CN108195904A - A kind of micro-extraction/microelectrode double function probe and its preparation method and application - Google Patents

A kind of micro-extraction/microelectrode double function probe and its preparation method and application Download PDF

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CN108195904A
CN108195904A CN201711434996.7A CN201711434996A CN108195904A CN 108195904 A CN108195904 A CN 108195904A CN 201711434996 A CN201711434996 A CN 201711434996A CN 108195904 A CN108195904 A CN 108195904A
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CN108195904B (en
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李东浩
邹依霖
孟龙月
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Yanbian University
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Abstract

The present invention provides a kind of preparation methods of micro-extraction/microelectrode double function probe, belong to biogenic signaling molecule detection field.Carbon nano-fiber (CNFs)/carbon fiber (CF) has high adsorption activity in micro-extraction of the present invention/microelectrode double function probe, integrates micro-extraction and microelectrode.By magnetic nanoparticle Fe3O4It modifies and not only overcomes magnetic nanoparticle Fe in CNFs surfaces3O4The shortcomings that easily reuniting, and improve the magnetic response ability of CF.Fe is regulated and controled by magnetic field3O4/ CNFs/CF motion paths realize magnetic navigation, pass through CNFs/CF and Fe3O4/ CNFs/CF electrochemical signals change, and realize signaling molecule release site precise positioning;By magnetic field and the double regulation control of electric signal, novel detection method is provided for the analysis of cell signaling molecule positioning and quantitative, necessary theoretical direction can be provided for the new and effective cytoanalyze of subsequent design.

Description

A kind of micro-extraction/microelectrode double function probe and its preparation method and application
Technical field
The present invention relates to biogenic signaling molecule detection technique field more particularly to a kind of difunctional spies of micro-extraction/microelectrode Needle and its preparation method and application.
Background technology
In recent years, realize that accurately classification of diseases and diagnosis, formulation have by control accurate intraor extracellular signal transduction Personalized disease prevention and therapeutic scheme, quietly as the central issue in life science, research " multi-path signal point The synergistic effect of son " is to realize the most effective premise of control accurate cell signalling system.Due to cell signalling process Multiple accesses is needed to complete (collaboration or antagonism) jointly, therefore understand the composition of signal transduction system and multi-path signal point The synergistic effect of son is of great significance for deep understanding life process and the essence for disclosing life, helps to illustrate disease Occurrence and development mechanism, and provide thinking for accurate medicine, achieve the purpose that prevent and treat disease.
Cell signalling systematic research for many years achieves many breathtaking progress.It is multipath, multi-level Cell-signaling pathways have the characteristics that restrain or dissipate.The main method used in cell signaling molecule synergistic effect research is base Many intermolecular interactions such as interaction, large biological molecule and small molecular phase interaction between intracellular biological macromolecular The acquisition of information, chemical signal molecule are the communications between signal path as the key factor in signal transduction pathway system Matrix.When detecting small molecule signaling molecule both at home and abroad at present, generally use high performance liquid chromatography, electrochemistry, Capillary Electrophoresis The methods of method, Surface Enhanced Raman Scattering Spectrum method, colorimetric method, fluorescence and Mass Spectrometer Method.Although these method comparative maturities, It is complicated for operation there are many shortcomings, it can not realize multi-path precise positioning, real-time quantitative analysis.
Invention content
In view of this, the purpose of the present invention is to provide a kind of micro-extraction/microelectrode double function probes and preparation method thereof And application.Double function probe produced by the present invention integrates micro-extraction and microelectrode, fixed with magnetic navigation, real-time and precise Position, high enrichment performance are, it can be achieved that the efficient mixed mode positioning and quantitative of signaling molecule divides in multi-level sophisticated signal transductive process Analysis.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme:
A kind of preparation method of micro-extraction/microelectrode double function probe, includes the following steps:
(1) carbon nano-fiber/carbon fibre material is provided, the carbon nano-fiber is grown in carbon fiber surface, has bionical Caterpillar space multistory three-dimensional structure;
(2) one end of carbon fiber carries out surface chemistry in the carbon nano-fiber/carbon fibre material obtained to the step (1) Activation process obtains activation carbon nano-fiber/carbon fiber;
(3) by Fe3O4Nanoparticulate dispersion is coated to activation carbon nano-fiber/carbon fiber that the step (2) obtains On, obtain Fe3O4/ carbon nano-fiber/carbon fiber;
(4) what the carbon nano-fiber/carbon fiber obtained a step (1) and a step (3) obtained Fe3O4/ carbon nano-fiber/carbon fiber is packed into dialysis membrane, obtains micro-extraction/microelectrode double function probe.
Preferably, a diameter of 5~8 μm of carbon fiber in the step (1), the carbon nano-fiber a diameter of 20~ 70nm。
Preferably, surface chemistry activation process is oxidation or amidation in the step (2).
Preferably, the length that one end of surface chemistry activation process is carried out in the step (2) is 0.5~2cm.
Preferably, Fe in the step (3)3O4The diameter of nano particle is less than 50nm.
Preferably, applied to spraying or dipping in the step (3).
Preferably, Fe in the step (3)3O4A concentration of 0.05~0.1mg/mL of nanoparticulate dispersion.
Preferably, the Fe3O4The coated weight of nanoparticulate dispersion is 0.05~0.1mg/cm2
The present invention also provides micro-extraction made from preparation method described in above-mentioned technical proposal/microelectrode double function probe, The micro-extraction/microelectrode double function probe includes carbon nano-fiber/carbon fiber and Fe3O4/ carbon nano-fiber/carbon fiber, it is described Carbon nano-fiber/carbon fiber has bionical caterpillar structure, the Fe3O4/ carbon nano-fiber/carbon fiber has Bionic glasses snake Structure.
The present invention also provides micro-extraction described in above-mentioned technical proposal/microelectrode double function probe multi-path traces in the cell Measure the application in signaling molecule detection.
The present invention provides a kind of preparation methods of micro-extraction/microelectrode double function probe, include the following steps:Carbon is provided Nanofiber/carbon fibre material, the carbon nano-fiber are grown in carbon fiber surface, have bionical caterpillar space multistory three-dimensional Structure is carried out Fe one end of carbon fiber in the carbon nano-fiber/carbon fibre material after surface chemistry activation process3O4It receives On rice grain dispersion to activation carbon nano-fiber/carbon fiber, Fe is obtained3O4/ carbon nano-fiber/carbon fiber, finally by one Root carbon nano-fiber/carbon fiber and a Fe3O4/ carbon nano-fiber/carbon fiber is packed into dialysis membrane, obtains micro-extraction/microelectrode Double function probe.Carbon nano-fiber (CNFs)/carbon fiber (CF) tool in micro-extraction produced by the present invention/microelectrode double function probe There are high adsorption activity and chemical property, can realize that micro-extraction and microelectrode are difunctional, by magnetic nanoparticle Fe3O4Modification Magnetic nanoparticle Fe is not only overcome in CNFs surfaces3O4The shortcomings that easily reuniting, and the magnetic response ability of CF is improved, Pass through CNFs and Fe3O4Double regulation control, prepare Fe3O4/ CNFs/CF answers micro-extraction/microelectrode double function probe, applied to thin The synchronous detection of multi-path signaling molecule is realized in the high sensitivity of born of the same parents' multi-path trace signaling molecule, high enrichment, synchronous detection, Novel detection method is provided, while can be the new and effective cell analysis of subsequent design for the analysis of cell signaling molecule positioning and quantitative Instrument provides necessary theoretical experiment instruction.
Description of the drawings
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the structure diagram of carbon nano-fiber/carbon fiber made from the embodiment of the present invention 1;
Fig. 2 prepares Fe for the embodiment of the present invention 13O4The flow chart of/carbon nano-fiber/carbon fiber;
Fig. 3 is the structure diagram of micro-extraction/microelectrode double function probe made from the embodiment of the present invention 1;
Fig. 4 is micro-extraction/microelectrode double function probe made from the embodiment of the present invention 1 for signal point in cavy corpus straitum Sub- detects schematic diagram.
Specific embodiment
The present invention provides a kind of preparation methods of micro-extraction/microelectrode double function probe, include the following steps:
(1) carbon nano-fiber/carbon fibre material is provided, the carbon nano-fiber is grown in carbon fiber surface, has bionical Caterpillar space multistory three-dimensional structure;
(2) one end of carbon fiber carries out surface chemistry in the carbon nano-fiber/carbon fibre material obtained to the step (1) Activation process obtains activation carbon nano-fiber/carbon fiber;
(3) by Fe3O4Nanoparticulate dispersion is coated to activation carbon nano-fiber/carbon fiber that the step (2) obtains On, obtain Fe3O4/ carbon nano-fiber/carbon fiber;
(4) what the carbon nano-fiber/carbon fiber obtained a step (1) and a step (3) obtained Fe3O4/ carbon nano-fiber/carbon fiber is packed into dialysis membrane, obtains micro-extraction/microelectrode double function probe.
The present invention provides carbon nano-fiber/carbon fibre material, and the carbon nano-fiber is modified in carbon fiber surface, is had imitative Setation caterpillar space multistory three-dimensional structure.The present invention does not have special limit to the source of the carbon nano-fiber/carbon fibre material It is fixed, it is made using preparation method well known to those skilled in the art, specifically, with reference to the system disclosed in CN106353439A Preparation Method is made.
In the present invention, the diameter of the carbon fiber is preferably 5~8 μm, more preferably 6~7 μm;The carbon nano-fiber Diameter be preferably 20~70nm, more preferably 30~50nm.
After obtaining carbon nano-fiber/carbon fibre material, the present invention is to carbon fiber in the carbon nano-fiber/carbon fibre material One end carry out surface chemistry activation process, obtain activation carbon nano-fiber/carbon fiber.In the present invention, the surface chemistry Activation process can introduce different oxygen-containing and/or nitrogen-containing functional groups on carbon nano-fiber surface, improve the table of carbon nano-fiber Face energy, increases the binding site of magnetic nano-particle particle, is conducive to magnetic nano-particle particle being attached to carbon nano-fiber Surface, while coming off for carbon nano-fiber can be prevented, maintain the primary morphology on the carbon fiber of carbon nano-fiber.In the present invention In, the surface chemistry activation process preferably aoxidizes or amidation.The present invention is to the oxidation or amidated detailed process There is no special restriction, it is specific as used using oxidation well known to those skilled in the art or amidation usual manner Carbon dioxide gas oxidation, carboxylic acid are reacted with the direct polycondensation of amine, specifically, being such as packed into carbon nano-fiber/carbon fibre material In quartz capillary, one end of carbon nano-fiber/carbon fiber is exposed to quartz capillary outer end.To exposed on the outside of capillary Carbon nano-fiber/carbon fiber tip carries out surface chemistry activation process.
In the present invention, the length of one end of the carbon fiber for carrying out surface chemistry activation process be preferably 0.5~ 2cm, more preferably 1~1.5cm.
It is of the invention by Fe after obtaining activation carbon nano-fiber/carbon fiber3O4Nanoparticulate dispersion is coated to the activation On carbon nano-fiber/carbon fiber, Fe is obtained3O4/ carbon nano-fiber/carbon fiber.In the present invention, the Fe3O4Nano particle Diameter is preferably smaller than 50nm, more preferably less than 20nm.The present invention is to the Fe3O4The source of nano particle does not have special limit It is fixed, it is made using preparation method well known to those skilled in the art, Fe is such as prepared using chemical precipitation method3O4Nano particle, Specifically, by FeCl3·6H2O and FeCl2·4H2O and concentrated hydrochloric acid are dissolved in advance through N2In the deionized water of deoxidation;At 80 DEG C Under water-bath and mechanical agitation, more than solution is added drop-wise to N dropwise2In the alkaline aqueous solution of protection, continue to lead to after dripping Enter N2, while insulated and stirred;After reaction, iron oxide nano particle obtained is separated using externally-applied magnetic field;It will Twice of washes of absolute alcohol of obtained ferroferric oxide magnetic nanoparticle, again with toluene are cleaned twice.
In the present invention, the coating is preferably sprayed or is impregnated.The present invention is to the concrete mode of the spraying or dipping There is no special restriction, using mode well known to those skilled in the art, specifically, such as by Fe3O4Nanoparticulate dispersion It is coated on activation carbon nano-fiber/carbon fiber or Fe will be immersed on activation carbon nano-fiber/carbon fiber3O4Nano particle point In dispersion liquid.
In the present invention, the Fe3O4The concentration of nanoparticulate dispersion is preferably 0.05~0.1mg/mL, more preferably 0.05~0.07mg/mL.
In the present invention, the Fe3O4The coated weight of nanoparticulate dispersion is preferably 0.05~0.1mg/cm2, more preferably For 0.05~0.8mg/cm2.In the present invention, the position of the coating is the position by surface chemistry activation process.
Obtain carbon nano-fiber/carbon fibre material and Fe3O4After/carbon nano-fiber/carbon fiber, the present invention will be described in one Carbon nano-fiber/carbon fiber and a Fe3O4/ carbon nano-fiber/carbon fiber is packed into dialysis membrane, obtains micro-extraction/micro- electricity Pole double function probe.
The present invention also provides micro-extraction made from preparation method described in above-mentioned technical proposal/microelectrode double function probe, The micro-extraction/microelectrode double function probe includes carbon nano-fiber/carbon fiber and Fe3O4/ carbon nano-fiber/carbon fiber, it is described Carbon nano-fiber/carbon fiber has bionical caterpillar structure, the Fe3O4/ carbon nano-fiber/carbon fiber has Bionic glasses snake Structure.
In the present invention, the carbon nano-fiber/carbon fiber and Fe3O4The quantity of/carbon nano-fiber/carbon fiber is than 1:1.
In the present invention, the Fe with Bionic glasses snake structure3O4Fe in/carbon nano-fiber/carbon fiber3O4It is imitative Two eyes of raw cobra.
The present invention also provides micro-extraction described in above-mentioned technical proposal/microelectrode double function probe multi-path traces in the cell Measure the application in signaling molecule detection.
It is studied the present invention provides above-mentioned technical proposal for detecting neurotransmitter cell-signaling pathways in cavy corpus straitum.
With reference to embodiment to micro-extraction provided by the invention/microelectrode double function probe and its preparation method and application It is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The preparation of carbon nano-fiber/carbon fiber
Carbon nano-fiber/carbon fiber, carbon Nanowire are prepared using the chemical vapour deposition technique disclosed in CN106353439A A diameter of 20nm of dimension, a diameter of 5 μm of carbon fiber, the structure diagram of carbon nano-fiber/carbon fiber obtained is Fig. 1, by Fig. 1, which can be seen that carbon nano-fiber modification in carbon nano-fiber/carbon fiber obtained, on carbon fiber, has bionical caterpillar Space multistory three-dimensional structure.
Fe3O4/ carbon nano-fiber/carbon fiber (Fe3O4/ CNFs/CF) preparation
Fig. 2 is prepares Fe3O4The flow chart of/carbon nano-fiber/carbon fiber.First Fe is prepared with iron presoma3O4Magnetic Nano Particle:By FeCl3·6H2O and FeCl2·4H2O and concentrated hydrochloric acid are dissolved in advance through N2In the deionized water of deoxidation;In 80 DEG C of water Under bath and mechanical agitation, more than solution is added drop-wise to N dropwise2In the alkaline aqueous solution of protection, continue to be passed through after dripping N2, while insulated and stirred;After reaction, using externally-applied magnetic field by iron oxide nano particle obtained (diameter be less than 50nm) It separates;By twice of washes of absolute alcohol of obtained ferroferric oxide magnetic nanoparticle, again with toluene is cleaned twice.
5 centimetres of carbon nano-fiber/carbon fiber is fitted into quartz capillary (10 μm of diameter), 1 centimetre is exposed to quartz Capillary outer end.Carbon dioxide oxidation processes are carried out to exposed carbon nano-fiber/carbon fiber tip on the outside of capillary, are passed through By carbon nano-fiber/impregnated carbon fiber of activation to Fe3O4In magnetic nanoparticle dispersion liquid (concentration 0.07mg/mL), make Fe3O4Magnetic nanoparticle is attached to the surface of carbon nano-fiber, is heat-treated at a temperature of 60 DEG C, removes quartz capillary, most Cobra structural formula Fe in the present invention is obtained eventually3O4/CNFs/CF。
The preparation of micro-extraction/microelectrode double function probe
Micro-extraction/microelectrode double function probe device is improved in CMA microdialysis probes (dialysis length:4mm;Diameter: 0.24mm).The carbon fiber of two root functionalities is packed into dialysis membrane, wherein one for bionical caterpillar structural formula carbon nano-fiber/ Carbon fiber, another is Bionic glasses snake structural formula Fe3O4/CNFs/CF.Fig. 3 is the knot of micro-extraction/microelectrode double function probe Structure schematic diagram, it is bionical caterpillar structural formula carbon nano-fiber/carbon fiber that micro-extraction/microelectrode double function probe, which includes one, Another is Bionic glasses snake structural formula Fe3O4/CNFs/CF。
Signaling molecule precise positioning is enriched with
Bull cavy is raised in room temperature and natural lighting periodic environment.Cavy is noted through 10% hydration chloric acid abdominal cavity After penetrating anesthesia, it is placed on accurate stereotaxic instrument and maintains normal body temperature with constant-temp. cushion.Cavy through open cranium and removal pia mater after, Utilize microdialysis guide rail (CMA, length of dialysing:4mm, diameter:0.24mm) with standard stereo finder by micro-extraction/microelectrode Double function probe implantation cavy corpus straitum (AP=0mm, L=3mm from bregma, V=4.5mm from dura), then It is fixed with nail and dental cement.The precise positioning of cavy corpus straitum, bionical caterpillar structure are realized by stereoscopic localized program Formula carbon nano-fiber/carbon fiber carries out signaling molecule as the electrochemical signals and micro-extracting head of microelectrode response corpus straitum simultaneously Full enrichment is (see Fig. 4);Cavy brains applies magnetic field, and cobra structural formula Fe is controlled by regulating and controlling magnetic field3O4/ CNFs/CF is transported Dynamic path, the cerebrospinal fluid on scanning corpus straitum periphery, utilizes cobra structural formula Fe3O4The electrochemical signals of/CNFs/CF microelectrodes Variation, positioning signal molecule release site, utilizes cobra structural formula Fe3O4The high enrichment performance of/CNFs/CF materials realizes letter The full enrichment of number molecule release position point compound.
Bionical caterpillar structural formula carbon nano-fiber/carbon fiber and Bionic glasses snake structural formula Fe3O4/ CNFs/CF makees first Detect change in electric in corpus straitum and corpus straitum periphery cerebrospinal fluid simultaneously for microelectrode;The environmental stimulis such as cavy blowing are given, Observe the change in electric of two microelectrodes;Carbon nano-fiber/carbon fiber microelectrodes with micro pipette tips captures electric signal in situ in cavy corpus straitum, Fe3O4/ CNFs/CF microelectrodes scanning corpus straitum periphery cerebrospinal fluid under external magnetic field auxiliary, while observe electric signal.Pass through two The change in electric of microelectrode determines that signaling molecule discharges site in the cerebrospinal fluid of cavy corpus straitum periphery, and records under environmental stimuli Externally-applied magnetic field movement locus and application magnetic field size;After realizing signaling molecule release position point location, power supply, bionical caterpillar are removed Structural formula carbon nano-fiber/carbon fiber and cobra structural formula Fe3O4/ CNFs/CF is used as micro extraction probe, is kept additional Magnetic field is constant, carbon nano-fiber/carbon fiber and Fe3O4/ CNFs/CF micro extraction probes carry out full enrichment signaling molecule in situ;
Pass through carbon nano-fiber/carbon fiber and Fe3O4Two microelectrode change in electric situations of/CNFs/CF can be determined that line Signaling molecule release sequencing and release site in shape body and corpus straitum periphery cerebrospinal fluid.Pass through carbon nano-fiber/carbon fiber And Fe3O4The signaling molecule of two micro extraction probe enrichments of/CNFs/CF can probe into the synergistic effect between signaling molecule, for research Cell-signaling pathways provide guide.
Embodiment 2
The preparation of carbon nano-fiber/carbon fiber
Carbon nano-fiber/carbon fiber, carbon Nanowire are prepared using the chemical vapour deposition technique disclosed in CN106353439A A diameter of 50nm of dimension, a diameter of 7 μm of carbon fiber, carbon nano-fiber modification is in carbon in carbon nano-fiber/carbon fiber obtained On fiber, there is bionical caterpillar space multistory three-dimensional structure.
Fe3O4/ carbon nano-fiber/carbon fiber (Fe3O4/ CNFs/CF) preparation
By FeCl3·6H2O and FeCl2·4H2O and concentrated hydrochloric acid are dissolved in advance through N2In the deionized water of deoxidation;At 80 DEG C Under water-bath and mechanical agitation, more than solution is added drop-wise to N dropwise2In the alkaline aqueous solution of protection, continue to lead to after dripping Enter N2, while insulated and stirred;After reaction, using externally-applied magnetic field, by iron oxide nano particle obtained, (diameter is less than 20nm) separate;By twice of washes of absolute alcohol of obtained ferroferric oxide magnetic nanoparticle, again with toluene cleaning two Time.
5 centimetres of carbon nano-fiber/carbon fiber is fitted into 10 μm of quartz capillary, 2 centimetres are exposed to quartzy capillary Pipe outer end.Carboxylic acid is carried out to exposed carbon nano-fiber/carbon fiber tip on the outside of capillary to react with the direct polycondensation of amine, is led to It crosses carbon nano-fiber/impregnated carbon fiber of activation to Fe3O4In magnetic nanoparticle dispersion liquid (concentration 0.05mg/mL), make Fe3O4Magnetic nanoparticle is attached to the surface of carbon nano-fiber, is heat-treated at a temperature of 60 DEG C, removes quartz capillary, most Cobra structural formula Fe in the present invention is obtained eventually3O4/CNFs/CF。
The preparation of micro-extraction/microelectrode double function probe
Micro-extraction/microelectrode double function probe device is improved in CMA microdialysis probes (dialysis length:4mm;Diameter: 0.24mm).The carbon fiber of two root functionalities is packed into dialysis membrane, wherein one for bionical caterpillar structural formula carbon nano-fiber/ Carbon fiber, another is Bionic glasses snake structural formula Fe3O4/CNFs/CF.Fig. 3 is the knot of micro-extraction/microelectrode double function probe Structure schematic diagram, it is bionical caterpillar structural formula carbon nano-fiber/carbon fiber that micro-extraction/microelectrode double function probe, which includes one, Another is Bionic glasses snake structural formula Fe3O4/CNFs/CF。
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (10)

1. a kind of preparation method of micro-extraction/microelectrode double function probe, includes the following steps:
(1) carbon nano-fiber/carbon fibre material is provided, the carbon nano-fiber is grown in carbon fiber surface, has bionical mao mao Worm space multistory three-dimensional structure;
(2) one end of carbon fiber carries out surface chemistry activation in the carbon nano-fiber/carbon fibre material obtained to the step (1) Processing obtains activation carbon nano-fiber/carbon fiber;
(3) by Fe3O4Nanoparticulate dispersion is coated to activation carbon nano-fiber/carbon fiber surface that the step (2) obtains, Obtain Fe3O4/ carbon nano-fiber/carbon fiber;
(4) Fe that the carbon nano-fiber/carbon fiber obtained a step (1) and a step (3) obtain3O4/ carbon Nanofiber/carbon fiber is packed into dialysis membrane, obtains micro-extraction/microelectrode double function probe.
2. preparation method according to claim 1, which is characterized in that a diameter of 5~8 μ of carbon fiber in the step (1) M, a diameter of 20~70nm of the carbon nano-fiber.
3. preparation method according to claim 1, which is characterized in that surface chemistry activation process is in the step (2) Oxidation or amidation.
4. preparation method according to claim 1, which is characterized in that carried out at surface chemistry activation in the step (2) The length of one end of reason is 0.5~2cm.
5. preparation method according to claim 1, which is characterized in that Fe in the step (3)3O4The diameter of nano particle Less than 50nm.
6. preparation method according to claim 1 or 5, which is characterized in that applied to spraying or leaching in the step (3) Stain.
7. preparation method according to claim 1 or 5, which is characterized in that Fe in the step (3)3O4Nano particle disperses A concentration of 0.05~0.1mg/mL of liquid.
8. preparation method according to claim 7, which is characterized in that the Fe3O4The coated weight of nanoparticulate dispersion is 0.05~0.1mg/cm2
9. micro-extraction made from preparation method described in claim 1~8 any one/microelectrode double function probe, feature exist In the micro-extraction/microelectrode double function probe includes carbon nano-fiber/carbon fiber and Fe3O4/ carbon nano-fiber/carbon fiber, Carbon nano-fiber/the carbon fiber has bionical caterpillar structure, the Fe3O4/ carbon nano-fiber/carbon fiber has bionic eye Mirror snake structure.
10. in the multi-path trace signaling molecule detection in the cell of micro-extraction described in claim 9/microelectrode double function probe Using.
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CN112759065B (en) * 2021-01-13 2022-05-24 中国科学院城市环境研究所 Method for quickly starting anaerobic ammonia oxidation reactor and recovering activity of anaerobic ammonia oxidation bacteria

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