院 | Drug resistance monitoring device for drug resistance bacterium culture and implementation method thereof |
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