CN105806920A - Preparation method of chlordimeform non-enzymatic sensor constructed on basis of molybdenum sulfide composite material and application - Google Patents
Preparation method of chlordimeform non-enzymatic sensor constructed on basis of molybdenum sulfide composite material and application Download PDFInfo
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Abstract
The invention discloses a preparation method of a biological immunosensor which has an electrochemiluminescence and photoelectrochemistry dual signal developed strategy and is constructed on the basis of a functional nano material.The prepared sensor is easy to operate, convenient to carry, rapid in detection, low in cost and capable of being used for rapid and sensitive detection on chlordimeform in the fields of daily production and life and the like.
Description
Technical field
The preparation method that the present invention relates to a kind of sensor for detecting Spanon, this sensor integration electrochemiluminescence and Optical Electro-Chemistry dual-use function.Belong to Nano-function thin films and electrochemical biosensor analysis technical field.
Background technology
Spanon is a kind of agricultural chemical insecticide, and in soil, Spanon slightly can be migrated to deep subsoil by the eluviation of water.The animal of Spanon chronic poisoning may occur in which weight loss, packed cell volume, hemoglobin and red blood cell count(RBC) decline, leukocyte count increase etc., according to the WHO of 1972, if human body Long Term Contact Spanon can cause canceration.
At present, the method detecting Spanon mainly has chromatography, mass spectrography etc..This type of method instrument is valuable, complicated operation, and laboratory personnel just can detect after needing professional training.Therefore, R&D costs are low, it is fast, highly sensitive to detect, the Spanon sensor of high specificity is significant.
Electrochemical biosensor analytical technology, due to easy and simple to handle, the detection advantages such as speed is fast, obtains the attention of people day by day.The electrochemical biosensor analytical technology being presently used for detection Spanon is divided according to detection means and is mainly had electrochemical sensor, electrochemical luminous sensor and Optical Electro-Chemistry sensor three kinds.Wherein, electrochemical luminous sensor and Optical Electro-Chemistry sensor, relative to electrochemical sensor, have the features such as background signal noise is few, highly sensitive, testing cost is low, were paid close attention to by increasing researcher in recent years.
Electrochemiluminescence is also referred to as electrochemiluminescence, refer to and produce some special materials by electrochemical method at electrode surface, between these materials or and system in form excited state by electron transmission between other components, excited state return to ground state and produce luminescence phenomenon.Namely electrochemical luminous sensor by changing the decorative material of electrode surface, produces electrochemiluminescence with analyte, in optimal conditions, realizes the qualitative and quantitative analysis to analyte according to the associated change of analyte concentration with electrochemiluminescence intensity.
Optical Electro-Chemistry sensor is based on additional light source activation Electrophotosensitivmaterial material and causes that electron-hole pair is easily separated, under suitable inclined potential condition, it is achieved the electronics quick transmission on electrode, quasiconductor and trim and analyte, and forms photoelectric current.In optimal conditions, the change of analyte concentration can directly affect the size of photoelectric current, it is possible to realizes the qualitative and quantitative analysis to analyte according to the change of photoelectric current.
But, owing to electrochemical luminous sensor needs external optical signal to catch equipment such as photodiode etc., and Optical Electro-Chemistry sensor needs peripheral hardware light source to excite Electrophotosensitivmaterial material, this have impact on the convenience of the two operation to a certain extent, limits them and is more widely applied in actual production, life.Therefore, the electrochemical biosensor analytical technology designing, preparing more simple, fast detection Spanon has highly important practical value.
Summary of the invention
It is an object of the invention to provide a kind of simple to operate, easy to carry, detection is fast, cost is low Spanon preparation method without enzyme sensor, prepared sensor, can be used for quick, the Sensitive Detection to Spanon in the fields such as daily production, life.Based on this purpose, the present invention, in same electrolyzer, adopts four electrode systems, namely two working electrodes, one to electrode and a reference electrode, wherein working electrode 1 adopts the molybdenum bisuphide composite Zn-MoS of zinc doping2Jointly modifying with electropolymerization luminol, as electrochemiluminescence working electrode W1, working electrode 2 adopts reduced graphene carried titanium dioxide nano-film sol rGO/TiO2Jointly modify with Spanon antibody, as Optical Electro-Chemistry working electrode W2.When detecting, after electrolyzer adds the hydrogen peroxide of fixed concentration, W1 applies step voltage, due to Zn-MoS2Having bigger serface and good electric conductivity can load and stablize the effect of luminol, sufficient luminol and hydroperoxidation, produce electrochemiluminescence, this is just equivalent to " turning on light ", when step voltage is 0, electrochemiluminescence disappears, and this is just equivalent to " turning off the light ", on W2, meanwhile apply constant voltage, due to rGO/TiO always2Can because the luminescence that electrochemiluminescence produces excites causes that electron-hole pair is easily separated, it is marked at the chlorhematin Hemin catalyzing hydrogen peroxide generation oxygen that Spanon two resists, hydrogen peroxide is made to become hole " donor ", thus obtaining photoelectric current on W2, when electrogenerated chemiluminescence disappears, when namely " turning off the light ", photoelectric current disappears immediately.Due under the premise of fixing concentration of hydrogen peroxide, photoelectric current size and Hemin concentration positive correlation, when in measured object, Spanon concentration is more big, when being attached on W2 with primary antibodie immunity, the concentration that immunity incorporation of markings has the Spanon two of Hemin anti-again will be more big, the photoelectric current produced is also more big, therefore can realize the detection to Spanon by the size of recording light electric current.
Based on above inventive principle, the concrete technical scheme that the present invention adopts is as follows:
1. the Spanon built based on molybdenum sulfide composite is without the preparation method of enzyme sensor, and it is characterized in that, preparation process is:
(1) preparation method of electrochemiluminescence working electrode W1, described W1 is by Zn-MoS2The ITO electro-conductive glass jointly modified with electropolymerization luminol, is characterized in, concrete preparation process is:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating Zn-MoS2, area coverage is 1cm × 1cm, dries under room temperature；
2) by 1) working electrode that obtains, immerse in electrolyte, immersion area is Zn-MoS2The area covered, utilizes three-electrode system that working electrode is carried out electrochemical deposition, takes out working electrode after deposition, uses ultra-pure water to clean, and at 4 DEG C, lucifuge dries, and prepares electrochemiluminescence working electrode W1；
Described Zn-MoS2For the molybdenum bisuphide two-dimension nano materials doped with zinc ion, described two-dimension nano materials is scraps of paper shape, and thickness is about 10 ~ 20nm；Described Zn-MoS2Preparation method be: by 0.005 ~ 0.01g zinc chloride ZnCl2, the 0.1mol/L ascorbic acid solution of 2 ~ 6mL, 0.5 ~ 1.5mL sodium molybdate Na2MoO4Solution and 0.01 ~ 0.03g sodium sulfide Na2S, after being mixed and stirred for 15 minutes, puts in reactor, at 150 ~ 220 DEG C, reacts 12 ~ 16 hours；After being cooled to room temperature, use deionized water centrifuge washing, at 40 DEG C, carry out vacuum drying, namely prepare Zn-MoS2, it is dissolved in deionized water and prepares Zn-MoS2Solution；
Described electrolyte is the sulfuric acid solution containing luminol, and in described electrolyte, the concentration of luminol is 1 ~ 10mmol/L, and sulfuric acid concentration is 0.1 ~ 1.0mol/L；
Described three-electrode system, including working electrode, reference electrode and to electrode, described reference electrode is saturated calomel electrode, and described is platinum electrode to electrode；
Described electrochemical deposition process, the electrochemical method of employing is cyclic voltammetry, and starting voltage is-0.2V, and final voltage is 1.5V, sweeps speed for 100mv/s, circulation 20 ~ 30 circle；
(2) preparation method of Optical Electro-Chemistry working electrode W2, described W2 is by rGO/TiO2The ITO electro-conductive glass jointly modified with Spanon antibody, is characterized in, concrete preparation process is:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating 8 ~ 12 μ LrGO/TiO2, dry under room temperature；
2) by 1) in the working electrode that obtains put in Muffle furnace, be annealed processing at 450 DEG C, after process, be cooled to room temperature；
3) by 2) in working electrode surface drop coating 8 ~ 12 μ L Spanon antibody-solutions that obtains, dry at 4 DEG C, clean with ultra-pure water after drying, dry at 4 DEG C, prepare Optical Electro-Chemistry working electrode W2；
Described rGO/TiO2For the aqueous solution of reduced graphene carried titanium dioxide nanometer sheet, described titanium dioxide nanoplate is the titanium dioxide nano-particle of square lamellar, and the length of side is 60 ~ 80nm；
The concentration of described Spanon antibody-solutions is 300 μ g/mL；
(3) Spanon built based on molybdenum sulfide composite is without the preparation method of enzyme sensor:
1) one side that W1 and W2 conducts electricity relatively being inserted in electrolyzer, W1 and W2 spacing is 0.5cm ~ 1.5cm；
2) with Ag/AgCl be reference electrode RE, platinum electrode be to electrode CE, insert in electrolyzer, collectively constitute four electrode systems with W1 and W2；
3) in electrolyzer add 10mLpH value be 11 ~ 13 NaOH solution and 0.2mL concentration be the hydrogenperoxide steam generator of 1mmol/L；
4) by 1) ~ 3) obtained by four electrode systems and electrolyzer be placed in magazine, namely prepare the Spanon built based on molybdenum sulfide composite without enzyme sensor.
2. the Spanon built based on molybdenum sulfide composite of the present invention is without the detection being applied to hydrogen peroxide of enzyme sensor, and the detection method being characterized in concrete is:
(1) on W2, drip the Spanon standard solution of 10 μ L variable concentrations, after hatching 30min, Spanon and the Spanon antibody on W2 carry out immunity combination, after flushing, the Spanon two dripping 10 μ L chlorhematin Hemin labellings again resists, and after hatching 30min, the Spanon two of Hemin labelling is anti-carries out immunity combination with Spanon, after flushing, prepare W2 to be measured；
(2) utilizing electrochemical workstation, adopt the method for step voltage that W1 applies step voltage on W1, initial voltage is 0v, and step voltage is 0.7 ~ 0.9v, and snap time is 10 ~ 30s；Meanwhile, when adopting on W2 to be measured, W2 to be measured is applied constant voltage by m-current methods, and voltage is 0 ~ 0.6v；Electric current on W2 to be measured can increase accordingly along with the increase of Spanon concentration, according to the relation between gained electric current increase value and Spanon concentration, drawing curve；；
(3) Spanon solution to be measured replaces the standard solution of Spanon, and the Spanon detection method described in (1) and (2) detects, and draws the concentration of Spanon solution to be measured according to obtained electric current increase value and the working curve drawn；
The concentration that the Spanon two of described Hemin labelling is anti-is 300 μ g/mL.
The useful achievement of the present invention
(1) Spanon built based on molybdenum sulfide composite of the present invention is simple without enzyme sensor preparation, easy to operate, without external accessory, utilize the microminiaturization of detection equipment, portability, and achieve the selective enumeration method quick, sensitive, high to Spanon, there is wide market development prospect；
(2) present invention adopts four electrode system detection Spanons first in same electrolyzer, and achieves electrochemiluminescence signal amplification strategy difunctional with Optical Electro-Chemistry.Along with the increase of Spanon concentration in electrolyzer, the Spanon two of the Hemin labelling being modified on W2 is anti-will be increased, and also implies that Hemin is to hydrogen peroxide catalyzed raising.Since so, on the one hand, make electrochemiluminescence intensity linearly increasing, the linear increase of photoelectric current excited；On the other hand, hydrogen peroxide is as electron donor so that the linear increase of photoelectric current in Optical Electro-Chemistry reaction.Therefore, electrochemiluminescence and two kinds of methods of Optical Electro-Chemistry are reaction jointly, interaction in same electrolyzer, under same electrochemical workstation, achieve the dual amplification that Spanon is detected the signal of telecommunication, drastically increase detection sensitivity and detection limit, simultaneously because do not use enzyme, thus detection environmental requirement is more loose, there is important scientific meaning and market using value.
Detailed description of the invention
The Spanon that embodiment 1 one kinds builds based on molybdenum sulfide composite is without enzyme sensor, and concrete preparation process is:
(1) Zn-MoS2Preparation:
By 0.005g zinc chloride ZnCl2, the 0.1mol/L ascorbic acid solution of 2mL, 0.5mL sodium molybdate Na2MoO4Solution and 0.01g sodium sulfide Na2S, after being mixed and stirred for 15 minutes, puts in reactor, at 150 DEG C, reacts 16 hours；After being cooled to room temperature, use deionized water centrifuge washing, at 40 DEG C, carry out vacuum drying, namely prepare Zn-MoS2, it is dissolved in deionized water and prepares Zn-MoS2Solution.
(2) preparation of electrochemiluminescence working electrode W1:
1) with ITO electro-conductive glass for working electrode, the Zn-MoS of preparation in electrode surface drop coating (1)2Solution, area coverage is 1cm × 1cm, dries under room temperature；
2) by 1) working electrode that obtains, immerse in electrolyte, immersion area is Zn-MoS2The area covered, utilizes three-electrode system that working electrode is carried out electrochemical deposition, takes out working electrode after deposition, uses ultra-pure water to clean, and at 4 DEG C, lucifuge dries, and prepares electrochemiluminescence working electrode W1；
Described electrolyte is the sulfuric acid solution containing luminol, and in described electrolyte, the concentration of luminol is 1mmol/L, and sulfuric acid concentration is 0.1mol/L；
Described three-electrode system, including working electrode, reference electrode and to electrode, described reference electrode is saturated calomel electrode, and described is platinum electrode to electrode；
Described electrochemical deposition process, the electrochemical method of employing is cyclic voltammetry, and starting voltage is-0.2V, and final voltage is 1.5V, sweeps speed for 100mv/s, circulation 20 circle.
(3) preparation of Optical Electro-Chemistry working electrode W2:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating 8 μ LrGO/TiO2, dry under room temperature；
2) by 1) in the working electrode that obtains put in Muffle furnace, be annealed processing at 450 DEG C, after process, be cooled to room temperature；
3) by 2) in the working electrode surface drop coating 8 μ L Spanon antibody-solutions that obtains, dry at 4 DEG C, clean with ultra-pure water after drying, dry at 4 DEG C, prepare Optical Electro-Chemistry working electrode W2；
Described rGO/TiO2For the aqueous solution of reduced graphene carried titanium dioxide nanometer sheet, described titanium dioxide nanoplate is the titanium dioxide nano-particle of square lamellar, and the length of side is 60 ~ 80nm；
The concentration of described Spanon antibody-solutions is 300 μ g/mL；
(4) Spanon built based on molybdenum sulfide composite is without the preparation method of enzyme sensor:
1) being inserted face to face in electrolyzer by the W1 of preparation in (2) and the W2 of (3) middle preparation, W1 and W2 spacing is 0.5cm；
2) with Ag/AgCl be reference electrode RE, platinum electrode be to electrode CE, insert in electrolyzer, collectively constitute four electrode systems with W1 and W2；
3) in electrolyzer add 10mLpH value be 11 NaOH solution and 0.2mL concentration be the hydrogenperoxide steam generator of 1mmol/L；
4) by 1) ~ 3) obtained by four electrode systems and electrolyzer be placed in magazine, namely prepare the Spanon built based on molybdenum sulfide composite without enzyme sensor.
The Spanon that embodiment 2 one kinds builds based on molybdenum sulfide composite is without enzyme sensor, and concrete preparation process is:
(1) Zn-MoS2Preparation:
Preparation process is with Zn-MoS in embodiment 12The preparation method of solution, difference is: ZnCl2Addition be 0.008g, ascorbic acid solution addition be 4mL, Na2MoO4The addition of solution is 1.0mL and Na2The addition of S is 0.02g, at 220 DEG C, reacts 12 hours.
(2) preparation of electrochemiluminescence working electrode W1:
Preparation process is with the preparation process of W1 in embodiment 1, and difference is: use the Zn-MoS obtained by (1) in the present embodiment2Modified electrode；In electrolyte, the concentration of luminol is 5mmol/L, and sulfuric acid concentration is 0.5mol/L, when cyclic voltammetry carries out electrochemical deposition, and circulation 25 circle.
(3) preparation of Optical Electro-Chemistry working electrode W2:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating 10 μ LrGO/TiO2, dry under room temperature；
2) by 1) in the working electrode that obtains put in Muffle furnace, be annealed processing at 450 DEG C, after process, be cooled to room temperature；
3) by 2) in the working electrode surface drop coating 10 μ L Spanon antibody-solutions that obtains, dry at 4 DEG C, clean with ultra-pure water after drying, dry at 4 DEG C, prepare Optical Electro-Chemistry working electrode W2；
All the other are with the preparation process of W2 in embodiment 1.
(4) Spanon built based on molybdenum sulfide composite is without the preparation method of enzyme sensor:
Preparation process is with embodiment 1, and difference is W1 and W2 spacing is 1.0cm, and the pH value of the NaOH solution added in electrolyzer is 12.
The Spanon that embodiment 3 one kinds builds based on molybdenum sulfide composite is without enzyme sensor, and concrete preparation process is:
(1) Zn-MoS2Preparation:
Preparation process is with Zn-MoS in embodiment 12The preparation method of solution, difference is: ZnCl2Addition be 0.01g, ascorbic acid solution addition be 6mL, Na2MoO4The addition of solution is 1.5mL and Na2The addition of S is 0.03g, at 220 DEG C, reacts 12 hours.
(2) preparation of electrochemiluminescence working electrode W1:
Preparation process is with the preparation process of W1 in embodiment 1, and difference is: use the Zn-MoS obtained by (1) in the present embodiment2Modified electrode；In electrolyte, the concentration of luminol is 10mmol/L, and sulfuric acid concentration is 1.0mol/L, when cyclic voltammetry carries out electrochemical deposition, and circulation 30 circle.
(3) preparation of Optical Electro-Chemistry working electrode W2:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating 12 μ LrGO/TiO2, dry under room temperature；
2) by 1) in the working electrode that obtains put in Muffle furnace, be annealed processing at 450 DEG C, after process, be cooled to room temperature；
3) by 2) in the working electrode surface drop coating 12 μ L Spanon antibody-solutions that obtains, dry at 4 DEG C, clean with ultra-pure water after drying, dry at 4 DEG C, prepare Optical Electro-Chemistry working electrode W2；
All the other are with the preparation process of W2 in embodiment 1.
(4) Spanon built based on molybdenum sulfide composite is without the preparation method of enzyme sensor:
Preparation process is with embodiment 1, and difference is W1 and W2 spacing is 1.5cm, and the pH value of the NaOH solution added in electrolyzer is 13.
The Spanon that embodiment 4 one kinds builds based on molybdenum sulfide composite is without the application of enzyme sensor
A kind of Spanon built based on molybdenum sulfide composite of embodiment 1 preparation is applied to the detection of Spanon without enzyme sensor, and its detecting step is:
(1) on W2, drip the Spanon standard solution of 10 μ L variable concentrations, after hatching 30min, Spanon and the Spanon antibody on W2 carry out immunity combination, after flushing, the Spanon two dripping 10 μ LHemin labellings again resists, and after hatching 30min, the Spanon two of Hemin labelling is anti-carries out immunity combination with Spanon, after flushing, prepare W2 to be measured；
(2) utilizing electrochemical workstation, adopt the method for step voltage that W1 applies step voltage on W1, initial voltage is 0v, and step voltage is 0.7v, and snap time is 10s；Meanwhile, when adopting on W2 to be measured, W2 to be measured is applied constant voltage by m-current methods, and voltage is 0v；Electric current on W2 to be measured can increase accordingly along with the increase of Spanon concentration, according to the relation between gained electric current increase value and Spanon concentration, drawing curve；
(3) Spanon solution to be measured replaces the standard solution of Spanon, and the Spanon detection method described in (1) and (2) detects, and draws the concentration of Spanon solution to be measured according to obtained electric current increase value and the working curve drawn；
The concentration that the Spanon two of described Hemin labelling is anti-is 300 μ g/mL.
The Spanon that embodiment 5 one kinds builds based on molybdenum sulfide composite is without the application of enzyme sensor
A kind of Spanon built based on molybdenum sulfide composite of embodiment 2 preparation is applied to the detection of hydrogen peroxide without enzyme sensor, and its detecting step is except following steps, and all the other steps are with embodiment 4:
Step (2) utilizes electrochemical workstation, adopts the method for step voltage that W1 applies step voltage on W1, and initial voltage is 0v, and step voltage is 0.8v, and snap time is 20s；Meanwhile, when adopting on W2 to be measured, W2 to be measured is applied constant voltage by m-current methods, and voltage is 0.3v；Electric current on W2 to be measured can increase accordingly along with the increase of Spanon concentration, according to the relation between gained electric current increase value and Spanon concentration, drawing curve.
The Spanon that embodiment 6 one kinds builds based on molybdenum sulfide composite is without the application of enzyme sensor
A kind of Spanon built based on molybdenum sulfide composite of embodiment 3 preparation is applied to the detection of hydrogen peroxide without enzyme sensor, and its detecting step is except following steps, and all the other steps are with embodiment 4:
Step (2) utilizes electrochemical workstation, adopts the method for step voltage that W1 applies step voltage on W1, and initial voltage is 0v, and step voltage is 0.9v, and snap time is 30s；Meanwhile, when adopting on W2 to be measured, W2 to be measured is applied constant voltage by m-current methods, and voltage is 0.6v；Electric current on W2 to be measured can increase accordingly along with the increase of Spanon concentration, according to the relation between gained electric current increase value and Spanon concentration, drawing curve.
The Spanon based on molybdenum sulfide composite structure prepared by embodiment 7 embodiment 1-3, without enzyme sensor, is applied to the detection of Spanon according to the detecting step of embodiment 4-6, has excellent Detection results, and detection is limited to 30pmol/L.
Claims (5)
1. the Spanon built based on molybdenum sulfide composite is without the preparation method of enzyme sensor, it is characterised in that adopt the molybdenum bisuphide composite Zn-MoS of zinc doping2The ITO electro-conductive glass jointly modified with electropolymerization luminol is as electrochemiluminescence working electrode W1, reduced graphene carried titanium dioxide nano-film sol rGO/TiO2The ITO electro-conductive glass jointly modified with Spanon antibody is as Optical Electro-Chemistry working electrode W2, Ag/AgCl electrode as reference electrode RE, platinum electrode as to electrode CE, four electrodes are inserted jointly same electrolyzer forms four electrode systems, four prepared electrode systems are placed in magazine, namely prepare the Spanon based on molybdenum sulfide composite structure without enzyme sensor.
2. the Spanon built based on molybdenum sulfide composite according to claim 1 is without the preparation method of enzyme sensor, it is characterised in that the molybdenum bisuphide composite Zn-MoS of described zinc doping2For the molybdenum bisuphide two-dimension nano materials doped with zinc ion, described two-dimension nano materials is scraps of paper shape, and thickness is about 10 ~ 20nm.
3. the Spanon built based on molybdenum sulfide composite according to claim 1 is without the preparation method of enzyme sensor, it is characterised in that described reduced graphene carried titanium dioxide nano-film sol rGO/TiO2For the aqueous solution of reduced graphene carried titanium dioxide nanometer sheet, described titanium dioxide nanoplate is the titanium dioxide nano-particle of square lamellar, and the length of side is 60 ~ 80nm.
4. the Spanon built based on molybdenum sulfide composite according to claim 1 is without the preparation method of enzyme sensor, it is characterised in that the one side that W1 and W2 conducts electricity relatively being inserted in electrolyzer, W1 and W2 spacing is 0.5cm ~ 1.5cm.
5. the Spanon Optical Electro-Chemistry sensor that prepared by preparation method according to claim 1, it is characterised in that described Spanon Optical Electro-Chemistry sensor is applied to the detection of Spanon, and detecting step is:
(1) on W2, Spanon solution to be measured is dripped, after the Spanon in Spanon solution to be measured Spanon antibody mediated immunity on W2 is combined, rinse out all the other materials, drip that the Spanon two of chlorhematin Hemin labelling is anti-carries out immunity combination again, the Spanon two washing unnecessary Hemin labelling in conjunction with backlash off resists, and prepares W2 to be measured；
(2) utilizing electrochemical workstation, in the electrolyte containing fixed concentration hydrogen peroxide, adopt the method for step voltage that W1 applies step voltage on W1, initial voltage is 0v, and step voltage is 0.7 ~ 0.9v, and snap time is 10 ~ 30s；Meanwhile, when adopting on W2 to be measured, W2 to be measured is applied constant voltage by m-current methods, and voltage is 0 ~ 0.6v；Electric current on W2 to be measured can along with in Spanon solution to be measured the concentration of Spanon increase and increase accordingly, increasing according to gained electric current is worth in Spanon solution to be measured the concentration of Spanon.
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