CN102520038B - Method for preparing graphene biosensor - Google Patents
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Abstract
The invention relates to a method for preparing a graphene biosensor, belonging to the technical field of electrochemistry. The method comprises the following steps of: immersing a processed gold electrode into graphene oxide and a sodium sulphate solution, electrically depositing the electrode through a control electric potential, taking out the electrode, washing the electrode by using water, after drying the electrode at room temperature, putting the electrode in a chloroauric acid solution, electrically depositing the electrode through the control electric potential, taking out the electrode, washing the electrode by using water, and drying the electrode at room temperature; putting a modified electrode in a conductive polymer monomer and a supporting electrolyte solution, polymerizing the electrode through the control electric potential by adopting a cyclic voltammetry, taking out the electrode, washing the electrode by using water, and drying the electrode at room temperature; and activating the modified electrode in an EDC/NHS (Dichloroethane/N-Hydroxysuccinimide) solution, and immersing the modified electrode in a vomiting toxin antibody. The method disclosed by the invention is used for fixing graphene, gold nanoparticles and conducting polymers through electro-deposition; therefore, the method is very green and environment-friendly; furthermore, the thickness of a coating and sizes and distribution densities of the gold nanoparticles can be precisely controlled, thus, the batch production repeatability of the modified electrode is good.
Description
Technical field
The present invention relates to a kind of preparation method of graphene biosensor, belong to technical field of electrochemistry.
Background technology
Graphene is the crystal of six side's honeycomb crystalline networks of the tightly packed formation of monolayer carbon atom, unique two-dimensional structure makes it have excellent electricity, calorifics, mechanics and chemical property, but there is larger Van der Waals force in the graphene film interlayer, easily occur to pile up and assemble, thereby limited its application in many aspects.In order to overcome the above problems, people wait metal nanoparticle at graphene film interlayer doping gold, and this is not only avoided graphene sheet layer to come back to graphite crystal because of gathering effectively, and has greatly improved the electronic conductivity (Zhong of grapheme material, Z.Y., Wu, W., Wang, D., Wang, D., Shan, J.L., Qing, Y., Zhang, Z.M., Biosensors and Bioelectronics, 2010,25:2379-2382).Recently, the application of Graphene/metallic composite in biology sensor be subject to extensive concern (Wan, Y., Wang, Y., Wu, J.J., Zhang, D., Anal.Chem., 2011,83:648-652).
Grapheme material and enzyme fixing is to graphene-based performance of biosensor and use most important.At present, fixing physisorphtions that adopt of grapheme material and enzyme more.Normally adopt first the Hummer method to synthesize graphite oxide, more ultrasonic being dispersed in water of graphite oxide made the graphene oxide dispersion liquid, then mix with metal precursor, adding the strong reductant such as sodium borohydride makes graphene oxide and metal precursor in-situ reducing and prepares Graphene/metallic composite, compound substance again is scattered in later the dripping of water and is applied to electrode surface (Gu, Z.G., Yang under stabilizer function, S.P., Li, Z.J., Sun, X.L., Wang, G.L., Fang, Y.J., Liu, J.K., Anal.Chim.Acta, 2011,701:75-80).Drop-coating is consuming time more, needs to use poisonous chemical reagent, the products obtained therefrom bad dispersibility, and coating is coarse, and thickness is difficult to accurate control, thereby causes the electrocatalysis characteristic of material to descend.Recently, the researchist has proposed a kind of new electrochemical method.Electrode is inserted the mixed solution of graphene oxide and gold chloride, adopt cyclic voltammetry scan once to finish composite manufacture and fixing (Liu, C.B., Wang, K., Luo, S.L., Tang, Y.H., Chen, L.Y., Small, 2011,7:1203-1206).The distinguishing features such as it is simple, quick and green that method has, but redox reaction easily occurs between graphite oxide and the noble metal precursor body, cause the rotten electrode modification layer fast and that obtain of mixed solution more coarse.Shitosan is a kind of biological material, and the film forming ability of its excellence often is used to enzyme at fixing (Yang, Y.C., Dong, S.W., the Shen of electrode surface, T., Jian, C.X., Chang, H.J., Li, Y., Zhou, J.X., Electrochim.Acta, 2011,56:6021-6025).But the enzyme that this physisorphtion is fixed easily comes off, and makes the stability of sensor and reappearance be difficult to satisfy real work to the requirement of detection accuracy.In addition, the use of the non-conductive material such as shitosan also can affect the electrochemical response of electrode.In order to address this problem, people attempt utilizing graphene oxide to contain and enrich the characteristics of carboxyl, take DHC/NHS as activator with covalently bound on modified electrode, but graphene oxide poorly conductive, prepared biosensor analysis performance is undesirable.Therefore set up preparation method green, easy and reliable graphene biosensor imperative.
Find through widely research and repeatedly test, adopt electrochemical process successively electro-deposition Graphene, nm of gold and electrochromic conducting polymer be deposited on electrode surface, then with the covalent bonding mode will enzyme or antibody be fixed on the conducting polymer film.Electrochemical process has realized that not only fixing on electrode of electrochemical reaction and material finish simultaneously, can also realize the particle diameter of Graphene and conducting polymer coating thickness and golden nanometer particle and the accurate control of distribution density, and the material preparation process does not have " three wastes " to produce.The inventor further is in optimized selection electrodeposition condition, has finally realized improving the purpose of stability, sensitivity and the precision of graphene biosensor.
Summary of the invention
The object of the invention is to exist for existing graphene biosensor that Graphene and enzyme easily come off, sensitivity is not high and the deficiency of the poor reproducibility of sensor production, a kind of preparation method of new graphene biosensor is provided.Method has been improved stability, sensitivity and the precision of graphene biosensor significantly, and also environmental protection can not cause environmental pollution.
According to technical scheme provided by the invention, a kind of preparation method of graphene biosensor, step is:
1) preparation of graphene modified electrode: be scattered in that the stable concentration of formation is 0.0001～0.1mg/mL graphene oxide dispersion liquid in the deionized water with graphite oxide is ultrasonic, ultrasonic frequency is 55kHz-60kHz, add supporting electrolyte, being adjusted to supporting electrolyte concentration is 0～1mol/L; Take platinized platinum as basic electrode, electricity workstation control current potential-0.9～-1.2V place electro-deposition 10～50s, take out electrode, wash drying at room temperature with deionized water;
2) the graphene modified electrode that gold chloride processing: with step 1) makes is put into 0.002～0.2mmol/L chlorauric acid solution, control current potential at-0.25～0.4V place electro-deposition 10～50s at electrochemical workstation, take out electrode, with deionized water washing, drying at room temperature;
3) cyclic voltammetry scan: multiple weigh 1) and 2) operation 5～50 times, then resulting electrode is put into the solution that contains 0.01～0.2mol/L conductive high polymer monomer and 0.001～0.005mol/L supporting electrolyte and carried out cyclic voltammetry scan, the cyclic voltammetry scan voltage range is 0～1.0V, sweep speed is 10～400mV/s, cycle index is 2～10 times, and temperature is 0～40 ℃, taking-up electrode after scanning is finished, with deionized water washing, drying at room temperature;
4) preparation of graphene biosensor: with step 3) resulting electrode activates 4～6h in 18～22mMEDC/NHS solution, then in 8～12mg/mL hydrogen peroxidase, soak 22～26h, wash with deionized water, 4 ℃ lower dry, then tests the analytical performance of graphene biosensor at electrochemical workstation.
Described conductive polymer high polymer monomer is as shown in the formula the compound 2 shown in 1,5-two (2-thiophene)-1-R-pyrroles;
Wherein, R is substituting group, for alkane, alkene, alkynes base or the aromatic radical of carbon number between 1～20, connects 1～3 carboxyl thereafter again.
Step 1) described supporting electrolyte is with K
+Or Na
+Be kation, with SO
4 2-, CO
3 2-, CH
3COO
-, Cl
-, ClO
4 -, ClO
3 -Or NO
3 -Any in the compound that forms for negative ion.
Step 3) describedly multiple weigh 1) and 2) the number of times of operation be 10～20 times.
Step 3) described supporting electrolyte is take the quaternary amine base as kation, take chlorion, bromide ion, chlorate anions, perchlorate, tetrafluoroborate or hexafluoro-phosphate radical as the compound that negative ion was formed, and perhaps their potpourri.
The present invention has following advantage: one embodiment of the present of invention adopt the control current potential at gold electrode surfaces electro-deposition Graphene take graphite oxide as presoma, then adopt the control current potential at Graphene surface electro-deposition gold nanoparticles take gold chloride as presoma.After operating 20 times more than repeating, electrode is put in 2,5-two (2-thiophene)-1-para Toluic Acid pyrrole monomer solution, adopted cyclic voltammetry to carry out electropolymerization, multiple scanning 6 times.At last, take EDC/NHS as activator hydrogen peroxidase covalent bonding mode is combined on the conducting polymer film, and tests the analytical performance of this biology sensor at electrochemical workstation.Studies show that, resulting hydrogen peroxide bio-sensing has very sensitive electrochemical response to hydrogen peroxide, and its detection limit reaches 2 * 10
-8Mol/L, concrete advantage is as follows:
1) fixedly Graphene, gold nano and conducting polymer of electro-deposition, the size of not only very environmental protection, and coating thickness and golden nanometer particle and distribution density can precisely be controlled, thereby make the good reproducibility of batch producing of modified electrode.
2) resulting Graphene/metal/composite material favorable dispersibility shows significant electro catalytic activity, and the sensitivity of its Electrochemical Detection is apparently higher than prior art.
3) covalent bonding mode immobilizing biologically active macromolecular substances has overcome the enzyme of drop-coating or the antibody deficiency that easily comes off, and has greatly improved stability and the accuracy of detection of biology sensor.
Description of drawings
Fig. 1 process chart of the present invention.
Embodiment
The below further specifies the present invention with embodiment, but the present invention is not limited.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer." room temperature " described in the present invention, " normal pressure " refer to temperature and the air pressure between regular job, are generally 25 ℃, an atmospheric pressure.
Among the following embodiment, used working electrode is gold electrode (φ=1mm).Electrode is that the alumina powder of 50nm carries out polishing with particle diameter before use, embathes 10min in the second absolute alcohol, then ultrasonic cleaning, and drying is weighed.The working electrode that electro-deposition and electro-chemical test are used and all be naked gold electrode or various modified electrode to electrode, participating in electrode is the AgCl/Ag normal electrode.Electro-chemical test adopts cyclic voltammetry, and operating voltage is-0.8～0.8V, and sweep speed is 100mV/s, and test end liquid is that pH is 7 phosphate buffer solution.
Embodiment 1
Gold electrode after processing is immersed in the 0.05mg/mL graphene oxide dispersion liquid, at 20 ℃ of lower control current potentials at-1.2V place electro-deposition 50s, take out electrode, wash with water, be placed on after the drying at room temperature in the chlorauric acid solution of 0.05mmol/L, at 20 ℃ of lower control current potentials at-0.25V place electro-deposition 50s, taking-up electrode, wash drying at room temperature with water.After substrates operation cycle 20 times, modified electrode is inserted 3mL contain 2, in the dichloromethane solution of 5-two (2-thiophene)-1-para Toluic Acid pyrroles (1mmol/L) and tetrabutylammonium perchlorate amine (0.1mol/L), the control current potential adopts cyclic voltammetry to carry out polymerization between 0～1V, with the rate scanning of 100mV/s six times, take out electrode, wash drying at room temperature with water.Then modified electrode soaks 24h at 20mmol/L EDC/NHS solution activation 4h in the 10mg/mL hydrogen peroxidase, the detection limit that resulting Hydrogen Peroxide Biosensor detects hydrogen peroxide reaches 2.0 * 10
-8Mol/L, 20 times the replication relative standard deviation is 1.8%.
Embodiment 2
Gold electrode after processing is immersed in the 0.02mg/mL graphene oxide dispersion liquid, at 0 ℃ of lower control current potential at-1.0V place electro-deposition 20s, take out electrode, wash with water, be placed on after the drying at room temperature in the chlorauric acid solution of 0.01mmol/L, at 25 ℃ of control current potentials at-0.3V place electro-deposition 40s, the taking-up electrode, wash drying at room temperature with water.After substrates operation cycle 30 times, modified electrode is inserted 3mL contain 2, in the dichloromethane solution of 5-two (2-thiophene)-1-para Toluic Acid pyrroles (1mmol/L) and tetrabutylammonium chloride (0.1mol/L), the control current potential adopts cyclic voltammetry to carry out polymerization between 0～1V, with the rate scanning of 200mV/s six times, take out electrode, wash drying at room temperature with water.Then modified electrode soaks 24h at 20mmol/L EDC/NHS solution activation 4h in the 10mg/mL glucose oxidase, the detection limit that resulting glucose biological sensor detects glucose reaches 1.0 * 10
-9Mol/L, 20 times the replication relative standard deviation is 1.0%.
Embodiment 3
Gold electrode immersion after processing is contained 0.02mg/mL graphene oxide and 0.1mol/L Klorvess Liquid, at 40 ℃ of lower control current potentials at-1.0V place electro-deposition 20s, take out electrode, wash with water, be placed on after the drying at room temperature in the chlorauric acid solution of 0.01mmol/L, at 0 ℃ of lower control current potential at-0.4V place electro-deposition 20s, taking-up electrode, wash drying at room temperature with water.After substrates operation cycle 50 times, modified electrode is inserted 3mL contain 2, in the dichloromethane solution (0.1mol/L) of 5-two (2-thiophene)-1-para Toluic Acid pyrroles (1.0mmol/L) and four octyl amine tetrafluoroborates, the control current potential adopts cyclic voltammetry to carry out polymerization between 0～1V, with the rate scanning of 300mV/s six times, take out electrode, wash drying at room temperature with water.Modified electrode is at 20mmol/L EDC/NHS solution activation 4h, then at the 20mg/mL AFB
1Soak 24h in the antibody, the detection limit of resulting glucose biological sensor reaches 1.0 * 10
-10Mol/L, 20 times the replication relative standard deviation is 1.8%.
Embodiment 4
Gold electrode immersion after processing is contained 0.01mg/mL graphene oxide and 0.1mol/L potassium sulfate solution, at 0 ℃ of lower control current potential at-1.2V place electro-deposition 10s, take out electrode, wash with water, be placed on after the drying at room temperature in the chlorauric acid solution of 0.02mmol/L, at 0 ℃ of lower control current potential at-0.25V place electro-deposition 30s, taking-up electrode, wash drying at room temperature with water.After substrates operation cycle 30 times, modified electrode is inserted 3mL contain 2, in the dichloromethane solution (0.2mol/L) of 5-two (2-thiophene)-1-o-benzoic acid pyrroles (1mmol/L) and four octyl group ammonium bromides, the control current potential adopts cyclic voltammetry to carry out polymerization between 0～1V, with the rate scanning of 50mV/s 2 times, take out electrode, wash drying at room temperature with water.Then modified electrode soaks 24h at 20mMEDC/NHS solution activation 4h in the 20mg/mL hydrogen peroxidase, the detection limit of resulting Hydrogen Peroxide Biosensor reaches 1.0 * 10
-7Mol/L, 20 times the replication relative standard deviation is 1.1%.
Embodiment 5
Gold electrode immersion after processing is contained 0.05mg/mL graphene oxide and 0.1mol/L metabisulfite solution, at 10 ℃ of lower control current potentials at-1.0V place electro-deposition 20s, take out electrode, wash with water, be placed on after the drying at room temperature in the chlorauric acid solution of 0.01mmol/L, at 0 ℃ of lower control current potential at-0.35V place electro-deposition 10s, taking-up electrode, wash drying at room temperature with water.After substrates operation cycle 15 times, modified electrode is inserted 3mL contain 2, in the dichloromethane solution (0.2mol/L) of 5-two (2-thiophene)-1-propionic acid pyrroles (1mmol/L) and four octyl group ammonium bromides, the control current potential adopts cyclic voltammetry to carry out polymerization between 0～1V, with the rate scanning of 20mV/s 8 times, take out electrode, wash drying at room temperature with water.Then modified electrode soaks 24h at 20mM EDC/NHS solution activation 4h in 20mg/mL vomitoxin antibody, the detection limit of resulting vomitoxin biology sensor reaches 2.5 * 10
-11Mol/L, 20 times the replication relative standard deviation is 1.0%.
Embodiment 6
Gold electrode immersion after processing is contained 0.1mg/mL graphene oxide and 0.3mol/L metabisulfite solution, at 0 ℃ of lower control current potential at-0.9V place electro-deposition 20s, take out electrode, wash with water, be placed on after the drying at room temperature in the chlorauric acid solution of 0.02mmol/L, at 10 ℃ of lower control current potentials at-0.25V place electro-deposition 20s, taking-up electrode, wash drying at room temperature with water.After substrates operation cycle 15 times, modified electrode is inserted 3mL contain 2, in the dichloromethane solution (0.2mol/L) of 5-two (2-thiophene)-1-acrylic acid pyrroles (1mmol/L) and four octyl group ammonium bromides, the control current potential adopts cyclic voltammetry to carry out polymerization between 0～1V, with the rate scanning of 20mV/s 6 times, take out electrode, wash drying at room temperature with water.Then modified electrode soaks 24h at 20mM EDC/NHS solution activation 4h in the 20mg/mL shrimp allergen, the detection limit of resulting shrimp allergen biology sensor reaches 3.3 * 10
-8Mol/L, 20 times the replication relative standard deviation is 2.1%.
Claims (3)
1. the preparation method of a graphene biosensor is characterized in that step is:
1) preparation of graphene modified electrode: be scattered in that the stable concentration of formation is 0.0001～0.1mg/mL graphene oxide dispersion liquid in the deionized water with graphite oxide is ultrasonic, ultrasonic frequency is 55kHz-60kHz, add supporting electrolyte, being adjusted to supporting electrolyte concentration is 0～1mol/L; Take platinized platinum as basic electrode, electricity workstation control current potential-0.9～-1.2V place electro-deposition 10～50s, take out electrode, wash drying at room temperature with deionized water;
2) gold chloride is processed: the graphene modified electrode that step 1) makes is put into 0.002～0.2mmol/L chlorauric acid solution, control current potential at-0.25～0.4V place electro-deposition 10～50s at electrochemical workstation, take out electrode, with deionized water washing, drying at room temperature;
3) cyclic voltammetry scan: multiple weigh 1) and 2) operation 5～50 times, then resulting electrode is put into the solution that contains 0.01～0.2mol/L conductive high polymer monomer and 0.001～0.005mol/L supporting electrolyte and carried out cyclic voltammetry scan, the cyclic voltammetry scan voltage range is 0～1.0V, sweep speed is 10～400mV/s, cycle index is 2～10 times, and temperature is 0～40 ℃, taking-up electrode after scanning is finished, with deionized water washing, drying at room temperature;
4) preparation of graphene biosensor: the resulting electrode of step 3) is activated 4～6h in 18～22mMEDC/NHS solution, then in 8～12mg/mL hydrogen peroxidase, soak 22～26h, wash with deionized water, 4 ℃ lower dry, then tests the analytical performance of graphene biosensor at electrochemical workstation;
Described conductive polymer high polymer monomer is as shown in the formula the compound 2 shown in 1,5-two (2-thiophene)-l-R-pyrroles;
Wherein, R is substituting group, for alkane, alkene, alkynes base or the aromatic radical of carbon number between 1～20, connects 1～3 carboxyl thereafter again;
Step 1) described supporting electrolyte is with K
+Or Na
+Be kation, with S0
4 2-, CO
3 2-, CH
3COO
-, Cl
-, C1O
4 -, ClO
3 -Or NO
3 -Any in the compound that forms for negative ion.
2. the preparation method of graphene biosensor as claimed in claim 1 is characterized in that: step 3) is described to weigh 1 again) and 2) the number of times of operation be 10～20 times.
3. the preparation method of graphene biosensor as claimed in claim 1, it is characterized in that: the described supporting electrolyte of step 3) is as kation take the quaternary amine base, take chlorion, bromide ion, chlorate anions, perchlorate, tetrafluoroborate or hexafluoro-phosphate radical as the compound that negative ion was formed, perhaps their potpourri.
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| CN103063715B (en) * | 2012-11-03 | 2015-07-01 | 福建医科大学 | Method for detecting surviving gene based on graphene-gold composite material electrochemical DNA (Deoxyribose Nucleic Acid) biosensor |
| CN102944598A (en) * | 2012-11-29 | 2013-02-27 | 江南大学 | Preparation method and application of cell based sensor based on electrochemical reduction graphite oxide/gold nanoparticle composite membrane |
| CN103033544A (en) * | 2012-12-11 | 2013-04-10 | 常州大学 | Electrochemical DNA sensor based on graphene-precious metal composite and preparation method thereof |
| US9891184B2 (en) | 2012-12-31 | 2018-02-13 | Jiangnan University | Dithienylpyrrole-based biosensors and methods for their preparation and use |
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| CN103630574B (en) * | 2013-11-14 | 2016-06-15 | 江苏大学 | The preparation method of a kind of Graphene DNA sensor |
| CN105891289B (en) * | 2014-12-05 | 2019-04-09 | 江南大学 | A kind of electrochemical method measuring Oxidation of Fat and Oils induction time |
| CN106290494B (en) * | 2015-06-01 | 2018-11-16 | 江南大学 | A kind of electrochemical method for evaluating oil oxidative stability |
| JP6754259B2 (en) * | 2015-10-15 | 2020-09-09 | アークレイ株式会社 | Biosensor and its manufacturing method |
| CN105136890B (en) * | 2015-10-15 | 2018-09-04 | 河北北方学院 | A kind of N doped graphenes biosensor |
| CN106053557B (en) * | 2016-05-23 | 2018-10-26 | 济南大学 | A kind of preparation method of the human fibroblastic growth factor immunosensor based on sheet black phosphorus |
| CN105911123A (en) * | 2016-06-30 | 2016-08-31 | 重庆医科大学 | Electrochemical detection method for vomitoxin |
| CN106226370B (en) * | 2016-08-08 | 2018-04-27 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of preparation method of glyphosate molecular imprinting electrochemical sensor |
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