CN110146563A - It is a kind of based on Prussian blue no enzymuria acid sensor - Google Patents

It is a kind of based on Prussian blue no enzymuria acid sensor Download PDF

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Publication number
CN110146563A
CN110146563A CN201811539838.2A CN201811539838A CN110146563A CN 110146563 A CN110146563 A CN 110146563A CN 201811539838 A CN201811539838 A CN 201811539838A CN 110146563 A CN110146563 A CN 110146563A
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China
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prussian blue
electrode
enzymuria
carbon slurry
acid sensor
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叶学松
梁波
赵欢萍
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Shandong Xianyi Medical Technology Co Ltd
Shandong Industrial Technology Research Institute of ZJU
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Shandong Xianyi Medical Technology Co Ltd
Shandong Industrial Technology Research Institute of ZJU
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Priority to CN201811539838.2A priority Critical patent/CN110146563A/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416Systems
    • G01N27/48Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Analytical Chemistry (AREA)
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  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
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  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)

Abstract

The present invention provides that a kind of detection accuracy is high, speed is fast, performance is stable based on Prussian blue no enzymuria acid sensor.This is without enzymuria acid sensor, and including the substrate, conductor layer and electrode layer successively to splice, electrode layer includes to electrode and working electrode, and working electrode is the Prussian blue carbon slurry coating on substrate, and Prussian blue carbon slurry is mixed by prussian blue powder and carbon slurry.There is respective electrode terminal to electrode and working electrode, pass through the first conducting wire respectively to electrode and working electrode to connect with respective electrode terminal, electrode terminal and the first conducting wire are respectively positioned on conductor layer, and the first conducting wire includes argentine chloride coating and the Prussian blue carbon being covered on argentine chloride coating slurry coating.

Description

It is a kind of based on Prussian blue no enzymuria acid sensor
Technical field
The present invention relates to electrochemical fields, more particularly to a kind of based on Prussian blue no enzymuria acid sensor.
Background technique
Following background technique is used to help reader and understands the present invention, and is not construed as the prior art.
The testing principle of electrode is to pass through enzymatic reaction on enzyme modification to working electrode corresponding to substrate mostly at present Measure electric signal, therefore uric acid sensor generally uses urinary acidification.But the rigid condition of enzyme on the working electrode (s compares Harshness needs to keep in immobilization process the activity of enzyme unaffected, and temperature and humidity requires to consider when enzyme is fixed.This Outside, the price of uricase is generally all more expensive, limits its use scope, increases the production cost of electrode test piece.It is general Shandong scholar's indigo plant have excellent electrochemical reversibility, stability, with Prussian blue preparation can be effective without enzyme type uric acid sensor The various drawbacks for avoiding urinary acidification from detecting.
Chinese patent 201510605173.0 disclose a kind of Prussian blue/N- doping carbon nano-composite material preparation and Using, take 2 μ L it is Prussian blue/working electrode in screen printing electrode is added dropwise in N- doped carbon Nanocomposite solution On, room temperature is dried;Add dehydrated alcohol dilute solution on the surface that material was added dropwise after drying, up to no enzyme type uric acid biography after drying Sensor.The shortcomings that patent, is: 1, needing to form working electrode first on substrate, then coats general Shandong on the working electrode (s Scholar's indigo plant/N- adulterates carbon nano-composite material, complex process;And Prussian blue/N- doping carbon nano-composite material is easy from work It falls off as electrode surface, leads to the failure of electrode slice.2, the preparation step of Prussian blue/N- doping carbon nano-composite material is multiple It is miscellaneous, increase production cost.
Summary of the invention
The purpose of the present invention is to provide a kind of detection accuracy height, speed is fast, performance is stable based on Prussian blue nothing Enzymuria acid sensor.
It is industrial based on Prussian blue no enzymuria suitable for high-volume that the object of the invention is also to provide a kind of The preparation method of acid sensor.
It is a kind of based on Prussian blue no enzymuria acid sensor, including the substrate, conductor layer and electrode layer successively to splice, electricity Pole layer includes to electrode and working electrode, and working electrode is starched with Prussian blue carbon, and Prussian blue carbon slurry is by prussian blue powder It is mixed with carbon slurry.Preferably, the mixture that electrode is silver coating, argentine chloride coating or silver and silver chlorate on substrate is applied Layer.
Further, working electrode is the Prussian blue carbon slurry coating on substrate;Alternatively, working electrode includes being printed on substrate On carbon starch coating, have Prussian blue carbon slurry coating on carbon slurry coating.
Further, mass fraction Prussian blue in Prussian blue carbon slurry is 0.5%~5%.
Further, there is respective electrode terminal to electrode and working electrode, the is passed through respectively to electrode and working electrode One conducting wire is connect with respective electrode terminal, and electrode terminal and the first conducting wire are respectively positioned on conductor layer, and the first conducting wire includes silver chlorate Coating and the Prussian blue carbon being covered on argentine chloride coating starch coating.Argentine chloride coating is clipped in substrate and Prussian blue carbon slurry applies Between layer.Preferably, electrode terminal is printed on substrate by chlorination silver paste and is formed.
Further, conductor layer includes two recognition terminals and the second conducting wire for connecting two recognition terminals, identifies end Son and the second conducting wire include argentine chloride coating and the Prussian blue carbon being covered on argentine chloride coating slurry coating.
Further, this further includes the insulating layer successively to splice, layers of two-sided and hydrophilic membrane, insulation without enzymuria acid sensor Stacking is connected on electrode layer, and insulating layer and layers of two-sided are all provided with jagged, and notch intersects with to electrode and working electrode, base Plate, insulating layer notch, layers of two-sided notch and hydrophilic membrane are collectively formed for sample to be tested to be drained to working electrode and right The siphon passage of electrode.Preferably, insulating layer notch and layers of two-sided notch are overlapped.Preferably, the shape of notch be rectangle, Square, ellipse or round.Preferably, insulating layer is prepared by hydrophobic material.For example, insulating layer can be with dissolved with The organic solvent of epoxy resin prints.
Further, hydrophilic membrane has air hole, and air hole is provided at the through-hole on hydrophilic membrane, and air hole and siphon are logical Road is connected close to one end of substrate center.
Further, Prussian blue carbon slurry is Prussia's blue powder to be added in carbon slurry, stir 200~500 with machine mixer Turn, the slurry that 10~60min is formed then is stirred by ultrasonic with ultrasonic oscillation instrument.Preferably, machine mixer stirs 300 turns, Then 30min is stirred by ultrasonic with ultrasonic oscillation instrument.
A kind of the case where working electrode is Prussian blue carbon slurry coating: system based on Prussian blue no enzymuria acid sensor Preparation Method, successively the following steps are included:
1) prussian blue powder, which is added in carbon slurry, is mixed, prepares Prussian blue carbon slurry, general Shandong in Prussian blue carbon slurry The mass fraction of scholar's indigo plant is 0.5%~5%;
2) it prints Prussian blue carbon on substrate to starch to form Prussian blue carbon slurry coating, Prussian blue carbon slurry coating is as work Make electrode;
3) it dries, drying temperature is 80 DEG C~100 DEG C, and drying time is 8~15min.
In some cases, step 2) is substituted for: Prussian blue carbon is added dropwise on substrate and starches to form Prussian blue carbon slurry Coating, Prussian blue carbon slurry coating is as working electrode.
Further, after the step 3) also successively the following steps are included:
4) it in organic solvent by epoxy resin dissolution, is printed on electrode layer with the organic solvent dissolved with epoxy resin absolutely Edge layer dries, organic solvent is made to volatilize, and insulating layer has the notch intersected with to electrode and working electrode;
5) notch is made on double-sided adhesive, on the insulating layer by sticking double faced adhesive tape, sticking double faced adhesive tape in insulating layer, it is two-sided Glue notch is overlapped with insulating layer notch, double-sided adhesive with a thickness of 0.1~0.2mm;
6) hydrophilic membrane is covered on double-sided adhesive.
Working electrode includes the case where carbon slurry coating and Prussian blue carbon slurry coating: a kind of based on Prussian blue no enzymuria The preparation method of acid sensor, successively the following steps are included:
1) carbon is printed on substrate to starch to form carbon slurry coating, drying;
2) prussian blue powder, which is added in carbon slurry, is mixed, prepares Prussian blue carbon slurry, general Shandong in Prussian blue carbon slurry The mass fraction of scholar's indigo plant is 0.5%~5%;
3) Prussian blue carbon is printed on carbon slurry coating to starch to form Prussian blue carbon slurry coating;
4) it dries, drying temperature is 80 DEG C~100 DEG C, and drying time is 8~15min.
In some cases, step 3) is substituted for: carbon slurry coating on be added dropwise Prussian blue carbon starch to be formed it is Prussian blue Carbon starches coating.
Further, after the step 4) also successively the following steps are included:
5) it in organic solvent by epoxy resin dissolution, is printed on electrode layer with the organic solvent dissolved with epoxy resin absolutely Edge layer dries, organic solvent is made to volatilize, and insulating layer has the notch intersected with to electrode and working electrode;
6) notch is made on double-sided adhesive, on the insulating layer by sticking double faced adhesive tape, sticking double faced adhesive tape in insulating layer, it is two-sided Glue notch is overlapped with insulating layer notch, double-sided adhesive with a thickness of 0.1~0.2mm;
7) hydrophilic membrane is covered on double-sided adhesive.
Further, substrate is placed in pure water before step 1) and is cleaned by ultrasonic, dries.
Beneficial effects of the present invention:
1, the Prussian blue mass fraction in Prussian blue carbon slurry is 0.5%~5%, realizes detecting without enzyme for uric acid, and And sensor detection signal is strong, performance is stable, high sensitivity, accuracy is high, detection speed is fast, uric acid concentration model that can be detected It encloses big.
2, the Prussian blue carbon slurry coating on substrate can directly form working electrode, and preparation process is simple, save the cost.
3, the first conducting wire of conductor layer, the second conducting wire and recognition terminal include that argentine chloride coating and Prussian blue carbon slurry apply Layer, double coatings can preferably avoid argentine chloride coating width is smaller, conducting wire be easy open circuit problem;And work is prepared in printing When making electrode, only need to improve printing stencil;It is needed when preparation work electrode, only in a manner of being added dropwise corresponding in conductor layer Prussian blue carbon slurry is added dropwise in region, and Prussian blue carbon slurry coating can be made to be covered on conductor layer while preparation work electrode On argentine chloride coating, simple process.
4, Prussian blue carbon slurry is printed on preparation work electrode on substrate, is suitable for large-scale industrial production, the work of preparation It is uniform, not easily to fall off to make thickness of electrode, either liquid wash or foreign object friction will not all have an impact working electrode.
Detailed description of the invention
Fig. 1 is the appearance diagram without enzymuria acid sensor in one embodiment of the invention.
Fig. 2 is substrate without enzymuria acid sensor in one embodiment of the invention, conductor layer, electrode layer, insulating layer, two-sided The schematic diagram of glue-line and hydrophilic membrane.
Fig. 3 is in the embodiment of the present invention 1 without the time current curve under enzymuria acid sensor difference uric acid concentration.
Fig. 4 is uric acid concentration-electric current Linear Fit Chart in the embodiment of the present invention 1 without enzymuria acid sensor.
Fig. 5 be in the embodiment of the present invention 2 without enzymuria acid sensor in various concentration uric acid solution cyclic voltammogram.
Fig. 6 is in the embodiment of the present invention 2 without the time current curve under enzymuria acid sensor difference uric acid concentration.
Fig. 7 is uric acid concentration-electric current Linear Fit Chart in the embodiment of the present invention 2 without enzymuria acid sensor.
Fig. 8 is in the embodiment of the present invention 3 without the time current curve under enzymuria acid sensor difference uric acid concentration.
Fig. 9 is uric acid concentration-electric current Linear Fit Chart in the embodiment of the present invention 3 without enzymuria acid sensor.
Figure 10 is in the embodiment of the present invention 4 without the time current curve under enzymuria acid sensor difference uric acid concentration.
Figure 11 is uric acid concentration-electric current Linear Fit Chart in the embodiment of the present invention 4 without enzymuria acid sensor.
Figure 12 is in the embodiment of the present invention 5 without the time current curve under enzymuria acid sensor difference uric acid concentration.
Figure 13 is uric acid concentration-electric current Linear Fit Chart in the embodiment of the present invention 5 without enzymuria acid sensor.
Figure 14 is in the embodiment of the present invention 6 without the time current curve under enzymuria acid sensor difference uric acid concentration.
Figure 15 is uric acid concentration-electric current Linear Fit Chart in the embodiment of the present invention 6 without enzymuria acid sensor.
Figure 16 is in comparative example 1 of the present invention without the time current curve under enzymuria acid sensor difference uric acid concentration.
Figure 17 is uric acid concentration-electric current Linear Fit Chart in comparative example 1 of the present invention without enzymuria acid sensor.
Figure 18 is in comparative example 2 of the present invention without the time current curve under enzymuria acid sensor difference uric acid concentration.
Figure 19 is uric acid concentration-electric current Linear Fit Chart in comparative example 2 of the present invention without enzymuria acid sensor.
Specific embodiment
The present invention is further described in detail combined with specific embodiments below.
Embodiment 1
As depicted in figs. 1 and 2, a kind of based on Prussian blue no enzymuria acid sensor, including successively splice substrate 1, Conductor layer 2, electrode layer 3, insulating layer 4, layers of two-sided 5 and hydrophilic membrane 6.Electrode layer include to electrode 31 and working electrode 32, Working electrode 32 is the Prussian blue carbon slurry coating on substrate, and Prussian blue carbon slurry is mixed by Prussian blue (PB) powder with carbon slurry It forms.Prussian blue mass fraction is 0.5% in Prussian blue carbon slurry.It is Prussian blue to be used to detect uric acid.It is to electrode 31 Argentine chloride coating on substrate.Prussian blue mass fraction refers to that Prussian blue quality accounts for Prussian blue carbon slurry gross mass Percentage.It is parallel with working electrode to electrode, it is vertical with substrate axis to electrode and working electrode.
It in some embodiments, is the mixture coating of silver coating or silver and silver chlorate on substrate to electrode.
As shown in Fig. 2, there is respective electrode terminal to electrode 31 and working electrode 32, have to electrode corresponding Have to electrode terminal 21, working electrode corresponding to working electrode terminal 22.Electrode 31 and working electrode are led to respectively It crosses the first conducting wire to connect with respective electrode terminal, electrode 31 is connect by the first conducting wire 201 with to electrode terminal 21, is worked Electrode 32 is connect by the first conducting wire 202 with working electrode terminal 31.Electrode cross-talk 21, working electrode terminal 31, first are led Line 201, the first conducting wire 202 are respectively positioned on conductor layer, and the first conducting wire includes argentine chloride coating and is covered on general on argentine chloride coating Shandong scholar's indigo plant carbon starches coating.Argentine chloride coating is clipped between substrate and Prussian blue carbon slurry coating.Electrode terminal is by chlorination silver paste It is printed on substrate and is formed.It only is easy to appear conductive bad or even broken string with conducting wire prepared by chlorination silver paste, in silver chlorate Prussian blue carbon slurry coating is covered on coating, reduces the conductive bad situation of conducting wire.
As shown in Fig. 2, conductor layer includes two recognition terminals 23 and the second conducting wire for connecting two recognition terminals 203, recognition terminal 23 and the second conducting wire 203 include argentine chloride coating and the Prussian blue carbon being covered on argentine chloride coating slurry Coating.Recognition terminal judges whether sensor is inserted into for detecting instrument: detecting instrument to two recognition terminals one of them Output voltage, if another recognition terminal can detect that voltage, detecting instrument judge that sensor is already inserted into, starts to telecommunications It number is detected;If another recognition terminal cannot detect that voltage, detecting instrument judge that sensor is not inserted into.
As shown in Fig. 2, insulating layer 4 is equipped with notch 41, layers of two-sided 5 is equipped with notch 51, insulating layer notch 41 and double-sided adhesive Break mouth 51 intersects with to electrode 31 and working electrode 32, substrate 1, insulating layer notch 41, layers of two-sided notch 51 and hydrophilic film Layer 6 is collectively formed for sample to be tested to be drained to working electrode and to the siphon passage of electrode.Insulating layer notch and double-sided adhesive The salty conjunction of break.The shape of notch is rectangle.Insulating layer is prepared by hydrophobic material.Insulating layer notch, layers of two-sided Notch is respectively positioned on working electrode and the surface to electrode.Siphon passage has siphon port, and siphon passage will using capillarity Sample to be tested sucks siphon passage from siphon port, and sample to be tested is guided to working electrode and to electrode by siphon passage.
In some embodiments, the shape of notch is square, ellipse or round.
In the present embodiment, insulating layer epoxy resin is prepared.
As shown in Fig. 2, hydrophilic membrane 6 has air hole 61, air hole 61 is provided at the through-hole on hydrophilic membrane 6, breathes freely Hole and siphon passage are connected close to one end of substrate center.Air hole prevents remaining gas in siphon passage from producing for breathing freely Anger pressure hinders sample to be tested from siphon passage to be drained to working electrode and to electrode.
A kind of preparation method based on Prussian blue no enzymuria acid sensor, successively the following steps are included:
1) pet substrate is placed in pure water and is cleaned by ultrasonic 15min, be put into baking oven 90 DEG C, 30min drying.
2) with chlorination silver paste in substrate surface printed circuit cable layer and to electrode, 120 DEG C, 15min baking are put into baking oven It is dry;Conductor layer includes electrode terminal, two recognition terminals, the first conducting wire and the second conducting wire.
3) prussian blue powder, which is added in carbon slurry, is mixed, prepares Prussian blue carbon slurry, general Shandong in Prussian blue carbon slurry The mass fraction of scholar's indigo plant is 0.5%;The method for mixing Prussian blue and carbon slurry is Prussia's blue powder to be added in carbon slurry, with machinery Blender stirs 500 turns, and 60min then is stirred by ultrasonic with ultrasonic oscillation instrument.
4) it prints Prussian blue carbon on substrate to starch to form Prussian blue carbon slurry coating, Prussian blue carbon slurry coating is as work Make electrode;And conducting wire and recognition terminal in printing covering conductor layer are starched with Prussian blue carbon.
5) 80 DEG C, 15min drying are put into baking oven.
6) it in organic solvent by epoxy resin dissolution, is printed on electrode layer with the organic solvent dissolved with epoxy resin absolutely Edge layer is put into baking oven 90 DEG C, 15min drying, organic solvent is made to volatilize, and insulating layer has to intersect with to electrode and working electrode Notch.The organic solvent of dissolved epoxy can be acetone, dimethylbenzene or n-butanol.
7) notch is made on double-sided adhesive, on the insulating layer by sticking double faced adhesive tape, sticking double faced adhesive tape in insulating layer, it is two-sided Glue notch is overlapped with insulating layer notch, double-sided adhesive with a thickness of 0.1mm.
8) hydrophilic membrane is covered on double-sided adhesive.
Embodiment 2
Prepared in the present embodiment based on Prussian blue no enzymuria acid sensor, except the Prussia in Prussian blue carbon slurry Blue mass fraction is except 3.5%, remaining structure is identical without enzymuria acid sensor as in embodiment 1.
Preparation method based on Prussian blue no enzymuria acid sensor in the present embodiment, successively the following steps are included:
1) pet substrate is placed in pure water and is cleaned by ultrasonic 15min, be put into baking oven 90 DEG C, 30min drying.
2) with chlorination silver paste in substrate surface printed circuit cable layer and to electrode, 120 DEG C, 15min baking are put into baking oven It is dry;Conductor layer includes electrode terminal, two recognition terminals, the first conducting wire and the second conducting wire.
3) prussian blue powder, which is added in carbon slurry, is mixed, prepares Prussian blue carbon slurry, general Shandong in Prussian blue carbon slurry The mass fraction of scholar's indigo plant is 3.5%;The method for mixing Prussian blue and carbon slurry is Prussia's blue powder to be added in carbon slurry, with machinery Blender stirs 300 turns, and 30min then is stirred by ultrasonic with ultrasonic oscillation instrument.
4) it prints Prussian blue carbon on substrate to starch to form Prussian blue carbon slurry coating, Prussian blue carbon slurry coating is as work Make electrode;And conducting wire and recognition terminal in printing covering conductor layer are starched with Prussian blue carbon.
5) 90 DEG C, 10min drying are put into baking oven.
6) it in organic solvent by epoxy resin dissolution, is printed on electrode layer with the organic solvent dissolved with epoxy resin absolutely Edge layer is put into baking oven 90 DEG C, 15min drying, organic solvent is made to volatilize, and insulating layer has to intersect with to electrode and working electrode Notch.
7) notch is made on double-sided adhesive, on the insulating layer by sticking double faced adhesive tape, sticking double faced adhesive tape in insulating layer, it is two-sided Glue notch is overlapped with insulating layer notch, double-sided adhesive with a thickness of 0.15mm.
8) hydrophilic membrane is covered on double-sided adhesive.
Embodiment 3
Prepared in the present embodiment based on Prussian blue no enzymuria acid sensor, except the Prussia in Prussian blue carbon slurry Blue mass fraction is except 5%, remaining structure is identical without enzymuria acid sensor as in embodiment 1.
In the present embodiment, based on the preparation method of Prussian blue no enzymuria acid sensor, successively the following steps are included:
1) pet substrate is placed in pure water and is cleaned by ultrasonic 15min, be put into baking oven 90 DEG C, 30min drying.
2) with chlorination silver paste in substrate surface printed circuit cable layer and to electrode, 120 DEG C, 15min baking are put into baking oven It is dry;Conductor layer includes electrode terminal, two recognition terminals, the first conducting wire and the second conducting wire.
3) prussian blue powder, which is added in carbon slurry, is mixed, prepares Prussian blue carbon slurry, general Shandong in Prussian blue carbon slurry The mass fraction of scholar's indigo plant is 5%;The method for mixing Prussian blue and carbon slurry is Prussia's blue powder to be added in carbon slurry, stirred with machinery It mixes machine and stirs 200 turns, 10min then is stirred by ultrasonic with ultrasonic oscillation instrument.
4) it prints Prussian blue carbon on substrate to starch to form Prussian blue carbon slurry coating, Prussian blue carbon slurry coating is as work Make electrode;And conducting wire and recognition terminal in printing covering conductor layer are starched with Prussian blue carbon.
5) 100 DEG C, 8min drying are put into baking oven.
6) it in organic solvent by epoxy resin dissolution, is printed on electrode layer with the organic solvent dissolved with epoxy resin absolutely Edge layer, is put into baking oven 90 DEG C, 15min drying, and insulating layer has the notch intersected with to electrode and working electrode.
7) notch is made on double-sided adhesive, on the insulating layer by sticking double faced adhesive tape, sticking double faced adhesive tape in insulating layer, it is two-sided Glue notch is overlapped with insulating layer notch, double-sided adhesive with a thickness of 0.2mm.
8) hydrophilic membrane is covered on double-sided adhesive.
Embodiment 4
The present embodiment it is identical without enzymuria acid sensor as embodiment 2 based on Prussian blue no enzymuria acid sensor.
Preparation method of the present embodiment based on Prussian blue no enzymuria acid sensor is different from embodiment 2, difference It is for the step 4) in embodiment 2 to be substituted for: Prussian blue carbon is added dropwise on substrate and starches to form Prussian blue carbon slurry coating, it is general Shandong scholar's indigo plant carbon starches coating as working electrode;And the conducting wire in Prussian blue carbon slurry covering conductor layer and recognition terminal is added dropwise.This Remaining step of preparation method without enzymuria acid sensor in embodiment is identical as the step in embodiment 2.
Embodiment 5
The present embodiment based on Prussian blue no enzymuria acid sensor, except working electrode includes carbon slurry coating, carbon pulp layer On have except Prussian blue carbon slurry coating, remaining structure is identical without enzymuria acid sensor as in embodiment 2.
Preparation method based on Prussian blue no enzymuria acid sensor in the present embodiment, successively the following steps are included:
1) pet substrate is placed in pure water and is cleaned by ultrasonic 15min, be put into baking oven 90 DEG C, 30min drying.
2) with chlorination silver paste in substrate surface printed circuit cable layer and to electrode, 120 DEG C, 15min baking are put into baking oven It is dry;Conductor layer includes electrode terminal, two recognition terminals, the first conducting wire and the second conducting wire.
3) carbon is printed on substrate to starch to form carbon slurry coating, drying.
4) prussian blue powder, which is added in carbon slurry, is mixed, prepares Prussian blue carbon slurry, general Shandong in Prussian blue carbon slurry The mass fraction of scholar's indigo plant is 3.5%;The method for mixing Prussian blue and carbon slurry is Prussia's blue powder to be added in carbon slurry, with machinery Blender stirs 300 turns, and 30min then is stirred by ultrasonic with ultrasonic oscillation instrument.
5) Prussian blue carbon is printed on carbon slurry coating to starch to form Prussian blue carbon slurry coating;And it is starched and is printed with Prussian blue carbon Conducting wire and recognition terminal in brush covering conductor layer.
6) it dries, drying temperature is 80 DEG C~100 DEG C, and drying time is 8~15min.
7) it in organic solvent by epoxy resin dissolution, is printed on electrode layer with the organic solvent dissolved with epoxy resin absolutely Edge layer is put into baking oven 90 DEG C, 15min drying, organic solvent is made to volatilize, and insulating layer has to intersect with to electrode and working electrode Notch.
8) notch is made on double-sided adhesive, on the insulating layer by sticking double faced adhesive tape, sticking double faced adhesive tape in insulating layer, it is two-sided Glue notch is overlapped with insulating layer notch, double-sided adhesive with a thickness of 0.15mm.
9) hydrophilic membrane is covered on double-sided adhesive.
Embodiment 6
The present embodiment it is identical without enzymuria acid sensor as embodiment 5 based on Prussian blue no enzymuria acid sensor.
Preparation method of the present embodiment based on Prussian blue no enzymuria acid sensor is different from embodiment 5.Difference It is, the preparation method based on Prussian blue no enzymuria acid sensor in the present embodiment replaces the step 5) in embodiment 5 It changes into: Prussian blue carbon being added dropwise on carbon slurry coating and starches to form Prussian blue carbon slurry coating;And it is covered with Prussian blue carbon slurry is added dropwise Conducting wire and recognition terminal in lid conductor layer.Preparation method based on Prussian blue no enzymuria acid sensor in the present embodiment Remaining step is identical as the step in embodiment 5.
Comparative example 1
Prepared in the present embodiment based on Prussian blue no enzymuria acid sensor, except the Prussia in Prussian blue carbon slurry Blue mass fraction is except 0.2%, remaining structure can be identical without enzymuria acid sensor as in embodiment 1.
In the present embodiment, based on the preparation method of Prussian blue no enzymuria acid sensor, successively the following steps are included:
1) pet substrate is placed in pure water and is cleaned by ultrasonic 15min, be put into baking oven 90 DEG C, 30min drying.
2) with chlorination silver paste in substrate surface printed circuit cable layer and to electrode, 120 DEG C, 15min baking are put into baking oven It is dry;Conductor layer includes electrode terminal, two recognition terminals, leads for connection electrode terminal and working electrode or to the first of electrode Line and the second conducting wire for connecting two recognition terminals.
3) prussian blue powder, which is added in carbon slurry, is mixed, prepares Prussian blue carbon slurry, general Shandong in Prussian blue carbon slurry The mass fraction of scholar's indigo plant is 0.2%;The method for mixing Prussian blue and carbon slurry is Prussia's blue powder to be added in carbon slurry, with machinery Blender stirs 300 turns, and 30min then is stirred by ultrasonic with ultrasonic oscillation instrument.
4) with Prussian blue carbon starch printing work electrode, and with Prussian blue carbon slurry printing covering conductor layer in conducting wire with Recognition terminal is put into baking oven 90 DEG C, 10min drying.
5) it in organic solvent by epoxy resin dissolution, is printed on electrode layer with the organic solvent dissolved with epoxy resin absolutely Edge layer, be put into baking oven 90 DEG C, 15min drying, so that organic solvent is sufficiently volatilized, insulating layer have with to electrode and working electrode The notch of intersection.
6) notch is made on double-sided adhesive, on the insulating layer by sticking double faced adhesive tape, sticking double faced adhesive tape in insulating layer, it is two-sided Glue notch is overlapped with insulating layer notch, double-sided adhesive with a thickness of 0.15mm.
7) hydrophilic membrane is covered on double-sided adhesive.
Comparative example 2
Prepared in the present embodiment based on Prussian blue no enzymuria acid sensor, except the Prussia in Prussian blue carbon slurry Blue mass fraction is except 6%, remaining structure can be identical without enzymuria acid sensor as in embodiment 1.
In the present embodiment, based on the preparation method of Prussian blue no enzymuria acid sensor, successively the following steps are included:
1) pet substrate is placed in pure water and is cleaned by ultrasonic 15min, be put into baking oven 90 DEG C, 30min drying.
2) with chlorination silver paste in substrate surface printed circuit cable layer and to electrode, 120 DEG C, 15min baking are put into baking oven It is dry;Conductor layer includes electrode terminal, two recognition terminals, leads for connection electrode terminal and working electrode or to the first of electrode Line and the second conducting wire for connecting two recognition terminals.
3) prussian blue powder, which is added in carbon slurry, is mixed, prepares Prussian blue carbon slurry, general Shandong in Prussian blue carbon slurry The mass fraction of scholar's indigo plant is 6%;The method for mixing Prussian blue and carbon slurry is Prussia's blue powder to be added in carbon slurry, stirred with machinery It mixes machine and stirs 300 turns, 30min then is stirred by ultrasonic with ultrasonic oscillation instrument.
4) with Prussian blue carbon starch printing work electrode, and with Prussian blue carbon slurry printing covering conductor layer in conducting wire with Recognition terminal is put into baking oven 90 DEG C, 10min drying.
5) it in organic solvent by epoxy resin dissolution, is printed on electrode layer with the organic solvent dissolved with epoxy resin absolutely Edge layer, be put into baking oven 90 DEG C, 15min drying, so that organic solvent is sufficiently volatilized, insulating layer have with to electrode and working electrode The notch of intersection.
6) notch is made on double-sided adhesive, on the insulating layer by sticking double faced adhesive tape, sticking double faced adhesive tape in insulating layer, it is two-sided Glue notch is overlapped with insulating layer notch, double-sided adhesive with a thickness of 0.15mm.
7) hydrophilic membrane is covered on double-sided adhesive.
Examples 1 to 6, the comparison of the testing result of comparative example 1~2
At room temperature, it is had studied in embodiment 2 using cyclic voltammetry (CV) and is in concentration without enzymuria acid sensor Electrochemical behavior in the uric acid solution of 0mmol/L, 0.4mmol/L, 1mmol/L and 2mmol/L.Fig. 5 is embodiment 2 without enzyme Cyclic voltammogram of the uric acid sensor in various concentration uric acid solution.It it can be seen that, is 0.4~0.5V in voltage from Fig. 5 Between occur an oxidation peak;And with the increase of uric acid concentration, the oxidation peak of uric acid also gradually increases between 0.4~0.5V Add.At room temperature, the uric acid solution time electricity that different, concentration range is 0~2mmol/L to a variety of concentration under 0.45V voltage Stream method is tested, and time current curve shown in fig. 6 is obtained.Detection time is chosen from the time current curve of Fig. 6 is Multiple test points of 5s, multiple test points are marked in uric acid concentration-current graph of Fig. 7, and are carried out to multiple test points linear Fitting obtains uric acid concentration-electric current fitting a straight line that detection time is 5s.With same method obtain embodiment 2 without enzymuria Acid sensor when detecting between for uric acid concentration-electric current fitting a straight line under 10s and 15s, as shown in Figure 7.It is also shown in Fig. 7 each The corresponding linear equation of fitting a straight line.Calculate related coefficient square (R2).In the present invention, related coefficient square refers to electric current Variation total sum of squares in, the shared ratio of the variation of the quadratic sum as caused by uric acid concentration.The size table of related coefficient square Bright electric current level of intimate relevant to uric acid concentration.Work as R2When closer 1, indicate that linear fit is more accurate, uric acid sensor Detection accuracy is higher;On the contrary, R2When closer 0, indicate that linear fit is more inaccurate, the detection accuracy of uric acid sensor is got over It is low.
It is detected in embodiment 1, embodiment 3~6, comparative example 1 and comparative example 2 with method similarly to Example 2 without enzymuria Acid sensor concentration range be 0~2mmol/L, multiple and different concentration uric acid solution in electrochemical behavior.That is, Cyclic voltammogram of the measurement without enzymuria acid sensor in various concentration uric acid solution first, passes through Prussia in cyclic voltammogram The oxidation peak of indigo plant oxidation uric acid finds response voltage range, a voltage is then chosen within the scope of response voltage, in the voltage The lower time current curve detected under different uric acid concentrations;It is respectively 5s, 10s that detection time is chosen from time current curve It is marked in uric acid concentration-current graph with multiple test points of 15s, and dense to the uric acid that detection time is 5s, 10s and 15s respectively Degree-current detecting point carries out linear fit, obtains uric acid concentration-electric current Linear Fit Chart.Fig. 3, Fig. 6, Fig. 8, Figure 10, Figure 12, Figure 14, Figure 16 and Figure 18 be respectively in Examples 1 to 6, comparative example 1 and comparative example 2 without enzymuria acid sensor in concentration range For 0~2mmol/L, a variety of various concentrations uric acid solution in carry out detecting resulting when m- current curve.Fig. 4, Fig. 9, figure 11, Figure 13, Figure 15, Figure 17 and Figure 19 are respectively and pass in embodiment 1, embodiment 3~6, comparative example 1 and comparative example 2 without enzymuria acid Uric acid concentration-electric current Linear Fit Chart of sensor.Comparison diagram 4, Fig. 7, Fig. 9, Figure 11, Figure 13, Figure 15, Figure 17 and Figure 19 can be with Find out, when mass fraction Prussian blue in Prussian blue carbon slurry is 0.5% or more, have between multiple test points preferable Linear relationship;When Prussian blue mass fraction is lower than 0.5%, sensor detection signal is weak, the line between multiple test points Sexual intercourse is poor.Table 1 list Examples 1 to 6 and comparative example 1~2 without enzymuria acid sensor when detecting between for 10s when it is related Coefficient square R2.As can be seen from Table 1, when mass fraction Prussian blue in Prussian blue carbon slurry is 0.5% or more, sensing Device related coefficient square is greater than 0.98, illustrates that sensor detection results are accurate;When Prussian blue mass fraction is lower than 0.5% When, related coefficient square is up to 0.931, illustrates that sensor detection results are more inaccurate.
Related coefficient square without enzymuria acid sensor in 1 Examples 1 to 6 of table and comparative example 1~2
Repeated detection is carried out with uric acid solution of no enzymuria acid sensor to same concentration, obtains multiple current values, is calculated The relative standard deviation (RSD) of multiple current values.RSD is the standard deviation and calculated result arithmetic mean of instantaneous value of electric current in the present invention Ratio.The RSD of electric current is smaller, the consistency of sensor detection is better, shows that the stability of sensor is good.Table 2 is embodiment 1 ~6 and comparative example 1~2 in the surveyed electric current without enzymuria acid sensor relative standard deviation (RSD).As can be seen from Table 2, when When Prussian blue mass fraction is 5% or less in Prussian blue carbon slurry, RSD is smaller, sensor stability is good;When Prussian blue Mass fraction be higher than 5% when, RSD is larger, sensor stability is poor.
Relative standard deviation (RSD) in 2 Examples 1 to 6 of table and comparative example 1~2 without the surveyed electric current of enzymuria acid sensor
Table 3 is the detection time without enzymuria acid sensor in Examples 1 to 6 and comparative example 1~2.It can from table 3 It arrives, with the increase of Prussian blue concentration, detection time shortens.When Prussian blue mass fraction is 0.5%~5%, detection Time is 20~25s.When Prussian blue concentration is lower than 0.5%, detection speed is slower.
Detection time without enzymuria acid sensor in 3 Examples 1 to 6 of table and comparative example 1~2
According to Fig. 3~19, table 1~3 experimental result it is found that when Prussian blue mass fraction be 0.5%~5% when, The present invention is based on Prussian blue no enzymuria acid sensors to have stronger sensor detection signal, accuracy in detection height, performance Stablize and detection speed is fast.
Content described in this specification embodiment is only enumerating to the way of realization of inventive concept, protection of the invention Range should not be construed as being limited to the specific forms stated in the embodiments, and protection scope of the present invention is also and in art technology Personnel conceive according to the present invention it is conceivable that equivalent technologies mean.

Claims (6)

1. it is a kind of based on Prussian blue no enzymuria acid sensor, including the substrate, conductor layer and electrode layer successively to splice, electrode Layer includes to electrode and working electrode, it is characterised in that: working electrode is the Prussian blue carbon slurry coating on substrate, Prussian blue Carbon slurry is mixed by prussian blue powder and carbon slurry.
2. as described in claim 1 based on Prussian blue no enzymuria acid sensor, it is characterised in that: to electrode and work electricity It is great to have respective electrode terminal, the first conducting wire is passed through to electrode and working electrode respectively and is connect with respective electrode terminal, electricity Extreme son and the first conducting wire are respectively positioned on conductor layer, and the first conducting wire includes argentine chloride coating and the Pu Lu that is covered on argentine chloride coating Scholar's indigo plant carbon starches coating.
3. as claimed in claim 2 based on Prussian blue no enzymuria acid sensor, it is characterised in that: conductor layer includes two Recognition terminal and the second conducting wire for connecting two recognition terminals, recognition terminal and the second conducting wire include argentine chloride coating and The Prussian blue carbon slurry coating being covered on argentine chloride coating.
4. as claimed in claim 3 based on Prussian blue no enzymuria acid sensor, it is characterised in that: this is sensed without enzymuria acid Device further includes the insulating layer successively to splice, layers of two-sided and hydrophilic membrane, and insulating layer splices on electrode layer, insulating layer and double Face glue-line is all provided with jagged, and notch intersects with to electrode and working electrode, substrate, insulating layer notch, layers of two-sided notch and parent Water film is collectively formed for sample to be tested to be drained to working electrode and to the siphon passage of electrode.
5. as claimed in claim 4 based on Prussian blue no enzymuria acid sensor, it is characterised in that: hydrophilic membrane has saturating Stomata, air hole are provided at the through-hole on hydrophilic membrane, air hole and siphon passage and connect close to one end of substrate center.
6. the preparation method as claimed in claim 5 based on Prussian blue no enzymuria acid sensor, it is characterised in that: general Scholar's indigo plant carbon slurry in Shandong is Prussia's blue powder to be added in carbon slurry, stir 200 ~ 500 turns with machine mixer, then uses ultrasonic oscillation The slurry that 10 ~ 60 min are formed is stirred by ultrasonic in instrument.
CN201811539838.2A 2018-12-17 2018-12-17 It is a kind of based on Prussian blue no enzymuria acid sensor Pending CN110146563A (en)

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CN101825601A (en) * 2010-05-28 2010-09-08 沈阳师范大学 Method for preparing high-performance Prussian blue modified electrode
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