CN108120652A - A kind of preparation method of amantadine molecular engram film piezoelectric transducer - Google Patents
A kind of preparation method of amantadine molecular engram film piezoelectric transducer Download PDFInfo
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- CN108120652A CN108120652A CN201611072477.6A CN201611072477A CN108120652A CN 108120652 A CN108120652 A CN 108120652A CN 201611072477 A CN201611072477 A CN 201611072477A CN 108120652 A CN108120652 A CN 108120652A
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- amantadine
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- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229960003805 amantadine Drugs 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052737 gold Inorganic materials 0.000 claims abstract description 26
- 239000010931 gold Substances 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 23
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002114 nanocomposite Substances 0.000 claims abstract description 21
- 229920000344 molecularly imprinted polymer Polymers 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 238000010828 elution Methods 0.000 claims abstract description 8
- 230000004044 response Effects 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical class NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 claims description 14
- 238000004070 electrodeposition Methods 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 12
- 239000010453 quartz Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- -1 graphite alkene Chemical class 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000002484 cyclic voltammetry Methods 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 6
- 238000001338 self-assembly Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 241000252506 Characiformes Species 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 230000002045 lasting effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000002094 self assembled monolayer Substances 0.000 claims description 2
- 239000013545 self-assembled monolayer Substances 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- CTRSTUUBBQTFST-UHFFFAOYSA-N [S].NC1=CC=CC=C1 Chemical group [S].NC1=CC=CC=C1 CTRSTUUBBQTFST-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 13
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 235000013305 food Nutrition 0.000 abstract description 6
- 241001465754 Metazoa Species 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000011540 sensing material Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 11
- 238000003380 quartz crystal microbalance Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000276 potassium ferrocyanide Substances 0.000 description 4
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 4
- 239000003443 antiviral agent Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 208000031295 Animal disease Diseases 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 241000272201 Columbiformes Species 0.000 description 1
- 244000118681 Iresine herbstii Species 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 206010029350 Neurotoxicity Diseases 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 206010064097 avian influenza Diseases 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 206010022000 influenza Diseases 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000001012 micellar electrokinetic chromatography Methods 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
- 230000007135 neurotoxicity Effects 0.000 description 1
- 231100000228 neurotoxicity Toxicity 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 239000011238 particulate composite Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- 230000002463 transducing effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01G—WEIGHING
- G01G3/00—Weighing apparatus characterised by the use of elastically-deformable members, e.g. spring balances
- G01G3/12—Weighing apparatus characterised by the use of elastically-deformable members, e.g. spring balances wherein the weighing element is in the form of a solid body stressed by pressure or tension during weighing
- G01G3/13—Weighing apparatus characterised by the use of elastically-deformable members, e.g. spring balances wherein the weighing element is in the form of a solid body stressed by pressure or tension during weighing having piezoelectric or piezoresistive properties
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
- G01N29/04—Analysing solids
- G01N29/12—Analysing solids by measuring frequency or resonance of acoustic waves
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2291/00—Indexing codes associated with group G01N29/00
- G01N2291/01—Indexing codes associated with the measuring variable
- G01N2291/014—Resonance or resonant frequency
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Acoustics & Sound (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation method and application of amantadine molecular engram film piezoelectric transducer.Amantadine molecular engram film piezoelectric transducer is prepared by pretreatment, the modification of graphene oxide Jenner's nano composite material, electric polymerization reaction, template molecule elution step successively in quartzy gold electrode.Molecular engram sensing material prepared by the present invention is adulterated by graphene oxide and gold nano grain, increases imprinted sites to improve sensitivity.Molecularly imprinted polymer selection specific recognition is miniaturized the molecular engram piezoelectric transducer with piezoelectric transducer, it is label-free, the advantages that high sensitivity and quick response, combines, a kind of simple, quick, special, sensitive piezoelectric sensing detection method is provided to the amantadine residual in animal derived food, the detection range of linearity to amantadine is 1.0 × 10‑5~1.0 × 10‑3mmol L‑1。
Description
Technical field
The invention belongs to technical field of analysis and detection, and in particular to a kind of amantadine molecular engram film piezoelectric transducer
Preparation method.
Background technology
Antiviral drugs amantadine tool is usually used in treating influenza and Parkinson's synthesis there are one the tricyclic amine structure stablized
Sign.Excessive can cause a series of side effect, such as viral resistance and neurotoxicity (including neural mistake using amantadine
It is quick, anxiety, illusion etc.).Due to its harm to the mankind, many countries have been prohibited using amantadine as a kind of antiviral
Drug is used for home poultry raising.However, this drug is still illegally applied to the treatment and prevention of the Animal diseases such as bird flu.Cause
This, foundation is a kind of sensitive, highly selective, and quick, low cost method is to detect amantadine residual in animal derived food
It is very necessary.At present, a variety of analysis methods based on different principle are had built up for antiviral drugs amantadine residual,
Including high performance liquid chromatography, LC-MS technology, gas chromatography, low-polarity components, Capillary Electrophoresis, micellar electrokinetic chromatography
Method and bioanalysis etc..
Quartz crystal microbalance (Quartz Crystal Microbalance, QCM) is a kind of simple, of low cost, tool
There is the novel device of high quality sensing resolution ratio, since it can other mass change carries out spirit to being supported on the nanogram level on its surface
Quick response, and label-free reaction process can be directly researched, it is widely used in biochemistry, environment, food and clinical analysis
Etc. every field.Molecularly imprinted polymer (Molecularly imprinting polymer, MIP) is due to it has selectivity
It is applied in QCM.Molecular imprinting technology is combined with QCM, the advantage for realizing two kinds of new technologies combines, and can realize pair
The Selective recognition of trace materials and highly sensitive detection.Electropolymerization is a kind of common molecularly imprinted polymer synthesis mode, can
Control property is good, can be in the uniform analyte identification film of the direct preparation structure of transducer face.Gold nano grain can enhance transducing electricity
The electron transfer rate of pole overcomes electron transmission barrier, and then effectively improves the sensitivity of electrochemical sensing detection.Graphene material
Material also has fabulous electric conductivity, and with big specific surface area, composite material has electro catalytic activity synergistic effect, can be with
For enhancing the sensitivity of sensor.
Here we one kind is constructed by way of electro-deposition near amino thiophenols can be to amantadine specific recognition
With the molecular engram qcm sensor of detection.The molecular engram qcm sensor of the preparation provides one kind simply, convenient, cheaply,
Amantadine of the highly sensitive method for directly measuring in animal derived food remains.This research is by the specificity of molecular engram
Identification is combined with highly sensitive, the convenience of qcm sensor, is increased by electro deposition oxidation graphene-Jenner's nano composite material
Bonus point sub- imprinted sites improve sensitivity.Advantage of the molecular engram qcm sensor prepared simultaneously in terms of application also obtains
Verification is arrived.
Preparing amantadine molecular engram film piezoelectric transducer and its application study with electrodeposition process at present, there is not been reported.
The content of the invention
In view of this, the present invention constructs confrontation for the first time using amantadine as template by electro-deposition near amino thiophenols
Virus drugs amantadine has the molecular engram piezoelectric transducer of unique identification feature；Simultaneously based on graphene and gold nano
Particulate composite acts synergistically with electro catalytic activity, improves sensor detection sensitivity.The sensor provides a kind of letter
Single, convenient, cheaply, amantadine of the highly sensitive method for directly measuring in animal derived food remains.It is above-mentioned to reach
Purpose, what the technical solution of the invention was realized in：
A kind of preparation method of amantadine molecular engram film piezoelectric transducer, the electrochemical sensing system include work
Electrode, reference electrode and the stone modified for molecular engram graphene oxide-Jenner's nano composite material electrode, the working electrode
English crystal oscillator gold electrode, reference electrode are saturation potassium chloride electrode, are platinum electrode to electrode, include the following steps：
(1) AT cuts the pretreatment of quartz crystal oscillator gold electrode；
(2) modification of graphene oxide-Jenner's nano composite material
(step 1) will be pre-processed, and quartzy gold electrode is placed in 20mL graphene oxides/HAuCl afterwards4Mixed liquor (HAuCl4And oxygen
The concentration of graphite alkene is respectively 1mmol/L and 1mg/mL) in, lasting to stir, voltage range is -1.5~0.5V, sweep speed
For 50mV s-1, cycle twice, electro deposition oxidation graphene-Jenner's nano composite material.
(3) near amino thiophenols self assembly
The quartzy gold electrode of step 2 deposited oxide graphene-Jenner's nano composite material is immersed in 10mmol/L neighbour's amino
It is handled overnight in benzenethiol solution, forms near amino thiophenols self assembled monolayer.
(4) electro-deposition amantadine molecular imprinted polymer membrane
By the gold electrode of monomer self assembly in step 3 in methanol pre-polymer solution, electro-deposition prepares amantadine molecule
Imprinted polymer.The condition of scanning is+0.2V to+1.4V, sweeps fast 50mV s-115 circle of effect.
(5) elution of template molecule
With 1.0mol L-1HCl solution elution is trapped in the amantadine molecule in molecular imprinted polymer membrane, dosage 30
μ L, action time are 15 minutes, in triplicate.
Further, the electrode pretreatment is that AT cutting quartz crystal oscillator gold electrodes are placed in ultrasound in ethyl alcohol, is then submerged
(the 30%H in " Piranha " solution2O2:98%H2SO4=1:3, v/v) 5min is impregnated, then cleans to remove with distilled water
Other pollutants；Then, by electrode in 0.05mol L-1H2SO4In solution+1.5V models are arrived in -0.2V using cyclic voltammetry
Interior scanning is enclosed, until obtaining stable electrochemical response, is then dried in air；
Further, graphene oxide-Jenner's nano composite material that step (2) obtains is, it is necessary to which the condition in lasting stirring is electric
Deposition obtains, and wherein voltage range is -1.5~0.5V, and sweep speed is 50mV s-1, Xun Huan is twice.
Further, the electrode for the near amino thiophenols monolayer modification that step (3) obtains is by the way that quartz crystal oscillator is golden
Electrode is immersed in what processing overnight in 10mmol/L near amino thiophenols solution obtained.
Further, near amino thiophenols 30mmol L are included in step (4) in methanol prepolymerization liquid-1；Amantadine
10mmol L-1；Tetrabutylammonium perchlorate 5mmol L-1；HCl 10mmol L-1；Dosage is 50mL, advance letting nitrogen in and deoxidizing 10min；
Cyclic voltammetry scan method is 15 circle of scanning in the range of+0.2V~+1.4V, and sweep speed is 50mV s-1。
Further, HCl concentration described in step (5) is 1.0mol L-1, dosage is 30 μ L, and elution time is 15 minutes.
Detection method
At room temperature i.e. 25 DEG C, it is 1.0 × 10 that molecular imprinting modification electrode made from step (5), which is placed in containing concentration,- 5mmol L-1To 1.0 × 10-3mmol L-1Amantadine-methanol solution in, according to the frequency of qcm sensor under various concentration
Change different measure target analytes contents.
The assay method of amantadine content：
As object amantadine concentration gradually increases, molecular engram film can combine more and more target molecules, draw
Play quartz crystal frequency attenuation.In amantadine concentration 1.0 × 10-5-1.0×10-3mmol L-1In the range of, the molecule print of preparation
The frequency variation of mark qcm sensor has good linear corresponding relation with amantadine concentration.The detection of amantadine is limited to
5.40×10-6mmol L-1(S/N=3).
The method have the advantages that：The building process of mentioned molecular engram qcm sensor is simple, controllable, favorable reproducibility, institute
The molecular engram qcm sensor of structure is good to the detection stability of object amantadine, high sensitivity, detection limit are low, for
The detection of trace amantadine is easy to automate in actual sample.
Description of the drawings
The attached drawing for forming the part of the invention is used for providing further understanding the invention.
Six different modifying electrodes of Fig. 1 are in 1.0mmol L-1Cyclic voltammogram in potassium ferricyanide solution.(a) naked gold electricity
Pole；(b) graphene oxide-Jenner's nano composite material modified electrode；(c) the amantadine trace electrode of removing template is not removed；(d) go
Amantadine trace electrode after removing template；(e) the amantadine trace electrode after adsorbing again；(f) non-trace electrode.
Tri- Different electrodes of Fig. 2 are in 2.50mmol L-1Impedance diagram in the potassium ferricyanide/potassium ferrocyanide solution.(a) naked gold
Electrode；(b) graphene oxide-Jenner's nano composite material modified electrode；(c) the amantadine trace electrode after removing template is removed；(d)
Amantadine trace electrode after adsorbing again；(e) non-trace electrode.
Specific embodiment
The schematic description and description of the invention does not form and the present invention is created for explaining the invention
The improper restriction made.Explanation and specific embodiment are described in further detail the present invention below in conjunction with the accompanying drawings.
Embodiment 1
(1) electrode pre-processes；
(2) modification of graphene oxide-Jenner's nano composite material
(3) near amino thiophenols self assembly
(4) electro-deposition
(5) template molecule elution
Different modified electrodes is in 1.0mmol L shown in Fig. 1-1Cyclic voltammetry scan collection of illustrative plates in potassium ferricyanide solution.Such as figure
Shown, bare electrode shows a pair of typical redox peaks (curve a).When electrode surface covers graphene oxide-Jenner
Rice function and service object, redox current significantly increase (curve b).(curve c), molecular engram oxidation stone before template removal
The electric current very little of black alkene-Jenner's nano composite material modified electrode；(curve d), a pair of of redox peaks weight after template removes
It is new to occur.This forms trace hole the result shows that after template molecule is removed in molecular engram polymeric film surface.Iron cyanogen
Redox reaction can be completed by hole in electrode surface diffusion by changing potassium probe.And then demonstrate graphene oxide-gold
Nano functional compound is effectively increased electrode active area and catalytic activity.Curve e is molecular engram graphene oxide-gold
Nanocomposite modified electrode is 1.0 × 10-3mmol L-1Cyclic voltammogram after being impregnated in amantadine solution.This can
Diffusion of the potassium ferricyanide probe in electrode surface is prevented to be construed to being re-incorporated into behind trace hole for amantadine.With molecule
Trace graphene oxide-Jenner's nano composite material modified electrode compares, and non-trace graphene oxide-Jenner's nano composite material is repaiied
Adoring electrode, (curve f) is barely perceivable electrochemical response, this may be because non-conductive non-imprinted polymer film film covers
Surface, it is suppressed that electronics shifts.
Fig. 2 is shown in 2.5mmol L-1To the electronics of different modified electrodes in the potassium ferricyanide/potassium ferrocyanide solution
The impedance spectra that transfer case is characterized.Such as Fig. 2, (curve a) is to the probe potassium ferricyanide/potassium ferrocyanide solution exhibition for bare electrode
Low electronics transfer resistance is shown.When electrode face finish after graphene oxide-Jenner's nano composite material, in curve b we
It almost observed straight line.This is because graphene oxide-gold nano decorative layer accelerates electronic transfer process.Curve e
Show the electrochemical impedance collection of illustrative plates on non-imprinted polymer modified electrode surface as expected, half circular diameter of curve e
It significantly expands, this shows that nonconducting non-imprinted polymer film prevents the infiltration of redox probe.With curve e ratios
Compared with curve c shows relatively small half circular diameter, this is because in graphene oxide-Jenner's nano composite material modification
Electrode surface forms substantial amounts of specific recognition site, when passing through molecular imprinted polymer membrane which enhance redox probe
Diffusivity, accelerate electronic transfer process.When by molecular imprinted polymer membrane modified electrode 1.0 × 10-3mmol L-1Gold
After being impregnated in firm alkanamine solution, it can be found that an electronics shifts the increase of resistance, this is because amantadine molecule in curve d
It is combined site capture, it is suppressed that the potassium ferricyanide/potassium ferrocyanide solution-The diffusion process of probe.These results illustrate to modify
Graphene oxide-gold nano function and service object can effectively accelerate electronic transfer process, expand electroactive area, therefore,
Molecular engram graphene oxide-Jenner's nano composite material modified electrode successfully constructs.
(6) detection process
At room temperature i.e. 25 DEG C, molecular imprinting modification electrode made from step (5) is placed in concentration as 1.0 × 10-5~1.0
×10-3mmol L-1Amantadine methanol solution in, record quartz crystal oscillator gold electrode frequency variation.The linear correspondence of gained
Equation is：- Δ f=3.166CAM+11.18(R2=0.995).5.40 × 10 are limited to the detection of amantadine-6mmol L-1
(S/N=3).
Embodiment 2
(7) in actual sample amantadine content measure：
The amantadine residual in actual sample (pigeon breast, chicken gizzard, egg) is analyzed using inventive sensor
It measures.Sample is pre-processed by Solid Phase Extraction, and extract is redissolved in 20.0mL methanol, for constructed molecular engram QCM
Biosensor analysis.
Specific data such as table 1：
1 sample recovery of standard addition of table
It is this using electro-deposition method quartz crystal gold electrode surfaces synthesizing amantadine molecular imprinted polymer membrane as
The piezoelectric transducer of recognition component structure, can be applied to the accurate analysis of trace amantadine in animal derived food.
It should be noted that in the case where there is no conflict, the feature in embodiment and embodiment in the invention can
To be mutually combined.
The foregoing is merely the preferred embodiments of the invention, are not intended to limit the invention creation, all at this
Within the spirit and principle of innovation and creation, any modifications, equivalent replacements and improvements are made should be included in the invention
Protection.
Claims (6)
- A kind of 1. preparation method of amantadine molecular engram film piezoelectric transducer, which is characterized in that the piezoelectric transducer system It is standby to include the following steps：(1) electrode pre-processes；Quartz crystal gold electrode is ultrasonic in ethanol, it is then impregnated 5 minutes with freshly prepd " Piranha " solution, with double steamings Water cleans up, in 0.05mol L-1H2SO4Cyclic voltammetric (potential range is carried out in solution：- 0.2V~+1.5V) scanning until Electric current is stablized, and then quartz crystal gold electrode is dried up with nitrogen, is fixed on flow cell；(2) modification of graphene oxide-Jenner's nano composite material(step 1) will be pre-processed, and quartz crystal oscillator gold electrode is placed in 20mL graphene oxides/HAuCl afterwards4Mixed liquor (HAuCl4And oxygen The concentration of graphite alkene is respectively 1mmol/L and 1mg/mL) in, lasting to stir, voltage range is -1.5~0.5V, sweep speed For 50mV s-1, it cycles twice, electro deposition oxidation graphene-Jenner's nano composite material, after distilled water and washes of absolute alcohol, Nitrogen dry up, be stored in 4 DEG C it is spare；(3) near amino thiophenols self assemblyThe quartz crystal oscillator gold electrode of deposited oxide graphene-Jenner's nano composite material is immersed in 10mmol L-1Adjacent aminobenzene sulphur It handles, is protected from light overnight in phenol solution, form near amino thiophenols self assembled monolayer；(4) electro-deposition amantadine molecularly imprinted polymerThe gold electrode of monomer self assembly in step 3 is taken out, is cleaned up with ethyl alcohol and distilled water, it is molten in 50mL methanol prepolymerizations It in liquid, is enclosed in potential range+0.2V~+1.4V cyclic voltammetry scans 15, electro-deposition amantadine poly near amino thiophenols molecule Imprinted polymer sweeps speed as 50mV s-1；(5) elution of template moleculeUse 30 μ L 1.0mol L-1HCl solution elution is trapped in the template amantadine molecule in molecular imprinted polymer membrane, Each 15min, in triplicate, then, after the molecularly imprinted polymer modified electrode of acquisition is cleaned with distilled water and methanol, nitrogen It dries up spare.
- 2. a kind of preparation method of amantadine molecular engram film piezoelectric transducer according to claim 1, feature exist In in step (1), quartz crystal gold electrode surfaces use absolute ethyl alcohol ultrasound 10min, are then immersed in " Piranha " solution Middle 5min；Afterwards in 0.05mol L-1H2SO4Cyclic voltammetry scan in solution, potential range is -0.2V~+1.5V, until obtaining Stable electrochemical response.
- 3. a kind of preparation method of amantadine molecular engram film piezoelectric transducer according to claim 1, feature exist In, in step (2), gold electrode surfaces electro-deposition synthesize graphene oxide-Jenner's nano composite material, electric potential scanning scope for- 1.5~0.5V sweeps speed as 50mVs-1, Xun Huan is twice.
- 4. a kind of preparation method of amantadine molecular engram film piezoelectric transducer according to claim 1, feature exist When, step (3) self assembly near amino thiophenols monolayer, near amino thiophenols solution concentration is 10mmol L-1, locate overnight Reason.
- 5. a kind of preparation method of amantadine molecular engram film piezoelectric transducer according to claim 1, feature exist In the potential range of step (4) electro-deposition near amino thiophenols is+0.2V~+1.4V, and 15 circle of scanning sweeps speed as 50mV s-1。
- 6. a kind of preparation method of amantadine molecular engram film piezoelectric transducer according to claim 1, feature exist In HCl concentration is 1.0mol L described in step (5)-1, dosage is 30 μ L, and elution time is each for 15 minutes.
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| CN110186974A (en) * | 2019-06-01 | 2019-08-30 | 温州生物材料与工程研究所 | A kind of wearable lactate detection device and preparation method thereof |
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| CN110186974A (en) * | 2019-06-01 | 2019-08-30 | 温州生物材料与工程研究所 | A kind of wearable lactate detection device and preparation method thereof |
| CN110186974B (en) * | 2019-06-01 | 2024-01-09 | 温州生物材料与工程研究所 | Wearable lactic acid detection device and preparation method thereof |
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Application publication date: 20180605 |