CN106290518A - A kind of molecular imprinting electrochemical sensor for albuterol detection by quantitative and preparation method thereof - Google Patents
A kind of molecular imprinting electrochemical sensor for albuterol detection by quantitative and preparation method thereof Download PDFInfo
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- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
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Abstract
The present invention relates to Electroanalytical Chemistry technical field, specifically disclose a kind of molecular imprinting electrochemical sensor for albuterol detection by quantitative and preparation method thereof.Described preparation method, comprises the steps of: S1～S4. prepares N RGO；S5. take N RGO ultrasonic disperse in water, be subsequently adding glucose and form solution A；S6. by NH3·H2O solution joins in silver nitrate solution, forms solution B；S7. solution B and solution A are mixed, stirring, be then aged, by centrifugation, wash, be dried and to obtain Ag N RGO nano composite material；S8. take Ag N RGO nano composite material to be scattered in organic solvent, be then coated with the surface at working electrode, obtain Ag N RGO modified electrode；S9. Ag N RGO modified electrode is placed in the PBS buffer solution containing o-phenylenediamine and albuterol and is circulated voltammetry scanning；S10. the electrode processed through step S9 is removed the albuterol in polymeric membrane, obtain MIP/Ag N RGO trace electrode.Described chemical electrode or chemical sensor have extremely low detection limit and good stability, anti-interference and repeatability.
Description
Technical field
The present invention relates to Electroanalytical Chemistry technical field, be specifically related to a kind of molecule for albuterol detection by quantitative and print
Trace form electrochemical sensor and preparation method thereof.
Background technology
Albuterol chemical name is 1-(4-hydroxyl-3-hydroxymethyl phenyl)-2-(tertiary fourth amino) ethanol, breathes heavily also known as relaxing
Spirit, Salbutamol, coughing peaceful, it is that one has selective receptor,β analeptic.Albuterol can be by hydroxyl
Benzoylformaldoxime prepares through the series of chemical such as chloromethylation, esterification, and it is mainly used in bronchial asthma, asthmatic bronchus
Inflammation, emphysema and chronic congestion cardiorenal failure, pharmacological action is the release being caused anaphylaxis material by effectively suppression histamine, anti-
Only bronchospasm, emphysema etc..Albuterol may additionally facilitate growth of animal, makes the nutritional labeling in animal body by fatty tissue
Convert to muscular tissue, be therefore also referred to as " clenbuterol hydrochloride ".Owing to albuterol can remain in animal tissue, can be by food
Thing chain enters human body, can cause the symptoms such as headache, dizziness, insomnia, and also muscle and finger tremor, cardiopalmus, fluctuation of blood pressure etc. are no
Good reaction occurs, and causes health and has a strong impact on.Therefore, for ensuring food safety and human physical and mental health, having very much must
Set up a kind of quick, easy albuterol detection method.
The main method being currently used for albuterol mensuration has chromatography, chemoluminescence method, fluorescence method and euzymelinked immunosorbent assay (ELISA)
Deng.But these methods or instrument price are expensive, or the process of analysis is loaded down with trivial details or detection sensitivity is relatively low, it is impossible to carry out on-the-spot quick
Analyze and continuous on-line monitoring.And electrochemical sensing method because it is highly sensitive, response fast, low cost and equipment simple etc. excellent
Point is widely used.The most modified direct use of working electrode in electrochemical sensor can cause the electrochemistry of analyte to be rung
Should be weak, sensitivity for analysis is the highest.As document report under DNA effect on naked glass-carbon electrode the detection of albuterol be limited to
511nm (Wang Y, Ni Y, Kokot S, Analytical Biochemistry, 419 (2011) 76 80), at CNT
On modified electrode and chitosan/Multiwalled Carbon Nanotubes Modified Electrode the detection limit of albuterol be respectively 100nm (Lin K C,
Hong C P, Chen S M, Sensors and Actuators B 177 (2013) 428 436) and 86nm (Cao Z, Zhao
T Y,Dai Y M,Long S,Guo X C,Yang R H,Sensor letters(2011)1985–1989).Although electrode warp
Cross detection limit after conventional carbon nanomaterial is modified to decrease, but in view of the susceptiveness of electrochemical method, these detection limits are still
There is the space of reduction further.It addition, traditional chemical modified electrode is easily subject to other electric active matter in actual sample detects
The interference of matter, causes its selectivity to reduce.Therefore, development one can improve transducer sensitivity, also can improve its selectivity
Method particularly important.
Summary of the invention
The technical problem to be solved is, in order to overcome above-mentioned deficiency present in prior art, it is provided that a kind of
Molecular imprinting electrochemical sensor for albuterol detection by quantitative and preparation method thereof.
Above-mentioned technical problem to be solved by this invention, is achieved by the following technical programs:
A kind of preparation method of the molecular imprinting electrode for albuterol detection by quantitative, it is characterised in that comprise as
Lower step:
S1. graphene oxide is dispersed in water, obtain the amount ratio of dispersion liquid, graphene oxide and water be 1mg:1～
3mL；
S2. the pH value of dispersion liquid is adjusted to 9～11, adds carbamide the most under agitation and form mixed liquor, carbamide
Addition quality is 80～150 times of graphene oxide quality described in step S1；
S3. after above-mentioned mixed liquor being stirred 20～50min at 15～30 DEG C, be heated to 100～130 DEG C reaction 8～
16h；
S4. centrifuging and taking precipitation after reactant liquor cooling step S3 obtained, washing, dried N doping oxygen reduction fossil
Ink alkene (N-RGO)；
S5. take N doping redox graphene ultrasonic disperse in water, be subsequently adding glucose and form solution A, described
The amount ratio of N doping redox graphene, water and glucose be 1～3mg:1～3mL:10～30mg；
S6. by NH3·H2O solution joins in silver nitrate solution, precipitation first occurs, continuously adds NH3·H2O solution is straight
Silver ammino solution (Ag (NH is obtained to precipitation disappearance3)2OH solution), form solution B, described NH3·H2The concentration of O be 0.3～
0.4mol/L, the concentration of silver nitrate solution is 0.03～0.05mol/L；
S7. solution B and solution A are mixed, stirring reaction 0.5～2h, then ageing 3～6h, by centrifugation, wash, be dried
Obtaining silver-colored/nitrogen co-doped redox graphene (Ag-N-RGO) nano composite material, the volume ratio of described solution B and solution A is
1:1～3；
S8. take silver/nitrogen co-doped redox graphene nano composite material to be scattered in organic solvent, be then coated with
The surface of working electrode, obtains silver-colored/nitrogen co-doped redox graphene modified electrode (Ag-N-RGO modified electrode), described
Silver/nitrogen co-doped redox graphene nano composite material is 1mg:1～2mL with the amount ratio of organic solvent；
S9. silver/nitrogen co-doped redox graphene modified electrode is placed in containing 1.0～2.0mmol/L o-phenylenediamines and
The PBS buffer solution of 0.3～1.0mmol/L albuterol is circulated voltammetry scanning；
S10. the electrode processed through step S9 is placed in the H of 0.2～0.5mol/L2SO4Solution is circulated voltammetry
Scanning removes the albuterol in polymeric membrane, obtains silver-colored/nitrogen co-doped redox graphene base trace electrode (MIP/Ag-N-RGO
Trace electrode), the i.e. described molecular imprinting electrode for albuterol detection by quantitative.
For using the electrode of nano composite material formation determination certain chemical composition content concrete, then need inventor's root
Different nano composite materials is prepared according to the character of chemical substance the most to be determined.The electrode prepared is to material to be measured
The quality of the effect such as detection limit, sensitivity, stability and anti-interference mainly determined by the preparation method of nano composite material.
The preparation method of nano composite material mainly includes raw-material selection, raw-material proportioning, and each step reaction condition
Deng.For the nano composite material as electrode, raw-material selection in its preparation method, proportioning and each step reaction bar
The difference of part all can cause the greatest differences of the follow-up electrode electrical property prepared, thus cause detection limit, sensitivity, stablize
The greatest differences of the effect such as property and anti-interference.
According to the characteristic of albuterol, for obtaining the albuterol detecting electrode with high selectivity and low detection limit, this
Invention inventor, by substantial amounts of experiment, constantly adjusts the technological parameter in raw material composition, proportioning and preparation process；It is prepared into
To the Ag nanoparticle that particle diameter is 10～30nm and successfully by its uniform holdfast on N doping redox graphene lamella,
This technique the most successfully overcomes the phenomenon that graphene sheet layer is easily reunited so that the Ag-N-RGO modified electrode prepared has
Excellent electrochemical response performance, by complex film modified at this for the further electropolymerization of molecular engram film with specific recognition performance
On electrode, obtaining MIP/Ag-N-RGO trace electrode, this electrode can significantly reduce the detection limit of albuterol in sample, and
Improve sensitivity, stability and the anti-interference of detection.
Preferably, in step S1, the amount ratio of graphene oxide and water is 1mg:2～3mL.
Most preferably, the amount ratio of graphene oxide and water is 1mg:2mL.
Preferably, in step S2 addition quality is graphene oxide quality described in step S1 100～the 150 of carbamide
Times.
Most preferably, addition quality is graphene oxide quality described in step S1 100 times of carbamide.
Preferably, with the NH that mass fraction is 20～40% in step S23·H2The pH value of O regulation dispersion liquid is to 9～11.
Most preferably, it is the NH of 30% with mass fraction3·H2The pH value of O regulation dispersion liquid is to 10.
Preferably, the heating described in step S3 is to heat at hydrothermal reaction kettle；It is heated to 120～130 DEG C of reactions
10～14h.
Most preferably, 120 DEG C of reaction 12h it are heated to.
Preferably, the amount ratio of N doping redox graphene, water and the glucose described in step S5 is 1～2mg:
1～2mL:20～30mg.
Most preferably, the amount ratio of described N doping redox graphene, water and glucose is 1mg:1mL:21mg；
NH described in step S63·H2The concentration of O is 0.37mol/L, and the concentration of silver nitrate solution is 0.04mol/L.
Preferably, the volume ratio of solution B described in step S7 and solution A is 1:2；Stirring reaction 1～2h, is then aged 5
～6h.
Most preferably, stirring reaction 1h, then it is aged 5h.
Preferably, the silver described in step S8/nitrogen co-doped redox graphene nano composite material and organic solvent
Amount ratio be 1mg:1mL；Organic solvent described in step S8 is dimethylformamide.
Preferably, in step S9, the concentration of o-phenylenediamine is 1.5mmol/L, and the concentration of albuterol is 0.5mmol/L；Step
Cyclic voltammetry scanning voltage described in rapid S9 is-0.3～1.0V, and sweeping speed is 0.05V/s, and the circulating polymerization number of turns is 10 circles.
Preferably, H in step S102SO4The concentration of solution is 0.3mol/L；Cyclic voltammetry scanning voltage in step S10
For-0.3～1.0V, sweep speed for 0.05V/s.
The preparation method of a kind of molecular imprinting electrochemical sensor for albuterol detection by quantitative, including walking as follows
Rapid: to be working electrode by the above-mentioned silver/nitrogen co-doped redox graphene base trace electrode prepared, with saturated calomel electricity
Extremely reference electrode, with platinum electrode as auxiliary electrode, utilizes three-electrode method to assemble electrode test system, connects electrochemical operation
Stand for the electrochemical sensor of albuterol detection by quantitative.
The present invention also provides for a kind of molecule for albuterol detection by quantitative prepared by above-mentioned preparation method and prints
Trace form electrochemical sensor.
A kind of method of albuterol detection by quantitative, uses above-mentioned electrochemical sensor, detects with differential pulse voltammetry
Albuterol content in sample, the actual conditions of described differential pulse voltammetry detection is: end liquid is that the phosphoric acid of pH 6.4 delays
Rushing liquid, enrichment time is 120s；The operating condition that described differential pulse voltammetry is arranged is: current potential increment 0.0035V, amplitude
0.050V, pulse width 0.055s, test sample width 0.017s, pulse period 0.45s；Equation of linear regression is: ipa(μ A)=
0.1288C(μmol/L)+0.4536(R2=0.9925), in the equation, C is albuterol concentration, ipFor differential pulse voltammetry
Obtain oxidation peak current value.Albuterol in 0.03～20.00 μm ol/L concentration ranges and between its oxidation peak current value in
Good linear relation.
Beneficial effect: (1) the invention provides a kind of brand-new molecular imprinting for albuterol detection by quantitative
Learn electrode and chemical sensor, this electrode or sensor have excellent selectivity to albuterol；(2) being used for described in is husky
The chemical electrode of butylamine alcohol detection by quantitative or chemical sensor have extremely low detection limit, and (embodiment shows that its detection is limited to
7.0nmol/L, well below 511nmol/L, 100nmol/L and 86nmol/L of the prior art) and good stability,
Anti-interference and repeatability；(3) the albuterol electrochemical sensor built based on the present invention is simple to operate, with low cost,
Drug and food quality controls, the clinical aspect such as medical assistance and environmental monitoring has a wide range of applications.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph (A) of Ag-N-RGO nano composite material of the present invention, transmission electron microscope picture (B), energy
Spectrogram (C) and Raman spectrogram (D).
Fig. 2 is the preparation process of MIP/Ag-N-RGO trace electrode of the present invention.
Fig. 3 is MIP/Ag-N-RGO trace electrode (a) prepared by the present invention and non-trace electrode (b) of NIP/Ag-N-RGO
At 10mmol/L [Fe (CN)6]3-/4-Cyclic voltammetric (A) in+0.1mol/L KCl solution and AC impedance (B) collection of illustrative plates.
Fig. 4 albuterol following on MIP/Ag-N-RGO trace electrode (a) and non-trace electrode (b) of NIP/Ag-N-RGO
Ring volt-ampere curve.
Fig. 5 (A) variable concentrations albuterol DPV curve on MIP/Ag-N-RGO trace electrode, (B) variable concentrations is husky
Butylamine alcohol linear relationship chart on MIP/Ag-N-RGO trace electrode and between its oxidation peak current value.
Fig. 6 albuterol and interfering material are on MIP/Ag-N-RGO trace electrode and NIP/Ag-N-RGO non-trace electrode
Current-responsive.
Detailed description of the invention
The present invention is explained further below in conjunction with specific embodiment, but the present invention is not done any type of limit by embodiment
Fixed.
Unreceipted actual conditions person in embodiment, the condition advised according to normal condition or manufacturer is carried out.Wherein, used
Reagent or instrument unreceipted production firm person, be can by city available from conventional products.
Embodiment 1 for the molecular imprinting electrode of albuterol detection by quantitative preparation (MIP/Ag-N-RGO electrode
Preparation)
S1. being dispersed in water by graphene oxide, obtain dispersion liquid, described graphene oxide and the amount ratio of water are 1mg:
2mL；
S2. it is the NH of 30% with mass fraction3·H2The pH value of dispersion liquid is adjusted to 10 by O, adds the most under agitation
Carbamide forms mixed liquor, addition quality is graphene oxide quality described in step S1 100 times of described carbamide；
S3. carry out being heated to 120 DEG C of reaction 12h at hydrothermal reaction kettle by above-mentioned mixed liquor；
S4. centrifuging and taking precipitation after reactant liquor cooling step S3 obtained, washing, dried N doping oxygen reduction fossil
Ink alkene (N-RGO)；
S5. take N doping redox graphene ultrasonic disperse in water, be subsequently adding glucose and form solution A, described
The amount ratio of N doping redox graphene, water and glucose be 1mg:1mL:21mg；
S6. by NH3·H2O solution joins in silver nitrate solution, precipitation first occurs, continuously adds NH3·H2O solution is straight
Silver ammino solution (Ag (NH is obtained to precipitation disappearance3)2OH solution), form solution B, described NH3·H2The concentration of O is
0.37mol/L, the concentration of silver nitrate solution is 0.04mol/L；
S7. solution B and solution A are mixed, stirring reaction 1h, are then aged 5h, by centrifugation, wash, be dried silver-colored/nitrogen is common
Doping redox graphene (Ag-N-RGO) nano composite material, the volume ratio of described solution B and solution A is 1:2；
S8. take silver/nitrogen co-doped redox graphene nano composite material to be scattered in dimethylformamide, be then coated with
Overlay on the surface of working electrode, obtain silver-colored/nitrogen co-doped redox graphene modified electrode (Ag-N-RGO modified electrode), described
The amount ratio of silver/nitrogen co-doped redox graphene nano composite material and organic solvent be 1mg:1mL；Described work
Electrode is glass-carbon electrode；
S9. silver/nitrogen co-doped redox graphene modified electrode is placed in containing 1.5mmol/L o-phenylenediamine and
The PBS buffer solution of 0.5mmol/L albuterol is circulated voltammetry scanning；Described cyclic voltammetry scanning voltage
For-0.3～1.0V, sweeping speed is 0.05V/s, and the circulating polymerization number of turns is 10 circles；
S10. the electrode processed through step S9 is placed in the H of 0.3mol/L2SO4Solution is circulated voltammetry scanning
Remove the albuterol in polymeric membrane, obtain silver-colored/nitrogen co-doped redox graphene base trace electrode (MIP/Ag-N-RGO trace
Electrode).
The Ag-N-RGO nano composite material that Fig. 1 step display S7 prepares is put at 2000 times (A) and 50000 times (B)
Scanning electron microscope under big multiplying power and transmission electron microscope picture, the most undersized random high dispersive of Ag nano-particle is in oxygen reduction
On functionalized graphene lamella, whole composite presents gauffer, many layer structures, and the metal nanoparticle particle diameter of load is 10
Between 30nm.Nanoparticle size is little, dispersion is high and soilless sticking phenomenon, is conducive to improving the electro-catalysis of complex film modified electrode
Specific surface area active.It addition, EDAX results (C) display, in composite main in addition to N, C, O possibly together with Ag element,
Illustrate that the success of Ag nano-particle is supported on N-RGO.Raman spectrum analysis result (D) display graphene oxide (GO), N doping
Redox graphene (N-RGO) and Ag/N doping redox graphene (Ag-N-RGO) occur in that obvious D peak and G
Peak, correspond to the SP of C atom in graphite material respectively3Sp in vibration and grapheme material face2Vibration.Meanwhile, D/G peak intensity
Than the defect concentration having reacted place material with carbon element.The D/G peak intensity ratio respectively 1.23 and 1.05 of Ag-N-RGO and N-RGO, far
Much larger than the D/G peak intensity ratio 0.48 of GO, illustrate that N and Ag is doped into grapheme material and can cause the distortion of graphene sheet layer
Or on Graphene lattice, create new omission, further demonstrate that Ag is successfully supported on N-RGO lamella.
Fig. 2 gives the step S9 schematic diagram about preparing MIP/Ag-N-RGO trace electrode.It can be seen that molecule print
The preparation process of apodized electrode mainly includes the steps such as electrode modification, electropolymerization, removal template molecule, the molecular engram film obtained
Electrode surface has the loose structure in many holes, is conducive to template molecule is carried out specific recognition, improves Sha Ding simultaneously
Amine alcohol, at the mass transfer rate of electrode surface, is also beneficial to improve the electron transfer rate of albuterol electro-oxidation process.
Preparation (the non-trace of NIP/Ag-N-RGO of comparative example 1 silver medal/nitrogen co-doped redox graphene base non-trace electrode
The preparation of electrode)
In the preparation process of NIP/Ag-N-RGO electrode, S1～S8 is with embodiment 1；Step S9 is: by silver/nitrogen co-doped also
Former graphene oxide modified electrode is placed in the PBS buffer solution containing 1.5mmol/L o-phenylenediamine between-0.3～1.0V
NIP/Ag-N-RGO non-trace electrode is obtained with sweeping after speed circulating polymerization 10 encloses of 0.05V/s.
Embodiment 2 one kinds is for the electrochemical sensor of albuterol detection by quantitative
MIP/Ag-N-RGO trace electrode embodiment 1 prepared is as working electrode, with platinum electrode for electricity
Pole, saturated calomel electrode are that reference electrode is assembled into three electrode test systems, and connect electrochemical workstation and must be used for husky butylamine
The electrochemical sensor of alcohol detection by quantitative.
Embodiment 3 is for the electrical performance testing of the electrochemical sensor of albuterol detection by quantitative
(1) the electron transmission performance comparison of Different electrodes
In the three electrode test systems that such as embodiment 2 prepares, respectively with MIP/Ag-N-RGO trace electrode (a) and
Non-trace type electrode (b) of NIP/Ag-N-RGO is working electrode, at 10mmol/L [Fe (CN)6]3-/4-Mixing 0.1mol/L KCl
End liquid in be circulated volt-ampere and ac impedance measurement, volt-ampere test condition is: sweep limits-0.2～0.6V, scanning speed
0.1V/s；Ac impedance measurement condition is: frequency range 105～0.1HZ, amplitude 5mV, current potential 0.20V, test result such as Fig. 3.
[Fe (CN) as seen from Figure 36]3-/4-Probe ion on molecular engram film electrode peak current response more than its for non-trace
Current-responsive on membrane electrode, electrochemical impedance is respectively 130k Ω and 160k Ω on above two electrode, the present invention is described
The MIP/Ag-N-RGO trace electrode provided improves its surface mass transfer rate and electron transfer rate, and MIP/Ag-N-RGO print
Apodized electrode is conducive to improving the sensor specific recognition capability to albuterol, not only improves the selectivity improving sensor.
(2) electrocatalysis characteristic of albuterol is contrasted by Different electrodes
In the three electrode test systems that such as embodiment 2 prepares, respectively with MIP/Ag-N-RGO trace electrode (a) and
Non-trace type electrode (b) of NIP/Ag-N-RGO is that working electrode is circulated volt-ampere survey in 0.1mmol/L albuterol solution
Examination, the potential range of test is 0.3～0.8V, scanning speed be 0.1V/s, Fig. 4 be test result.Husky butylamine as seen from the figure
Alcohol oxidation peak current on MIP/Ag-N-RGO trace electrode of the present invention is maximum (11.5 μ A), and spike potential is
0.540V.Work with NIP/Ag-N-RGO electrode time compared with, albuterol is at MIP/Ag-N-RGO trace of the present invention
Oxidation overpotential on electrode have dropped about 20mV, illustrates that the MIP/Ag-N-RGO trace electrode prepared by the present invention is to husky fourth
Amine alcohol has preferable electro catalytic activity, is conducive to improving the sensitivity of sensor.
(3) the Electrochemical Detection performance test of the electrochemical sensor that the present invention prepares
MIP/Ag-N-RGO trace electrode embodiment 1 prepared utilizes three-electrode method to assemble electrode test system,
And connect electrochemical workstation (construction method is as described in Example 2)；In liquid at the bottom of the phosphoric acid that pH is 6.4, with enrichment time it is
A series of albuterol solution are carried out differential pulse voltammetry test by 120s.The operating condition that differential pulse voltammetry is arranged
For: current potential increment 0.0035V, amplitude 0.050V, pulse width 0.055s, test sample width 0.017s, pulse period 0.45s.Knot
Fruit shows that the oxidation peak current of (see Fig. 5) albuterol increases with its concentration and increases, at 0.03～20.00 μm ol/L concentration models
Enclosing between interior and its oxidation peak current value in good linear relation, equation of linear regression is: ipa(μ A)=0.1288C (μm ol/L)
+0.4536(R2=0.9925), in the equation, C is albuterol concentration, ipOxidation peak current is obtained for differential pulse voltammetry
Value；Detection limit is calculated as 7.0nmol/L.Illustrate that the preparation-obtained electrode of the present invention has good linear relationship and extremely low
Detection limit.
(4) stability of the MIP/Ag-N-RGO trace electrode that the present invention prepares and repeatability test
Prepare 6 identical MIP/Ag-N-RGO trace electrodes according to the step of embodiment 1, with these 6 electrodes be respectively
Working electrode, assembles electrode test system with three-electrode method and connects electrochemical workstation (construction method is as described in Example 2),
In liquid at the bottom of the phosphoric acid that pH is 6.4, with enrichment time as 120s, utilize the differential pulse voltammetry albuterol to same concentration
It is measured.The operating condition that differential pulse voltammetry is arranged is: current potential increment 0.0035V, amplitude 0.050V, pulse width
0.055s, test sample width 0.017s, pulse period 0.45s, the relative standard deviation of measurement result is 4.13%.Will wherein one
MIP/Ag-N-RGO trace electrode is saved in 4 DEG C of refrigerators, choose 6 different time periods (preserve before test the 1st time, then
Tested 1 time every 1 day), utilize above-mentioned similarity condition and method that the albuterol of same concentration is measured, mensuration relative
Standard deviation is 1.96%；Show that the MIP/Ag-N-RGO trace electrode that the present invention provides has preferable stability and reproduction
Property.
(5) the detection selectivity test of the MIP/Ag-N-RGO trace electrode that the present invention prepares
For carrying out comparative illustration, the MIP/Ag-N-RGO trace electrode that embodiment 1 is prepared and NIP/Ag-N-RGO
Non-trace electrode utilizes three-electrode method to assemble electrode test system, and connects electrochemical workstation composition electrochemical sensor (structure
Construction method is as described in Example 2), utilize differential pulse voltammetry to investigate in several analog and actual sample and often coexist
The impact that albuterol is measured of several external interfering material.The operating condition that differential pulse voltammetry is arranged is: current potential increases
Amount 0.0035V, amplitude 0.050V, pulse width 0.055s, test sample width 0.017s, pulse period 0.45s.Concrete method of testing
It is that regulating albuterol concentration in liquid at the bottom of the phosphoric acid that pH is 6.4 is 10 μMs, is lied prostrate by differential pulse with enrichment time for 120s
Peace method measures its oxidation peak current value；Under the same conditions the interfering material of 10 times of concentration is surveyed with identical electrode again
Fixed.As shown in Fig. 6 result, Clenbuterol, Ractopamine, terbutaline, dopamine, epinephrine, ascorbic acid and uric acid
Deng interfering material current-responsive on MIP/Ag-N-RGO trace electrode than albuterol low 5.6 times this concludes the description of this
The electrode of bright offer has and preferably detects selectivity.It addition, determine these interfering materials and albuterol at NIP/Ag-N-
Current-responsive on RGO non-trace electrode, by its being used in trace electrode and the oxidation peak current value on non-trace electrode
Imprinting factor, the imprinting factor obtaining albuterol is 11.2；Clenbuterol, Ractopamine, terbutaline, dopamine, kidney
The imprinting factor of upper parathyrine, ascorbic acid and uric acid is respectively 1.35,1.43,1.22,1.21,1.05,1.03 and 1.07；Enter one
MIP/Ag-N-RGO trace electrode prepared by the step explanation present invention has preferable specific recognition ability to albuterol, can be quickly
Efficiently identify template molecule, and provide accurate testing result.
Embodiment 4 actual sample detects
Somewhere Marketing pork is taken 100mg, after chopping, is placed in 10mL pure water and filters after ultrasonic 2h, by filtrate
It is settled to 1L as actual measurement sample with the phosphoric acid solution that pH is 6.4.The MIP/Ag-N-RGO trace electricity that embodiment 1 is prepared
Pole utilizes three-electrode method to assemble electrode test system, and connects electrochemical workstation composition electrochemical sensor, utilizes difference arteries and veins
Rush the albuterol content in the above-mentioned sample of voltammetric determination.The operating condition that differential pulse voltammetry is arranged is: current potential increment
0.0035V, amplitude 0.050V, pulse width 0.055s, test sample width 0.017s, pulse period 0.45s.Concrete method of testing
Being to take above-mentioned actual measurement sample 5mL, being sequentially added into standard albuterol solution content is 0 μM, 5 μMs, 10 μMs, and regulation end liquid pH is
6.4, measured the oxidation peak current value of albuterol by differential pulse voltammetry with enrichment time for 120s, according to embodiment 3
The linear relationship obtained finds the albuterol concentration value of correspondence.The relative mark of albuterol measured value is obtained according to said method
Quasi-deviation is between 2.72～3.95%, and the response rate is between 103.6～105.3%；Illustrate the chemical-electrical that the present invention provides
Pole or sensor can be used for the Accurate Determining of albuterol content in the actual sample such as food, medicine.
Claims (10)
1. the preparation method for the molecular imprinting electrode of albuterol detection by quantitative, it is characterised in that comprise as follows
Step:
S1. being dispersed in water by graphene oxide, the amount ratio obtaining dispersion liquid, graphene oxide and water is 1mg:1～3mL；
S2. the pH value of dispersion liquid is adjusted to 9～11, adds carbamide the most under agitation and form mixed liquor, the addition of carbamide
Quality is 80～150 times of graphene oxide quality described in step S1；
S3., after above-mentioned mixed liquor being stirred 20～50min at 15～30 DEG C, it is heated to 100～130 DEG C of reactions 8～16h；
S4. centrifuging and taking precipitation after reactant liquor cooling step 3 obtained, washing, dried N doping redox graphene；
S5. take N doping redox graphene ultrasonic disperse in water, be subsequently adding glucose and form solution A, described nitrogen
The amount ratio of doping redox graphene, water and glucose is 1～3mg:1～3mL:10～30mg；
S6. by NH3·H2O solution joins in silver nitrate solution, precipitation first occurs, continuously adds NH3·H2O solution is until precipitating
Disappearance obtains silver ammino solution, forms solution B, described NH3·H2The concentration of O is 0.3～0.4mol/L, silver nitrate solution dense
Degree is 0.03～0.05mol/L；
S7. solution B and solution A are mixed, stirring reaction 0.5～2h, then ageing 3～6h, by centrifugation, wash, be dried silver-colored/
Nitrogen co-doped redox graphene nano composite material, the volume ratio of described solution B and solution A is 1:1～3；
S8. take silver/nitrogen co-doped redox graphene nano composite material to be scattered in organic solvent, be then coated with in work
The surface of electrode, obtains silver-colored/nitrogen co-doped redox graphene modified electrode, described silver/nitrogen co-doped reduction-oxidation graphite
Alkene nano composite material is 1mg:1～2mL with the amount ratio of organic solvent；
S9. silver/nitrogen co-doped redox graphene modified electrode is placed in containing 1.0～2.0mmol/L o-phenylenediamines and 0.3～
The PBS buffer solution of 1.0mmol/L albuterol is circulated voltammetry scanning；
S10. the electrode processed through step S9 is placed in the H of 0.2～0.5mol/L2SO4Solution is circulated voltammetry scanning
Removing the albuterol in polymeric membrane, obtain silver-colored/nitrogen co-doped redox graphene base trace electrode, i.e. described is used for husky fourth
The molecular imprinting electrode of amine alcohol detection by quantitative.
Preparation method the most according to claim 1, it is characterised in that in step S1, the amount ratio of graphene oxide and water is
1mg:2～3mL；Most preferably, the amount ratio of graphene oxide and water is 1mg:2mL.
Preparation method the most according to claim 1, it is characterised in that in step S2, the addition quality of carbamide is in step S1
100～150 times of described graphene oxide quality；With the NH that mass fraction is 20～40% in step S23·H2O regulates dispersion
The pH value of liquid is to 9～11；Most preferably, addition quality is graphene oxide quality described in step S1 100 times of carbamide；?
Preferably, it is the NH of 30% with mass fraction3·H2The pH value of O regulation dispersion liquid is to 10.
Preparation method the most according to claim 1, it is characterised in that the heating described in step S3 is at hydrothermal reaction kettle
Heat；It is heated to 120～130 DEG C of reactions 10～14h；Most preferably, 120 DEG C of reaction 12h it are heated to.
Preparation method the most according to claim 1, it is characterised in that the N doping reduction-oxidation graphite described in step S5
The amount ratio of alkene, water and glucose is 1～2mg:1～2mL:20～30mg；Most preferably, described N doping oxygen reduction fossil
The amount ratio of ink alkene, water and glucose is 1mg:1mL:21mg；NH described in step S63·H2The concentration of O is 0.37mol/L,
The concentration of silver nitrate solution is 0.04mol/L.
Preparation method the most according to claim 1, it is characterised in that solution B described in step S7 and the volume ratio of solution A
For 1:2；Stirring reaction 1～2h, then ageing 5～6h；Most preferably, stirring reaction 1h, then it is aged 5h；Described in step S8
The amount ratio of silver/nitrogen co-doped redox graphene nano composite material and organic solvent be 1mg:1mL；Institute in step S8
The organic solvent stated is dimethylformamide.
Preparation method the most according to claim 1, it is characterised in that in step S9, the concentration of o-phenylenediamine is 1.5mmol/
L, the concentration of albuterol is 0.5mmol/L；Cyclic voltammetry scanning voltage described in step S9 is-0.3～1.0V, sweeps speed
For 0.05V/s, the circulating polymerization number of turns is 10 circles；H in step S102SO4The concentration of solution is 0.3mol/L；Step S10 circulates
Voltammetry scanning voltage is-0.3～1.0V, sweeps speed for 0.05V/s.
8. the preparation method for the molecular imprinting electrochemical sensor of albuterol detection by quantitative, it is characterised in that
Comprise the steps: silver/nitrogen co-doped redox graphene base trace electricity any one of claim 1～7 prepared
Extremely working electrode, with saturated calomel electrode as reference electrode, with platinum electrode as auxiliary electrode, utilizes three-electrode method to assemble electricity
Pole test system, connects electrochemical workstation and must be used for the electrochemical sensor of albuterol detection by quantitative.
9. the molecular imprinting for albuterol detection by quantitative prepared by the preparation method described in claim 8
Electrochemical sensor.
10. the method for an albuterol detection by quantitative, it is characterised in that use the electrochemical sensor described in claim 9,
With the albuterol content in differential pulse voltammetry detection sample, the actual conditions of described differential pulse voltammetry detection is:
End liquid be pH be the phosphate buffer of 6.4, enrichment time is 120s；The operating condition that described differential pulse voltammetry is arranged
For: current potential increment 0.0035V, amplitude 0.050V, pulse width 0.055s, test sample width 0.017s, pulse period 0.45s；Line
Property regression equation is: ipa(μ A)=0.1288C (μm ol/L)+0.4536 (R2=0.9925), in the equation, C is that albuterol is dense
Degree, ipOxidation peak current value is obtained for differential pulse voltammetry.
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