CN110161101A - A kind of adrenaline detection method and sensor based on complex film modified electrode - Google Patents
A kind of adrenaline detection method and sensor based on complex film modified electrode Download PDFInfo
- Publication number
- CN110161101A CN110161101A CN201910490391.2A CN201910490391A CN110161101A CN 110161101 A CN110161101 A CN 110161101A CN 201910490391 A CN201910490391 A CN 201910490391A CN 110161101 A CN110161101 A CN 110161101A
- Authority
- CN
- China
- Prior art keywords
- mwcnts
- gqds
- electrode
- nfs
- adrenaline
- 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.)
- Withdrawn
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
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
-
- 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
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Nanotechnology (AREA)
- Engineering & Computer Science (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
Adrenaline (EP) detection method based on complex film modified electrode that the invention discloses a kind of, detected the method includes preparation Pt NFs and MWCNTs-GQDs composite nano materials, the complex film modified electrode of preparation Pt NFs/MWCNTs-GQDs/GCE and adrenaline and etc..The result shows that Pt NFs/MWCNTs-GQDs/GCE shows good electrocatalytic oxidation property to EP.In the PBS buffer solution (pH=5.5) of 0.10mol/L, there are good linear relationships for the concentration of the response peak current of the modified electrode and EP, the range of linearity is 1.0 μm of ol/L~800 μm ol/L, and detection is limited to 81nmol/L (S/N=3).The electrode has good reproducibility, stability and anti-interference ability.The electrode is used for the measurement of EP in Swine serum and pig urcine sample, the rate of recovery to be respectively 98.41%~104.28% and 97.01%~103.50%, illustrates that the electrode has potential application value in the fields such as food safety and animal husbandry healthy aquaculture.
Description
Technical field
The invention belongs to chemical/biological field of sensing technologies, and in particular on a kind of kidney based on complex film modified electrode
Parathyrine detection method and sensor.
Background technique
Adrenaline (Epinephrine, EP) be present in it is most important in mammalian central nervous system and body fluid
One of neurotransmitter, be the hormone secreted by adrenal medella sympathetic nerve endings, ceased with various physiological processes and disease breath
It is related.On clinical medicine, EP has the function of making myocardial contractive power reinforcement, increase heart rate, vasoconstriction, diastole air flue, therefore
It can be used for treating the illnesss such as sudden cardiac arrest, myocardial infarction, bronchial asthma, nasal congestion.In sports tournament, adrenaline was once
By illegal for enhancing the strength and speed of athletes, to achieve the effect that improve games results.Therefore, international committee difficult to understand
The stimulant substance of disabling can be assigned therein as.In addition, monitoring biological fluid in EP concentration measurement often facilitate spirit,
The diagnosing and treating of the diseases such as nerve and angiocarpy.The horizontal disorder that nearest some researchs have had proven to internal EP is easy to lead
Cause the illnesss such as Parkinson's disease, Alzheimer's disease, schizophrenia, Huntington disease.Therefore, establish it is a kind of quickly, it is accurate,
The method of epinephrine contents has great importance in life science and biochemical analysis field in Sensitive Detection biological fluid.
There are many methods for detecting EP, such as spectrophotometry, fluorescent spectrometry, high performance liquid chromatography, hair at present
Cons electrophoresis method, chemoluminescence method etc., that there are sample processing times is long for these methods, detection process is cumbersome, expensive equipment, is difficult to
The disadvantages of operation；However electrochemical sensor method due to it is sensitive, quick, economical, easy, be easy to be miniaturized it is excellent with array etc.
Point, it has also become the important trend of EP analysis detection.Wherein, Wierzbicka etc. is prepared for depositing high-sequential on surface
The anodic oxidation aluminium electrode of nanoporous gold thin film has very high electro catalytic activity to EP, and average catalyst rate constant is
1.027×106M-1·s-1, linear sweep voltammetry (LSV), Differential Pulse Voltammetry (DPV), chronoamperometry is respectively adopted
(chronoamperometry) EP of various concentration is measured, the electric current and concentration measured is in a linear relationship, the range of linearity
Respectively 25 μM~500 μM, 20 μM~100 μM, 25 μM~600 μM, however DPV method shows highest sensitivity
(1.13mA·cm-2·mM-1) and minimum detection limit (2.42 μM).Sochr etc. uses the boron-doped diamond without any modification
Membrane electrode studies the electrochemical behavior of EP, it is found that redox reaction that will definitely be inverse has occurred in electrode surface in EP,
It is limited to 0.21 μM using the detection that square wave voltammetry (SWV) method measures EP, and the EP in human urine is detected, the rate of recovery
It is 98%~102%.It was accordingly found that the electrochemical sensor based on nano material has become a kind of important means of detection EP,
So the nano material of development of new with more rapidly, accurate detection EP it is very necessary.
Carbon nanomaterial due to it is conductive good, stability is high, good biocompatibility the advantages that, it has also become a kind of application
Very mature electrode modified material.Wherein multi-walled carbon nanotube (MWCNTs) is by multilayer sp2The circle that the graphene film of hydridization is rolled
Cylindricality tubulose, between several nanometers to several microns, diameter is adjusted in 100nm length again, therefore is more advantageous to the transmission of electronics.
And MWCNTs has unique mechanics and electric property, and the surface easily modified is more advantageous to it and applies as carrier in electricity
Pole surface.Graphene quantum dot (GQDs) is a kind of novel zero dimension carbon nanomaterial, and diameter is in 10nm hereinafter, having very much
Excellent performance such as large specific surface area, nontoxic, chemical inertness, synthesis cost be low, good water solubility, variable band-gap energy etc.；GQDs
Surface has many oxygen-containing group such as-OH ,-COOH, it is easy to other molecules in modification.GQDs can rely on electrostatic interaction with
MWCNTs orderly combination between layers, the excellent properties for the MWCNTs that can have both played, while also having had both the property of GQDs
Energy.
Platinum nano material is widely used in fuel cell, sensor and environmental science etc. with its excellent catalytic performance
Field, therefore cause the interest of numerous researchers.There are some researches prove, the catalytic performance of platinum nano material and its pattern, size,
Being exposed to the plane on surface, to have very big relationship, especially pattern to play the role of its active site critical.Cao etc.
It is prepared for porous platinum nanocube, there is high porosity and large specific surface area, compared to non-porous nano platinum, porous platinum is received
Rice cube shows higher electrocatalytic oxidation ability to methanol and formic acid.But so far, it is based on porous platinum nano flower (Pt
NFs) electrochemical sensor of composite membrane there is no report for adrenergic detection.
Summary of the invention
The present invention is directed to overcome the deficiencies of the prior art and provide a kind of adrenaline detection based on complex film modified electrode
Method and sensor.
In order to achieve the above object, technical solution provided by the invention are as follows:
The adrenaline detection method based on complex film modified electrode includes the following steps:
(1) Pt NFs and MWCNTs-GQDs composite nano materials are prepared:
A) Pt NFs is prepared；
B) MWCNTs of preparation acidification；
C) MWCNTs by the acidification of step b) preparation is added in GQDs solution, and GQDs's is dense in the GQDs solution
Degree is 0.8mg/mL~1.2mg/mL, and the mass volume ratio of MWCNTs and the GQDs solution of the acidification is (0.01~0.015)
G:(10~15) mL, excusing from death mixing 3~7h after at 100 DEG C 3~5h of back flow reaction, obtain dark solution, will be after cooling black
Color solution 8~12min of centrifugal treating under the conditions of revolving speed is 10000rpm, removes supernatant, obtained precipitating is MWCNTs-
GQDs composite nano materials；
(2) it prepares the complex film modified electrode of Pt NFs/MWCNTs-GQDs/GCE: glassy carbon electrode surface is polished, surpass
Sound dries after cleaning, and MWCNTs-GQDs composite nano materials are carried out to the MWCNTs-GQDs dispersion liquid obtained after ultrasonic disperse
Drop coating is in glassy carbon electrode surface and dries, and obtains the glass-carbon electrode that surface is modified by MWCNTs-GQDs, and Pt NFs solution is carried out
The Pt NFs obtained after ultrasonic disperse is even, and the drop that mixes is applied on the glass-carbon electrode that surface is modified by MWCNTs-GQDs, is dried, i.e.,
Obtain the complex film modified electrode of Pt NFs/MWCNTs-GQDs/GCE；MWCNTs-GQDs in the MWCNTs-GQDs dispersion liquid
Concentration is 0.5~2.0mg/mL；The concentration of Pt NFs is 0.5~2.0mg/mL, preferably 1.0mg/ in the Pt NFs solution
mL；
(3) using the complex film modified electrode of Pt NFs/MWCNTs-GQDs/GCE as working electrode, made with silver/silver chloride electrode
Three-electrode system is constituted using platinum electrode as to electrode for reference electrode；Then it is investigated on kidney using Differential Pulse Voltammetry
Electrochemical behavior of the parathyrine on different modifying electrode, and the adrenaline of various concentration is tested, draw working stamndard
Curve, then the adrenaline in sample to be tested is detected using standard addition method.
Preferably, the Pt NFs shape is that porous spherical is flower-shaped, and globe daisy diameter is 10~30nm, preferably 20nm.
Preferably, carrying out polishing to glassy carbon electrode surface in step (2) is respectively with 0.3 μm and 0.05 μm of α-Al2O3Powder
Glassy carbon electrode surface is polished.
Preferably, glass-carbon electrode diameter described in step (2) is 3mm, and 5 μ L MWCNTs-GQDs dispersant liquid drops are applied to glass
Carbon electrodes are simultaneously dried, and the 5 even drops that mix of μ L Pt NFs are applied to the glass carbon that surface has been coated with MWCNTs-GQDs and dries
On electrode.
It preferably, is that electricity of the l-tyrosine on different modifying electrode is investigated using Differential Pulse Voltammetry in step (3)
Chemical behavior, be arranged Differential Pulse Voltammetry parameter are as follows: amplitude 0.05V, pulse width 0.2s, sampling width be 0.02, arteries and veins
Rushing the period is 0.5s, is tested the adrenaline of various concentration, draws Working calibration curve, then use standard addition method pair
Adrenaline in sample to be tested is detected.
The adrenaline detection sensor based on complex film modified electrode includes repairing as the composite membrane of working electrode
Adorn electrode；The complex film modified electrode includes glass carbon matrix (5), and glass carbon matrix (5) surface modification has acidification F-
MWCNTs-GQDs layers (6), load has NFs layers of Pt (7) in F-MWCNTs-GQDs layers of the acidification (6).
Preferably, the sensor includes glass carbon matrix (5) with a thickness of 1.0~5.0mm, the acidification F-MWCNTs-
GQDs layers (6) with a thickness of 20~200nm, Pt NFs layers (7) with a thickness of 20~200nm；Pt NFs layers (7)
In Pt NFs shape be porous spherical it is flower-shaped, globe daisy diameter be 10~30nm, preferably 20nm.
Preferably, to adrenergic concentration there are good linear relationship, the range of linearity of detection is the sensor
1.0 μm of ol/L~800 μm ol/L, detection are limited to 81nmol/L.
Pt NFs is assembled on MWCNTs-GQDs composite nano materials by the present invention by LBL self-assembly method, forms Pt
The nano combined film modified electrode of NFs/MWCNTs-GQDs/GCE.Using transmission electron microscope to the pattern of nanocomposite
It is characterized, adrenaline (EP) has been inquired into different modifying using cyclic voltammetry (CV) and Differential Pulse Voltammetry (DPV)
Electrochemical behavior on electrode.The result shows that Pt NFs/MWCNTs-GQDs/GCE shows good electrocatalytic oxidation to EP
Energy.In the PBS buffer solution (pH=5.5) of 0.10mol/L, there are good for the concentration of the response peak current of the modified electrode and EP
Good linear relationship, the range of linearity are 1.0 μm of ol/L~800 μm ol/L, and detection is limited to 81nmol/L (S/N=3).The electrode
With good reproducibility, stability and anti-interference ability.The electrode is used for the measurement of EP in Swine serum and pig urcine sample,
The rate of recovery is respectively 98.41%~104.28% and 97.01%~103.50%, illustrates the electrode in food safety and animal husbandry
There is potential application value in the fields such as healthy aquaculture.
Detailed description of the invention
Fig. 1 is the work structure diagram of the adrenaline detection sensor based on complex film modified electrode.
In Fig. 1: 1, silver/silver chloride electrode；2, platinum electrode；3, glass-carbon electrode；4, solution to be measured；5, glass carbon matrix；6,
F-MWCNTs layers of acidification；7, Pt NFs layers；8,EP.
Specific embodiment
Agents useful for same is to analyze pure (AR) in embodiment, and experimental water is ultrapure water (resistivity >=18.3M Ω
cm).In being described below, the description of amino acid is all made of english abbreviation.
One, experimentation
1, the preparation of Pt NFs
It prepares Pt NFs: firstly, taking 2.5mL ethylene glycol in the round-bottomed flask of 50mL, adding after the 5min that flows back at 170 DEG C
Enter the HCl (35wt%) of 1.7mL；Then the H of 1.5mL is added dropwise in 16min2PtCl6·H2O (0.625mol/L) and
The PVP (0.375mol/L) of 3.2mL, continues the 30min that flows back at 170 DEG C, and the color change of solution is orange-yellow-brown-
Black.It after solution is cooled to room temperature, is transferred into centrifuge tube, is centrifuged 15 min in the case where revolving speed is 8000rpm.Finally,
Supernatant is poured out, obtained black precipitate is successively washed and is centrifuged with acetone, ethyl alcohol, hexane, in 80 DEG C of vacuum drying
In case after dry 10h, obtained black solid.
2, the preparation of MWCNTs-GQDs composite nano materials
A) (V in the mixed acid of 40mL the acidification of MWCNTs: is added in the MWCNTs of 300mgThe concentrated sulfuric acid:VConcentrated nitric acid=3:1), so
Return stirring 20min in 150 DEG C of oil bath pan is placed it in afterwards.After solution is cooled to room temperature, it is transferred into centrifuge tube,
10min is centrifuged in the case where revolving speed is 10000rpm.Supernatant is poured out, lower black sediment is with milli-Q water 3 times, to remove
Excessive mixed acid and the impurity etc. for being adsorbed on the surface MWCNTs, then place the product in dry in 80 DEG C of vacuum oven
For 24 hours, finally obtained black solid product MWCNTs is ground spare；
B) MWCNTs for taking 0.013g step a) to be acidified adds in the GQDs solution of people 13mL, in the GQDs solution
The concentration of GQDs is 1mg/mL, excusing from death mixing 5h.It is then transferred in the round-bottomed flask of 50mL, flows back at 100 DEG C anti-
4h is answered, the solution of black is obtained.After solution is cooled to room temperature, by dark solution revolving speed be 10000rpm under centrifugal treating
10min removes supernatant, obtained precipitating i.e. MWCNTs-GQDs composite nano materials.
3, the preparation of the complex film modified electrode of Pt NFs/MWCNTs-GQDs/GCE
The surface GCE (glass-carbon electrode, 3mm) is used to 0.3 μm and 0.05 μm of α-Al respectively2O3Powder sanding and polishing at mirror surface, then
It is cleaned up, is dried with ultrapure water, EtOH Sonicate respectively.It is obtained after taking the MWCNTs-GQDs of 5 μ L to carry out ultrasonic disperse
MWCNTs-GQDs dispersion liquid (1.0mg/mL) drop coating on the surface GCE, then again 5 μ L of drop coating by Pt NFs solution (1.0mg/mL)
The even phase solution of Pt NFs obtained after ultrasonic disperse is carried out, is saved backup after natural drying in 4 DEG C.
4, the Electrochemical Detection of EP
Referring to Fig. 1, using CHI760B type electrochemical workstation, using the glass-carbon electrode 3 of surface modification as working electrode,
Silver/silver chlorate (including saturated potassium chloride solution) electrode 1 is used as reference electrode, and platinum electrode 2 is as three electrode bodies to electrode
System, in the PBS buffer solution that background solution is 0.10mol/L, Differential Pulse Voltammetry (DPV) parameter is arranged: amplitude is
0.05V, pulse width 0.2s, sampling width are 0.02, pulse period 0.5s.
Wherein, the glass-carbon electrode 3 of the surface modification is the adrenal gland of the present invention based on complex film modified electrode
Complex film modified electrode in plain detection sensor；The complex film modified electrode includes glass carbon matrix 5, the glass carbon matrix 5
Surface modification has acidification F-MWCNTs layer 6, and load has Pt NFs layer 7 on the acidification F-MWCNTs layer 6.
Electrochemical behavior of the EP on different modifying electrode is investigated using DPV method, and to the EP of various concentration 8 (6.000,
8.000,10.00,20.00,50.00,80.00,200.0,500.0,800.0 μm of ol/L) it is tested, draw working curve.
EP in sample to be tested 4 (Swine serum and pig urcine sample) is detected using standard addition method.Swine serum and pig urcine sample
(deriving from 5 miscellaneous piggys of living body ternary, weight is 7~15Kg) is by the Institute of Subtropical Agriculture, The Chinese Academy of Sciences (Changsha)
It provides.5 kinds of different pig anteserum samples and pig urcine sample (50.00 μ L) are added to the PBS buffer solution of pH=6.5 respectively
100 times of dilution in (4.950mL), then be added into Swine serum and pig urcine solution various concentration EP (0.100,0.200,
0.400,0.600,0.800 μm of ol/L), it is measured using DPV method.
Two, experimental result and analysis
1, the characterization of material
Using transmission electron microscope (TEM) respectively to MWCNTs, GQDs, MWCNTs-GQDs, Pt NFs, Pt NFs/
The structure and surface topography of MWCNTs-GQDs is characterized.The result shows that the tubulose of a rule, tool is presented in the surface of MWCNTs
There is bigger specific surface area.GQDs is in tiny dotted particle, uniform in size, and dispersibility is preferably.Since GQDs partial size is too small,
It is covered by MWCNTs, but its surface topography and individual MWCNTs have significant difference, it can be said that bright MWCNTs and GQDs are
Through being combined with each other.Flower-shaped in porous spherical shape on the surface of Pt NFs, diameter is in 20nm or so.Pt NFs and MWCNTs-GQD
It is combined with each other, has obtained the spherical flower-like nanometer composite material of porous structure, can not only increase specific surface area, but also be target
The absorption enrichment of object EP provides more active sites, to further increase the sensitivity of detection.
2, the Cyclic voltamogram of modified electrode
Naked GCE (a), MWCNTs-GQDs (b) and Pt NFs/MWCNTs-GQDs (c) are investigated respectively is containing 0.1mol/L
1.0mmol/L [the Fe (CN) of KCl6]4-/3-Cycle voltammetry behavior (CV) in solution.It is 50mV/s sweeping speed, scans current potential
When 0.00~0.60V, there are a pair of of redox peaks on naked GCE.After modifying MWCNTs-GQDs, redox peak current is obvious
Increase many enhancings, and spike potential generates certain negative shifting, illustrates that MWCNTs-GQDs complex carbon material has stronger lead
Electrically, to [Fe (CN)6]4-/3-There is certain catalytic action.And after MWCNTs-GQDs area load Pt NFs, redox
The increase of peak current further, this illustrates that Pt NFs has excellent electric conductivity, hence it is evident that improves [Fe (CN)6]4-/3-Oxidation is also
The delivery rate of electronics during original.Illustrate the Pt NFs/MWCNTs-GQDs composite nano materials to [Fe (CN)6]4-/3-Have
Superior electro catalytic activity.
3, electrochemical behavior of the EP in electrode surface
Naked GCE is investigated, MWCNTs-GQDs/GCE and Pt NFs/MWCNTs-GQDs/GCE is containing 6.000 × 10-4
Cyclic voltammetric voltammetric behaviors (CV) in the 0.10mol/L PBS buffer solution of the EP of mol/L, EP is in naked GCE and MWCNTs-
Without response on GQDs/GCE, there is not apparent response signal peak, illustrates EP on naked GCE and MWCNTs-GQDs/GCE
It is more difficult to be oxidated or reduced；And relative to naked GCE and MWCNTs-GQDs/GCE, EP is on Pt NFs/MWCNTs-GQDs/GCE
There is a fairly obvious oxidation peak, illustrates that Pt NFs/MWCNTs-GQDs/GCE has certain electrocatalytic oxidation to act on EP.This
Be due to Pt NFs and MWCNTs-GQDs it is compound after, increase the specific surface area of composite material, this is provided more for EP molecule
More attachment sites, while the synergistic effect of two kinds of materials is played, it is exaggerated response signal.
4, influence of the pH value to EP electrochemical behavior
DPV method is used to investigate in pH as in 4.5~7.5 PBS solution (0.10mol/L), modified electrode Pt NFs/
MWCNTs-GQDs/GCE is to EP (2.000 × 10-4Mol/L) the influence of electrocatalytic oxidation property.When pH is from 4.5 to 5.5, EP
Oxidation peak current be gradually increased with the increase of pH value；When pH increases to 7.5 from 5.5, oxidation peak current with pH increase
And it gradually reduces.As pH=5.5, the oxidation peak current of EP reaches maximum value.Therefore the PBS buffering of experimental selection pH=5.5
Best bottom liquid of the solution as detection EP.The spike potential of EP is linear with pH value, illustrates that EP was reacted in its electrode interface
There are the transfer processes of proton and electronics in journey；Its linear fit equation is Epa=-0.0539pH+0.5310, linear correlation system
Number R=0.9979, according to Nernst equation: Ep=E0- 0.05916 (m/n) pH, wherein m is the proton number of reaction transfer, and n is
Thus the electron number of transfer can extrapolate m=0.911n, i.e. m ≈ n, illustrate the electricity of transfer of the EP on the modified electrode interface
Subnumber and proton number are equal.
5, the discussion of EP oxidation mechanism on modified electrode
Using the relationship that CV method investigates the peak current of EP, spike potential changes with speed is swept.It is 20~200mV/s range sweeping speed
Interior, the oxidation peak current of EP increases with the increase for sweeping speed, therefore available EP is repaired in Pt NFs/MWCNTs-GQDs/GCE
An irreversible oxidation reaction has occurred in decorations electrode surface.The oxidation peak current of EP presents linear well with the variation for sweeping speed
Relationship, linear equation can be fitted to Ip=2.1766-0.1103v, linearly dependent coefficient R=0.9991, this illustrates that EP is being modified
Oxidation reaction on electrode is one by absorption and control process.The spike potential of EP and the logarithm for sweeping speed are in a linear relationship, linear side
Journey can be fitted to Ep=0.2776+0.0577lgv, linearly dependent coefficient R=0.9991, according to Laviron formula:
Wherein, EpIt is oxidation spike potential, E0'It is formula weight current potential, α is electron transmission coefficient, and n is transmitting electron number, and T is temperature
Degree, R is mol gas constant, and F is Faraday constant, k0For standard heterogeneous electron delivery rate constant, v is sweep speed.It is right
Than above formula, α n=1.0245 can be obtained, due to α=0.4~0.6 of irreversible electrode reaction under room temperature, n ≈ 2 can be calculated,
Therefore it show that the electron number n of EP oxidation process transfer is about 2, and is to wait the reaction of the protons such as electronics according to the oxidation reaction of EP
Journey, then the proton number m=2 shifted.
6, the range of linearity and detection limit
Under optimal experiment condition, the EP of various concentration is had studied in Pt Fs/MWCNTs-GQDs/ using DPV method respectively
Reaction process on GCE.Oxidation peak current becomes larger with the increase of concentration.The oxidation peak current of EP and its concentration 1.0~
800 μm of ol/L ranges have good linear relationship, and linear equation can be fitted are as follows: Ip=0.0178C+0.18674, coefficient R
=0.9969, detection limit reaches 81nmol/L (S/N=3).In addition, by the modified electrode of preparation and related modification reported in the literature
Electrode is compared and (is shown in Table 1), it is found that the modified electrode has the superior range of linearity and detection limit to the detection of EP.
The performance of 1 different modifying electrode of table compares
Table 1 Comparison of performance with different modified electrodes
Note: Poly (caffeic acid): poly- caffeic acid；Poly (taurine): poly- (taurine)；Poly
(isonicotinic acid): poly- (isonicotinic acid)；2,3-dimercaptosuccinic acid:2,3- dimercaptosuccinic acid；
CPE: carbon paste electrode；GCE: glass-carbon electrode；Au electrode: gold electrode
The related document (Reference) mentioned in table 1 is as follows:
[1]Li N.B.,Ren W.,Luo H.Q.,Caffeic acid-modified glassy carbon
electrode for the simultaneous determination of epinephrine and dopamine[J]
.Electroanalysis,2007,19(14):1496-1502.
[2]Wang Y,Chen Z.A novel poly(taurine)modified glassy carbon
electrode for the simultaneous determination of epinephrine and dopamine[J]
.Colloids and Surfaces B:Biointerfaces,2009,74(1): 322-327.
[3]Zhou Y.Z.,Zhang L.J.,Chen S.L.,Dong S.Y.,Zheng X.H.,
Electroanalysis and simultaneous determination of dopamine and epinephrine at
poly(isonicotinic acid)-modified carbon paste electrode in the presence of
ascorbic acid[J].Chinese Chemical Letters,2009,20(2):217-220.
[4]Kang W.J.,Niu L.M.,Ma L.,2,3-Dimercaptosuccinic acid self-
assembled gold electrode for the simultaneous determination of epinephrine
and dopamine[J].Chinese Chemical Letters,2009,20(2): 221-224.
7, the reproducibility, repeatability and stability of electrode
Using the 6 Pt NFs/MWCNTs-GQDs/GCE electrodes prepared under same batch to 8.000 × 10-5Mol/L's
EP is repeatedly measured, and the relative standard deviation of test result is 3.83% several times, illustrates that the electrode has good reproducibility.
Moreover, using same branch Pt NFs/MWCNTs-GQDs/GCE electrode to 8.000 × 10-5The EP of mol/L is continuously detected 6 times, several
The relative standard deviation of secondary test result is 3.44%, illustrates that the electrode has preferable repeatability.In addition, being repaired to investigate
The stability that electrode is used for a long time is adornd, modified electrode is stored in refrigerating chamber 20 days of 4 DEG C, the electrode was tested every four days to EP
Response performance.Experiment discovery, after continuous use 20 days, when modified electrode can reach initial to the response signal of EP
84.59%, show that the modified electrode has good long-time service stability.
8, anti-interference is tested
Detect the influence of common several biological micromolecule substances and metal ion to EP.Containing 8.000 × 10-5moL/
In the PBS buffer solution of the EP sample of L, it is separately added into Cys, Lys, Glu, His, Leu, AA, Ade, K of 10 times of concentration+、Mg2 +、Ca2+Interfering component detects it using DPV method.The result shows that after this 10 kinds of interfering components are added, modified electrode
Peak current is almost without generation significant change.It can be seen that Pt NFs/MWCNTs-GQDs/GCE to EP have well it is anti-interference
Property.
9, analysis application
Pt NFs/MWCNTs-GQDs/GCE modified electrode is investigated to EP in different actual samples (Swine serum and pig urcine)
Analysis detection application.Swine serum and pig urcine sample (being derived from 5 miscellaneous piggys of living body ternary, weight is 7~15Kg) are by China
Subtropical zone Agro-ecology research institute, the academy of sciences provides.It is measured using standard addition method, i.e., to Swine serum and pig urcine solution
The middle EP (20.00,30.00,40.00,50.00,60.00 μm of ol/L) that various concentration is added, is detected and is counted using DPV method
Calculate recovery of standard addition.As shown in Table 2, recovery of standard addition is respectively 98.41%~104.28% and 97.01%~103.50%,
Show that the modified electrode has relatively good accuracy, can be applied to the rapid sensitive of EP in practical Swine serum and pig urcine sample
Detection has potential using value in biochemistry detection and cultivation industry.
Adrenergic measurement in 2 Swine serum of table and pig urcine sample
Table 2 Application of Pt NFs/MWCNTs-GQDs/GCE to determination of EP
in pork serum and pork urine samples
The present invention has synthesized MWCNTs-GQDs nanocomposite first, and by self-assembly method, Pt NFs modification is arrived
Its surface has been successfully prepared the complex film modified electrode of Pt NFs/MWCNTs-GQDs/GCE.Modification electricity is inquired into using CV method
Extremely to the electro oxidation mechanism of EP, and the measurement by the modified electrode applied to EP in Swine serum and pig urcine sample, performance
Good selectivity, reproducibility and stability out, detection limit reach 81nmol/L, have in biochemical analysis and medical diagnosis field
Good practical application value.
Claims (8)
1. a kind of adrenaline detection method based on complex film modified electrode, which is characterized in that the method includes walking as follows
It is rapid:
(1) Pt NFs and MWCNTs-GQDs composite nano materials are prepared:
A) Pt NFs is prepared；
B) MWCNTs of preparation acidification；
C) MWCNTs by the acidification of step b) preparation is added in GQDs solution, and the concentration of GQDs is in the GQDs solution
0.8mg/mL~1.2mg/mL, the mass volume ratio of MWCNTs and the GQDs solution of the acidification are (0.01~0.015) g:(10
~15) mL, excusing from death mixing 3~7h after at 100 DEG C 3~5h of back flow reaction, dark solution is obtained, by dark solution after cooling
8~12min of centrifugal treating under the conditions of revolving speed is 10000rpm, removes supernatant, and obtained precipitating is MWCNTs-GQDs multiple
Close nano material；
(2) it prepares the complex film modified electrode of Pt NFs/MWCNTs-GQDs/GCE: glassy carbon electrode surface being polished, ultrasound is washed
It is dried after net, the MWCNTs-GQDs dispersant liquid drop that MWCNTs-GQDs composite nano materials obtain after ultrasonic disperse is applied to
Glassy carbon electrode surface is simultaneously dried, and the glass-carbon electrode that surface is modified by MWCNTs-GQDs is obtained, and Pt NFs solution is carried out ultrasound point
The even drop that mixes of Pt NFs obtained after dissipating is applied on the glass-carbon electrode that surface is modified by MWCNTs-GQDs, is dried to get Pt
The complex film modified electrode of NFs/MWCNTs-GQDs/GCE；The concentration of MWCNTs-GQDs is in the MWCNTs-GQDs dispersion liquid
0.5~2.0mg/mL；The concentration of Pt NFs is 0.5~2.0mg/mL in the Pt NFs solution；
(3) using the complex film modified electrode of Pt NFs/MWCNTs-GQDs/GCE as working electrode, using silver/silver chloride electrode as ginseng
Three-electrode system is constituted using platinum electrode as to electrode than electrode；Then adrenaline is investigated using Differential Pulse Voltammetry
Electrochemical behavior on different modifying electrode, and the adrenaline of various concentration is tested, Working calibration curve is drawn,
The adrenaline in sample to be tested is detected using standard addition method again.
2. the method as described in claim 1, which is characterized in that the Pt NFs shape is that porous spherical is flower-shaped.
3. the method as described in claim 1, which is characterized in that carrying out polishing to glassy carbon electrode surface in step (2) is difference
With 0.3 μm and 0.05 μm of α-Al2O3Powder polishes glassy carbon electrode surface.
4. the method as described in claim 1, which is characterized in that glass-carbon electrode diameter described in step (2) is 3mm, by 5 μ L
MWCNTs-GQDs dispersant liquid drop is applied to glassy carbon electrode surface and dries, and the 5 even drops that mix of μ L Pt NFs are applied to surface and have been applied
There is MWCNTs-GQDs and on the glass-carbon electrode that dries.
5. the method as described in claim 1, which is characterized in that be to investigate L- junket using Differential Pulse Voltammetry in step (3)
Differential Pulse Voltammetry parameter is arranged are as follows: amplitude 0.05V, pulse width in electrochemical behavior of the propylhomoserin on different modifying electrode
For 0.2s, sampling width be 0.02, pulse period 0.5s, the adrenaline of various concentration is tested, draw work mark
Directrix curve, then the adrenaline in sample to be tested is detected using standard addition method.
6. a kind of adrenaline detection sensor based on complex film modified electrode, which is characterized in that affiliated sensor includes making
For the complex film modified electrode of working electrode；The complex film modified electrode includes glass carbon matrix (5), the glass carbon matrix (5)
Surface modification has F-MWCNTs-GQDs layers (6) of acidification, and load has NFs layers of Pt in F-MWCNTs-GQDs layers of the acidification (6)
(7)。
7. sensor as claimed in claim 6, which is characterized in that the sensor includes glass carbon matrix (5) with a thickness of 1.0
~5.0mm, acidification F-MWCNTs-GQDs layers (6) with a thickness of 20~200nm, Pt NFs layers (7) with a thickness of 20
~200nm；Pt NFs shape in Pt NFs layers (7) is that porous spherical is flower-shaped, and globe daisy diameter is 10~30nm.
8. sensor as claimed in claims 6 or 7, which is characterized in that there are good to adrenergic concentration for the sensor
Good linear relationship, the range of linearity of detection are 1.0 μm of ol/L~800 μm ol/L, and detection is limited to 81nmol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910490391.2A CN110161101A (en) | 2019-06-06 | 2019-06-06 | A kind of adrenaline detection method and sensor based on complex film modified electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910490391.2A CN110161101A (en) | 2019-06-06 | 2019-06-06 | A kind of adrenaline detection method and sensor based on complex film modified electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110161101A true CN110161101A (en) | 2019-08-23 |
Family
ID=67627950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910490391.2A Withdrawn CN110161101A (en) | 2019-06-06 | 2019-06-06 | A kind of adrenaline detection method and sensor based on complex film modified electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110161101A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110887880A (en) * | 2019-11-25 | 2020-03-17 | 长沙理工大学 | Method for selectively detecting L-tyrosine based on formaldehyde medium action |
| CN114566392A (en) * | 2022-03-18 | 2022-05-31 | 南昌航空大学 | Oxygen-enriched defect epsilon-MnO2Preparation method of/carbon quantum dot composite film |
-
2019
- 2019-06-06 CN CN201910490391.2A patent/CN110161101A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110887880A (en) * | 2019-11-25 | 2020-03-17 | 长沙理工大学 | Method for selectively detecting L-tyrosine based on formaldehyde medium action |
| CN110887880B (en) * | 2019-11-25 | 2021-05-11 | 长沙理工大学 | Method for selectively detecting L-tyrosine based on formaldehyde medium action |
| CN114566392A (en) * | 2022-03-18 | 2022-05-31 | 南昌航空大学 | Oxygen-enriched defect epsilon-MnO2Preparation method of/carbon quantum dot composite film |
| CN114566392B (en) * | 2022-03-18 | 2023-04-11 | 南昌航空大学 | Oxygen-enriched defect epsilon-MnO 2 Preparation method of/carbon quantum dot composite film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Abdelwahab et al. | Simultaneous determination of ascorbic acid, dopamine, uric acid and folic acid based on activated graphene/MWCNT nanocomposite loaded Au nanoclusters | |
| Yang et al. | A zeolitic imidazolate framework/carbon nanofiber nanocomposite based electrochemical sensor for simultaneous detection of co-existing dihydroxybenzene isomers | |
| Ting et al. | Gold nanoparticles decorated reduced graphene oxide for detecting the presence and cellular release of nitric oxide | |
| CN106383158B (en) | A kind of hydrogen peroxide based on silver-graphene nano-complex is without enzyme sensor and preparation method thereof | |
| US20200158678A1 (en) | Nanostructured graphene-modified graphite pencil electrode system for simultaneous detection of analytes | |
| CN110082413A (en) | A kind of l-tyrosine detection method and sensor based on complex film modified electrode | |
| CN109187679B (en) | Electrochemical sensor and preparation method and application thereof | |
| CN110082416A (en) | A kind of l-tyrosine and dopamine Simultaneous Detection and sensor based on complex film modified electrode | |
| Liu et al. | Research on nonenzymatic electrochemical sensor using HO-BiONO3 nanocomposites for glucose detection | |
| CN109490390B (en) | Preparation method of graphene oxide-multiwalled carbon nanotube-Au @ Pt NPs enzyme-free glucose electrochemical sensor | |
| CN106053564B (en) | A kind of method that graphite-phase nitrogen carbide-chitosan-modified electrode detects protocatechuic acid as working electrode | |
| CN109046429A (en) | Mat gold nano particle/graphite phase carbon nitride composite material electrochemical sensor is detected for chloramphenicol | |
| Ekabutr et al. | Electrospinning: a carbonized gold/graphene/PAN nanofiber for high performance biosensing | |
| CN110161101A (en) | A kind of adrenaline detection method and sensor based on complex film modified electrode | |
| CN106770547A (en) | A kind of synthetic method of cobalt acid nickel hollow ball non-enzymatic biological sensor sensing material | |
| Zhai et al. | Core-shell composite N-doped-Co-MOF@ polydopamine decorated with Ag nanoparticles for nonenzymatic glucose sensors | |
| Zhang et al. | Electrochemical sensor for procaine based on a glassy carbon electrode modified with poly-amidosulfonic acid and multi-walled carbon nanotubes | |
| Samadzadeh et al. | Simultaneous determination of epinephrine and tyrosine using a glassy carbon electrode amplified with ZnO-Pt/CNTs nanocomposite | |
| CN101576530B (en) | Method for measuring dopamine by utilizing graphite nano-sheet/Nafion composite film to modify electrode | |
| Hu et al. | Simultaneous determination of dopamine and ascorbic acid using the nano‐gold self‐assembled glassy carbon electrode | |
| CN110133077A (en) | A kind of phenolethanolamine A detection method and sensor based on complex film modified electrode | |
| CN107167502B (en) | Construction method and application based on carbon nanotube-fullerene complex non-enzymatic electrochemical sensor | |
| Shabalina et al. | Copper nanoparticles for ascorbic acid sensing in water on carbon screen-printed electrodes | |
| Hamtak et al. | Improved performance for acyclovir sensing in the presence of deep eutectic solvent and nanostructures and polymer | |
| CN110039043A (en) | Three-dimensional copper@carbon core shell nanoparticles, preparation method and the application as enzyme-free glucose electrochemical sensor |
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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190823 |