CN106290518B - A kind of molecular imprinting electrochemical sensor and preparation method thereof quantitatively detected for salbutamol - Google Patents
A kind of molecular imprinting electrochemical sensor and preparation method thereof quantitatively detected for salbutamol Download PDFInfo
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- CN106290518B CN106290518B CN201610705752.7A CN201610705752A CN106290518B CN 106290518 B CN106290518 B CN 106290518B CN 201610705752 A CN201610705752 A CN 201610705752A CN 106290518 B CN106290518 B CN 106290518B
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- NDAUXUAQIAJITI-UHFFFAOYSA-N albuterol Chemical compound CC(C)(C)NCC(O)C1=CC=C(O)C(CO)=C1 NDAUXUAQIAJITI-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229960002052 salbutamol Drugs 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002114 nanocomposite Substances 0.000 claims abstract description 20
- 238000001514 detection method Methods 0.000 claims abstract description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 12
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 11
- 239000008103 glucose Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 7
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007853 buffer solution Substances 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims abstract description 5
- 238000005119 centrifugation Methods 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 60
- 229910021389 graphene Inorganic materials 0.000 claims description 56
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 238000012360 testing method Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 19
- 238000001903 differential pulse voltammetry Methods 0.000 claims description 18
- 229910052709 silver Inorganic materials 0.000 claims description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- 239000004332 silver Substances 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
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- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000012417 linear regression Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000004987 o-phenylenediamines Chemical class 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 1
- 230000008034 disappearance Effects 0.000 claims 1
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- 239000000126 substance Substances 0.000 abstract description 17
- 238000003756 stirring Methods 0.000 abstract 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 9
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 8
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- 229910052799 carbon Inorganic materials 0.000 description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 4
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- XWTYSIMOBUGWOL-UHFFFAOYSA-N (+-)-Terbutaline Chemical compound CC(C)(C)NCC(O)C1=CC(O)=CC(O)=C1 XWTYSIMOBUGWOL-UHFFFAOYSA-N 0.000 description 2
- 206010014561 Emphysema Diseases 0.000 description 2
- NTYJJOPFIAHURM-UHFFFAOYSA-N Histamine Chemical compound NCCC1=CN=CN1 NTYJJOPFIAHURM-UHFFFAOYSA-N 0.000 description 2
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 2
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 2
- UCTWMZQNUQWSLP-UHFFFAOYSA-N adrenaline Chemical compound CNCC(O)C1=CC=C(O)C(O)=C1 UCTWMZQNUQWSLP-UHFFFAOYSA-N 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- STJMRWALKKWQGH-UHFFFAOYSA-N clenbuterol Chemical compound CC(C)(C)NCC(O)C1=CC(Cl)=C(N)C(Cl)=C1 STJMRWALKKWQGH-UHFFFAOYSA-N 0.000 description 2
- 229960001117 clenbuterol Drugs 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
- YJQZYXCXBBCEAQ-UHFFFAOYSA-N ractopamine Chemical compound C=1C=C(O)C=CC=1C(O)CNC(C)CCC1=CC=C(O)C=C1 YJQZYXCXBBCEAQ-UHFFFAOYSA-N 0.000 description 2
- 229940074095 ractopamine Drugs 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 229960000195 terbutaline Drugs 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 229960001399 clenbuterol hydrochloride Drugs 0.000 description 1
- OPXKTCUYRHXSBK-UHFFFAOYSA-N clenbuterol hydrochloride Chemical compound Cl.CC(C)(C)NCC(O)C1=CC(Cl)=C(N)C(Cl)=C1 OPXKTCUYRHXSBK-UHFFFAOYSA-N 0.000 description 1
- 208000027744 congestion Diseases 0.000 description 1
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- 238000002795 fluorescence method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- -1 graphite alkene Chemical class 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229960001340 histamine Drugs 0.000 description 1
- 230000003053 immunization Effects 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
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- 210000003205 muscle Anatomy 0.000 description 1
- CJJXBVHJNDUGDC-UHFFFAOYSA-N n-hydroxy-2-oxo-2-phenylacetamide Chemical compound ONC(=O)C(=O)C1=CC=CC=C1 CJJXBVHJNDUGDC-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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Classifications
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- 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
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Biological Materials (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention relates to Electroanalytical Chemistry technical fields, specifically disclose a kind of molecular imprinting electrochemical sensor and preparation method thereof quantitatively detected for salbutamol.The preparation method, comprises the following steps：S1~S4. prepares N RGO；S5. N RGO ultrasonic disperses in water are taken, glucose is then added and forms solution A；S6. by NH3·H2O solution is added in silver nitrate solution, forms solution B；S7. solution B and solution A are mixed, then stirring is aged, through centrifugation, washing, dry Ag N RGO nanocomposites；S8. it takes Ag N RGO nanocomposites to be scattered in organic solvent, is then coated on the surface of working electrode, obtain Ag N RGO modified electrodes；S9. Ag N RGO modified electrodes are placed in progress cyclic voltammetry scanning in the PBS buffer solutions containing o-phenylenediamine and salbutamol；S10. the salbutamol in polymeric membrane will be removed through the processed electrodes of step S9, obtains MIP/Ag N RGO trace electrodes.The chemical electrode or chemical sensor has extremely low detection limit and good stability, anti-interference and reproducibility.
Description
Technical field
The present invention relates to Electroanalytical Chemistry technical fields, and in particular to a kind of molecule print quantitatively detected for salbutamol
Trace form electrochemical sensor and preparation method thereof.
Background technology
Salbutamol chemical name is 1- (4- hydroxyl -3- hydroxymethyl phenyls) -2- (tertiary fourth amino) ethyl alcohol, asthma of also known as relaxing
Spirit, Salbutamol, cough are peaceful, it is a kind of selective receptor,β excitant.Salbutamol can be by hydroxyl
Benzoylformaldoxime is made through series of chemical such as chloromethylation, esterifications, is mainly used for bronchial asthma, asthmatic bronchus
Scorching, pulmonary emphysema and chronic congestion cardiorenal failure, pharmacological action are the release by effectively inhibiting histamine to cause anaphylaxis substance, are prevented
Only bronchial spasm, pulmonary emphysema etc..Salbutamol may additionally facilitate growth of animal, make the nutritional ingredient in animal body by adipose tissue
It is converted to musculature, therefore also referred to as " clenbuterol hydrochloride ".Since salbutamol can remain in animal tissue, food can be passed through
Object chain enters human body, can lead to the symptoms, also muscle and finger tremor, palpitaition, fluctuation of blood pressure etc. such as headache, dizzy, insomnia not
Good reaction occurs, and causes to seriously affect to health.Therefore, to ensure food safety and human physical and mental health, having very much must
Establish a kind of salbutamol detection method quickly, easy.
The main method measured currently used for salbutamol has chromatography, chemoluminescence method, fluorescence method and enzyme-linked immunization
Deng.But these methods or instrument price are expensive or analytic process is cumbersome or detection sensitivity is relatively low, can not carry out it is live quickly
Analysis and continuous on-line monitoring.And electrochemical sensing method is because its high sensitivity, fast, the at low cost and equipment of response are simple etc. excellent
Point is widely used.The unmodified direct use of working electrode in electrochemical sensor can cause the electrochemistry of analyte to be rung
Answer weak, sensitivity for analysis is not high.As the detection of salbutamol is limited to document report in bare glassy carbon electrode under DNA effects
511nm (Wang Y, Ni Y, Kokot S, Analytical Biochemistry, 419 (2011) 76-80), in carbon nanotube
On modified electrode and chitosan/Multiwalled Carbon Nanotubes Modified Electrode the detection limit of salbutamol 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 passes through
Detection limit decreases after crossing conventional carbon nanomaterial modification, but in view of the sensitivity of electrochemical method, these detection limits are still
There is the space further decreased.In addition, traditional chemical modified electrode is easy in actual sample detection by other electric active matters
The interference of matter causes it selectively to reduce.Therefore, development one kind can improve transducer sensitivity, can also improve its selectivity
Method it is particularly important.
Invention content
The technical problem to be solved by the present invention is in order to overcome above-mentioned deficiency existing in the prior art, provide one kind
The molecular imprinting electrochemical sensor and preparation method thereof quantitatively detected for salbutamol.
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 quantitatively detected for salbutamol, which is characterized in that comprising such as
Lower step：
S1. graphene oxide is dispersed in water, obtains dispersion liquid, the amount ratio of graphene oxide and water is 1mg:1~
3mL；
S2. the pH value of dispersion liquid is adjusted to 9~11, urea is then added under agitation and forms mixed liquor, urea
80~150 times that quality is graphene oxide quality described in step S1 are added；
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 precipitates after reaction solution cooling step S3 obtained, and N doping oxygen reduction fossil is obtained after washing, drying
Black alkene (N-RGO)；
S5. N doping redox graphene ultrasonic disperse in water is taken, glucose is then added and forms solution A, it is described
N doping redox graphene, water and glucose amount ratio be 1~3mg:1~3mL:10~30mg；
S6. by NH3·H2O solution is added in silver nitrate solution, is first precipitated, and NH is continuously added3·H2O solution is straight
It disappears to precipitation and obtains silver ammino solution (Ag (NH3)2OH solution), form solution B, the NH3·H2A concentration of the 0.3 of O~
0.4mol/L, a concentration of 0.03~0.05mol/L of silver nitrate solution；
S7. solution B and solution A are mixed, is stirred to react 0.5~2h, 3~6h is then aged, through centrifugation, washing, drying
Silver-colored/nitrogen co-doped redox graphene (Ag-N-RGO) nanocomposite, the volume ratio of the solution B and solution A are
1:1~3；
S8. it takes silver/nitrogen co-doped redox graphene nanocomposite to be scattered in organic solvent, is then coated with
The surface of working electrode obtains silver-colored/nitrogen co-doped redox graphene modified electrode (Ag-N-RGO modified electrodes), described
The amount ratio of silver/nitrogen co-doped redox graphene nanocomposite and organic solvent is 1mg:1~2mL；
S9. silver/nitrogen co-doped redox graphene modified electrode is placed in containing 1.0~2.0mmol/L o-phenylenediamines and
Cyclic voltammetry scanning is carried out in the PBS buffer solutions of 0.3~1.0mmol/L salbutamols；
S10. the H of 0.2~0.5mol/L will be placed in through the processed electrodes of step S92SO4Cyclic voltammetry is carried out in solution
Scanning removes the salbutamol in polymeric membrane, obtains silver-colored/nitrogen co-doped redox graphene base trace electrode (MIP/Ag-N-RGO
Trace electrode), i.e., described molecular imprinting electrode quantitatively detected for salbutamol.
For using nanocomposite to prepare the electrode of certain specific chemical composition content of measurement, then inventor's root is needed
Different nanocomposites is prepared according to the property of specific chemical substance to be determined.The electrode prepared is to the substance of being measured
The quality of detection limit, sensitivity, stability and anti-interference and other effects mainly determined by the preparation method of nanocomposite.
The preparation method of nanocomposite includes mainly the selection of raw material, the proportioning of raw material and each step reaction condition
Deng.For the nanocomposite as electrode, the selection of raw material, proportioning and each step reaction item in preparation method
The difference of part can all lead to the greatest differences for the electrode electrical property being subsequently prepared, so as to cause detection limit, sensitivity, stabilization
The greatest differences of property and anti-interference and other effects.
According to the characteristic of salbutamol, to obtain having highly selective and low detection limits salbutamol detecting electrodes, this
It invents inventor through a large number of experiments, constantly adjusts the technological parameter in raw material composition, proportioning and preparation process；It is prepared into
To the Ag nano-particles that grain size is 10~30nm and successfully by its uniform holdfast on N doping redox graphene lamella,
The technique also successfully overcomes the phenomenon that graphene sheet layer is easy to reunite so that the Ag-N-RGO modified electrodes being prepared have
Excellent electrochemical response performance, the further electropolymerization of molecular engram film with specific recognition performance is complex film modified at this
On electrode, MIP/Ag-N-RGO trace electrodes are obtained, which can significantly reduce the detection limit of salbutamol in sample, and
Improve sensitivity, stability and the anti-interference of detection.
Preferably, the amount ratio of graphene oxide and water is 1mg in step S1:2~3mL.
Most preferably, the amount ratio of graphene oxide and water is 1mg:2mL.
Preferably, the addition quality of urea is 100~150 of graphene oxide quality described in step S1 in step S2
Times.
Most preferably, the addition quality of urea is 100 times of graphene oxide quality described in step S1.
Preferably, the NH for being 20~40% with mass fraction in step S23·H2O adjusts the pH value of dispersion liquid to 9~11.
Most preferably, the NH for being 30% with mass fraction3·H2O adjusts the pH value of dispersion liquid to 10.
Preferably, the heating described in step S3 is heated in hydrothermal reaction kettle；It is heated to 120~130 DEG C of reactions
10~14h.
Most preferably, 120 DEG C of reaction 12h are heated to.
Preferably, the amount ratio of the N doping redox graphene described in step S5, water and glucose is 1~2mg:
1~2mL:20~30mg.
Most preferably, the amount ratio of the N doping redox graphene, water and glucose is 1mg:1mL:21mg；
NH described in step S63·H2A concentration of 0.37mol/L of O, a concentration of 0.04mol/L of silver nitrate solution.
Preferably, the volume ratio of solution B and solution A described in step S7 is 1:2；It is stirred to react 1~2h, is then aged 5
~6h.
Most preferably, it is stirred to react 1h, is then aged 5h.
Preferably, the silver described in step S8/nitrogen co-doped redox graphene nanocomposite and organic solvent
Amount ratio be 1mg:1mL；Organic solvent described in step S8 is dimethylformamide.
Preferably, in step S9 o-phenylenediamine a concentration of 1.5mmol/L, a concentration of 0.5mmol/L of salbutamol；Step
Cyclic voltammetry scanning voltage described in rapid S9 is -0.3~1.0V, and it is 0.05V/s to sweep speed, and the circulating polymerization number of turns is 10 circles.
Preferably, H in step S102SO4A concentration of 0.3mol/L of solution；Cyclic voltammetry scanning voltage in step S10
For -0.3~1.0V, it is 0.05V/s to sweep speed.
A kind of preparation method of the molecular imprinting electrochemical sensor quantitatively detected for salbutamol, including walk as follows
Suddenly：It is working electrode by the above-mentioned silver being prepared/nitrogen co-doped redox graphene base trace electrode, to be saturated calomel electricity
Extremely reference electrode assembles electrode test system using three-electrode method, connects electrochemical operation using platinum electrode as auxiliary electrode
The electrochemical sensor for standing quantitatively to detect for salbutamol.
The present invention also provides a kind of molecule prints quantitatively detected for salbutamol being prepared by above-mentioned preparation method
Trace form electrochemical sensor.
A kind of method that salbutamol quantitatively detects is detected using above-mentioned electrochemical sensor with differential pulse voltammetry
Salbutamol content in sample, the actual conditions that the differential pulse voltammetry detects are：The phosphoric acid that bottom liquid is pH 6.4 is slow
Fliud flushing, enrichment time 120s；The operating condition of the described differential pulse voltammetry setting 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), C is salbutamol concentration, i in the equationpFor differential pulse voltammetry
Obtain oxidation peak current value.Salbutamol is between its oxidation peak current value in 0.03~20.00 μm of ol/L concentration range
Good linear relationship.
Advantageous effect：(1) the present invention provides a kind of completely new molecular imprintings quantitatively detected for salbutamol
Learn electrode and chemical sensor, the electrode or sensor has excellent selectivity to salbutamol；(2) sand is used for described in
The chemical electrode or chemical sensor that butylamine alcohol quantitatively detects 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 in the prior art) and good stability,
Anti-interference and reproducibility；(3) easy to operate, of low cost based on the salbutamol electrochemical sensor of the invention built,
Drug and food quality control, clinical medical assistance and environmental monitoring etc. have a wide range of applications.
Description of the drawings
Fig. 1 is scanning electron microscope (SEM) photograph (A), transmission electron microscope picture (B), the energy of Ag-N-RGO nanocomposites of the present invention
Spectrogram (C) and Raman spectrogram (D).
Fig. 2 is the preparation process of MIP/Ag-N-RGO traces electrode of the present invention.
Fig. 3 is the MIP/Ag-N-RGO trace electrodes (a) and the non-trace electrodes (b) of NIP/Ag-N-RGO prepared by the present invention
In 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 salbutamols following on MIP/Ag-N-RGO trace electrodes (a) and the non-trace electrodes (b) of NIP/Ag-N-RGO
Ring volt-ampere curve.
DPV curve of Fig. 5 (A) various concentration salbutamols on MIP/Ag-N-RGO trace electrodes, (B) various concentration are husky
Linear relationship chart of the butylamine alcohol on MIP/Ag-N-RGO trace electrodes between its oxidation peak current value.
Fig. 6 salbutamols and interfering substance are on MIP/Ag-N-RGO traces electrode and the non-trace electrodes of NIP/Ag-N-RGO
Current-responsive.
Specific implementation mode
The present invention is explained further below in conjunction with specific embodiment, but embodiment does not do any type of limit to the present invention
It is fixed.
The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Wherein, used
Production firm person is not specified in reagent or instrument, and being can be with conventional products that are commercially available.
The preparation for the molecular imprinting electrode that embodiment 1 is quantitatively detected for salbutamol be (MIP/Ag-N-RGO electrodes
It prepares)
S1. graphene oxide is dispersed in water, obtains dispersion liquid, the amount ratio of the graphene oxide and water is 1mg:
2mL；
S2. it is 30% NH to use mass fraction3·H2The pH value of dispersion liquid is adjusted to 10 by O, is then added under agitation
Urea forms mixed liquor, and the addition quality of the urea is 100 times of graphene oxide quality described in step S1；
S3. above-mentioned mixed liquor is carried out being heated to 120 DEG C of reaction 12h in hydrothermal reaction kettle；
S4. centrifuging and taking precipitates after reaction solution cooling step S3 obtained, and N doping oxygen reduction fossil is obtained after washing, drying
Black alkene (N-RGO)；
S5. N doping redox graphene ultrasonic disperse in water is taken, glucose is then added and forms solution A, it is described
N doping redox graphene, water and glucose amount ratio be 1mg:1mL:21mg；
S6. by NH3·H2O solution is added in silver nitrate solution, is first precipitated, and NH is continuously added3·H2O solution is straight
It disappears to precipitation and obtains silver ammino solution (Ag (NH3)2OH solution), form solution B, the NH3·H2O's is a concentration of
0.37mol/L, a concentration of 0.04mol/L of silver nitrate solution；
S7. solution B and solution A are mixed, is stirred to react 1h, is then aged 5h, through centrifugation, washing, dry that silver-colored/nitrogen is total
The volume ratio of doping redox graphene (Ag-N-RGO) nanocomposite, the solution B and solution A is 1:2；
S8. it takes silver/nitrogen co-doped redox graphene nanocomposite to be scattered in dimethylformamide, then applies
The surface for overlaying on working electrode obtains silver-colored/nitrogen co-doped redox graphene modified electrode (Ag-N-RGO modified electrodes), described
Silver/nitrogen co-doped redox graphene nanocomposite and organic solvent amount ratio be 1mg:1mL；The work
Electrode is glass-carbon electrode；
S9. by silver/nitrogen co-doped redox graphene modified electrode be placed in o-phenylenediamine containing 1.5mmol/L and
Cyclic voltammetry scanning is carried out in the PBS buffer solutions of 0.5mmol/L salbutamols；The cyclic voltammetry scanning voltage
For -0.3~1.0V, it is 0.05V/s to sweep speed, and the circulating polymerization number of turns is 10 circles；
S10. the H of 0.3mol/L will be placed in through the processed electrodes of step S92SO4Cyclic voltammetry scanning is carried out in solution
The salbutamol in polymeric membrane is removed, silver-colored/nitrogen co-doped redox graphene base trace electrode (MIP/Ag-N-RGO traces are obtained
Electrode).
Fig. 1 shows that the Ag-N-RGO nanocomposites that step S7 is prepared are put in 2000 times (A) and 50000 times (B)
Scanning electron microscope under big multiplying power and transmission electron microscope picture, the random high dispersive of Ag nano particles of small size is in oxygen reduction as seen from the figure
On graphite alkene lamella, entire composite material shows gauffer, more layer structures, and the metal nanoparticle grain size of load is 10-
Between 30nm.Nanoparticle size is small, dispersion degree is high and soilless sticking phenomenon, is conducive to the electro-catalysis for improving complex film modified electrode
Specific surface area active.In addition, EDAX results (C) are shown, mainly also contain Ag elements in composite material other than N, C, O,
Illustrate that the success of Ag nano particles is supported on N-RGO.Raman spectrum analysis result (D) shows graphene oxide (GO), N doping
All there is the apparent peaks D and G in redox graphene (N-RGO) and Ag/N doping redox graphenes (Ag-N-RGO)
Peak corresponds to the SP of C atoms in graphite material respectively3Sp in vibration and grapheme material face2Vibration.Meanwhile D/G peak intensities
Than the defect concentration of carbon material where having reacted.The D/G peak intensity ratios of Ag-N-RGO and N-RGO are respectively 1.23 and 1.05, far
D/G peak intensities much larger than GO illustrate that N and Ag are doped into grapheme material and can cause the distortion of graphene sheet layer than 0.48
Or new omission is produced on graphene lattice, it further demonstrates Ag and is successfully supported on N-RGO lamellas.
Fig. 2 gives step S9 about the schematic diagram for preparing MIP/Ag-N-RGO trace electrodes.It can be seen that molecule prints
The preparation process of apodized electrode includes mainly electrode modification, electropolymerization, removal template molecule, obtained molecular engram film
Electrode surface has the porous structure in many holes, is conducive to carry out specific recognition to template molecule, while improving Sha Ding
Amine alcohol is also beneficial to improve the electron transfer rate of salbutamol electro-oxidation process in the mass transfer rate of electrode surface.
Preparation (the non-traces of NIP/Ag-N-RGO of the non-trace electrode of 1 silver medal of comparative example/nitrogen co-doped redox graphene base
The preparation of electrode)
S1~S8 is the same as embodiment 1 in the preparation process of NIP/Ag-N-RGO electrodes；Step S9 is：It is gone back silver-colored/nitrogen co-doped
Former graphene oxide modified electrode is placed in the PBS buffer solutions of the o-phenylenediamine containing 1.5mmol/L between -0.3~1.0V
The non-trace electrodes of NIP/Ag-N-RGO are obtained with sweeping after fast circulating polymerization 10 encloses for 0.05V/s.
A kind of electrochemical sensor quantitatively detected for salbutamol of embodiment 2
The MIP/Ag-N-RGO traces electrode that embodiment 1 is prepared is to electricity with platinum electrode as working electrode
Pole, saturated calomel electrode are that reference electrode is assembled into three electrode test systems, and connects electrochemical workstation and must be used for husky butylamine
The electrochemical sensor that alcohol quantitatively detects.
The electrical performance testing for the electrochemical sensor that embodiment 3 is quantitatively detected for salbutamol
(1) the electron transmission performance comparison of Different electrodes
In the three electrode test systems that such as embodiment 2 is prepared, respectively with MIP/Ag-N-RGO trace electrodes (a) and
The non-trace type electrodes (b) of NIP/Ag-N-RGO are working electrode, in 10mmol/L [Fe (CN)6]3-/4-Mix 0.1mol/L KCl
Bottom liquid in carry out cyclic voltammetric and ac impedance measurement, volt-ampere test condition and be：Scanning range -0.2~0.6V, sweep 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 be more than its for non-trace
Current-responsive on membrane electrode, electrochemical impedance are respectively 130k Ω and 160k Ω on above two electrode, illustrate the present invention
The MIP/Ag-N-RGO trace electrodes of offer improve its surface mass transfer rate and electron transfer rate, and MIP/Ag-N-RGO prints
Apodized electrode is conducive to the specific recognition capability for improving sensor to salbutamol, not only improves the selectivity for improving sensor.
(2) Different electrodes compare the electrocatalysis characteristic of salbutamol
In the three electrode test systems that such as embodiment 2 is prepared, respectively with MIP/Ag-N-RGO trace electrodes (a) and
The non-trace type electrodes (b) of NIP/Ag-N-RGO are that working electrode carries out cyclic voltammetric survey in 0.1mmol/L albuterol solutions
Examination, the potential range of test is 0.3~0.8V, sweep speed 0.1V/s, Fig. 4 are test result.Husky butylamine as seen from the figure
Oxidation peak current of the alcohol on MIP/Ag-N-RGO traces electrode of the present invention is maximum (11.5 μ A), and spike potential is
0.540V.Compared with when NIP/Ag-N-RGO works electrode, salbutamol is in MIP/Ag-N-RGO traces of the present invention
Oxidation overpotential on electrode has dropped about 20mV, illustrates the MIP/Ag-N-RGO traces electrode prepared by the present invention to husky fourth
Amine alcohol has preferable electro catalytic activity, is conducive to the sensitivity for improving sensor.
(3) the Electrochemical Detection performance test for the electrochemical sensor that the present invention is prepared
The MIP/Ag-N-RGO trace electrodes that embodiment 1 is prepared assemble electrode test system using three-electrode method,
And connect electrochemical workstation (construction method is as described in Example 2)；In the phosphoric acid bottom liquid that pH is 6.4, it is with enrichment time
120s carries out differential pulse voltammetry test to a series of albuterol solutions.The operating condition of differential pulse voltammetry setting
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 the salbutamol (see Fig. 5) increases with its concentration and increased, in 0.03~20.00 μm of ol/L concentration model
It is in good linear relationship, equation of linear regression between its oxidation peak current value in enclosing：ipa(μ A)=0.1288C (μm ol/L)
+0.4536(R2=0.9925), C is salbutamol concentration, i in the equationpOxidation 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 and the reproducibility test for the MIP/Ag-N-RGO trace electrodes that the present invention is prepared
According to 6 identical MIP/Ag-N-RGO traces electrodes are prepared the step of embodiment 1, it is with this 6 electrodes respectively
Working electrode assembles electrode test system with three-electrode method and connects electrochemical workstation (construction method is as described in Example 2),
It is 120s with enrichment time, using differential pulse voltammetry to the salbutamol of same concentration in the phosphoric acid bottom liquid that pH is 6.4
It is measured.Differential pulse voltammetry setting operating condition be：Current potential increment 0.0035V, amplitude 0.050V, pulse width
The relative standard deviation of 0.055s, test sample width 0.017s, pulse period 0.45s, measurement result are 4.13%.It will be wherein one
MIP/Ag-N-RGO trace electrodes are stored in 4 DEG C of refrigerators, and the different periods of selection 6 (test the 1st time before preserving, then
Every 1 day test 1 time), the salbutamol of same concentration is measured using above-mentioned similarity condition and method, measurement it is opposite
Standard deviation is 1.96%；Show that MIP/Ag-N-RGO traces electrode provided by the invention has preferable stability and reproduction
Property.
(5) the detecting and selecting property test for the MIP/Ag-N-RGO trace electrodes that the present invention is prepared
To carry out comparative illustration, the MIP/Ag-N-RGO traces electrode and NIP/Ag-N-RGO that embodiment 1 is prepared
Non- trace electrode assembles electrode test system using three-electrode method, and connects electrochemical workstation and constitute electrochemical sensor (structure
Construction method is as described in Example 2), it has been investigated in several analogues and actual sample using differential pulse voltammetry and has often been coexisted
The influence that salbutamol is measured of several external interfering substances.Differential pulse voltammetry setting operating condition be：Current potential increases
Measure 0.0035V, amplitude 0.050V, pulse width 0.055s, test sample width 0.017s, pulse period 0.45s.Specific test method
It is to adjust a concentration of 10 μM of salbutamol in the phosphoric acid bottom liquid that pH is 6.4, is that 120s is lied prostrate by differential pulse with enrichment time
Peace method measures its oxidation peak current value；The interfering substance of 10 times of concentration is surveyed under the same conditions with identical electrode again
It is fixed.As shown in Fig. 6 results, Clenbuterol, Ractopamine, Terbutaline, dopamine, adrenaline, ascorbic acid and uric acid
Current-responsive than salbutamol lower 5.6 times of the equal interfering substances on MIP/Ag-N-RGO trace electrodes this concludes the description of this hair
The electrode of bright offer has preferable detecting and selecting property.In addition, determining these interfering substances and salbutamol in NIP/Ag-N-
Current-responsive on the non-trace electrodes of RGO, by the conduct of the ratio between its oxidation peak current value on trace electrode and non-trace electrode
Imprinting factor, the imprinting factor for obtaining salbutamol are 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；Into one
Step illustrates that MIP/Ag-N-RGO traces electrode prepared by the present invention has preferable specific recognition ability to salbutamol, can be quickly
Template molecule is efficiently identified, and provides accurate testing result.
4 actual sample of embodiment detects
Somewhere Marketing pork is taken into 100mg, after chopping, places it in 10mL pure water and is filtered after ultrasound 2h, by filtrate
It is that 6.4 phosphoric acid solution is settled to 1L as actual measurement sample to use pH.The MIP/Ag-N-RGO trace electricity that embodiment 1 is prepared
Pole assembles electrode test system using three-electrode method, and connects electrochemical workstation and constitute electrochemical sensor, utilizes difference arteries and veins
Rush the salbutamol content in the above-mentioned sample of voltammetric determination.Differential pulse voltammetry setting operating condition be：Current potential increment
0.0035V, amplitude 0.050V, pulse width 0.055s, test sample width 0.017s, pulse period 0.45s.Specific test method
It is to take above-mentioned actual measurement sample 5mL, it is 0 μM, 5 μM, 10 μM to sequentially add standard albuterol solution content, adjusts bottom liquid pH and is
6.4, it is oxidation peak current values of the 120s by differential pulse voltammetry measurement salbutamol with enrichment time, according to embodiment 3
Obtained linear relationship finds corresponding salbutamol concentration value.The opposite mark of salbutamol measured value is obtained according to the above method
Quasi- deviation is between 2.72~3.95%, and the rate of recovery is between 103.6~105.3%；Illustrate chemical-electrical provided by the invention
Pole or sensor can be used for the Accurate Determining of salbutamol content in the actual samples such as food, drug.
Claims (15)
1. a kind of preparation method of the molecular imprinting electrode quantitatively detected for salbutamol, which is characterized in that comprising as follows
Step：
S1. graphene oxide is dispersed in water, obtains dispersion liquid, the amount ratio of graphene oxide and water is 1mg:1~3mL；
S2. the pH value of dispersion liquid is adjusted to 9~11, urea is then added under agitation and forms mixed liquor, the addition of urea
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, 100~130 DEG C of 8~16h of reaction are heated to；
S4. centrifuging and taking precipitates after reaction solution cooling step 3 obtained, and N doping redox graphene is obtained after washing, drying；
S5. N doping redox graphene ultrasonic disperse in water is taken, glucose is then added and forms solution A, the nitrogen
The amount ratio for adulterating redox graphene, water and glucose is 1~3mg:1~3mL:10~30mg；
S6. by NH3·H2O solution is added in silver nitrate solution, is first precipitated, and NH is continuously added3·H2O solution is until precipitation
Disappearance obtains silver ammino solution, forms solution B, the NH3·H2A concentration of 0.3~0.4mol/L of O, silver nitrate solution it is dense
Degree is 0.03~0.05mol/L；
S7. solution B and solution A are mixed, are stirred to react 0.5~2h, be then aged 3~6h, through centrifugation, washing, it is dry it is silver-colored/
The volume ratio of nitrogen co-doped redox graphene nanocomposite, the solution B and solution A is 1:1~3；
S8. it takes silver/nitrogen co-doped redox graphene nanocomposite to be scattered in organic solvent, is then coated with and is working
The surface of electrode obtains silver-colored/nitrogen co-doped redox graphene modified electrode, the silver/nitrogen co-doped reduction-oxidation graphite
The amount ratio of alkene nanocomposite and organic solvent is 1mg:1~2mL；The organic solvent is dimethylformamide；
S9. silver/nitrogen co-doped redox graphene modified electrode is placed in containing 1.0~2.0mmol/L o-phenylenediamines and 0.3~
Cyclic voltammetry scanning is carried out in the PBS buffer solutions of 1.0mmol/L salbutamols；
S10. the H of 0.2~0.5mol/L will be placed in through the processed electrodes of step S92SO4Cyclic voltammetry scanning is carried out in solution
The salbutamol in polymeric membrane is removed, silver-colored/nitrogen co-doped redox graphene base trace electrode is obtained, i.e., described is used for husky fourth
The molecular imprinting electrode that amine alcohol quantitatively detects；
Cyclic voltammetry scanning voltage described in step S9 is -0.3~1.0V, and it is 0.05V/s to sweep speed, and the circulating polymerization number of turns is
10 circles；Cyclic voltammetry scanning voltage is -0.3~1.0V in step S10, and it is 0.05V/s to sweep speed.
2. preparation method according to claim 1, which is characterized in that the amount ratio of graphene oxide and water is in step S1
1mg:2~3mL.
3. preparation method according to claim 2, which is characterized in that the amount ratio of graphene oxide and water is 1mg:2mL.
4. preparation method according to claim 1, which is characterized in that the addition quality of urea is in step S1 in step S2
100~150 times of the graphene oxide quality；The NH for being 20~40% with mass fraction in step S23·H2O adjusts dispersion
The pH value of liquid is to 9~11.
5. preparation method according to claim 4, which is characterized in that the addition quality of urea is to be aoxidized described in step S1
100 times of graphene quality；The NH for being 30% with mass fraction3·H2O adjusts the pH value of dispersion liquid to 10.
6. preparation method according to claim 1, which is characterized in that the heating described in step S3 is in hydrothermal reaction kettle
It is heated；It is heated to 120~130 DEG C of 10~14h of reaction.
7. preparation method according to claim 6, which is characterized in that be heated to 120 DEG C of reaction 12h.
8. preparation method according to claim 1, which is characterized 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；NH described in step S63·H2O's is a concentration of
0.37mol/L, a concentration of 0.04mol/L of silver nitrate solution.
9. preparation method according to claim 8, which is characterized in that the N doping reduction-oxidation graphite described in step S5
The amount ratio of alkene, water and glucose is 1mg:1mL:21mg.
10. preparation method according to claim 1, which is characterized in that the volume of solution B and solution A described in step S7
Than being 1:2；It is stirred to react 1~2h, is then aged 5~6h；Silver/nitrogen co-doped redox graphene described in step S8 is received
The amount ratio of nano composite material and organic solvent is 1mg:1mL.
11. preparation method according to claim 10, which is characterized in that be stirred to react 1h in step S7, be then aged 5h.
12. preparation method according to claim 1, which is characterized in that o-phenylenediamine is a concentration of in step S9
1.5mmol/ L, a concentration of 0.5mmol/L of salbutamol；H in step S102SO4A concentration of 0.3mol/L of solution.
13. a kind of preparation method of the molecular imprinting electrochemical sensor quantitatively detected for salbutamol, which is characterized in that
Include the following steps：The silver that any one of claim 1~12 is prepared/nitrogen co-doped redox graphene base trace electricity
Extremely working electrode, using platinum electrode as auxiliary electrode, electricity is assembled using three-electrode method using saturated calomel electrode as reference electrode
Pole test system, connection electrochemical workstation must be used for the electrochemical sensor that salbutamol quantitatively detects.
14. the molecular engram quantitatively detected for salbutamol that a kind of preparation method by described in claim 13 is prepared
Type electrochemical sensor.
15. a kind of method that salbutamol quantitatively detects, which is characterized in that use the electrochemical sensing described in claim 14
Device detects the salbutamol content in sample, the actual conditions of the differential pulse voltammetry detection with differential pulse voltammetry
For：Bottom liquid is the phosphate buffer that pH is 6.4, enrichment time 120s；The operation item of the differential pulse voltammetry setting
Part 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=0.1288C+0.4536, linearly dependent coefficient R2=0.9925, C is salbutamol in the equation
Concentration, unit are μm ol/L；Ipa is that differential pulse voltammetry obtains oxidation peak current value, and unit is μ A.
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