CN102749372A - SnO2 based electrochemical biological chip and preparation method and application - Google Patents
SnO2 based electrochemical biological chip and preparation method and application Download PDFInfo
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- CN102749372A CN102749372A CN2012101840159A CN201210184015A CN102749372A CN 102749372 A CN102749372 A CN 102749372A CN 2012101840159 A CN2012101840159 A CN 2012101840159A CN 201210184015 A CN201210184015 A CN 201210184015A CN 102749372 A CN102749372 A CN 102749372A
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Abstract
The invention relates to a SnO2 based electrochemical biological chip and a preparation method and an application, a liquid direct precipitation method is used for preparing a spherical SnO2 nano-material, a spin coating method is used for coating the SnO2 nano particles on a silicon chip surface to form a SnO2-silicon combined electrode, and the SnO2-silicon combined electrode is taken as a sensitive membrane to assemble a biological detection chip from ethephon residual detection. In the process, an electrochemical impedance spectroscopy (EIS) is used for investigating the stability of the SnO2 nano membrane in a buffer solution and change of electrochemical property before ethephon adsorption and after ethephon adsorption, and a X-ray photoelectron spectroscopy (XPS) is used for investigating the material composition change before ethephon adsorption and after ethephon adsorption. The result shows that SnO2-silicon combined electrode has good stability, and the ethephon can successfully absorb on the ethephon nano coating, because the change of interfacial charge transfer constant enables sensitive detection for the existence of ethephon in the solution, when the ethephon concentration reaches as low as 3.58, the electrochemical impedance spectroscopy is used for detecting the Rct change.
Description
Technical field
The present invention relates to electrochemical field, be specifically related to a kind of SnO
2The based electrochemical biochip also relates to a kind of this SnO simultaneously
2The preparation method of based electrochemical biochip also relates to its application aspect the ethephon (CEPHA) residue detection simultaneously.
Background technology
Ethephon (CEPHA) (ethephon) can decompose generation ethene in plant, promote fruit maturation, is used as ripener and is widely used in the crops such as vegetables, fruit.According to pesticide toxicity grading criteria, ethephon (CEPHA) belongs to low toxicity plant growth regulator (LD
50Be 4290mg/kg, rat, per os) (He Rui, etc., the safety problem during plant growth regulator uses, 2003).Clinic study shows, certain density ethephon (CEPHA) can cause part and brain, renal damage (Chen Yusheng, etc., the three example reports of plant stimulant ethephon (CEPHA) agent acute poisoning, 1989).Therefore, long-term edible contain the residual fruits and vegetables that exceed standard of ethephon (CEPHA), can play consumer's slow poisoning or pathology, the consumer is had potential carcinogenic, teratogenesis and other many-sided adverse effect.
Although, the residual of ethephon (CEPHA) in the fruits and vegetables having been proposed the strict requirement of limiting the quantity of both at home and abroad, and a large amount of research has been carried out in the detection of ripener residual quantity, China does not also issue relevant detection standard and detection means so far.Therefore, be difficult to use ripener to carry out effective monitoring to the vegetable grower, cause abuse, blindly use ripener in violation of rules and regulations, detect national standard for formulating ripener as early as possible, research advanced person's ripener detection method is particularly necessary.
Nano SnO
2It is a kind of typical n type, semiconductor material; Characteristics such as have that specific surface area is big, high activity, low melting point, thermal conductivity are good, and then have good electrical property, catalytic performance and optical property and be widely used in aspects such as gas sensor, semiconductor element, electrode material, catalyzer and solar cell.In recent years, nano SnO
2As electrochemical sensor and bio-sensing modulator material report is arranged also, as with SnO
2Be coated in and can be used as glucose biological sensor on the electro-conductive glass and use (liao, C, etal, sensorrs and actuators B-chemical, 2007); And be compounded with SnO
2The graphite electrode of nano material also can be used as the sensitive membrane (Muti Mihrican, etal, colloids and surfaces B-biointerfaces, 2011) of DNA chip; Adopt the prepared SnO of going out of electrochemical deposition
2Nano thin-film has fixedly character (Chu DeWei, etal, chemical engineering journal, 2011) of good DNA.But SnO
2Application as food safety detection biochip aspect does not appear in the newspapers.
Summary of the invention
In order to solve above-mentioned ethephon (CEPHA) residue problem, the object of the present invention is to provide a kind of SnO
2The based electrochemical biochip.
The present invention also aims to provide a kind of SnO
2The preparation method of based electrochemical biochip and application thereof.
To achieve these goals, technical scheme of the present invention has adopted a kind of SnO
2The based electrochemical biochip, the employing three-electrode system in its described biochip is with the SnO of preparation
2-silicon combination electrode is as working electrode, and the AgAgCl electrode is as contrast electrode, and the Pt electrode is as auxiliary electrode.
Technical scheme of the present invention has also adopted a kind of SnO
2The preparation method of based electrochemical biochip may further comprise the steps:
(1) the liquid phase direct precipitation method prepares nano SnO
2
With NaOH solution and SnC
L45H
2SnO centrifugal, that be drying to obtain pressed powder is carried out in the reaction that is hydrolyzed of O solution then
2
(2) adopt spin-coating method with SnO
2Nano particle is coated in silicon chip surface, as ethephon (CEPHA) detection chip sensitive membrane, is assembled into SnO
2-silicon combination electrode, and accomplish SnO
2The assembling of based electrochemical biochip.
The ethephon solution compound concentration is 3.58 * 10-in the said step (2)
12Mol/L.
Technology of the present invention has also adopted a kind of biochip to the application in the ethephon (CEPHA) residue detection; The detection of ethephon (CEPHA) may further comprise the steps: (1) preparation potassium ferricyanide-potassium ferrocyanide electrolyte solution is prepared ethephon solution as solvent; (2) the ethephon (CEPHA) absorption behavior is tested the ethephon (CEPHA) absorption behavior through the electrochemical AC impedance spectrometry.
The present invention adopts the liquid phase direct precipitation method to prepare nano SnO
2Material, and through spin-coating method nano material is coated on the silicon electrode, and learn SnO by the electrochemical AC impedance collection of illustrative plates
2-silicon combination electrode has good stable property at biological buffer solution.When having ethephon (CEPHA) in the buffer solution and since the ethephon (CEPHA) molecule on have phosphate group, can with SnO
2The surface generates stable covalent bond, and then is adsorbed on SnO securely
2On the surface.Therefore, after ethephon (CEPHA) absorption, strong element P signal has appearred in XPS spectrum figure.Through related software the electrochemical AC impedance collection of illustrative plates is carried out sunykatuib analysis, the result shows, SnO
2Nanometer has been improved the electric conductivity of silicon electrode, causes the reduction of Rct value, and after ethephon (CEPHA) was gone up in absorption, organic molecule covered the combination electrode surface, has hindered the transfer of electric charge, causes R
CtIncrease.When ethephon (CEPHA) concentration is low when reaching 3.58pM, adopt the electricity AC impedence method still can detect R
CtVariation, thereby realized sensitive fast detecting to ripener ethephon (CEPHA) molecule.This result provides theory and experiment basis for nano material as the food safety detection sensor.
Description of drawings
Fig. 1: SnO
2The XRD figure spectrum of nano particle;
Fig. 2: a is pressed powder SnO
2SEM figure; B is pressed powder SnO
2TEM figure;
Fig. 3: at assembling back electrochemical AC impedance figure under the different time in buffer solution on the silicon electrode;
Fig. 4: silicon electrode, SnO
2Assembling back combination electrode and ethephon (CEPHA) micromolecule absorption back combination electrode are at Fe (CN)
6-/Fe (CN)
6AC impedance curve in the-reductant-oxidant;
Fig. 5: figure a, figure b and figure c are and adopt XPS to being adsorbed with the SnO of ethephon (CEPHA)
2Nano-material surface chemical composition analysis figure;
Fig. 6: SnO
2Electrochemical sensor constitutes schematic drawing.
Embodiment:
Following is main test reagent and instrument:
Crystallization butter of tin (SnCl
45H
2O): analyze pure, Tianjin Ke Miou chemical reagents corporation; NaOH (NaOH): analyze pure, Tianjin reagent three factories; Absolute ethyl alcohol (C
2H
5OH): analyze pure, Tianjin Fengchuan Chemical Reagent Science & Technology Co., Ltd.; Ethephon (CEPHA) (2 chloroethyl phosphoric acid, C
2H
6ClO
3P): 90%, Alfa Aesar; Deionized water: resistivity is made by oneself greater than 18.2MQcm; Heat collecting type heated at constant temperature magnetic stirring apparatus: DF-101D, Gongyi City give magnificent Instr Ltd.; Low speed tube centrifuge: TDL80-2C, last Hai'an booth instrument company; Electric heating constant temperature blast drier: DHG-9146A, the grand experimental facilities of last Nereid company limited; Electronic balance: EL104, Mettler-Toledo Instrument (Shanghai) Co., Ltd.; Desk-top sol evenning machine: Kw-4A, the Microelectronics Center, Academia Sinica; Muffle furnace: SRJS41-13, emerging great achievement Instr Ltd. in Beijing.
Do further explanation below in conjunction with following examples.
(1) the liquid phase direct precipitation method prepares nano SnO
2:
Take by weighing 2.698g NaOH, add the NaOH solution that the 75ml deionized water is configured to 0.9mol/L, be labeled as solution A; Take by weighing 5.522g SnCl
45H
2O adds the SnCl that the 25ml deionized water is mixed with 0.63mol/L
45H
2O solution is labeled as solution B; Dropwise be added drop-wise to B solution in the A solution with dropper, when dripping, put into constant temperature magnetic force water-bath to A solution, 80 ℃ of hydrolysis 45min; The magnetic agitation of not stopping during this time makes all even hydrolysis reaction of its better mixing, treats to take out beaker after hydrolysis is accomplished; Room temperature naturally cools to about 30 ℃, takes off layer milky suspension centrifuge tube of packing into, and hydro-extractor is centrifugal; 4000r/min, centrifugal 5min; Take off layer milky white precipitate in small beaker, clean at least 5 times, up to the existence that detects less than the Cl-ion with absolute ethyl alcohol; Put into drying box to milky white precipitate then, 60 ℃ of vacuum drying 10h get white powder, take out white powder, and 700 ℃ of high-temperature calcination 180min obtain white powder, i.e. SnO in the hot room muffle furnace
2
2) adopt spin-coating method with SnO
2Nano particle is coated in silicon chip surface, as ethephon (CEPHA) detection chip sensitive membrane, is assembled into SnO2-silicon combination electrode, and accomplishes SnO
2The assembling of based electrochemical biochip.
The detection of ethephon (CEPHA)
At first, prepare PBS, respectively with 23.88g Na
2HPO
412H
2O, 9.08g KH
2PO
4Be dissolved in the 1000mL deionized water, for use as mother liquor; When the electrolyte solution, in 100mLPBS solution, add 0.08gNaCl again and 0.02g KCl gets final product; Prepare the potassium ferricyanide-potassium ferrocyanide electrolyte solution, with 6.59g K
3Fe (CN)
6, 8.45g K
4Fe (CN)
63H
2O, 1.17g NaCl are dissolved in the above-mentioned 100mL PBS solution.
Secondly, as solvent, compound concentration is 3.58 * 10 with the potassium ferricyanide-potassium ferrocyanide electrolyte solution
-12The ethephon solution of mol/L.The ethephon (CEPHA) absorption behavior is through electrochemical AC impedance spectrometry (EIS) test.Use the potassium ferricyanide-potassium ferrocyanide solution to be electrolyte, the frequency range of test is 10
6-10
-3/ 10
-1Hz.Adopt three-electrode system, with the SnO of preparation
2-silicon combination electrode is as working electrode, and the Ag/AgCl electrode is as contrast electrode, and the Pt electrode is as auxiliary electrode.
Following instrument and material property explanation for tracking and testing in the test:
Used XRD instrument is the D8 Advance type X-ray diffractometer that Germany makes in the experiment, and scanning 2 θ angles is 10 ~ 80 °, obtains oscillogram through scanning.And the JSM-6490LV type scanning electron microscope that the scanning electron microscope that is adopted is produced for Japan, resolution is less than 3.0nm (30kV, high vacuum, tungsten filament, secondary electron); Less than 4.0nm (tungsten filament, backscattered electron); Accelerating potential minimum zone: 0.5 ~ 30KV, the 10V/ step; Enlargement factor scope: 20 ~ 300,000 times; Condition of high vacuum degree: 1.5 * 10
-3Pa; Low vacuum: 6 ~ 270Pa; Energy spectrometer Si (Li) detector: resolution is superior to 133eV; The useful area of eds detector: 10mm
2Power spectrum ultimate analysis scope: B5 ~ U92.
Experiment institute's high resolution transmission electron microscopy that adopts (HRTEM) is JEM-2100 (UHR) the type HRTEM of Japanese JEOL production; Accelerating potential 80-200KV; 1,500,000 times of high-amplification-factors; The resolution point resolution is 0.19nm, and lattice resolution is 0.14nm.
Experiment institute's electrochemical impedance that adopts is tested CHI600D galvanochemistry platform, three-electrode system; Data analysis adopts ZvieW to resolve software; Sinusoidal wave current potential amplitude is: ± 10mV, test frequency 1m Hz ~ 100kHz; The electrochemical impedance test is carried out under constant potential, and the potassium ferricyanide-potassium ferrocyanide solution that configures is an electrolyte.
The test findings of tracking and testing
1.SnO
2The crystalline network of nano particle and morphology analysis
From SnO
2The XRD figure spectrum of nano particle is in order to analyze SnO
2The phase composition of nano particle (Fig. 1), the result is presented at 26.7 °, 33.9 °, 38 °, 51.8 ° four main peak values, corresponds respectively to (110), (101), (200) and (211) four crystal faces of cubic rutile.
From pressed powder SnO
2SEM figure (Fig. 2 a), enlargement factor is 5000 times, can find out, particle flocks together in a large number and forms that spumescence is fluffy to have a pore structure.From TEM figure, then can find out (Fig. 2 b), nano SnO
2Particle becomes irregular spherulitic crystal structure, and to different face non-directional growths, its averaged particles is probably at 20nm.
2.SnO
2-silicon combination electrode is in the stability of buffer solution
Fig. 3 representes that spin coating has SnO
2The silicon electrode of nano material is its AC impedance spectrogram in buffer solution, as can be seen from the figure, though sweep increases in 10h to some extent among the figure, and not obvious.This explains SnO
2Nanometer layer can be good at absorption at silicon substrate.In fact, SnO
2Nano particle and silicon chip directly might produce covalent bonds, thereby make SnO
2Can stably be fixed on the silicon electrode surface, and also performance is stable preferably in solution.
3. adopt electrochemical AC impedance method test ethephon (CEPHA) at SnO
2The absorption of nano grain surface
The electrochemical AC impedance method can test out the variation of micromolecule absorption front and back combination electrode interfacial charge transfer constant delicately, uses through the context of detection of the electrochemica biological chip of being everlasting.Can find out that curve semicircle radius is at SnO among Fig. 4
2The nano particle assembling has diminished after going up, and after ethephon (CEPHA) absorption, then becomes big again.Interface electron transfer constant (R between combination electrode and the solution has been explained in this variation
Ct) variation taken place.The size of its numerical value can be carried out the equivalent circuit diagram simulation with the Ershler model to experimental data through the Randles that revises and obtained, and shown in figure, equivalent circuit diagram comprises solution resistance (Rs), often phase element (CPE) and interfacial migration resistance (Rct).Tabular goes out silicon electrode at SnO
2Each analog parameter value before and after assembling back and the ethephon (CEPHA) absorption.For silicon electrode, R
CtBe 83.9K Ω, and SnO is gone up in assembling
2After, its value is reduced to 4K Ω, after the ethephon (CEPHA) absorption, increases to 15.8K Ω again.This is because assembling SnO on the silicon electrode
2After the nano material, the electric conductivity of its combination electrode strengthens, and has strengthened the transfer between the electric charge, cause Rct to reduce, and after the ethylene adsorption profit, organic molecule covers the combination electrode surface, has hindered the transfer of electric charge, causes R
CtIncrease, can the existence of ethephon (CEPHA) in the solution be detected delicately just because of the variation of interfacial charge transfer constant, the ethephon (CEPHA) concentration that is adopted in this experiment is 3.58pM.
Each analog parameter value of AC impedance curve shown in table 1 Fig. 4
Rs | CPE1 | n1 | Rct1 | |
Si-6 | 28.04 | 4.38E-08 | 0.79153 | 83864 |
Si-SnO 2-11 | 1371 | 7.45E-06 | 0.88632 | 4012 |
Si-SnO 2-ethephon (CEPHA)-6 | 380.1 | 1.57E-06 | 0.7417 | 15757 |
4. SnO after the ethylene adsorption profit
2The nano grain surface chemical structure analysis
Adopt XPS to being adsorbed with the SnO of ethephon (CEPHA)
2Nano-material surface carries out chemical composition analysis, and is as shown in Figure 5.The ethephon (CEPHA) micromolecule is at SnO
2After the absorption, can cause the variation of material surface chemical composition.Contain the P element in the ethephon (CEPHA) molecular structure, therefore can whether material surface be contained the evidence of P element as ethephon (CEPHA) absorption.Two peak 486.96 eV that demonstrated in (a) at figure and 495.5 eV correspond respectively to the Sn 3d of Sn (IV)
5/2With Sn 3d
3/2And in (b), the C1s collection of illustrative plates can be decomposed into 284.8 eV, 285.65 eV and three peaks of 288 eV, corresponds respectively to C-C, C-OH and C=O key and mode.And in figure (c), can find out has tangible element P signal, and its collection of illustrative plates is decomposed, and then can resolve into 133.4eV and 134.5 eV, corresponds respectively to the 2p of P element
3/2And 2p
1/2The electronics peak value.Therefore, the result shows that the ethephon (CEPHA) micromolecule of low concentration can successfully be adsorbed on SnO
2Nano-material surface.
5. the ethephon (CEPHA) adsorption mechanism is analyzed
Micromolecule mainly comprises types such as covalent bonds power, Electrostatic Absorption power and model ylid bloom action power at the adsorption of material surface, and wherein stable with covalent bonds power, we also design SnO on this basis
2Electrochemical sensor.With SnO
2When being spin-coated on the silicon substrate after the nanoparticulate dispersed, SnO
2And produce covalent bond between the silicon substrate, make SnO
2Molecule can be stabilized on the silicon substrate, and this can be from SnO
2The stable electrochemical properties (see figure 6) that is confirmed.And when having the ethephon (CEPHA) micromolecule in the solution, the phosphate group on the ethephon (CEPHA) molecule possibly be fixed on SnO with two kinds of bonding modes
2On the surface (like Fig. 6 (b) and (c)), make micromolecule to stablize and be adsorbed on Nanosurface.
Claims (5)
1. SnO
2The based electrochemical biochip is characterized in that, the employing three-electrode system in the described biochip is with the SnO of preparation
2-silicon combination electrode is as working electrode, and the Ag/AgCl electrode is as contrast electrode, and the Pt electrode is as auxiliary electrode.
2. SnO according to claim 1
2The preparation method of based electrochemical biochip is characterized in that, may further comprise the steps:
(1) the liquid phase direct precipitation method prepares nano SnO
2:
With NaOH solution and SnC
L45H
2SnO centrifugal, that be drying to obtain pressed powder is carried out in the reaction that is hydrolyzed of O solution then
2
(2) adopt spin-coating method with SnO
2Nano particle is coated in silicon chip surface, as ethephon (CEPHA) detection chip sensitive membrane, is assembled into SnO
2-silicon combination electrode, and accomplish SnO
2The assembling of based electrochemical biochip.
3. preparation method according to claim 2 is characterized in that, the ethephon solution compound concentration is 3.58 * 10 in the said step (2)
-12Mol/L.
4. SnO as claimed in claim 1
2The based electrochemical biochip is to the application in the ethephon (CEPHA) residue detection.
5. application according to claim 4 is characterized in that, the detection of ethephon (CEPHA) is: (1) preparation potassium ferricyanide-potassium ferrocyanide electrolyte solution is prepared ethephon solution as solvent; (2) the ethephon (CEPHA) absorption behavior is tested the ethephon (CEPHA) absorption behavior through the electrochemical AC impedance spectrometry.
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CN109521147A (en) * | 2019-01-16 | 2019-03-26 | 江苏省农业科学院 | The mesoporous chip of carbon-based all print and preparation method and its method for being used for phosphatide detection |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN109521147A (en) * | 2019-01-16 | 2019-03-26 | 江苏省农业科学院 | The mesoporous chip of carbon-based all print and preparation method and its method for being used for phosphatide detection |
CN109521147B (en) * | 2019-01-16 | 2021-05-11 | 江苏省农业科学院 | Carbon-based full-printing mesoporous chip, preparation method thereof and method for phospholipid detection by using carbon-based full-printing mesoporous chip |
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