CN106841345A - A kind of preparation of glass-carbon electrode of the MOF templates without enzyme superoxide anion electrochemical sensor and its modification - Google Patents
A kind of preparation of glass-carbon electrode of the MOF templates without enzyme superoxide anion electrochemical sensor and its modification Download PDFInfo
- Publication number
- CN106841345A CN106841345A CN201710222485.2A CN201710222485A CN106841345A CN 106841345 A CN106841345 A CN 106841345A CN 201710222485 A CN201710222485 A CN 201710222485A CN 106841345 A CN106841345 A CN 106841345A
- Authority
- CN
- China
- Prior art keywords
- mwcnts
- mof
- electrode
- preparation
- templates
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Abstract
The invention provides a kind of new preparation method of the MOF templates without enzyme superoxide anion electrochemical sensor, the metal-organic framework material with metal node as cobalt nanometer particle（MOF）With CNT（MWCNTs）It is precursor, it is carbonized and is further aoxidized, a kind of little particle nano-particle Co is obtained3O4@C MWCNTs composites, are configured to solution drop coating in glassy carbon electrode surface, obtained modified electrode by material（Co3O4@C‑MWCNTs/GCE）To O2•−Have good electrochemical response, with the range of linearity it is wide, sensitivity is high, the response time is short, stability and it is reproducible the features such as, there is great potential value in life pathological analysis, and be expected to be applied to and O2•−Relevant medical conditions diagnosis.
Description
Technical field
The present invention relates to one kind without enzyme superoxide anion electrochemical sensor material, more particularly to a kind of MOF（Metal is organic
Framework material）Preparation method of the template without enzyme superoxide anion electrochemical sensor；The present invention also relates to electrochemistry biography
The preparation method of the glass-carbon electrode of sensor modification, for superoxide anion in living cells（O2•−）Electrochemical Detection, belong to electricity
Field of chemical detection and physiology and field of pathological research.
Background technology
Active oxygen (ROS) is important endocellular signal molecule, is mainly used in regulation DNA damage, protein synthesis, cell
Apoptosis etc..Wherein, superoxide anion (O2•−) as one of most important and most active ROS, take part in many physiology and pathology
Process, can cause to damage to biologic-organ.In recent years, O2•−Relation between concentration and human health causes greatly concern.From
The angle of vivo applications, it is desirable to O2•−The dynamic detection range of linearity it is wide, not only mM, micromolar molar concentration, very
To the molar concentration for needing to extend to nanomole rank.At the same time, due to O2•−It is extremely unstable, it is easy to decay for other are lived
Property oxygen unit.Therefore, it is still a difficult point to set up efficient, reliable method for qualitative and quantitative detection.
Electrochemical method is because its easy to use, inexpensive, reliability is high, sensitivity is high, selectivity good, detection limit is low
Receive significant attention.It is by copper-carbon composite (Cu-Zn SOD that research is relatively broad）It is fixed on electrode surface structure
Build enzyme sensor.However, because the activated centre of enzyme is covered by surface protein, causing electron transmission difficult.Additionally, the valency of enzyme
Lattice are expensive, and easily inactivation, higher to environmental requirement, and enzyme electrode is prepared relatively complicated and is difficult storage, and these deficiencies are all significantly
Limit the development of enzyme sensor.Therefore, develop and just seem particularly heavy without enzyme superoxide anion sensor with low test limit
Will.
With the development of nanometer technology, nano material especially noble metal and metal oxide are improving sensor performance
Aspect plays vital effect.Noble metal and metal oxide can reduce O due to it2•−Overpotential on bare electrode,
Therefore can be catalyzed O instead of enzyme well in electrochemical sensor2•−, thus it is widely used in O2•−The structure of sensor.
Co3O4There is good electro catalytic activity for the oxidation of active oxygen, so as to by extensive concern and application.However, O2•−Sensor
Catalytic performance and Co3O4The size of nano-particle, shape, crystallinity and distribution situation have close relationship.Therefore, select
A kind of suitable Co3O4Synthetic method is extremely important.
The content of the invention
It is an object of the invention to provide a kind of preparation side without enzyme superoxide anion electrochemical sensor based on MOF templates
Method；
It is another object of the present invention to it is a kind of based on above-mentioned electrochemical sensor modification glass-carbon electrode preparation method, mainly
For to the O in living cells2•−Detected.
First, preparation of the MOF templates without enzyme superoxide anion electrochemical sensor
Metal-organic framework material and CNT of the present invention with metal node as cobalt nanometer particle（MWCNTs）It is precursor,
It is carbonized and is further aoxidized, a kind of little particle cobaltosic oxide nanoparticles Co is obtained3O4@C-MWCNTs are combined
Material.Its specific preparation technology is as follows：
（1）The preparation of MOF-MWCNTs composites：By cabaltous nitrate hexahydrate, benzimidazole and multi-walled carbon nano-tubes ultrasound point
Dissipate in dimethylformamide, be heated to 100 ~ 130 DEG C with the speed of 3 ~ 5 DEG C/min and keep 24 ~ 36h, afterwards with 0.2
~ 0.4 DEG C/min is down to room temperature, the gray purple crystal for obtaining, centrifugation, washing, and vacuum drying obtains MOF-MWCNTs composites；
Cabaltous nitrate hexahydrate is 1 with the mass ratio of benzimidazole:0.8~1:1；The consumption of CNT is cabaltous nitrate hexahydrate and benzo
The 5 ~ 50% of imidazoles gross mass.
（2）Co3O4The synthesis of@C-MWCNTs composites：The MOF-MWCNTs composites of above-mentioned preparation are placed in tubular type
In stove, 500 ~ 700 DEG C and 1.5 ~ 2h of constant temperature are heated to the speed of 1 ~ 3 DEG C/min under argon gas protection, are subsequently reduced to room temperature, obtained
Black powder；Black powder continue in tube furnace with the speed of 1 ~ 2 DEG C/min be heated to 200 ~ 250 DEG C and constant temperature 60 ~
90min, is subsequently reduced to room temperature, obtains Co3O4@C-MWCNTs composites.
2nd, the preparation of modified electrode and chemical property
1st, the preparation of modified electrode
（1）Pretreatment of glassy carbon electrode：The glass-carbon electrode insertion of cleaned treatment is contained into 1.0mM potassium ferricyanide probe molecules
In 0.1M potassium chloride electrolyte solutions, and use with glass-carbon electrode as working electrode, platinum post is to be to electrode, saturated calomel electrode
The three-electrode system of reference electrode composition is circulated voltammetric scan；Electrode redistilled water is taken out to rinse and dry up.
The process conditions of cyclic voltammetry scan are：Sweep speed：50mV/s, scanning electrochemical window is set to -0.8V ~ 0.2V, scans
The number of turns is 3 ~ 4 circles.
（2）Co3O4The preparation of@C-MWCNTs modified electrodes：By Co3O4@C-MWCNTs composites are dissolved in water with ethanol
In mixed liquor, be made into the dispersion liquid of 0.2 ~ 1.0mg/mL, then drop coating on the above-mentioned glass-carbon electrode handled well, drying at room temperature,
Co is obtained3O4@C-MWCNTs modified glassy carbon electrodes.
In the mixed liquor of water and ethanol, the volume ratio of the two is 1:0.5~1:2.
2nd, the electrochemical property test of modified electrode
With Co3O4@C-MWCNTs modified electrodes be working electrode, platinum post be to electrode, saturated calomel electrode be reference electrode group
Into three-electrode system, its common immersion is contained into 1.0mM O2•−N2In the PBS of the 0.2M pH=7.0 of saturation
It is circulated voltammetric scan.Electrochemical Characterization result shows（Fig. 3）, Co3O4@C-MWCNTs/GCE are to O2•−It is also original substantially
Electrocatalysis, the Co with MOF as templated synthesis3O4@C-MWCNTs composites, not only effectively raise modified electrode
Electric conductivity, improve Co3O4The large scale and agglomeration of nano-particle, in addition, the composite has big specific surface area
And meso-hole structure, it is the O in fast Acquisition solution2•−Offer condition, further improves O2Electrochemistry on modified electrode is rung
Should.
The present invention has advantages below relative to prior art：
1st, the present invention using MOF for template is constructed a kind of new Co3O4@C-MWCNTs are without enzyme O2•−Sensor, compared to biography
System enzyme sensor, the sensor is prepared simply, and easy to operate, low cost can for a long time be preserved and used；
2nd, modified electrode of the invention is to O2−There are overdelicate electrochemical response, the range of linearity wide：5.00 × 10-12~
1.00 × 10-4Mol/L, low test limit：1.67 × 10-12Mol/L, and the advantages of good stability and repeatability,
There is great potential value in life pathological analysis, and be expected to be applied to and O2•−Relevant medical conditions diagnosis.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of different materials prepared by the present invention（TEM）.Wherein, A：MOF；B：Co3O4@C composite woods
Material；C、D：Co3O4@C-MWCNTs composites.
Fig. 2 is the scanning electron microscope (SEM) photograph of different materials prepared by the present invention（SEM）.Wherein, A：MOF；B：MWCNTs；C：
Co3O4@C composites；D：Co3O4(illustration is Co to@C-MWCNTs composite Co3O4@C-MWCNTs composites3O4Grain
Degree distribution map).E schemes and F schemes to be respectively the X-ray diffractogram of MWCNTs and Co3O4@C-MWCNTs composites（XRD）And drawing
Graceful spectrogram（Raman）.
Fig. 3 is a:Bare electrode；b: Co3O4@C-MWCNTs/GCE are in the O containing 1.0mM2•−N2The 0.2M PBS of saturation
（pH=7.0）In cyclic voltammetry curve.C is Co3O4@C-MWCNTs/GCE are without O2•−N2The 0.2M PBS of saturation（pH=
7.0）In cyclic voltammetry curve.
Fig. 4 is Co3O4Os of the@C-MWCNTs/GCE to various concentrations2•−The linear sweep voltammetry curve map of detection（Fig. 4 A,
4C）And O2•−Reduction peak current and its concentration between linear relationship chart（Fig. 4 B, 4D）.
Fig. 5 is Co3O4@C-MWCNTs/GCE are containing 1 × 105Individual mouse adrenal pheochromocytoma（PC12）Physiology PBS
The O that PC12 is discharged is detected in cushioning liquid under different situations2•−Chronoa mperometric plot figure.
Specific embodiment
Specific embodiment of the invention is further described below in conjunction with the accompanying drawings.
Instrument and medicine：CHI 660C electrochemical workstations（Shanghai Chen Hua instrument company）For being circulated volt-ampere, line
Property scanning volt-ampere, the experiment of chrono-amperometric, the automatic dual pure water distiller of quartz ampoule heated type（1810B, Shanghai Asia-Pacific technology glass
Glass company）For steaming ultra-pure water.Electronic balance（Beijing Sai Duolisi Instrument Ltd.）, for weighing medicine.Ultrasonic wave is clear
Wash device（Kunshan Ultrasonic Instruments Co., Ltd.）.Alundum (Al2O3) polishing powder（0.30 μm, 0.05 μm, Shanghai Chen Hua instrument reagent
Company）For processing glass-carbon electrode.Saturated calomel reference electrode, platinum is to electrode, potassium chloride, sodium chloride, sodium dihydrogen phosphate（Xi'an
Chemical reagent factory）；Multi-walled carbon nano-tubes（Shenzhen nanometer port Co., Ltd）；Benzimidazole, cabaltous nitrate hexahydrate, potassium superoxide
（Aladdin reagent）；Dimethyl sulfoxide (DMSO), N,N-dimethylformamide（Beijing chemical reagent factory）；18- crown ethers -6,4A type molecules
Sieve（Shanghai energy chemistry Co., Ltd）；Superoxide dismutase, 12- myristic acid -13- acetic acid phorbol, zymosan A, 3-
[3- (courage amido propyl) Dimethyl Ammonium] -1- propane sulfonic acid inner salts（U.S.'s Sigma-Aldrich）.
Embodiment 1, Co3O4The preparation of@C-MWCNTs electrochemical sensor materials
A. the preparation of MOF-MWCNTs composites：By 0.84g cabaltous nitrate hexahydrates, 0.68g benzimidazoles, different quality
CNT（5,10,20,30,40,50 wt% cabaltous nitrate hexahydrates and benzimidazole gross mass）, it is dispersed in and contains 72mL bis-
In the 100mL glass flasks of NMF, ultrasonic 1h is uniformly dispersed.Flask is placed in baking oven, is added with the speed of 5 DEG C/min
Heat is to 130 DEG C and keeps 36h, is down to room temperature with 0.4 DEG C/min afterwards, the gray purple crystal for obtaining, 1200rmp centrifugations, diformazan
Base formamide is washed 4 times, 60 DEG C of vacuum drying.
b. Co3O4The synthesis of@C-MWCNTs composites：MOF-MWCNTs composites prepared by step a are placed in pipe
In formula stove, argon gas protection 1h（Flow velocity is 30mL/h）.Afterwards with the heating rate of 3 DEG C/min to 700 DEG C and constant temperature 2h, with
After be down to room temperature, obtain black powder.And then black powder is continued to be heated to 250 with the speed of 1 DEG C/min in tube furnace
DEG C and constant temperature 90min, be subsequently reduced to room temperature, obtain Co3O4@C-MWCNTs composites.
Comparative example：
A. the synthesis of MOF：0.84g cabaltous nitrate hexahydrates and 0.68g benzimidazoles are dispersed in and contain 72mL dimethyl methyls
In the 100mL glass flasks of acid amides, ultrasonic disperse is uniform.Flask is placed in baking oven, 130 are heated to the speed of 5 DEG C/min
DEG C and keep 36h, room temperature is down to 0.4 DEG C/min afterwards, the purple crystals for obtaining, 1200rmp centrifugations, dimethylformamide washes
4 times, 60 DEG C of vacuum drying.
Co3O4The synthesis of@C：MOF is placed in tube furnace, argon gas protection 1h（Flow velocity is 30mL/h）.Afterwards with 3 DEG C/min
Heating rate to 700 DEG C and constant temperature 2h, be subsequently reduced to room temperature, obtain black powder.And then black powder is continued
250 DEG C and constant temperature 90min are heated to the speed of 1 DEG C/min in tube furnace, room temperature is subsequently reduced to, Co is obtained3O4@C composites
Fig. 1 is the transmission electron microscope picture TEM figures of the different materials of above-mentioned preparation.Wherein, A：MOF；B：Co3O4@C composites
TEM schemes, and figure C, D are respectively the Co of different amplification3O4The TEM figures of@C-MWCNTs composites.Can be clearly from figure A
Go out the crystal structure of MOF materials；Be can see from B figures, the carbon component part in MOF independently synthesizes graphitic carbon and carbon nanometer
Pipe, in addition, large-sized Co3O4Nano-particle is coated in remaining carbon substrate in aggregating state, and average-size is 50 ~ 60nm.From
Figure C, D can be seen that after multi-walled carbon nano-tubes is added, the Co of small size3O4Nano-particle（30~35nm）It is evenly dispersed in
On CNT tube wall, agglomeration is obviously improved.
Fig. 2 is the above-mentioned scanning electron microscope (SEM) photograph for preparing different materials（SEM）, X-ray diffractogram（XRD）And Raman spectrogram
（Raman）.Wherein, figure A and B is the ESEM structure chart of MOF and MWCNTs, knows that MOF is with corner angle from figure A, B
Polygonal crystal structure, highdensity MWCNTs closely weave ins in a tubular form.Figure C is Co3O4@C nano composites
SEM schemes, and figure D is Co3O4@C-MWCNTs composites（SEM）, the two is compared, it will be seen that when addition multi-wall carbon nano-tube
Guan Hou, Co3O4Large scale agglomeration disappear, the Co of small size3O4Nano-particle is securely attached on CNT, and
The mesoporous framework structure of MOF itself can be kept without caving in.Illustration in D is Co3O4The particle size distribution figure of nano-particle, by inserting
Figure understands Co3O4The particle diameter of nano-particle is about 30nm, and this result is consistent with described in TEM.Figure E is MWCNTs（a）And Co3O4@
C-MWCNTs（b）X-ray diffractogram（XRD）, 2 θ=22 ~ 25 ° and the two of 41 ° peaks correspond respectively to MWCNTs in curve a
(002), (101) crystal face.In curve b in addition to two crystal face peaks with CNT, remaining characteristic peak once corresponds to
Co3O4(111) of nano-particle, (220), (311), (222), (400), (422), (511), (440), (533) and (622) are brilliant
Face.Figure F is MWCNTs（a）And Co3O4@C-MWCNTs（b）Raman spectrogram（Raman）, wherein 1348cm-1The D peaks at place and
1598cm-1The G peaks at place are the significant peaks of carbon material.D peaks correspond to the sp of fault location on carbon material3Hydbridized carbon atoms, and G peaks
Corresponding to sp on carbon material2The plane carbon atom of hydridization.The strength ratio at D peaks and G peaks in our conventional Raman spectrums（ID/IG）Table
Show the defect concentration of carbon material.Such as scheme F, the ID/IG of b curves is 1.60, and a curves ID/IG is 1.21, this further demonstrates
Co3O4@C-MWCNTs have more faults of construction and meso pore characteristics.Additionally, 483.4cm on b curves-1And 696.0cm-1's
Two peaks are respectively the vibration peak of O and Co, and with reference to figure E, these results prove that final material is successfully prepared, and purity is very high.
To adding different quality CNT to do electric current optimization for the performance impact of electrochemical sensor, it is found that carbon
It is best to superoxide anion response performance when the quality of nanotube is the 30% of cabaltous nitrate hexahydrate and benzimidazole gross mass.
The preparation and application of the glass-carbon electrode of embodiment 2, electrochemical sensor modification
A. pretreatment of glassy carbon electrode.Glass-carbon electrode is polished to mirror with the alundum (Al2O3) suspension of 0.30 μm, 0.05 μm successively
Face, then successively after ethanol, redistilled water ultrasonic cleaning that volume fraction is 95 %, the glass-carbon electrode after being processed；Insert
In entering the 0.1M potassium chloride electrolyte solutions containing 1.0mM potassium ferricyanide probe molecules, and it is work electricity to use with glass-carbon electrode
Pole, platinum post are to electrode, saturated calomel electrode for the three-electrode system of reference electrode is circulated voltammetric scan, to naked glass carbon electricity
Pole is characterized；Electrode taking-up redistilled water is rinsed and dried up again, it is standby.
B. Co is prepared3O4@C-MWCNTs modified electrodes.The Co that embodiment 1 is obtained3O4@C-MWCNTs are dissolved in water and second
In the mixed liquor of alcohol（v:v=1:1）, it is made into 1.0mg.mL-1Dispersion liquid；Taking the dispersant liquid drop of 6 μ L, to be coated in a diameter of 3mm above-mentioned
On the glass-carbon electrode handled well, dry at room temperature, obtain Co3O4@C-MWCNTs modified glassy carbon electrodes.
C use step b gained modified electrode be working electrode, platinum post be to electrode, saturated calomel electrode be reference electrode
Composition three-electrode system（Sweep speed：50mV/s, electrochemical window is set to -0.8V ~ 0.2V.）, modified electrode is obtained to O2•−Electrochemistry
Response.
Fig. 3 is a:Bare electrode；b: Co3O4@C-MWCNTs/GCE are in the O containing 1.0mM2•−N2The 0.2M PBS of saturation
（pH=7.0）In cyclic voltammetry curve.C is Co3O4@C-MWCNTs/GCE are without O2•−N2The 0.2M PBS of saturation（pH=
7.0）In cyclic voltammetry curve.Can be obtained by Fig. 3：Compared to bare electrode, O2•−In Co3O4Reduction peak on@C-MWCNTs/GCE
Current potential there occurs and slightly shuffle, and reduction peak current significantly increases, and this shows Co3O4@C-MWCNTs/GCE are to O2•−Reduction
There is obvious electrocatalysis, this is mainly due to cobaltosic oxide nanoparticles to O2•−Also original very strong catalytic performance.
Co with MOF as templated synthesis3O4@C-MWCNTs composites, not only effectively raise the electric conductivity of modified electrode, improve
Co3O4The large scale and agglomeration of nano-particle, in addition, the composite has big specific surface area and meso-hole structure, be
O in fast Acquisition solution2•−Offer condition, further improves O2Electrochemical response on modified electrode.
Fig. 4 is Co3O4Os of the@C-MWCNTs/GCE to various concentrations2•−The chronoa mperometric plot figure of detection（A、C）、O2•−'s
The linear relationship chart of reduction peak current and its concentration（B、D）.As seen from the figure, the non-constant width of this linear sensor scope, reaches 9 numbers
Magnitude, we map with concentration as abscissa by ordinate of current value, it is found that overall two sections of presentation is linear, wherein, low concentration
In the range of electric current and lg [concentration] it is linear, electric current is directly linear with concentration in high concentration range.To O2•−The linear model of detection
Enclose is 5 × 10-12~3 × 10-6 mol/L、3×10-6~1×10-4Mol/L, detection is limited to 1.67 × 10-12 mol/L.This
Invention and other O2•−Sensor is compared（Table 1）, detection range is wide, and test limit is low, and detection process is simple, and sensitivity is high, quick letter
Just.
Table 1 is for of the invention with existing O2•−Sensor is to O2•−Detect the comparing of performance：
| Electrode | The range of linearity (μM) | Test limit (nM) |
| SOD/ sodium alginates/glass-carbon electrode | 0.4-229.9 | 230 |
| Poroid platinum-palladium/the screen printing electrodes of SOD/ | 16-536 | 130 |
| SOD/ platinum-palladiums/multi-walled carbon nano-tubes/screen printing electrode | 40-1550 | 710 |
| Zinc oxide/SOD/ indium-tin oxide electrodes | 0.12-250 | 100 |
| Diallyl dimethyl ammoniumchloride/multi-walled carbon nano-tubes-platinum/glass-carbon electrode | 0.7 -3000 | 100 |
| Nano silver grain/Cys-multi-walled carbon nano-tubes/glass-carbon electrode | ||
| Cobaltosic oxide@carbon substrates-multi-walled carbon nano-tubes/glass-carbon electrode |
3、Co3O4@C-MWCNTs/GCE are to superoxide anion in living cells（O2•−）Electrochemical Detection
A. mouse adrenal pheochromocytoma (PC12) is cultivated 24 hours in 37 DEG C of DMEM culture mediums of constant temperature that humidity is 95%, should
The main component of culture medium includes：10% heat-inactivated hyclone, the penicillin of 100U/mL, the streptomysin of 100mg/mL, 5%
CO2.The culture medium of cultured PC12 cells is removed, is washed with PBS three times, 3mL phosphate is added afterwards
Cushioning liquid is in cell to be measured.PC12 cell numbers are about 1 × 105Individual/orifice plate.
B. by above-mentioned three-electrode system, immersion contains mouse adrenal pheochromocytoma jointly（PC12）0.2M PBS（pH=
7.4）, stimulate PC12 to discharge O using three kinds of different stimulants of same concentration2•−（12- myristic acid -13- acetic acid phorbol（PMA）、
Zymosan A（Zymosan A）, 3- [3- (courage amido propyl) Dimethyl Ammonium] -1- propane sulfonic acid inner salts（CHAPS））, and use timing
Current method carries out detection and selects optimal stimulant, and then obtains modified electrode to O2•−Chronoa mperometric plot.
C. using the mapping of origin softwares, plot step cyclic voltammetry curve, chronoa mperometric plot and O2•−Peak current
With the linear relationship chart between its log concentration, concentration.
Fig. 5 shows Co3O4@C-MWCNTs/GCE are containing 1.5 × 105Individual mouse adrenal pheochromocytoma（PC12）'s
0.2M PBS（PH=7.4）The O that PC12 is discharged is detected under middle different situations2•−Chronoa mperometric plot figure.Figure A is to compare with dense
The different stimulant of three kinds of degree stimulates PC12 to discharge O2•−The chronoa mperometric plot figure of situation（12- myristic acid -13- acetic acid phorbol
（PMA）, zymosan A（Zymosan A）, 3- [3- (courage amido propyl) Dimethyl Ammonium] -1- propane sulfonic acid inner salts（CHAPS））.By
Figure understands, in the case where stimulant concentration is certain, PMA stimulates lower PC12 releases O2•−Current-responsive is maximum, therefore present invention choosing
PMA is selected for optimal stimulant is tested.From scheming B, as the dropwise addition 5mg/mL PMA in blank PBS（Curve a）Or do not pierce
Sharp PC12（Curve b）When, without obvious curent change produce, and curve b steady-state current apparently higher than curve a, this may
Because overdelicate modified electrode can detect the ROS produced by PC12 itself.Stimulate when 5mg/mL PMA are continuously added to
During PC12, current-responsive substantially increases（Curve c）.This explanation PC12 can discharge substantial amounts of O under stimulation in the short time2•−.For
Confirmation increased current-responsive is the O that the PC12 by stimulating is discharged2•−Cause, we add at curve c 200s
The enzyme-specific of 300U/mL superoxide anions（SOD）, now response current significantly reduce to baseline, this illustrates this modified electrode
The O that PC12 is discharged can be successfully be detected2•−, this is further research and O2•−Related physiology and pathology is established
Basis.
Claims (6)
1. a kind of preparation method of the MOF templates without enzyme superoxide anion electrochemical sensor, comprises the following steps that：
（1）The preparation of MOF-MWCNTs composites：By cabaltous nitrate hexahydrate, benzimidazole and CNT ultrasonic disperse in
In dimethylformamide, with the speed of 3 ~ 5 DEG C/min be heated to 100 ~ 130 DEG C and keep 24 ~ 36h, afterwards with 0.2 ~ 0.4 DEG C/
Min is down to room temperature, the gray purple crystal for obtaining, centrifugation, washing, and vacuum drying obtains MOF-MWCNTs composites；
（2）Co3O4The synthesis of@C-MWCNTs composites：The MOF-MWCNTs composites of above-mentioned preparation are placed in tube furnace
In, 500 ~ 700 DEG C and 1.5 ~ 2h of constant temperature are heated to the speed of 1 ~ 3 DEG C/min under argon gas protection, room temperature is subsequently reduced to, obtain black
Color powder；Black powder continues to be heated to 200 ~ 250 DEG C and 60 ~ 90min of constant temperature with the speed of 1 ~ 2 DEG C/min in tube furnace,
Room temperature is subsequently reduced to, Co is obtained3O4@C-MWCNTs composites.
2. preparation method of the MOF templates without enzyme superoxide anion electrochemical sensor as claimed in claim 1, it is characterised in that：
Step（1）In, cabaltous nitrate hexahydrate is 1 with the mass ratio of benzimidazole:0.8~1:1.
3. preparation method of the MOF templates without enzyme superoxide anion electrochemical sensor as claimed in claim 1, it is characterised in that：
Step（1）In, the consumption of CNT is the 5 ~ 50% of cabaltous nitrate hexahydrate and benzimidazole gross mass.
4. preparation method of the MOF templates without enzyme superoxide anion electrochemical sensor as claimed in claim 1, it is characterised in that：
Step（2）In, in the mixed liquor of water and ethanol, the volume ratio of the two is 1:0.5~1:2.
5. the glass carbon electricity that the MOF templates that prepared by method as claimed in claim 1 are modified without enzyme superoxide anion electrochemical sensor
The preparation method of pole, it is characterised in that：The glass-carbon electrode insertion that will be cleaned by ultrasonic contains 1.0mM potassium ferricyanide probe molecules
In 0.1M potassium chloride electrolyte solutions, and use with glass-carbon electrode as working electrode, platinum post is to be to electrode, saturated calomel electrode
The three-electrode system of reference electrode is circulated voltammetric scan, and electrode taking-up redistilled water is rinsed and dried up；By Co3O4@
C-MWCNTs is dissolved in the mixed liquor of water and ethanol, is made into the dispersion liquid of 0.2 ~ 1.0mg/mL, and then drop coating is handled well above-mentioned
Glass-carbon electrode on, dry at room temperature, be obtained Co3O4@C-MWCNTs modified glassy carbon electrodes.
6. Co as claimed in claim 53O4The preparation method of@C-MWCNTs modified electrodes, it is characterised in that：Cyclic voltammetry scan
Electrochemical window be set to -0.8V ~ 0.2V, sweep speed for 50mV/s, the number of turns 3 ~ 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710222485.2A CN106841345A (en) | 2017-04-07 | 2017-04-07 | A kind of preparation of glass-carbon electrode of the MOF templates without enzyme superoxide anion electrochemical sensor and its modification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710222485.2A CN106841345A (en) | 2017-04-07 | 2017-04-07 | A kind of preparation of glass-carbon electrode of the MOF templates without enzyme superoxide anion electrochemical sensor and its modification |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106841345A true CN106841345A (en) | 2017-06-13 |
Family
ID=59148275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710222485.2A Pending CN106841345A (en) | 2017-04-07 | 2017-04-07 | A kind of preparation of glass-carbon electrode of the MOF templates without enzyme superoxide anion electrochemical sensor and its modification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106841345A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108627558A (en) * | 2018-05-11 | 2018-10-09 | 西北师范大学 | A kind of preparation and application of N doping cotton carbon fiber modified electrode |
| CN109616333A (en) * | 2018-12-07 | 2019-04-12 | 武汉工程大学 | A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite material and preparation method thereof |
| CN110195052A (en) * | 2019-05-31 | 2019-09-03 | 浙江工业大学 | A kind of photosynthetic bacteria immobilization particle and the preparation method and application thereof |
| CN110400702A (en) * | 2019-04-15 | 2019-11-01 | 南京工业大学 | The composite material of a kind of extra small titanium dioxide granule and carbon and its application |
| CN111579620A (en) * | 2020-05-19 | 2020-08-25 | 西北师范大学 | Silver-based MOF (Metal organic framework) derivative nanomaterial, preparation of modified electrode of silver-based MOF derivative nanomaterial and application of silver-based MOF derivative nanomaterial as superoxide anion electrochemical sensor |
| CN112748169A (en) * | 2020-12-24 | 2021-05-04 | 西南大学 | Preparation method of nano-particle bionic enzyme sensitive element, product and application thereof |
| CN113578324A (en) * | 2021-07-20 | 2021-11-02 | 上海勘测设计研究院有限公司 | Composite mesoporous catalytic material for treating organic pollutants in water body and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150129426A1 (en) * | 2012-06-05 | 2015-05-14 | Middle Tennessee State University | Electrochemical sensing nanocomposite |
| US20150231622A1 (en) * | 2012-09-20 | 2015-08-20 | Kyoto University | Metal nanoparticle complex and method for producing same |
| WO2015144695A1 (en) * | 2014-03-27 | 2015-10-01 | Basf Se | Porous films comprising metal-organic framework materials |
| CN105806924A (en) * | 2016-05-10 | 2016-07-27 | 西北师范大学 | 8-OHdG sensor as well as preparation method and application thereof |
| CN105954336A (en) * | 2016-05-05 | 2016-09-21 | 西北师范大学 | Enzyme-free superoxide anion electrochemical sensor, and production method and application thereof |
| CN106290511A (en) * | 2016-08-16 | 2017-01-04 | 哈尔滨工业大学 | A kind of preparation method of enzyme-free glucose electrochemical sensor |
-
2017
- 2017-04-07 CN CN201710222485.2A patent/CN106841345A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150129426A1 (en) * | 2012-06-05 | 2015-05-14 | Middle Tennessee State University | Electrochemical sensing nanocomposite |
| US20150231622A1 (en) * | 2012-09-20 | 2015-08-20 | Kyoto University | Metal nanoparticle complex and method for producing same |
| WO2015144695A1 (en) * | 2014-03-27 | 2015-10-01 | Basf Se | Porous films comprising metal-organic framework materials |
| CN105954336A (en) * | 2016-05-05 | 2016-09-21 | 西北师范大学 | Enzyme-free superoxide anion electrochemical sensor, and production method and application thereof |
| CN105806924A (en) * | 2016-05-10 | 2016-07-27 | 西北师范大学 | 8-OHdG sensor as well as preparation method and application thereof |
| CN106290511A (en) * | 2016-08-16 | 2017-01-04 | 哈尔滨工业大学 | A kind of preparation method of enzyme-free glucose electrochemical sensor |
Non-Patent Citations (1)
| Title |
|---|
| XINZHE LI 等: "MOF derived Co3O4 nanoparticles embedded in Ndoped mesoporous carbon layer/MWCNT hybrids: extraordinary bi-functional electrocatalysts for OER and ORR", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108627558A (en) * | 2018-05-11 | 2018-10-09 | 西北师范大学 | A kind of preparation and application of N doping cotton carbon fiber modified electrode |
| CN109616333A (en) * | 2018-12-07 | 2019-04-12 | 武汉工程大学 | A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite material and preparation method thereof |
| CN110400702A (en) * | 2019-04-15 | 2019-11-01 | 南京工业大学 | The composite material of a kind of extra small titanium dioxide granule and carbon and its application |
| CN110195052A (en) * | 2019-05-31 | 2019-09-03 | 浙江工业大学 | A kind of photosynthetic bacteria immobilization particle and the preparation method and application thereof |
| CN110195052B (en) * | 2019-05-31 | 2021-04-06 | 浙江工业大学 | Photosynthetic bacteria immobilized particle and preparation method and application thereof |
| CN111579620A (en) * | 2020-05-19 | 2020-08-25 | 西北师范大学 | Silver-based MOF (Metal organic framework) derivative nanomaterial, preparation of modified electrode of silver-based MOF derivative nanomaterial and application of silver-based MOF derivative nanomaterial as superoxide anion electrochemical sensor |
| CN112748169A (en) * | 2020-12-24 | 2021-05-04 | 西南大学 | Preparation method of nano-particle bionic enzyme sensitive element, product and application thereof |
| CN113578324A (en) * | 2021-07-20 | 2021-11-02 | 上海勘测设计研究院有限公司 | Composite mesoporous catalytic material for treating organic pollutants in water body and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106841345A (en) | A kind of preparation of glass-carbon electrode of the MOF templates without enzyme superoxide anion electrochemical sensor and its modification | |
| Kang et al. | Glucose biosensors based on platinum nanoparticles-deposited carbon nanotubes in sol–gel chitosan/silica hybrid | |
| Tang et al. | Amperometric glucose biosensor based on adsorption of glucose oxidase at platinum nanoparticle-modified carbon nanotube electrode | |
| Joshi et al. | Mesoporous nitrogen containing carbon materials for the simultaneous detection of ascorbic acid, dopamine and uric acid | |
| Zhang et al. | A highly sensitive nonenzymatic glucose sensor based on CuO nanowires | |
| Ensafi et al. | A new non-enzymatic glucose sensor based on copper/porous silicon nanocomposite | |
| Wang et al. | Direct Electrochemistry of catalase at a gold electrode modified with single‐wall carbon nanotubes | |
| Bai et al. | Enzyme-free glucose sensor based on a three-dimensional gold film electrode | |
| Zhang et al. | A novel electrochemical sensor for formaldehyde based on palladium nanowire arrays electrode in alkaline media | |
| Du et al. | Nonenzymatic uric acid electrochemical sensor based on graphene-modified carbon fiber electrode | |
| Teymourian et al. | Electrocatalytic oxidation of NADH at electrogenerated NAD+ oxidation product immobilized onto multiwalled carbon nanotubes/ionic liquid nanocomposite: application to ethanol biosensing | |
| Ni et al. | In-situ growth of Co 3 O 4 nanoparticles on mesoporous carbon nanofibers: a new nanocomposite for nonenzymatic amperometric sensing of H 2 O 2 | |
| Shen et al. | Manganese phosphate self-assembled nanoparticle surface and its application for superoxide anion detection | |
| Wang et al. | A copper-based metal–organic framework/graphene nanocomposite for the sensitive and stable electrochemical detection of DNA bases | |
| Salimi et al. | Carbon Nanotubes‐Ionic Liquid and Chloropromazine Modified Electrode for Determination of NADH and Fabrication of Ethanol Biosensor | |
| CN103323516A (en) | Method for preparing non-enzyme H2O2 sensor based on ionic liquid functionalized carbon nanotube and silver nanometer compound | |
| Tang et al. | Pt-dispersed flower-like carbon nanosheet aggregation for low-overpotential electrochemical biosensing | |
| Tian et al. | Amperometric detection of glucose based on immobilizing glucose oxidase on g-C3N4 nanosheets | |
| Kun et al. | Electrochemical behavior of propranolol hydrochloride in neutral solution on platinum nanoparticles doped multi-walled carbon nanotubes modified glassy carbon electrode | |
| Yu et al. | Nonenzymatic sensing of glucose using a carbon ceramic electrode modified with a composite film made from copper oxide, overoxidized polypyrrole and multi-walled carbon nanotubes | |
| Du et al. | A nanocomposite-based electrochemical sensor for non-enzymatic detection of hydrogen peroxide | |
| Hao et al. | A mediator-free self-powered glucose biosensor based on a hybrid glucose/MnO 2 enzymatic biofuel cell | |
| Fu et al. | Highly sensitive nonenzymatic glucose sensor based on reduced graphene oxide/ultrasmall Pt nanowire nanocomposites | |
| CN113340958A (en) | Working electrode of high-sensitivity quercetin electrochemical sensor and application thereof | |
| Wu et al. | Electroanalytical application of graphite nanofibers paste electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170613 |