CN103424451A - Card type potassium ion sensor and method for preparing card type potassium ion sensor - Google Patents

Card type potassium ion sensor and method for preparing card type potassium ion sensor Download PDF

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CN103424451A
CN103424451A CN2013103743730A CN201310374373A CN103424451A CN 103424451 A CN103424451 A CN 103424451A CN 2013103743730 A CN2013103743730 A CN 2013103743730A CN 201310374373 A CN201310374373 A CN 201310374373A CN 103424451 A CN103424451 A CN 103424451A
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potassium ion
electrode
insulation course
sensitive membrane
card form
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CN103424451B (en
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刘辉
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SHENZHEN HORRON XLH MEDICAL ELECTRONICS CO Ltd
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SHENZHEN HORRON XLH MEDICAL ELECTRONICS CO Ltd
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Abstract

The invention relates to the technical field of electrochemical sensors, in particular to a card type potassium ion sensor and a method for preparing the card type potassium ion sensor. The sensor comprises a base plate (1), two potassium ion selective electrodes (2) arranged on the base plate (1) in parallel, an insulation layer (3) and a salt bridge (4). Each potassium ion selective electrode (2) comprises an electrode substrate system (20), an electrolyte layer (21) and a potassium ion sensitive membrane (22), wherein each electrode substrate system (20) is composed of a reaction electrode (201), a contact electrode (202) and a conductive wire (203), the reaction electrodes (201) and the contact electrodes (202) are arranged on the base plate (1), and the conductive wires (203) are connected with the reaction electrodes (201) and the contact electrodes (202). The electrolyte layers (21) are arranged on the reaction electrodes (201) of the electrode substrate systems (20), and the potassium ion sensitive membranes (22) surround the electrolyte layers (21). The sensor is convenient to carry, and has the advantages of being easy to operate, rapid in response and stable in work.

Description

A kind of card form potassium ion sensor and preparation method thereof
Technical field
The present invention relates to the electrochemical sensor technical field, relate in particular to a kind of card form potassium ion sensor and preparation method thereof.
   
Background technology
Potassium is indispensable macroelement in human body, and the human body of generally growing up includes potassium element 150 gram left and right.Its effect of potassium in human body is to maintain normal function neural, muscle, is normal osmotic pressure and the acid base equilibrium that keeps body, and involved in sugar and protein metabolism guarantee that nervimuscular normal function institute is essential.The human body potassium deficiency, can cause acid-base imbalance, metabolic disorder, muscle weakness etc. in body.Therefore.The detection of potassium ion has a wide range of applications in all many-sides such as medical science, biochemistry, pharmacy, chemical industry, environmental protection and food, and particularly in human body fluid, the detection of potassium ion has important clinical medicine meaning.
The detection of potassium concentration at present mainly adopts the blomelicalbloodgasandelectrolrteanalyzers based on electrochemical method.Blomelicalbloodgasandelectrolrteanalyzers all adopts potassium ion-selective electrode and outer contrast electrode to form potassium ion sensor, these two electrodes are inserted in solution to be measured simultaneously, and connect and compose an electrochemical cell with external measurement mechanism, measure the electromotive force of this electrochemical cell, according to Nernst equation, can extrapolate potassium concentration in solution to be measured.Traditional potassium ion-selective electrode is comprised of internal reference electrode, interior reference solution and sensitive membrane, and with high costs, volume is larger, is difficult to carry out the microminiaturization of electrode, is not easy to carry.This class potassium ion-selective electrode must match with outer contrast electrode when actual measurement, testing process is numerous and diverse, low-response, and detection time is longer, can't meet the demand of the occasions such as operation, emergency treatment, field rescue, also can't adapt to the trend of modern medical service POCT pattern.。
  
Summary of the invention
The present invention be during the existing traditional potassium concentration of solution detects the electrodes selective of potassium ion sensor with outer contrast electrode, separate caused not portable, detect the problems such as consuming time, a kind of new-type card form potassium ion sensor is provided.
A kind of card form potassium ion sensor of the present invention, its scheme is: comprise base plate, potassium ion-selective electrode, insulation course, salt bridge, two potassium ion-selective electrodes are set in parallel on base plate, described potassium ion-selective electrode comprises electrode basement system, dielectric substrate, potassium ion sensitive membrane, the electrode basement system is comprised of the conductive lead wire that is positioned at reaction electrode, the contact electrode on base plate and connects these two electrodes, described dielectric substrate is positioned on the reaction electrode of electrode basement system, and described potassium ion sensitive membrane is surrounded dielectric substrate; Scribble insulation course on described potassium ion sensitive membrane, insulation course is provided with the exposed opening of potassium ion sensitive membrane, the opening of insulation course and potassium ion sensitive membrane form the reaction chamber of potassium ion-selective electrode, salt bridge is arranged on the surface of insulation course, and be positioned at the both sides of insulation course upper shed, salt bridge connects two potassium ion-selective electrodes, is covered with cover plate on salt bridge.
Further, on described cover plate, the position corresponding with salt bridge is provided with pore.
The present invention also provides the preparation method of above-mentioned card form potassium ion sensor, comprises the following steps:
(1) reaction electrode, contact electrode and the conductive lead wire of coated with conductive material formation potassium ion-selective electrode on the high-molecular organic material base plate;
According to actual needs, can adopt method for printing screen printing conductive screen print materials on high-molecular organic material (as polypropylene, polyester, tygon and Polyvinylchloride etc.) base plate, also exploitation is conducted electricity screen print materials coating by vaporization by the film evaporation technology to the high-molecular organic material base plate by this, forms reaction electrode, contact electrode and the conductive lead wire of potassium ion-selective electrode;
Reaction electrode can adopt the materials such as carbon, gold, platinum or titanium to make, conductive lead wire and contact electrode can adopt the materials such as silver, carbon, gold, platinum or titanium to make, the electrochemical properties of silver is unstable, but electric conductivity is good, therefore generally be not used for making reaction electrode, and can be used to make contact electrode and conductive lead wire;
(2) use oxidizing solution to carry out surface treatment to the reaction electrode of potassium ion-selective electrode;
(3) will containing the inorganic salts of potassium ion, be dissolved in purified water, be mixed with the solution that concentration is 0.5mM~5.0mM, then add the xanthans that final mass number percent is 3.0%~8.0% in this solution, be mixed with electrolyte slurry, this electrolyte slurry is coated in to reaction electrode surface (can adopt the method for serigraphy that this electrolyte slurry is coated in to the reaction electrode surface), forms dielectric substrate;
(4) potassium ion active carrier, the large molecule of lipophilicity, non-conductive polymer polymkeric substance, plastifier are dissolved in cyclohexanone or acetone and are mixed with viscous solution, as potassium ion-selective electrode film liquid, gross mass in solution, wherein the mass percent of potassium ion active carrier is 0.2%~0.5%, the macromolecular mass percent of lipophilicity is 0.5%~1.0%, the mass percent of non-conductive polymer polymkeric substance is 30.0%~35.0%, the mass percent of plastifier is 8.0%~14.0%, remains as solvent; Electrode film liquid is coated in to the dielectric substrate surface of potassium ion-selective electrode, forms the potassium ion sensitive membrane, the lucifuge freeze-drying lyophilization is preserved;
(5) print insulation course on base plate, insulation course covers the potassium ion sensitive membrane, and insulation course is provided with the opening that makes the potassium ion sensitive membrane exposed, the conversion zone that when this open area is actual measurement, potassium ion sensitive membrane and solution to be measured come in contact;
(6) two double faced adhesive tape colloids are affixed on respectively to the both sides of insulation course upper shed, the length of colloid enough connects two potassium ion-selective electrodes, between two colloids, forms groove;
(7) cover plate of surface hydrophilicity is covered in to colloid surface, makes the card form potassium ion sensor.
Preferably,
The oxidizing solution that the reaction electrode surface is carried out to oxidation processes is potassium bichromate solution or the liquor potassic permanganate that mass percent is 15%~25%;
The described inorganic salts containing potassium ion are selected from one or more in sal tartari, dipotassium hydrogen phosphate, glazier's salt;
Described potassium ion active carrier is selected from a word used in person's names amino doxycycline, the 4-tert-butyl group-2,2,14, and 14-tetra-is with-2a, 14a, dioxy cup [4] aryl four acetic acid tetra-tert esters, two (phendioxin 5-crown ether-4)-4 ,-ylmethyl pimelate, 2-dodecyl-2-methyl isophthalic acid, 3-glyceryl-bis--[N-(5 ,-nitro (benzene-15-crown ether-5)-4 ,Base] one or more in carbamate;
The large molecule of described lipophilicity is selected from one or more in tetraphenylboron sodium, tetrachlorobenzene boron potassium, four [3,5-bis-(three fluoro methyl) phenyl] potassium borate;
Described non-conductive polymer polymkeric substance is selected from one or more in Polyvinylchloride, polyurethane, polyvinyl acetate, polymethylmethacrylate;
Described plastifier is selected from one or more in ortho-nitrophenyl octyl ether, amyl phthalate, dioctyl phthalate, di-n-octyl sebacate, dibutyl sebacate;
Described salt bridge is selected from one or more in following material: filter paper, cotton, chemical fibre, nonwoven fabrics, agar, gel.
A kind of card form potassium ion sensor of the present invention is integrated in traditional potassium ion-selective electrode and outer contrast electrode on a base plate, realized the integrated and microminiaturized of potassium ion sensor, be easy to carry, have advantages of simple to operate, response rapidly, working stability.The preparation method of card form potassium ion sensor of the present invention, simplified the making flow process, reduces cost of manufacture, is applicable to producing in enormous quantities.
Card form potassium ion sensor of the present invention, when actual measurement, by two potassium ion-selective electrodes in this card form potassium ion sensor respectively with the solution to be measured of unknown concentration and the reference solution of concentration known, two contact electrodes are connected with peripheral testing circuit.Because the present invention is very microminiaturized, the overall electrode area only has 1.5cm*2.3cm, open area on insulation course is less, between the colloid of insulation course upper shed both sides, spacing is very little, can play the syphonic effect of the capillary of being tired out to death, solution to be measured and reference solution be sucked respectively to the reaction chamber of two potassium ion-selective electrodes.Therefore detect required test solution amount seldom, detect required time shorter.In detecting serum, during potassium concentration, required blood sample is 10~15uL only, is less than 40s detection time.
Solution to be measured and reference solution by difference sucting reaction chamber, come in contact by the opening on insulation course and potassium ion sensitive membrane, and react with the potassium ion sensitive membrane.In the potassium ion sensitive membrane, the potassium ion active carrier is generally cage shape, ring-type or chain organic compound, a plurality of polarity dentates containing oxygen atom are arranged in molecule, because having two pairs of lone pair electrons, oxygen atom provides dipole moment-ions binding power, can with solution to be measured, reference solution in the potassium ion complexing, form the complex compound of 1:1, thereby change the membrane electrode current potential of potassium ion sensitive membrane.
Add the inorganic salts containing potassium ion in dielectric substrate, make to form Ohmic contact between dielectric substrate and reaction electrode, effectively reduce the resistance of electrode.
  
The accompanying drawing explanation
The vertical view that Fig. 1 is card form potassium ion sensor of the present invention;
The structural representation that Fig. 2 is potassium ion-selective electrode in card form potassium ion sensor of the present invention;
Fig. 3 is the potential response calibration curve of example 1 of the present invention in the KCl of variable concentrations solution;
The potential response calibration curve that Fig. 4 is potassium concentration in 1 pair of serum of example of the present invention;
The response gradient that Fig. 5 is example 1 of the present invention is relation over time;
Fig. 6 is the potential response calibration curve of example 2 of the present invention in the KCl of variable concentrations solution;
Fig. 7 is that example 2 of the present invention is at the potential response calibration curve containing in the serum of variable concentrations potassium ion.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, and protection scope of the present invention is not limited in these embodiment.
  
Embodiment 1
A kind of card form potassium ion sensor, as Fig. 1, shown in Fig. 2, card form potassium ion sensor of the present invention, comprise base plate 1, potassium ion-selective electrode 2, insulation course 3, salt bridge 4, two potassium ion-selective electrodes are set in parallel on base plate 1, described potassium ion-selective electrode 2 comprises electrode basement system 20, dielectric substrate 21, potassium ion sensitive membrane 22, electrode basement system 20 is by the reaction electrode 201 be positioned on base plate 1, contact electrode 202 and the conductive lead wire 203 that connects these two electrodes form, described dielectric substrate 21 is positioned on the reaction electrode 201 of electrode basement system, described potassium ion sensitive membrane 22 is surrounded dielectric substrate 21, scribble insulation course 3 on described potassium ion sensitive membrane 22, insulation course 3 is provided with the exposed opening of potassium ion sensitive membrane, the opening of insulation course 3 and potassium ion sensitive membrane 22 form the reaction chamber 5 of potassium ion-selective electrode 2, salt bridge 4 is arranged on the surface of insulation course 3, and be positioned at the both sides of insulation course 3 upper sheds, salt bridge 4 connects two potassium ion-selective electrodes 2, is covered with cover plate 6 on salt bridge 4.As improvement project, position corresponding with salt bridge on cover plate is provided with pore.
Card form potassium ion sensor preparation method of the present invention, step is as follows:
(1) silver-colored printing material is printed on the polypropylene base plate by screen printing technique, forms the reaction electrode of potassium ion-selective electrode; The platinum printing material is printed on the polypropylene base plate by screen printing technique, forms the conductive lead wire and the contact electrode that are connected with reaction electrode;
(2) use absolute ethyl alcohol to be cleaned the reaction electrode surface, then wiped clean;
(3) reaction electrode is dipped into to 10min in the liquor potassic permanganate that mass percent is 20%, effects on surface carries out oxidation processes, handles by purified water, to rinse well afterwards, in 80 ℃ of baking ovens, dries;
(4) by sal tartari (K 2CO 3, Shanghai traditional Chinese medicines group) and be dissolved in the solution that in purified water, formation concentration is 4.5mM concentration, until completely dissolved, add the xanthans that mass percent is 5% (Shanghai traditional Chinese medicines group), fully stir evenly, form the transparent dielectric substrate slurry of thickness, by the method for serigraphy, this dielectric substrate slurry is printed on to the reaction electrode surface of potassium ion-selective electrode, form dielectric substrate, thickness is about 50um, and web plate used is 250 orders, and net is apart from 1.5mm, scraper velocity 15mm/s, pressure 2.5kg/cm 2
(5) add the tetraphenylboron sodium of 18.9mg a word used in person's names amino doxycycline, 17.0mg and the PVC of 1120mg in the 2.2ml dibutyl sebacate, shake after 1 minute, add 8ml acetone, the potassium ion film forming liquid that obtains the homogeneous transparent thickness is dissolved in concussion, and the method for use serigraphy is the dielectric substrate surface at potassium ion-selective electrode by this potassium ion film forming liquid, form the potassium ion sensitive membrane, thickness is about 10um, and web plate used is 150 orders, and net is apart from 1.5mm, scraper velocity 15mm/s, pressure 2.5kg/cm 2
(6) adopt the method for serigraphy to print insulation course, insulation course surrounds the potassium ion sensitive membrane, insulation course is provided with the circular open of two diameter 3mm, make the potassium ion sensitive membrane exposed, conversion zone as the potassium ion sensitive membrane, the potassium ion sensitive membrane contacts with solution to be measured, reference solution in measuring process by opening, and insulating layer material adopts the insulation dyestuff SS8391 that in precious magnificent cause, Co., Ltd produces;
(7) double-sided tape of two wide 0.5cm, thick 0.25mm (3M) is affixed on to the both sides of insulation course upper shed, forms the wide groove of 2mm between two adhesive tape;
(8) the surface hydrophilicity cover plate is covered in to colloid surface, with colloid, forms the liquid sample flow channel, make the card form potassium ion sensor.
10ul solution to be measured will be splashed on the card form potassium ion sensor of preparation on one side, drip upper 10ul reference solution (in reference solution, potassium concentration is 8mM) on one side, measure the electrode potential of potassium ion sensor with homemade high input impedance amplifying circuit by the contact electrode of two potassium ion-selective electrodes, record 40s.This potential value is relevant to the log-linear of potassium concentration in fluid to be measured, obtains thus the response electromotive force, can extrapolate the potassium concentration in solution to be measured.
Card form potassium ion sensor prepared for this example of use by Fig. 3 is measured variable concentrations KCl solution, and (this solution is containing 1.0mM CaCl 2With 140mM NaCl back-ground electolyte) resulting potential response calibration curve, correction equation is EMF (mV)=60.5lgC(mmol/L)+80.7, as shown in the figure cathetus, EMF means to respond electromotive force, and C means potassium concentration in solution, coefficient R 2Be 99.97.
Card form potassium ion sensor prepared for this example of use by Fig. 4 is measured the potential response calibration curve of potassium concentration in serum, and its correction equation is EMF (mV)=62.5lgC(mmol/L)-36.7, as shown in the figure cathetus, coefficient R 2Be 99.76.
By Fig. 3 and Fig. 4, can be found out, card form potassium ion sensor response gradient prepared by this example meets Nernst equation.
Card form potassium ion sensor prepared by the present embodiment is preserved 60 days under the normal temperature normality, detect the response gradient of every day, draw out response gradient relation over time, as shown in Figure 5, card form potassium ion sensor its response gradient in 60 days that prepared by this example remains on 60mV/-pK substantially +, illustrate that the present invention has good job stability.
  
Embodiment 2
The preparation method of a kind of card form potassium ion sensor of the present invention:
(1) silver-colored printing material is printed on the polypropylene base plate by screen printing technique, forms the reaction electrode of potassium ion-selective electrode; The platinum printing material is printed on the polypropylene base plate by screen printing technique, forms the conductive lead wire and the contact electrode that are connected with reaction electrode;
(2) use absolute ethyl alcohol to be cleaned the reaction electrode surface, then wiped clean;
(3) reaction electrode is dipped into to 20min in the liquor potassic permanganate that mass percent is 15%, effects on surface carries out oxidation processes, handles by purified water, to rinse well afterwards, in 80 ℃ of baking ovens, dries;
(4) by dipotassium hydrogen phosphate (K 2HPO 4, Shanghai traditional Chinese medicines group) and be dissolved in the solution that in purified water, formation concentration is 3.0mM concentration, until completely dissolved, add the xanthans that mass percent is 5% (Shanghai traditional Chinese medicines group), fully stir evenly, form the transparent dielectric substrate slurry of thickness, by the method for serigraphy, this dielectric substrate slurry is printed on to the reaction electrode surface of potassium ion-selective electrode, form dielectric substrate, thickness is about 50um, and web plate used is 250 orders, and net is apart from 1.5mm, scraper velocity 15mm/s, pressure 2.5kg/cm 2
(5) add the tetraphenylboron sodium of 17.6mg a word used in person's names amino doxycycline, 8.8mg and the PVC of 1600mg in the 112.4ul dibutyl phthalate, shake after 1 minute, add the 8ml cyclohexanone, the potassium ion film forming liquid that obtains the homogeneous transparent thickness is dissolved in concussion, and the method for use serigraphy is the dielectric substrate surface at potassium ion-selective electrode by this potassium ion film forming liquid, form the potassium ion sensitive membrane, thickness is about 10um, and web plate used is 150 orders, and net is apart from 1.5mm, scraper velocity 15mm/s, pressure 2.5kg/cm 2
(6) adopt the method for serigraphy to print insulation course, insulation course surrounds the potassium ion sensitive membrane, insulation course is provided with the circular open of two diameter 3mm, make the potassium ion sensitive membrane exposed, conversion zone as the potassium ion sensitive membrane, the potassium ion sensitive membrane contacts with solution to be measured, reference solution in measuring process by opening, and insulating layer material adopts the insulation dyestuff SS8391 that in precious magnificent cause, Co., Ltd produces;
(7) double-sided tape of two wide 0.5cm, thick 0.25mm (3M) is affixed on to the both sides of insulation course upper shed, forms the wide groove of 2mm between two adhesive tape;
(8) the surface hydrophilicity cover plate is covered in to colloid surface, with colloid, forms the liquid sample flow channel, make the card form potassium ion sensor.
Card form potassium ion sensor prepared for use the present embodiment by Fig. 6 is measured variable concentrations KCl solution, and (this solution is containing 1.0mM CaCl 2With 140mM NaCl back-ground electolyte) resulting potential response calibration curve, correction equation is EMF (mV)=64.4lgC(mmol/L)+55.0, as shown in the figure cathetus, EMF means to respond electromotive force, and C means potassium concentration in solution, coefficient R 2Be 99.98.
As seen from Figure 7, the card form potassium ion sensor response gradient that prepared by the present embodiment slightly is more than the Nernst equation coefficient.
Embodiment 3
The preparation method of card form potassium ion sensor, step is as follows:
(1) silver-colored printing material is printed on the polypropylene base plate by screen printing technique, forms the reaction electrode of potassium ion-selective electrode; The platinum printing material is printed on the polypropylene base plate by screen printing technique, forms the conductive lead wire and the contact electrode that are connected with reaction electrode;
(2) use absolute ethyl alcohol to be cleaned the reaction electrode surface, then wiped clean;
(3) reaction electrode is dipped into to 20min in the liquor potassic permanganate that mass percent is 15%, effects on surface carries out oxidation processes, handles by purified water, to rinse well afterwards, in 80 ℃ of baking ovens, dries;
(4) by sal tartari (K 2CO 3, Shanghai traditional Chinese medicines group) and be dissolved in the solution that in purified water, formation concentration is 4.5mM concentration, until completely dissolved, add the xanthans that mass percent is 5% (Shanghai traditional Chinese medicines group), fully stir evenly, form the transparent dielectric substrate slurry of thickness, by the method for serigraphy, this dielectric substrate slurry is printed on to the reaction electrode surface of potassium ion-selective electrode, form dielectric substrate, thickness is about 50um, and web plate used is 250 orders, and net is apart from 1.5mm, scraper velocity 15mm/s, pressure 2.5kg/cm 2
(5) add the tetraphenylboron sodium of 18.9mg a word used in person's names amino doxycycline, 17.0mg and the PVC of 1120mg in the 2.2ml dibutyl sebacate, shake after 1 minute, add 8ml acetone, the potassium ion film forming liquid that obtains the homogeneous transparent thickness is dissolved in concussion, and the method for use serigraphy is the dielectric substrate surface at potassium ion-selective electrode by this potassium ion film forming liquid, form the potassium ion sensitive membrane, thickness is about 10um, and web plate used is 150 orders, and net is apart from 1.5mm, scraper velocity 15mm/s, pressure 2.5kg/cm 2
(6) adopt the method for serigraphy to print insulation course, insulation course surrounds the potassium ion sensitive membrane, insulation course is provided with the circular open of two diameter 3mm, make the potassium ion sensitive membrane exposed, conversion zone as the potassium ion sensitive membrane, the potassium ion sensitive membrane contacts with solution to be measured, reference solution in measuring process by opening, and insulating layer material adopts the insulation dyestuff SS8391 that in precious magnificent cause, Co., Ltd produces;
(7) double-sided tape of two wide 0.5cm, thick 0.25mm (3M) is affixed on to the both sides of insulation course upper shed, forms the wide groove of 2mm between two adhesive tape;
(8) the surface hydrophilicity cover plate is covered in to colloid surface, with colloid, forms the liquid sample flow channel, make the card form potassium ion sensor.
As an alternative solution, the potassium ion active carrier is the available 4-tert-butyl group-2,2,14 that are selected from also, and 14-tetra-is with-2a, 14a, dioxy cup [4] aryl four acetic acid tetra-tert esters, two (phendioxin 5-crown ether-4)-4 ,-ylmethyl pimelate, 2-dodecyl-2-methyl isophthalic acid, 3-glyceryl-bis--[N-(5 ,-nitro (benzene-15-crown ether-5)-4 ,Base] one or more in carbamate.
In the present embodiment the large molecule of lipophilicity also one or more in available tetrachlorobenzene boron potassium, four [3,5-bis-(three fluoro methyl) phenyl] potassium borate substitute.
The present embodiment non-conductive polymer polymkeric substance also can substitute by one or more in Polyvinylchloride, polyurethane, polyvinyl acetate, polymethylmethacrylate.
Plastifier used can substitute by one or more in ortho-nitrophenyl octyl ether, amyl phthalate, dioctyl phthalate.
Optional one or more in following material of salt bridge in each embodiment: filter paper, cotton, chemical fibre, nonwoven fabrics, agar, gel.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.

Claims (10)

1. a card form potassium ion sensor, comprise base plate (1), potassium ion-selective electrode (2), insulation course (3), salt bridge (4), two potassium ion-selective electrodes are set in parallel on base plate (1), it is characterized in that, described potassium ion-selective electrode (2) comprises electrode basement system (20), dielectric substrate (21), potassium ion sensitive membrane (22), electrode basement system (20) is by the reaction electrode (201) be positioned on base plate (1), contact electrode (202) and the conductive lead wire (203) that connects these two electrodes form, described dielectric substrate (21) is positioned on the reaction electrode (201) of electrode basement system, described potassium ion sensitive membrane (22) is surrounded dielectric substrate (21), scribble insulation course (3) on described potassium ion sensitive membrane (22), insulation course (3) is provided with the exposed opening of potassium ion sensitive membrane, the opening of insulation course (3) and potassium ion sensitive membrane (22) form the reaction chamber (5) of potassium ion-selective electrode (2), salt bridge (4) is arranged on the surface of insulation course (3), and be positioned at the both sides of insulation course (3) upper shed, salt bridge (4) connects two potassium ion-selective electrodes (2), is covered with cover plate (6) on salt bridge (4).
2. card form potassium ion sensor according to claim 1, is characterized in that, the upper position corresponding with salt bridge (4) of described cover plate (6) is provided with pore (7).
3. the preparation method of a card form potassium ion sensor, is characterized in that, comprises the following steps:
(1) reaction electrode, contact electrode and the conductive lead wire of coated with conductive material formation potassium ion-selective electrode on the high-molecular organic material base plate;
(2) use oxidizing solution to carry out surface treatment to the reaction electrode of potassium ion-selective electrode;
(3) will containing the inorganic salts of potassium ion, be dissolved in purified water, be mixed with the solution that concentration is 0.5mM~5.0mM, then add the xanthans that final mass number percent is 3.0%~8.0% in this solution, be mixed with electrolyte slurry, this electrolyte slurry is coated in to the reaction electrode surface, forms dielectric substrate;
(4) potassium ion active carrier, the large molecule of lipophilicity, non-conductive polymer polymkeric substance, plastifier are dissolved in cyclohexanone or acetone and are mixed with viscous solution, as potassium ion-selective electrode film liquid, gross mass in solution, wherein the mass percent of potassium ion active carrier is 0.2%~0.5%, the macromolecular mass percent of lipophilicity is 0.5%~1.0%, the mass percent of non-conductive polymer polymkeric substance is 30.0%~35.0%, the mass percent of plastifier is 8.0%~14.0%, remains as solvent; Electrode film liquid is coated in to the dielectric substrate surface of potassium ion-selective electrode, forms the potassium ion sensitive membrane, the lucifuge freeze-drying lyophilization is preserved;
(5) print insulation course on base plate, insulation course covers the potassium ion sensitive membrane, and insulation course is provided with the opening that makes the potassium ion sensitive membrane exposed, the conversion zone that when this open area is actual measurement, potassium ion sensitive membrane and solution to be measured come in contact;
(6) two double faced adhesive tape colloids are affixed on respectively to the both sides of insulation course upper shed, the length of colloid enough connects two potassium ion-selective electrodes, between two colloids, forms groove;
(7) cover plate of surface hydrophilicity is covered in to colloid surface, makes the card form potassium ion sensor.
4. the preparation method of card form potassium ion sensor according to claim 3, is characterized in that, the oxidizing solution that the reaction electrode surface is carried out to oxidation processes is potassium bichromate solution or the liquor potassic permanganate that mass percent is 15%~25%.
5. the preparation method of card form potassium ion sensor according to claim 3, is characterized in that, the described inorganic salts containing potassium ion are selected from one or more in sal tartari, dipotassium hydrogen phosphate, glazier's salt.
6. the preparation method of card form potassium ion sensor according to claim 3, is characterized in that, described potassium ion active carrier is selected from a word used in person's names amino doxycycline, the 4-tert-butyl group-2,2,14,14-tetra-is with-2a, 14a, dioxy cup [4] aryl four acetic acid tetra-tert esters, two (phendioxin 5-crown ether-4)-4 ,-ylmethyl pimelate, 2-dodecyl-2-methyl isophthalic acid, 3-glyceryl-bis--[N-(5 ,-nitro (benzene-15-crown ether-5)-4 ,Base] one or more in carbamate.
7. the preparation method of card form potassium ion sensor according to claim 3, is characterized in that, the large molecule of described lipophilicity is selected from one or more in tetraphenylboron sodium, tetrachlorobenzene boron potassium, four [3,5-bis-(three fluoro methyl) phenyl] potassium borate.
8. the preparation method of card form potassium ion sensor according to claim 3, is characterized in that, described non-conductive polymer polymkeric substance is selected from one or more in Polyvinylchloride, polyurethane, polyvinyl acetate, polymethylmethacrylate.
9. the preparation method of card form potassium ion sensor according to claim 3, it is characterized in that, described plastifier is selected from one or more in ortho-nitrophenyl octyl ether, amyl phthalate, dioctyl phthalate, di-n-octyl sebacate, dibutyl sebacate.
10. the preparation method of card form potassium ion sensor according to claim 3, is characterized in that, described salt bridge is selected from one or more in following material: filter paper, cotton, chemical fibre, nonwoven fabrics, agar, gel.
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CN111044580A (en) * 2019-12-20 2020-04-21 中国农业大学 Method for rapidly monitoring salting degree of freshwater fish in real time

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