CN102445482B - Metal/nano metal based solid glucose electrode and its preparation method - Google Patents
Metal/nano metal based solid glucose electrode and its preparation method Download PDFInfo
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- CN102445482B CN102445482B CN 201110352142 CN201110352142A CN102445482B CN 102445482 B CN102445482 B CN 102445482B CN 201110352142 CN201110352142 CN 201110352142 CN 201110352142 A CN201110352142 A CN 201110352142A CN 102445482 B CN102445482 B CN 102445482B
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Abstract
The invention discloses a metal/nano metal based solid glucose electrode and its preparation method. The metal/nano metal based solid glucose electrode possesses a first metal wire, a nanoparticle grade metal nano layer is coated on the surface at the lower part of the first metal wire, a polyacrylonitrile (PAN for short) porous membrane is coated on external surface of the metal nano layer, glucose oxidase (GOD) is carried on the polyacrylonitrile membrane. The metal is Ag, Au, Pt or other precious metals. The solid glucose electrode has the advantages of small volume, fast detection response, high sensitivity, low detection lower limit, long service life and the like, and is suitable for detecting blood sugar concentration and glucose content of the fruit juice, beverage, fruit and the like.
Description
Technical field
The present invention relates to the electrochemical detection technology, relate in particular to a kind of solid glucose electrode based on the metal/nanometer metal and preparation method thereof.
Background technology
Biology sensor is a new technology that grows up later 1960s.Its advantage is that selectivity is good, highly sensitive, measurement is quick, easy and simple to handle, cost of determination is low, can realizes continuous online, in place, detection in vivo.As the biological chemistry detection means, biology sensor has shown more and more important effect in biomedical engineering, clinical diagnosis, environmental monitoring, food hygiene and field of scientific study.
Bioactivator in biology sensor is generally all water-soluble, and itself is unstable, need to be fixed on various carriers, could extend its activity.What at present, fixation support was with the most use is macromolecular material.The polymer biological sensor is mainly to be carrier or clad material immobilizing biologically active composition (enzyme, antigen, antibody, microorganism, cell etc.) with polymkeric substance, and with this as sensitive element, then the device that is combined into the conversion of suitable signal and pick-up unit.
Prepare sensor research with conducting polymer in macromolecular material at present more.But conductive polymer sensors still has some aspects to improve:
(1) has the very difficult interference (when high potential uses) of eliminating electric active matter confrontation amperometric biosensor of conducting polymer (particularly polyaniline) of electrochemical activity.
(2) common, the conducting polymer with electrochemical activity has larger background current under electronegative potential, so can not be operated under negative potential by its biology sensor that directly prepares, this has limited its scope of application in the biology sensor preparation.
(3) sensitivity of some conducting polymer biology sensors and life-span can't be satisfied the needs of actual use.
Therefore seek the polymeric material of function admirable as carrier, superior, the reliable polymer biological sensor of processability also makes it practical (especially in the medicine and environmental monitoring field), and body plan polymer biological sensor array is the development trend in this field.
The porous polymer material that is rich in polar group has larger surface area and stronger adsorptive power, and unique using value is arranged in the field of galvanochemistry immobilized enzyme, so this base polymer has a wide range of applications as the carrier of immobilized enzyme.
Nanometer technology is a kind of new technique that development in recent years is got up, and is coated with the electrode of the precious metal preparation of nano metal particles, will be better than traditional conductive material aspect response speed, signal intensity.As novel nanometer conductive material, the sensitivity that improves biology sensor is had great importance.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of solid glucose electrode based on the metal/nanometer metal and preparation method thereof is provided.
Solid glucose electrode based on the metal/nanometer metal has the first tinsel, the first tinsel lower surface is coated with the metal nano layer of nanometer grade, top layer at the metal nano layer is coated with polyacrylonitrile porous membrane, is equipped with glucose oxidase on polyacrylonitrile film.
Described the first tinsel is Ag, Au, Pt or uses the surface to be coated with the copper wire of silver.
Step based on the preparation method of the solid glucose electrode of metal/nanometer metal is as follows:
1) be first tinsel of 5～15 centimetres with length, first remove surface and oil contaminant with acetone soln, then clean with 1～2M watery hydrochloric acid or rare nitric acid, remove oxide, dry after deionized water drip washing;
2) negative pole of the negative or positive electrode of function signal generator output voltage and diode or positive pole join, an other utmost point and the oscillographic signalling channel of diode are joined, the adjustment function signal generator, the observation oscilloscope figure, the power supply that obtains is that peak value is 450～800mV, and frequency is the half-sine wave carrier wave direct supply of 50HZ;
3) negative pole of first end wiry by wire function generator output voltage joined, second end wiry is joined by wire and diode cathode, and first other end wiry and second other end wiry insert simultaneously and are placed with the AgNO that concentration is 0.1～0.2M
31.5～3min switches in the electroplating pool of solution, the first tinsel lower surface forms length under the galvanic effect of carrier wave be the metal nano layer of 5～8 centimetres, first uses washed with de-ionized water, then clean with absolute ethyl alcohol, blot residual ethanol, be placed in brown exsiccator standby;
4) polyacrylonitrile is dissolved in dimethyl formamide, be mixed with the polyacrylonitrile solution of 1% ~ 3% concentration, dip this solution with the first tinsel, make solution covering metal nanometer layer, stand upside down and place, treat surperficial solvent dimethylformamide evaporation, subsequently it is moved into double dish, double dish is put into vacuum drying oven, and room temperature vacuum drying 2 ~ 7 hours is until solvent forms porous polypropylene nitrile film in the first wire surface after evaporating fully;
First part wiry that 5) will be coated with polyacrylonitrile porous membrane first immerses the NaH that concentration is 0.1M
2PO
4In solution, reductase 12 is 0 ~ 40 minute under constant potential-0.5V, NaH
2PO
4Solution is changed 3 ~ 5 times, then immerse and contain in the phosphate buffer of 10 ~ 40 μ M glucose oxidases, pH=6.5, total concentration is 0.1M, and oxidation is 20 ~ 40 minutes under 0.45 ~ 0.65V constant potential, in oxidizing process, zymoprotein with negative charge will be embedded in polyacrylonitrile porous membrane, formed glucose electrode, after prepared electrode fully washs with the pH=6.5 phosphate buffer, stored standby at-10 ℃ of temperature.
Described polyacrylonitrile is the polymkeric substance of vinyl cyanide, and the weight-average molecular weight of polyacrylonitrile is 1.0 * 10
4～4.0 * 10
4
The obtained electrode volume of the present invention is small and exquisite, has a probe response fast, highly sensitive, detects lower thresold low, and the advantages such as long service life are suitable for surveying blood sugar concentration, and the glucose content of the liquid such as fruit juice, beverage, fruit.
Description of drawings
Fig. 1 is based on the solid glucose electrode structure schematic diagram of metal/nanometer metal;
Fig. 2 is the solid glucose electrode preparation facilities schematic diagram of metal/nanometer metal.
Embodiment
Solid glucose electrode based on the metal/nanometer metal has the first tinsel 1, the first tinsel 1 lower surface is coated with the metal nano layer 2 of nanometer grade, be coated with polyacrylonitrile porous membrane 3 on the top layer of metal nano layer 2, be equipped with glucose oxidase on polyacrylonitrile film.
Described the first tinsel 1 is Ag, Au, Pt, and for reducing costs, the first tinsel 1 uses the surface to be coated with the copper wire of silver.
Step based on the preparation method of the solid glucose electrode of metal/nanometer metal is as follows:
1) be first tinsel 1 of 5～15 centimetres with length, first remove surface and oil contaminant with acetone soln, then clean with 1～2M watery hydrochloric acid or rare nitric acid, remove oxide, dry after deionized water drip washing;
2) negative pole or the positive pole of the negative or positive electrode of function signal generator 8 output voltages and diode 7 join, an other utmost point and the oscillographic signalling channel of diode 7 are joined, adjustment function signal generator 8, the observation oscilloscope figure, the power supply that obtains is that peak value is 450～800mV, and frequency is the half-sine wave carrier wave direct supply of 50HZ;
3) end of the first tinsel 1 negative pole by wire function signal generator 8 output voltages is joined, one end of the second tinsel 5 is joined by wire and diode 7 negative poles, and the other end of the other end of the first tinsel 1 and the second tinsel 5 inserts simultaneously and is placed with the AgNO that concentration is 0.1～0.2M
31.5～3min switches in the electroplating pool 6 of solution, the first tinsel 1 lower surface forms length under the galvanic effect of carrier wave be the metal nano layer 2 of 5～8 centimetres, first uses washed with de-ionized water, then clean with absolute ethyl alcohol, blot residual ethanol, be placed in brown exsiccator standby;
4) polyacrylonitrile is dissolved in dimethyl formamide, be mixed with the polyacrylonitrile solution of 1% ~ 3% concentration, dip this solution with the first tinsel 1, make solution covering metal nanometer layer 2, stand upside down and place, treat surperficial solvent dimethylformamide evaporation, subsequently it is moved into double dish, double dish is put into vacuum drying oven, and room temperature vacuum drying 2 ~ 7 hours is until solvent evaporates fully afterwards at the first tinsel 1 surface formation porous polypropylene nitrile film;
The part that 5) will be coated with the first tinsel 1 of polyacrylonitrile porous membrane first immerses the NaH that concentration is 0.1M
2PO
4In solution, reductase 12 is 0 ~ 40 minute under constant potential-0.5V, NaH
2PO
4Solution is changed 3 ~ 5 times, then immerse and contain in the phosphate buffer of 10 ~ 40 μ M glucose oxidases, pH=6.5, total concentration is 0.1M, and oxidation is 20 ~ 40 minutes under 0.45 ~ 0.65V constant potential, in oxidizing process, zymoprotein with negative charge will be embedded in polyacrylonitrile porous membrane, formed glucose electrode, after prepared electrode fully washs with the pH=6.5 phosphate buffer, stored standby at-10 ℃ of temperature.
Described polyacrylonitrile is the polymkeric substance of vinyl cyanide, and the weight-average molecular weight of polyacrylonitrile is 1.0 * 10
4～4.0 * 10
4
Below in conjunction with embodiment, the preparation of electrode of the present invention is elaborated.
1) with length being first tinsel 1 of 5 centimetres, polishes with schmigel in the surface, then cleans with 1M watery hydrochloric acid or rare nitric acid, dry after deionized water drip washing;
2) the auspicious special electronics SG1005A of adjustment function signal generator 8(), make it produce the sinusoidal wave function signal, peak value is 600 mV, and frequency is 50Hz; Then at the auspicious special electronics SG1005A of function signal generator 8() negative pole and the diode 7(schottky diode MBR1045 of output voltage) negative pole join, the signalling channel of positive pole diode 7(schottky diode MBR1045) and oscillograph (Tektronix TDS1002) is joined, the observation oscilloscope figure, show that the power supply that obtains is that peak value is 450mV, frequency is the half-sine wave carrier wave direct supply of 50HZ;
3) will polish an end of the first cleaned tinsel 1 by wire and diode 7(schottky diode MBR1045) positive pole joins, with an end of the second tinsel 5 by the auspicious special electronics SG1005A of wire function signal generator 8() positive pole of output voltage joins, the other end of the first tinsel 1 and the second tinsel 5 inserts simultaneously and is placed with the AgNO that concentration is 0.1 M
3Energising 1.5 min in the electroplating pool 6 of solution, the first tinsel 1 lower surface forms length under the galvanic effect of carrier wave be the metal nano layer 2 of 5 centimetres, first uses washed with de-ionized water, then clean with absolute ethyl alcohol, blot residual ethanol, be placed in brown exsiccator standby;
4) the first tinsel (1) being dipped concentration is 1% polyacrylonitrile solution, make solution covering metal nanometer layer (2), after taking-up, the first tinsel (1) is stood upside down and place, treat surperficial DMF solvent evaporation, subsequently it is moved into double dish, double dish is put into vacuum drying oven, and room temperature vacuum drying 7 hours is until solvent evaporates fully;
The part that 5) will be coated with first tinsel (1) of polyacrylonitrile porous membrane first immerses 0.1M NaH
2PO
4(pH4.5) in, reductase 12 0 minute (electrolytic solution need to be changed 4 times in this process) under constant potential-0.5V, then immerse and contain in the phosphate buffer (pH=6.5, total concentration is 0.1M) of 20 μ M glucose oxidases (GOD), oxidation is 20 minutes under the 0.45V constant potential.Prepared electrode fully washs with phosphate buffer (pH=6.5);
6) with 0.5 centimetre of electrode 3 bottoms reservation, remainder coats with heat-shrink tube 4, or the coatings coating, makes the solid glucose electrode based on the metal/nanometer metal.
1) with length being first tinsel 1 of 15 centimetres, polishes with schmigel in the surface, then cleans with 2M watery hydrochloric acid or rare nitric acid, dry after deionized water drip washing;
2) the auspicious special electronics SG1005A of adjustment function signal generator 8(), make it produce the sinusoidal wave function signal, peak value is 1000mV, and frequency is 50Hz; Then at the auspicious special electronics SG1005A of function signal generator 8() positive pole and the diode 7(schottky diode MBR1045 of output voltage) positive pole join, the signalling channel of negative pole diode 7(schottky diode MBR1045) and oscillograph (Tektronix TDS1002) is joined, the observation oscilloscope figure, show that the power supply that obtains is that peak value is 800mV, frequency is the half-sine wave carrier wave direct supply of 50HZ;
3) will polish an end of the first cleaned tinsel 1 by the auspicious special electronics SG1005A of wire function signal generator 8() negative pole of output voltage joins, with an end of the second tinsel 5 by wire and diode 7(schottky diode MBR1045) negative pole joins, the other end of the first tinsel 1 and the second tinsel 5 inserts simultaneously and is placed with the AgNO that concentration is 0.2M
33min switches in the electroplating pool 6 of solution, the first tinsel 1 lower surface forms length under the galvanic effect of carrier wave be the metal nano layer 2 of 8 centimetres, first uses washed with de-ionized water, then clean with absolute ethyl alcohol, blot residual ethanol, be placed in brown exsiccator standby;
4) the first tinsel (1) being dipped concentration is 1% polyacrylonitrile solution, make solution covering metal nanometer layer (2), after taking-up, the first tinsel (1) is stood upside down and place, treat surperficial DMF solvent evaporation, subsequently it is moved into double dish, double dish is put into vacuum drying oven, and room temperature vacuum drying 7 hours is until solvent evaporates fully;
The part that 5) will be coated with first tinsel (1) of polyacrylonitrile porous membrane first immerses 0.1M NaH
2PO
4(pH4.5) in, reductase 12 0 minute (electrolytic solution need to be changed 4 times in this process) under constant potential-0.5V, then immerse and contain in the phosphate buffer (pH=6.5, total concentration is 0.1M) of 20 μ M glucose oxidases (GOD), oxidation is 20 minutes under the 0.45V constant potential.Prepared electrode fully washs with phosphate buffer (pH=6.5);
6) with 0.5 centimetre of electrode 3 bottoms reservation, remainder coats with heat-shrink tube 4, or the coatings coating, makes the solid glucose electrode based on the metal/nanometer metal.
1) with length being first tinsel 1 of 10 3 centimetres, polishes with schmigel in the surface, then cleans with 2M watery hydrochloric acid or rare nitric acid, dry after deionized water drip washing;
2) the auspicious special electronics SG1005A of adjustment function signal generator 8(), make it produce the sinusoidal wave function signal, peak value is 800mV, and frequency is 50Hz; Then at the auspicious special electronics SG1005A of function signal generator 8() positive pole and the diode 7(schottky diode MBR1045 of output voltage) positive pole join, diode 7(schottky diode MBR1045) negative pole and oscillographic signalling channel are joined, the observation oscilloscope figure, show that the power supply that obtains is that peak value is 700mV, frequency is the half-sine wave carrier wave direct supply of 50HZ;
3) will polish an end of the first cleaned tinsel 1 by the auspicious special electronics SG1005A of wire function signal generator 8() negative pole of output voltage joins, with an end of the second tinsel 5 by wire and diode 7(schottky diode MBR1045) negative pole joins, the other end of the first tinsel 1 and the second tinsel 5 inserts simultaneously and is placed with the AgNO that concentration is 0.1M
32min switches in the electroplating pool 6 of solution, the first tinsel 1 lower surface forms length under the galvanic effect of carrier wave be the metal nano layer 2 of 7 centimetres, first uses washed with de-ionized water, then clean with absolute ethyl alcohol, blot residual ethanol, be placed in brown exsiccator standby;
4) the first tinsel (1) being dipped concentration is 1% polyacrylonitrile solution, make solution covering metal nanometer layer (2), after taking-up, the first tinsel (1) is stood upside down and place, treat surperficial DMF solvent evaporation, subsequently it is moved into double dish, double dish is put into vacuum drying oven, and room temperature vacuum drying 7 hours is until solvent evaporates fully;
The part that 5) will be coated with first tinsel (1) of polyacrylonitrile porous membrane first immerses 0.1M NaH
2PO
4(pH4.5) in, reductase 12 0 minute (electrolytic solution need to be changed 4 times in this process) under constant potential-0.5V, then immerse and contain in the phosphate buffer (pH=6.5, total concentration is 0.1M) of 20 μ M glucose oxidases (GOD), oxidation is 20 minutes under the 0.45V constant potential.Prepared electrode fully washs with phosphate buffer (pH=6.5);
6) with 0.5 centimetre of electrode 3 bottoms reservation, remainder coats with heat-shrink tube 4, or the coatings coating, makes the solid glucose electrode based on the metal/nanometer metal.
1) with length being first tinsel 1 of 10 3 centimetres, polishes with schmigel in the surface, then cleans with 2M watery hydrochloric acid or rare nitric acid, dry after deionized water drip washing;
2) the auspicious special electronics SG1005A of adjustment function signal generator 8(), make it produce the sinusoidal wave function signal, peak value is 800mV, and frequency is 50Hz; Then at the auspicious special electronics SG1005A of function signal generator 8() positive pole and the diode 7(schottky diode MBR1045 of output voltage) positive pole join, diode 7(schottky diode MBR1045) negative pole and oscillographic signalling channel are joined, the observation oscilloscope figure, show that the power supply that obtains is that peak value is 700mV, frequency is the half-sine wave carrier wave direct supply of 50HZ;
3) will polish an end of the first cleaned tinsel 1 by the auspicious special electronics SG1005A of wire function signal generator 8() negative pole of output voltage joins, with an end of the second tinsel 5 by wire and diode 7(schottky diode MBR1045) negative pole joins, the other end of the first tinsel 1 and the second tinsel 5 inserts simultaneously and is placed with the AgNO that concentration is 0.1M
32min switches in the electroplating pool 6 of solution, the first tinsel 1 lower surface forms length under the galvanic effect of carrier wave be the metal nano layer 2 of 7 centimetres, first uses washed with de-ionized water, then clean with absolute ethyl alcohol, blot residual ethanol, be placed in brown exsiccator standby;
4) the first tinsel (1) being dipped concentration is 3% polyacrylonitrile solution, make solution covering metal nanometer layer (2), after taking-up, the first tinsel (1) is stood upside down and place, treat surperficial DMF solvent evaporation, subsequently it is moved into double dish, double dish is put into vacuum drying oven, and room temperature vacuum drying 7 hours is until solvent evaporates fully;
The part that 5) will be coated with first tinsel (1) of polyacrylonitrile porous membrane first immerses 0.1M NaH
2PO
4(pH4.5) in, 40 minutes (electrolytic solution need to be changed 4 times in this process) of reduction under constant potential-0.5V, then immerse and contain in the phosphate buffer (pH=6.5, total concentration is 0.1M) of 20 μ M glucose oxidases (GOD), oxidation is 20 minutes under the 0.45V constant potential.Prepared electrode fully washs with phosphate buffer (pH=6.5);
6) with 0.5 centimetre of electrode 3 bottoms reservation, remainder coats with heat-shrink tube 4, or the coatings coating, makes the solid glucose electrode based on the metal/nanometer metal.
Embodiment 5
1) with length being first tinsel 1 of 10 3 centimetres, polishes with schmigel in the surface, then cleans with 2M watery hydrochloric acid or rare nitric acid, dry after deionized water drip washing;
2) the auspicious special electronics SG1005A of adjustment function signal generator 8(), make it produce the sinusoidal wave function signal, peak value is 800mV, and frequency is 50Hz; Then at the auspicious special electronics SG1005A of function signal generator 8() positive pole and the diode 7(schottky diode MBR1045 of output voltage) positive pole join, diode 7(schottky diode MBR1045) negative pole and oscillographic signalling channel are joined, the observation oscilloscope figure, show that the power supply that obtains is that peak value is 700mV, frequency is the half-sine wave carrier wave direct supply of 50HZ;
3) will polish an end of the first cleaned tinsel 1 by the auspicious special electronics SG1005A of wire function signal generator 8() negative pole of output voltage joins, with an end of the second tinsel 5 by wire and diode 7(schottky diode MBR1045) negative pole joins, the other end of the first tinsel 1 and the second tinsel 5 inserts simultaneously and is placed with the AgNO that concentration is 0.1M
32min switches in the electroplating pool 6 of solution, the first tinsel 1 lower surface forms length under the galvanic effect of carrier wave be the metal nano layer 2 of 7 centimetres, first uses washed with de-ionized water, then clean with absolute ethyl alcohol, blot residual ethanol, be placed in brown exsiccator standby;
4) the first tinsel (1) being dipped concentration is 2% polyacrylonitrile solution, make solution covering metal nanometer layer (2), after taking-up, the first tinsel (1) is stood upside down and place, treat surperficial DMF solvent evaporation, subsequently it is moved into double dish, double dish is put into vacuum drying oven, and room temperature vacuum drying 7 hours is until solvent evaporates fully;
The part that 5) will be coated with first tinsel (1) of polyacrylonitrile porous membrane first immerses 0.1M NaH
2PO
4(pH4.5) in, 40 minutes (electrolytic solution need to be changed 4 times in this process) of reduction under constant potential-0.5V, then immerse and contain in the phosphate buffer (pH=6.5, total concentration is 0.1M) of 30 μ M glucose oxidases (GOD), oxidation is 20 minutes under the 0.65V constant potential.Prepared electrode fully washs with phosphate buffer (pH=6.5);
6) with 0.5 centimetre of electrode 3 bottoms reservation, remainder coats with heat-shrink tube 4, or the coatings coating, makes the solid glucose electrode based on the metal/nanometer metal.
Embodiment 5
1) with length being first tinsel 1 of 10 3 centimetres, polishes with schmigel in the surface, then cleans with 2M watery hydrochloric acid or rare nitric acid, dry after deionized water drip washing;
2) the auspicious special electronics SG1005A of adjustment function signal generator 8(), make it produce the sinusoidal wave function signal, peak value is 800mV, and frequency is 50Hz; Then at the auspicious special electronics SG1005A of function signal generator 8() positive pole and the diode 7(schottky diode MBR1045 of output voltage) positive pole join, diode 7(schottky diode MBR1045) negative pole and oscillographic signalling channel are joined, the observation oscilloscope figure, show that the power supply that obtains is that peak value is 700mV, frequency is the half-sine wave carrier wave direct supply of 50HZ;
3) will polish an end of the first cleaned tinsel 1 by the auspicious special electronics SG1005A of wire function signal generator 8() negative pole of output voltage joins, with an end of the second tinsel 5 by wire and diode 7(schottky diode MBR1045) negative pole joins, the other end of the first tinsel 1 and the second tinsel 5 inserts simultaneously and is placed with the AgNO that concentration is 0.1M
32min switches in the electroplating pool 6 of solution, the first tinsel 1 lower surface forms length under the galvanic effect of carrier wave be the metal nano layer 2 of 7 centimetres, first uses washed with de-ionized water, then clean with absolute ethyl alcohol, blot residual ethanol, be placed in brown exsiccator standby;
4) the first tinsel (1) being dipped concentration is 2% polyacrylonitrile solution, make solution covering metal nanometer layer (2), after taking-up, the first tinsel (1) is stood upside down and place, treat surperficial DMF solvent evaporation, subsequently it is moved into double dish, double dish is put into vacuum drying oven, and room temperature vacuum drying 5 hours is until solvent evaporates fully;
The part that 5) will be coated with first tinsel (1) of polyacrylonitrile porous membrane first immerses 0.1M NaH
2PO
4(pH4.5) in, 40 minutes (electrolytic solution need to be changed 4 times in this process) of reduction under constant potential-0.5V, then immerse and contain in the phosphate buffer (pH=6.5, total concentration is 0.1M) of 30 μ M glucose oxidases (GOD), oxidation is 40 minutes under the 0.65V constant potential.Prepared electrode fully washs with phosphate buffer (pH=6.5);
6) with 0.5 centimetre of electrode 3 bottoms reservation, remainder coats with heat-shrink tube 4, or the coatings coating, makes the solid glucose electrode based on the metal/nanometer metal.
1) with length being first tinsel 1 of 10 3 centimetres, polishes with schmigel in the surface, then cleans with 2M watery hydrochloric acid or rare nitric acid, dry after deionized water drip washing;
2) the auspicious special electronics SG1005A of adjustment function signal generator 8(), make it produce the sinusoidal wave function signal, peak value is 800mV, and frequency is 50Hz; Then at the auspicious special electronics SG1005A of function signal generator 8() positive pole and the diode 7(schottky diode MBR1045 of output voltage) positive pole join, diode 7(schottky diode MBR1045) negative pole and oscillographic signalling channel are joined, the observation oscilloscope figure, show that the power supply that obtains is that peak value is 700mV, frequency is the half-sine wave carrier wave direct supply of 50HZ;
3) will polish an end of the first cleaned tinsel 1 by the auspicious special electronics SG1005A of wire function signal generator 8() negative pole of output voltage joins, with an end of the second tinsel 5 by wire and diode 7(schottky diode MBR1045) negative pole joins, the other end of the first tinsel 1 and the second tinsel 5 inserts simultaneously and is placed with the AgNO that concentration is 0.1M
32min switches in the electroplating pool 6 of solution, the first tinsel 1 lower surface forms length under the galvanic effect of carrier wave be the metal nano layer 2 of 7 centimetres, first uses washed with de-ionized water, then clean with absolute ethyl alcohol, blot residual ethanol, be placed in brown exsiccator standby;
4) the first tinsel (1) being dipped concentration is 2% polyacrylonitrile solution, make solution covering metal nanometer layer (2), after taking-up, the first tinsel (1) is stood upside down and place, treat surperficial DMF solvent evaporation, subsequently it is moved into double dish, double dish is put into vacuum drying oven, and room temperature vacuum drying 7 hours is until solvent evaporates fully;
The part that 5) will be coated with first tinsel (1) of polyacrylonitrile porous membrane immersed in the phosphate buffer (pH=6.5, total concentration is 0.1M) contain 30 μ M glucose oxidases (GOD) 20 minutes.Prepared electrode fully washs with phosphate buffer (pH=6.5);
6) with 0.5 centimetre of electrode 3 bottoms reservation, remainder coats with heat-shrink tube 4, or the coatings coating, makes the solid glucose electrode based on the metal/nanometer metal.
Claims (4)
1. preparation method based on the solid glucose electrode of metal/nanometer metal is characterized in that its step is as follows:
1) be first tinsel (1) of 5～15 centimetres with length, first remove surface and oil contaminant with acetone soln, then clean with 1～2M watery hydrochloric acid or rare nitric acid, remove oxide, dry after deionized water drip washing;
2) positive pole of the positive pole of function signal generator (8) output voltage and diode (7) joins, an other utmost point and the oscillographic signalling channel of diode (7) are joined, adjustment function signal generator (8), the observation oscilloscope figure, the power supply that obtains is that peak value is 450～800mV, and frequency is the half-sine wave carrier wave direct supply of 50HZ;
3) end of the first tinsel (1) negative pole by wire function signal generator (8) output voltage is joined, one end of the second tinsel (5) is joined by wire and diode (7) negative pole, and the other end of the other end of the first tinsel (1) and the second tinsel (5) inserts simultaneously and is placed with the AgNO that concentration is 0.1～0.2M
3Energising 1.5～3min in the electroplating pool of solution (6), the first tinsel (1) lower surface forms length under the galvanic effect of carrier wave be the metal nano layer (2) of 5～8 centimetres, first use washed with de-ionized water, clean with absolute ethyl alcohol again, blot residual ethanol, be placed in brown exsiccator standby;
4) polyacrylonitrile is dissolved in dimethyl formamide, be mixed with the polyacrylonitrile solution of 1% ~ 3% concentration, dip this solution with the first tinsel (1), make solution covering metal nanometer layer (2), stand upside down and place, treat surperficial solvent dimethylformamide evaporation, subsequently it is moved into double dish, double dish is put into vacuum drying oven, and room temperature vacuum drying 2 ~ 7 hours is until solvent evaporates fully afterwards in the first tinsel (1) surface formation polyacrylonitrile porous membrane;
The part that 5) will be coated with first tinsel (1) of polyacrylonitrile porous membrane first immerses the NaH that concentration is 0.1M
2PO
4In solution, reductase 12 is 0 ~ 40 minute under constant potential-0.5V, NaH
2PO
4Solution is changed 3 ~ 5 times, then immerse and contain in the phosphate buffer of 10 ~ 40 μ M glucose oxidases, pH=6.5, total concentration is 0.1M, and oxidation is 20 ~ 40 minutes under 0.45 ~ 0.65V constant potential, in oxidizing process, zymoprotein with negative charge will be embedded in polyacrylonitrile porous membrane, formed glucose electrode, after prepared electrode fully washs with the pH=6.5 phosphate buffer, stored standby at-10 ℃ of temperature.
2. the preparation method of a kind of solid glucose electrode based on the metal/nanometer metal according to claim 1, is characterized in that described polyacrylonitrile is the polymkeric substance of vinyl cyanide, and the weight-average molecular weight of polyacrylonitrile is 1.0 * 10
4～4.0 * 10
4
3. the solid glucose electrode based on the metal/nanometer metal of a preparation method according to claim 1 preparation, it is characterized in that having the first tinsel (1), the first tinsel (1) lower surface is coated with the metal nano layer (2) of nanometer grade, be coated with polyacrylonitrile porous membrane (3) on the top layer of metal nano layer (2), be equipped with glucose oxidase on polyacrylonitrile porous membrane.
4. the solid glucose electrode based on the metal/nanometer metal according to claim 3, is characterized in that, described the first tinsel (1) is Ag, Au, Pt or uses the surface to be coated with the copper wire of silver.
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Non-Patent Citations (8)
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| A glucose biosensor based on microporous polyacrylonitrile synthesized by single rare-earth catalyst;Hao Zheng等;《Biosensors and Bioelectronics》;20021231;第17卷(第6-7期);摘要、第542、545页 * |
| Chaoqun Zhang等.Silver nanoparticles grown on the surface of PAN nanofiber:Preparation, characterization and catalytic performance.《Colloids and Surfaces A: Physicochem. Eng. Aspects》.2010,第362卷(第1-3期),第58-64页. |
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| Silver nanoparticles grown on the surface of PAN nanofiber:Preparation, characterization and catalytic performance;Chaoqun Zhang等;《Colloids and Surfaces A: Physicochem. Eng. Aspects》;20100401;第362卷(第1-3期);第58-64页 * |
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