CN108732220A - A kind of diallyl dimethyl ammoniumchloride-graphene hybridized nanometer decorative material and its preparation method and application - Google Patents

A kind of diallyl dimethyl ammoniumchloride-graphene hybridized nanometer decorative material and its preparation method and application Download PDF

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CN108732220A
CN108732220A CN201810601509.XA CN201810601509A CN108732220A CN 108732220 A CN108732220 A CN 108732220A CN 201810601509 A CN201810601509 A CN 201810601509A CN 108732220 A CN108732220 A CN 108732220A
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pdda
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水玲玲
刘振平
王新
周国富
金名亮
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Zhaoqing South China Normal University Optoelectronics Industry Research Institute
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Abstract

The present invention relates to a kind of diallyl dimethyl ammoniumchloride-graphene hybridized nanometer decorative materials and its preparation method and application.The preparation method includes the following steps:Graphene oxide GO dispersion liquids, PDDA and hydrazine hydrate are mixed in water, are stirred to react at 90 ~ 100 DEG C, is centrifuged, washing is drying to obtain the PDDA-Gr hybridized nanometers decorative material;The amount ratio of the PDDA and GO is 2 ~ 4:The amount ratio of 1 mL/g, the hydrazine hydrate and GO are 4 ~ 8:1 mL/g.The PDDA-Gr hybridized nanometer decorative materials that preparation method provided by the invention is prepared have the advantages that good dispersion performance, large specific surface area, conductive capability be strong and good biocompatibility, thus obtained electrode sensitivity is high, selectivity is good, the range of linearity is wide, detection limit it is low, easy to use;Preparation method provided by the invention is simple for process.

Description

A kind of diallyl dimethyl ammoniumchloride-graphene hybridized nanometer decorative material and Preparation method and application
Technical field
The invention belongs to electrochemical fields, and in particular to a kind of diallyl dimethyl ammoniumchloride-graphene hydridization is received Rice decorative material and its preparation method and application.
Background technology
Neurotransmitter(neurotransmitter)It is a kind of chemical substance secreted by nerve endings, believes in chemical synapse Breath takes on the effect of " courier " in transmitting.Neurotransmitter can be mainly divided into five classes, i.e., monoamine, choline, amino acids, Neuropeptide and gas class.Wherein monoamine neurotransmitter includes:Dopamine, serotonin, norepinephrine and adrenal gland Element.The concentration variation of monoamine neurotransmitter is in close relations with the cerebration of the mankind in blood.Meanwhile in a kind of neuron Into the cell often can there are two types of or more coexistence of neurotransmitters, this phenomenon that coexists can contain phase in same nerve cell With the neurotransmitter that precursor substance generates, the coexistence of neurotransmitters of different precursors can also be derived from a kind of neuron It is interior.
Electrochemical analysis has many advantages, such as that easy to operate, clever lightness is high, analyze speed is fast, mainly by component to be measured in electricity Pole surface carries out redox reaction, and chemical signal is converted to the form of electric signal by the transfer of electronics, to realize inspection Survey a kind of analysis method of component to be measured.In the preparation process of electrochemical sensor, generally use nano-carbon material(Including carbon Nanotube, graphene)Deng modifying electrode, to improve the electrocatalysis characteristic of electrode, enhance the detectability of electrode.
Therefore, develop that a kind of good dispersion performance, large specific surface area, conductive capability be strong and the electrode material of good biocompatibility With important research significance and application value.
Invention content
It is an object of the invention to the defect for overcoming the performance of electrode material in the prior art bad and deficiencies, provide one kind The preparation method of diallyl dimethyl ammoniumchloride-graphene PDDA-Gr hybridized nanometer decorative materials.System provided by the invention The PDDA-Gr hybridized nanometer decorative materials that Preparation Method is prepared have that dispersion performance is good, large specific surface area, conductive capability are strong and The advantages of good biocompatibility, thus obtained electrode sensitivity is high, selectivity is good, the range of linearity is wide, detection limits low, user Just;Preparation method provided by the invention is simple for process.
Another object of the present invention is to provide above-mentioned PDDA-Gr hybridized nanometers decorative materials.
Another object of the present invention is to provide a kind of electrodes.
Another object of the present invention is to provide above-mentioned PDDA-Gr hybridized nanometers decorative materials or electrode to prepare electrochemistry Application in sensor.
Another object of the present invention is to provide a kind of microfluidic devices.
Another object of the present invention is to provide the preparation methods of above-mentioned microfluidic device.
For achieving the above object, the present invention adopts the following technical scheme that:
A kind of preparation method of diallyl dimethyl ammoniumchloride-graphene PDDA-Gr hybridized nanometer decorative materials, including such as Lower step:Graphene oxide GO dispersion liquids, PDDA and hydrazine hydrate are mixed in water, are stirred to react at 90 ~ 100 DEG C, from The heart, washing, is drying to obtain the PDDA-Gr hybridized nanometers decorative material;The amount ratio of the PDDA and GO is 2 ~ 4:1 mL/g, The amount ratio of the hydrazine hydrate and GO are 4 ~ 8:1 mL/g.
The present invention restores graphene oxide by way of hydrazine hydrate is added, prepare with high-specific surface area and The graphene Gr of electro catalytic activity.Diallyl dimethyl ammoniumchloride PDDA is added, passes through electrostatic force with graphene Gr The pi-conjugated mode with π-, one kind, which is prepared, has good dispersion performance, large specific surface area, conductive capability strong and biocompatibility Good PDDA-Gr hybridized nanometer decorative materials.
It should be understood that the graphene oxide GO dispersion liquids of present invention meaning, which are GO, preferably disperses obtained dispersion liquid, Under normal circumstances, when dispersion solvent is water, preferable dispersion can be achieved in the GO that mass concentration is≤1 mg/mL.
Graphene oxide provided by the invention can take graphite powder as starting principle, using potassium permanganate and the concentrated sulfuric acid as Strong oxidizer is prepared.
Preferably, the amount ratio of the PDDA and GO is 3.2:1 mL/g;The amount ratio of the hydrazine hydrate and GO are 6.4:1 mL/g 。
Preferably, the temperature of the reaction is 95 DEG C.
The present invention also asks the PDDA-Gr hybridized nanometer decorative materials that above-mentioned preparation method is prepared.
A kind of electrode modifies above-mentioned PDDA-Gr hybridized nanometers decorative material up to the electrode on basal electrode.
Electrode sensitivity provided by the invention is high, selectivity is good, the range of linearity is wide, detection limit is low, easy to use.
Conventional basal electrode may be incorporated in this electrode.
Preferably, the basal electrode is carbon paste electrode, spun gold electrode, platinum electrode or copper wire electrode.
The present invention provides a kind of homemade basal electrode.
Preferably, the basal electrode is prepared via a method which to obtain:
S1:Graphite powder, atoleine and multi-walled carbon nanotube are uniformly mixed;
S2:Copper wire is inserted into quartz capillary, the quartz capillary grows 2 ~ 4 cm, and copper wire is grown 3 ~ 5 cm, fixed with glue;
S3:Mixing material obtained by S1 is filled into quartz capillary, is compacted, is polishing to minute surface up to the basal electrode.
The preparation method of above-mentioned electrode, comprises the following processes:PDDA-Gr is dispersed in solvent and obtains PDDA-Gr nanometers of materials Expect dispersion liquid;Basal electrode is immersed in dispersion liquid to obtain the final product.
Preferably, the time of the immersion is 2 ~ 8 h.
It is further preferable that the time of the immersion is 4 h.
The application of above-mentioned PDDA-Gr hybridized nanometers decorative material or above-mentioned electrode in preparing electrochemical sensor is also at this In the protection domain of invention.
Preferably, the electrochemical sensor is for detecting monoamine neurotransmitter.
Preferably, the monoamine neurotransmitter is dopamine, serotonin, in adrenaline or norepinephrine It is one or more of.
Microfluidic device, which is one kind, can handle micro biological substance or the device of chemical substance, can realize micro substance Separation detection device.Microfluidic device includes sample feeding pond, detection cell and the connection fluid channel between them.It can be with It realizes complicated separation detection process integration on the device of microsize.Common microfluidic device can be integrated in device One several square micron, to reduce the consumption of test substance in detection process, realizes sample in the range of several square centimeters Microseparation detection.
Common Electrochemical Detection system is carried out in larger container, detection sample accommodating usually milliliter grade with On.In order to improve the consumption of sample in analyte detection process, microfluidic device(Micro-fluidic chip)It is to rapidly develop in recent years A kind of separation and analysis method that can realize that reduction sample volume consumes got up.The miniflow compared with traditional Electrochemical Detection window Body detection device has sample consumption few, and usual sample consumption is microlitre to nanoliter level.This new method will be the later stage The very tempting commercial promises of offers such as analysis detection blood plasma biological sample, environmental sample and food samples.
In this regard, the present invention also provides a kind of microfluidic device, including:The device sheet that PDMS substrates and glass are bonded Body, sample cell, waste liquid pool, working electrode channel, reference electrode channel, auxiliary electrode channel, the sample cell and waste liquid pool it Between be provided with chip microchannel, the chip microchannel is set to glass surface;The working electrode channel, reference electrode are logical Road, auxiliary electrode channel are connected with the sample cell, and working electrode, reference electrode and auxiliary electricity are respectively arranged in it Pole, the working electrode are any of the above-described electrode.
Electrode prepared by the present invention can be substantially reduced to the consumption for detecting sample for microfluidic device.
Preferably, the depth of the chip microchannel is 15 ~ 30 μm, and width is 60 ~ 100 μm;The working electrode is logical Road, reference electrode channel, auxiliary electrode channel diameter be 300 ~ 800 μm;The section of the sample cell and waste liquid pool is equal For circle, the diameter of section of the sample cell and waste liquid pool is 0.5 ~ 3 cm.
It is further preferable that the depth of the chip microchannel is 18 μm, width is 80 μm;The working electrode channel, Reference electrode channel, auxiliary electrode channel diameter be 250 μm;The diameter of section of the sample cell and waste liquid pool is 1.5 cm;The spacing of the sample cell and waste liquid pool is 1.5 cm.
The PDMS substrates can be prepared by conventional method.
Preferably, the PDMS substrates are obtained by the reaction by PDMS prepolymers and curing agent solidification.
Preferably, the mass ratio of the PDMS prepolymers and curing agent is 10:1.
Preferably, the temperature of the curing reaction is 90 DEG C, and the time is 30 min.
The preparation method of above-mentioned microfluidic device, includes the following steps:
S1:Chip microchannel is etched on glass;Laser pours out work electrode channel, reference electrode channel and auxiliary electrode Channel;
S2:Sample cell and waste liquid pool are prepared on PDMS substrates;
S3:PDMS substrates and glass are bonded up to the microfluidic device.
The chip microchannel and electrode channel that reduced size can be obtained with laser ablation by etching, realize microfluid.
Preferably, the time etched in S1 is 10 ~ 30 min;Sample cell and waste liquid is prepared using card punch in S2 Pond.
A method of detection monoamine neurotransmitter includes the following steps:
S1:Using electrochemical workstation as analytical instrument, above-mentioned electrode as working electrode, and with reference electrode and auxiliary electrode group At three-electrode system;
S2:Three-electrode system is placed in the buffer solution containing monoamine neurotransmitter, according between its concentration and oxidation peak current Relationship obtain standard curve;
S3:The content of monoamine neurotransmitter in determination sample.
Preferably, the reference electrode is Ag/AgCl electrodes;The auxiliary electrode is platinum electrode.
Compared with prior art, the present invention has the advantages that:
The PDDA-Gr hybridized nanometer decorative materials that preparation method provided by the invention is prepared are with dispersion performance is good, compares table The advantages of area is big, conductive capability is strong and good biocompatibility, thus obtained electrode sensitivity is high, good, the linear model of selectivity It is low, easy to use to enclose width, detection limit;Preparation method provided by the invention is simple for process.
Description of the drawings
Fig. 1 is the modified electrode schematic diagram and monoamine neurotransmitter compound concentration measuring principle figure that embodiment 1 provides;
Fig. 2 is the PDDA-Gr hybridized nanometer decorative material phenograms that embodiment 1 provides;
Fig. 3 is the microfluidic test device schematic diagram that embodiment 1 provides;
Fig. 4 a are the differential pulse voltammetry that the MWCNTs-CPE/PDDA-Gr modified electrodes that embodiment 1 provides measure various concentration dopamine Voltammogram(Serotonin concentration is fixed as 5.0 μm of ol/L), Fig. 4 b be dopamine concentration range 0.05 ~ 50.0 μm of ol/L with Oxidation peak current relational graph;
Fig. 5 is that the MWCNTs-CPE/PDDA-Gr modified electrodes that embodiment 1 provides measure dopamine and 5- hydroxyl colors in rat plasma Amine differential pulse voltammetry voltammogram;
The MWCNTs-CPE pairs of 10 μM of dopamines for the PDDA-pRGO and PDDA-Gr modifications that Fig. 6 provides for comparative example 1 show poor arteries and veins Rush voltammogram.
Specific implementation mode
With reference to embodiment, the present invention is further explained.These embodiments are merely to illustrate the present invention rather than limitation The scope of the present invention.Test method without specific conditions in lower example embodiment usually according to this field normal condition or is pressed The condition suggested according to manufacturer;Used raw material, reagent etc., unless otherwise specified, being can be from the business such as conventional market The raw materials and reagents that approach obtains.The variation for any unsubstantiality that those skilled in the art is done on the basis of the present invention And it replaces and belongs to scope of the present invention.
Embodiment 1
The present embodiment provides a kind of PDDA-Gr hybridized nanometers decorative material, which includes diallyl dimethyl chlorine Change ammonium PDDA and reduced graphene Gr.
The decorative material is prepared via a method which to obtain:
1)By graphene oxide(GO)Dispersion liquid(0.5 mg/mL(500 mL)), PDDA(4.0 mL(20 wt%))And hydrazine hydrate (2.0 mL(80 wt%))In water, 90 ~ 100 DEG C are heated to, is stirred to react, product PDDA-Gr hybridized nanometers modification material is obtained Material;
2)By step 1)The centrifugation of hybridized nanometer decorative material, washing remove unreacted PDDA and hydrazine hydrate;
3)By step 2)Sediment after centrifugation is dried;
4)By step 3)Dried object be dispersed to again in solution for use.
The PDDA-Gr modification nano materials of formation are carried out using 950 type ultraviolet-visible-near-infrared spectrum instrument of Lambda Characterization.For graphene oxide, there are two characteristic absorption peaks at 227 nm and 293 nm, wherein 237 nm are the π-due to C=C π * are conjugated to be formed, and the absorption peak at 293 nm is formed since the n- π * of C=O are conjugated.In graphene oxide by hydrazine hydrate reduction Its absorption peak significantly reduces afterwards, and the peak red shift of the absorption of 227 nm is to 238 nm, while the acromion of 293 nm disappears.For PDDA There are one strong absorption peaks at 268 nm.The absorption peak of the PDDA-Gr nano materials of formation, graphene distinguishes red shift to 268 Nm shows that conjugation occurs for PDDA and Gr, forms PDDA-Gr hybrid nano-materials(Such as Fig. 2).
Using PDDA-Gr provided in this embodiment as decorative material, multi-walled carbon nanotube carbon paste electrode is filled(MWCNTs- CPE)As basal electrode, a kind of modified electrode can be prepared, specific preparation process is as follows:
a)One section of quartz capillary of clip(3 cm long, 150 μm of internal diameters, 360 μm of outer diameters), end is polishing on 3000 mesh sand paper Mouth is smooth;
b)By step a)Quartz capillary as HNO3(0.1 mol/L), each ultrasonic 10 in absolute ethyl alcohol and deionized water Min, it is rear to take out as dry in 60 DEG C of vacuum drying ovens;
c)One section of copper wire of clip(5 cm long, 100 μ m diameters), one section is struck off copper wire surface enameled wire with scalpel(1.5 cm), By one section that does not remove enameled wire capillary never to polish flat, one section of insertion, copper wire with a distance from capillary exit ~ 2 mm, use ring Oxygen resin fixes quartz capillary and copper wire, waits for its solidification;
d)It weighs 300 mg multi-walled carbon nanotubes and 700 mg graphite powders is put into and 40 μ L atoleines are added into agate mortar fill Divide grinding uniform, fills into the quartz capillary being cured, and its carbon paste is compacted, will be pressed by hand uniform carbon paste is ground Real carbon paste electrode surface is polished into plane on pan paper and can be obtained MWCNTs-CPE electrodes;
e)By the copper wire section of MWCNTs-CPE, it is connect with conducting wire by way of electric welding.
The MWCNTs-CPE electrodes prepared are placed into 0.5 mg/mL PDDA-Gr dispersion liquids, 4 h is impregnated, takes Go out, at ambient temperature naturally dry, you can the MWCNTs-CPE/PDDA-Gr modified(Such as Fig. 1).
The assay of standard items dopamine
Control the concentration of serotonin(For 5.0 μm of ol/L), change the concentration of dopamine, be experiment with electrochemical workstation Analytical instrument, respectively with Ag/AgCl for reference electrode, platinum electrode is auxiliary electrode, MWCNTs- provided in this embodiment CPE/PDDA-Gr is working electrode, the three-electrode system of composition;Three-electrode system is inserted into microfluidic test device(Such as Fig. 3);In -0.2 ~ 0.6 V(vs. Ag/AgCl)Differential pulse voltammetry voltammetric scan is carried out in potential range, is recorded and stable is shown poor arteries and veins Rush voltammogram(Such as Fig. 4).
Wherein microfluidic test device is prepared via a method which to obtain:
1)Chip microchannel is prepared on glass using conventional glass etch technique, liquid proportional and etching are etched by control Time(20min)It it is 18 μm and 80 μm to control chip microchannel depth and width;
2)Sensor passage, including working electrode channel, reference electrode channel, auxiliary electrode are prepared using laser pouring technique Channel, channel width are respectively 400 μm, 400 μm and 700 μm, and channel depth is respectively 250 μm, 250 μm and 400 μm;
3)PDMS substrates are prepared using conventional method, PDMS substrates are obtained by controlling PDMS prepolymers and curing agent ratio;
4)Using card punch, punching prepares sample cell and waste liquid pool on PDMS, by controlling card punch diameter(0.5~3 cm) To control detection window size;
5)PDMS and glass are bonded using conventional method, obtain micro- detection device.
The assay of dopamine and serotonin in rat body
Dopamine in SD rat bodies and serotonin are contained according to standard items dopamine and serotonin identical test method Amount is measured, differential pulse voltammetry voltammogram such as Fig. 5.It as seen from the figure, can quick, spirit using combination electrode provided in this embodiment Quick is detected the content of dopamine and serotonin in rat body.
Embodiment 2
The present embodiment provides a kind of PDDA-Gr hybridized nanometers decorative material, which includes polydiene dimethylamine Ammonium chloride and reduced graphene Gr.
The decorative material is prepared via a method which to obtain:
1)By graphene oxide(GO)Dispersion liquid(0.5 mg/mL(500 mL)), PDDA(2.5 mL(20 wt%))And hydrazine hydrate (1.56 mL(80 wt%))In water, 90 ~ 100 DEG C are heated to, is stirred to react, the modification of product PDDA-Gr hybridized nanometers is obtained Material;
2)By step 1)The centrifugation of hybridized nanometer decorative material, washing remove unreacted PDDA and hydrazine hydrate;
3)By step 2)Sediment after centrifugation is dried;
4)By step 3)Dried object be dispersed to again in solution for use.
Using PDDA-Gr provided in this embodiment as decorative material, Pt electrodes can be prepared one as basal electrode Kind modified electrode, specific preparation process are as follows:
Clip one section Pt(3 cm long, 200 μ m diameters), it is connect with conducting wire by way of electric welding.By the Pt bases of preparation Hearth electrode is inserted into PDDA-Gr decorative materials, impregnates 4 h, is taken out, at ambient temperature naturally dry, you can modified Pt/PDDA-Gr modified electrodes.
The concentration for controlling dopamine, changes the concentration of serotonin, using electrochemical workstation as experimental analysis instrument, respectively With Ag/AgCl for reference electrode, platinum electrode is auxiliary electrode, and Pt/PDDA-Gr provided in this embodiment is working electrode, The three-electrode system of composition;Three-electrode system is inserted into microfluidic test device(With it is consistent in embodiment 1)In;- 0.2 ~ 0.6 V(vs. Ag/AgCl)Differential pulse voltammetry voltammetric scan is carried out in potential range, records stable differential pulse voltammetry voltammogram.
Embodiment 3
The present embodiment provides a kind of PDDA- Gr hybridized nanometer decorative materials, which includes polydiene dimethylamine Ammonium chloride and reduced graphene.
The decorative material is prepared via a method which to obtain:
1)By graphene oxide(GO)Dispersion liquid(0.5 mg/mL(500 mL)), PDDA(5 mL(20 wt%))And hydrazine hydrate (2.5 mL(80 wt%))In water, 90 ~ 100 DEG C are heated to, is stirred to react, product PDDA-Gr hybridized nanometers modification material is obtained Material;
2)By step 1)The centrifugation of hybridized nanometer decorative material, washing remove unreacted PDDA and hydrazine hydrate;
3)By step 2)Sediment after centrifugation is dried;
4)By step 3)Dried object be dispersed to again in solution for use.
Using PDDA-Gr provided in this embodiment as decorative material, Pt electrodes can be prepared one as basal electrode Kind modified electrode, specific preparation process are as follows:
Clip one section Au(3 cm long, 200 μ m diameters), it is connect with conducting wire by way of electric welding.By the Au bases of preparation Hearth electrode is inserted into PDDA-Gr decorative materials, impregnates 4 h, is taken out, at ambient temperature naturally dry, you can modified Au/PDDA-Gr modified electrodes.
The concentration for controlling serotonin, changes the concentration of norepinephrine, using electrochemical workstation as experimental analysis instrument Device, respectively with Ag/AgCl for reference electrode, platinum electrode is auxiliary electrode, and Au/PDDA-Gr provided in this embodiment is work Make electrode, the three-electrode system of composition;Three-electrode system is inserted into microfluidic test device;In -0.2 ~ 0.6 V(vs. Ag/AgCl)Differential pulse voltammetry voltammetric scan is carried out in potential range, records stable differential pulse voltammetry voltammogram.
Comparative example 1
This comparative example provides a kind of PDDA-Gr hybridized nanometers decorative material, and preparation method removes graphene oxide(GO)Dispersion liquid Dosage be 0.5 mg/mL(1000 mL)Outside, remaining operation and condition are consistent with embodiment 1.
This method obtains the reduzate of graphene oxide by controlling the amount of hydrazine hydrate and PDDA(That is graphene Gr or The graphene oxide pRGO of partial reduction)To the catalytic effect of dopamine.The result shows that:The deficiency of hydrazine hydrate can cause to aoxidize stone Black alkene cannot be completely reduced into graphene Gr.The carbon paste electrode with PDDA-pRGO modifications compares simultaneously, PDDA-Gr modifications Carbon paste electrode to dopamine have better electro-chemical activity.Show that the deficiency of hydrazine hydrate can influence going back for graphene oxide Original, at the same restore product PDDA-Gr compared with the dopamine determination of PDDA-pRGO MWCNTs/CPE couples of 10 μ 0 modified, Its oxidation peak current about increases 25%(Such as Fig. 6).

Claims (10)

1. a kind of preparation method of diallyl dimethyl ammoniumchloride-graphene PDDA-Gr hybridized nanometer decorative materials, special Sign is, includes the following steps:Graphene oxide GO dispersion liquids, PDDA and hydrazine hydrate are mixed in water, at 90 ~ 100 DEG C It is stirred to react, centrifuges, washs, be drying to obtain the PDDA-Gr hybridized nanometers decorative material;The amount ratio of the PDDA and GO is 2~4:The amount ratio of 1 mL/g, the hydrazine hydrate and GO are 4 ~ 8:1 mL/g.
2. preparation method according to claim 1, which is characterized in that the amount ratio of the PDDA and GO is 3.2:1mL/g;Institute The amount ratio for stating hydrazine hydrate and GO is 6.4:1 mL/g.
3. the PDDA-Gr hybridized nanometer decorative materials that any preparation method of claim 1 ~ 2 is prepared.
4. a kind of electrode, which is characterized in that modify any PDDA-Gr hybridized nanometers of claim 1 ~ 3 on basal electrode Decorative material is up to the electrode.
5. electrode according to claim 1, which is characterized in that the basal electrode is carbon paste electrode, spun gold electrode, platinum filament electricity Pole or copper wire electrode.
6. any PDDA-Gr hybridized nanometers decorative material of claim 1 ~ 2 or any electrode of claim 4 ~ 5 are being made Application in standby electrochemical sensor.
7. applying according to claim 6, which is characterized in that the electrochemical sensor is passed for detecting monoamine nerve Matter.
8. a kind of microfluidic device, which is characterized in that including:Device body that PDMS substrates and glass are bonded, sample cell, Waste liquid pool, working electrode channel, reference electrode channel, auxiliary electrode channel, core is provided between the sample cell and waste liquid pool Piece microchannel, the chip microchannel are set to glass surface;The working electrode channel, reference electrode channel, auxiliary electrode Channel is connected with the sample cell, and working electrode, reference electrode and auxiliary electrode can be respectively arranged in it, the work It is any electrode of claim 6 ~ 7 to make electrode.
9. microfluidic device according to claim 1, which is characterized in that the depth of the chip microchannel is 15 ~ 30 μm, Width is 60 ~ 100 μm;The working electrode channel, reference electrode channel, auxiliary electrode channel diameter be 300 ~ 800 μ m;The section of the sample cell and waste liquid pool is circle, and the diameter of section of the sample cell and waste liquid pool is 0.5 ~ 3 cm.
10. the preparation method of any microfluidic device of claim 9, which is characterized in that include the following steps:
S1:Chip microchannel is etched on glass;Laser pours out work electrode channel, reference electrode channel and auxiliary electrode Channel;
S2:Sample cell and waste liquid pool are prepared on PDMS substrates;
S3:PDMS substrates and glass are bonded up to the microfluidic device.
CN201810601509.XA 2018-06-12 2018-06-12 A kind of diallyl dimethyl ammoniumchloride-graphene hybridized nanometer decorative material and its preparation method and application Pending CN108732220A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110261450A (en) * 2019-05-20 2019-09-20 安徽科技学院 It is a kind of to detect dopamine and adrenaline modified glassy carbon electrode, preparation method and application simultaneously
CN113447559A (en) * 2021-04-29 2021-09-28 苏州科技大学 Ultrathin high-stability black phosphorus nanocomposite and preparation method and application thereof
CN114778614A (en) * 2022-04-20 2022-07-22 杭州汇馨传感技术有限公司 Conductive MOF modified gas-sensitive material and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1699984A (en) * 2005-05-19 2005-11-23 复旦大学 Multiple channel micro-flow control chip, process for making same and use thereof
CN102445472A (en) * 2010-10-14 2012-05-09 北京华凯瑞微流控芯片科技有限责任公司 Microfluidic chip-based sensor and preparation method thereof
CN103808779A (en) * 2014-01-22 2014-05-21 西北师范大学 Method for detecting p-nitrophenol by using PDDA (Poly Diallyldimethylammonium) functionalized graphene modified glassy carbon electrode
CN103954673A (en) * 2014-03-25 2014-07-30 西北师范大学 Method for applying ionic liquid functionalized graphene modified electrode in detection of 5-hydroxytryptamine and dopamine
CN106744890A (en) * 2015-11-18 2017-05-31 青岛智信生物科技有限公司 The preparation method of diallyl dimethyl ammoniumchloride functionalization graphene

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1699984A (en) * 2005-05-19 2005-11-23 复旦大学 Multiple channel micro-flow control chip, process for making same and use thereof
CN102445472A (en) * 2010-10-14 2012-05-09 北京华凯瑞微流控芯片科技有限责任公司 Microfluidic chip-based sensor and preparation method thereof
CN103808779A (en) * 2014-01-22 2014-05-21 西北师范大学 Method for detecting p-nitrophenol by using PDDA (Poly Diallyldimethylammonium) functionalized graphene modified glassy carbon electrode
CN103954673A (en) * 2014-03-25 2014-07-30 西北师范大学 Method for applying ionic liquid functionalized graphene modified electrode in detection of 5-hydroxytryptamine and dopamine
CN106744890A (en) * 2015-11-18 2017-05-31 青岛智信生物科技有限公司 The preparation method of diallyl dimethyl ammoniumchloride functionalization graphene

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
QING ZHU 等: "Ultrasensitive QDs based electrochemiluminescent immunosensor fordetecting ractopamine using AuNPs and Aunanoparticles@PDDA-graphene as amplifier", 《SENSORS AND ACTUATORS B: CHEMICAL》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110261450A (en) * 2019-05-20 2019-09-20 安徽科技学院 It is a kind of to detect dopamine and adrenaline modified glassy carbon electrode, preparation method and application simultaneously
CN110261450B (en) * 2019-05-20 2021-11-30 安徽科技学院 Glassy carbon electrode capable of simultaneously detecting dopamine and epinephrine modification, and preparation method and application thereof
CN113447559A (en) * 2021-04-29 2021-09-28 苏州科技大学 Ultrathin high-stability black phosphorus nanocomposite and preparation method and application thereof
CN113447559B (en) * 2021-04-29 2024-05-17 苏州科技大学 Ultrathin high-stability black phosphorus nanocomposite and preparation method and application thereof
CN114778614A (en) * 2022-04-20 2022-07-22 杭州汇馨传感技术有限公司 Conductive MOF modified gas-sensitive material and preparation method and application thereof

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