CN116178860A - Calcium ion selective response electrode sensitive film and preparation method thereof - Google Patents
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910001424 calcium ion Inorganic materials 0.000 title claims abstract description 58
- 230000004044 response Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004014 plasticizer Substances 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012528 membrane Substances 0.000 claims abstract description 14
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 10
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 10
- 238000001514 detection method Methods 0.000 claims abstract description 8
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 6
- CGSLYBDCEGBZCG-UHFFFAOYSA-N Octicizer Chemical compound C=1C=CC=CC=1OP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 CGSLYBDCEGBZCG-UHFFFAOYSA-N 0.000 claims abstract description 5
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- SLZBAWLUQYUDFI-UHFFFAOYSA-L [Ca+2].CCCCCCCCCCCCCCOP([O-])(=O)OCCCCCCCCCCCCCC.CCCCCCCCCCCCCCOP([O-])(=O)OCCCCCCCCCCCCCC Chemical group [Ca+2].CCCCCCCCCCCCCCOP([O-])(=O)OCCCCCCCCCCCCCC.CCCCCCCCCCCCCCOP([O-])(=O)OCCCCCCCCCCCCCC SLZBAWLUQYUDFI-UHFFFAOYSA-L 0.000 claims description 5
- DMYIMYPKMVWFOS-UHFFFAOYSA-L calcium;bis(2-ethylhexyl) phosphate Chemical compound [Ca+2].CCCCC(CC)COP([O-])(=O)OCC(CC)CCCC.CCCCC(CC)COP([O-])(=O)OCC(CC)CCCC DMYIMYPKMVWFOS-UHFFFAOYSA-L 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- GLPHNUSGXCFZDP-UHFFFAOYSA-N P(=O)(O)(O)O.C(C)C(C[Ca]CC(CCCC)CC)CCCC Chemical compound P(=O)(O)(O)O.C(C)C(C[Ca]CC(CCCC)CC)CCCC GLPHNUSGXCFZDP-UHFFFAOYSA-N 0.000 abstract 1
- OAXPPMZPPIZLAP-UHFFFAOYSA-N P(=O)(O)(O)O.C(CCCCCCCCCCCCC)[Ca]CCCCCCCCCCCCCC Chemical group P(=O)(O)(O)O.C(CCCCCCCCCCCCC)[Ca]CCCCCCCCCCCCCC OAXPPMZPPIZLAP-UHFFFAOYSA-N 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 14
- 230000000694 effects Effects 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- CQCXFCDTIITTJC-UHFFFAOYSA-N P(=O)(O)(O)O.C(CCCCCCCCC)[Ca]CCCCCCCCCC Chemical compound P(=O)(O)(O)O.C(CCCCCCCCC)[Ca]CCCCCCCCCC CQCXFCDTIITTJC-UHFFFAOYSA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000003710 calcium ionophore Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000008035 nerve activity Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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- Immunology (AREA)
- Pathology (AREA)
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Abstract
The invention discloses a calcium ion selective response electrode sensitive film, which is used for calcium ion detection and comprises the following components: the electrode sensitive membrane comprises a plurality of solutes and one or more solvents, wherein the solutes are dissolved in the one or more solvents and are fully stirred to form a mixed solution, and the solvents in the mixed solution slowly volatilize to form the electrode sensitive membrane with calcium ion selectivity; wherein, the plurality of solutes consist of a calcium ion selective active carrier, a polymer and a plasticizer, and the total mass of the three solutes accounts for 15 to 25 percent of the mixed solution; the various solutes consist of 28-40% of polymer, 3-12% of calcium ion selective active carrier and 62-75% of plasticizer; the polymer is high molecular weight polyvinyl chloride; the calcium ion selective active carrier is ditetradecyl calcium phosphate or bis (2-ethylhexyl) calcium phosphate; the plasticizer is one or more of trioctyl phosphate, 2-ethylhexyl diphenyl phosphate and triphenyl phosphate; the solvent is tetrahydrofuran or a mixture of tetrahydrofuran and dichloromethane. Also discloses a preparation method and application.
Description
Technical Field
The invention belongs to the technical field of electrochemical analysis and electrode sensitive films, and particularly relates to a calcium ion selective response electrode sensitive film and a preparation method thereof.
Background
Calcium is taken as a main component ion of water hardness, and detection of calcium ions in water is important to judgment of water hardness. In addition, calcium is also an indispensable element for normal operation of human body, and has important effects on growth of bones and teeth, transmission of nerve activity and regulation of heart rhythm, so that measurement of calcium content in human body has important effects on monitoring various physiological functions of human body.
Currently, methods for detecting calcium ions include EDTA titration, ion chromatography, atomic absorption spectrophotometry, ion selective electrode methods, and the like. Wherein, the EDTA titration method is long in time consumption and complicated in operation process; ion chromatography requires consideration of specific water quality conditions to determine analysis conditions; atomic absorption spectrophotometry is expensive in terms of equipment. Compared with the previous operation methods, the ion selective electrode method has the advantages of simple operation, high response speed, low cost, easy automation and the like, and plays an important role in the fields of industrial and agricultural production, water quality detection of domestic water, medical diagnosis and the like.
For the ion selective electrode method, the calcium ion selective electrode is an electrochemical sensor for measuring the ion activity by using a membrane potential, and is used as an indicating electrode and a reference electrode to form a primary cell together, wherein the electromotive force of the primary cell and the activity of the calcium ion accord with a Nernst equation, and the concentration of an unknown solution can be obtained by measuring the electromotive force. The core component of the indicating electrode is an ion sensing film with special selectivity, and the sensing film only has special response to calcium ions, so that the activity of the calcium ions can be converted into potential signals.
The first calcium ion selective electrode was developed and produced by 0rion company in the united states of the nineteenth century, 60 s, with di-n-decyl calcium phosphate as the calcium ion carrier and PVC as the base film material, where electrostatic complexation of calcium ions with negatively charged groups on the phosphate head is critical to achieving a calcium ion response. Generally, the electron density of the phosphate head can be changed by extending the length of the alkyl chain, introducing a phenyl group, or adding a substituent to the side chain, thereby affecting the complexing ability of the phosphate with calcium ions. However, the current electrode slope and selectivity are still not satisfactory. There is a need to prepare new types of electrode sensing films, particularly to explore more excellent calcium ionophores and suitable plasticizers to improve electrode slope and selectivity.
Disclosure of Invention
The invention aims to provide a calcium ion selective response electrode sensitive film and a preparation method thereof, which are characterized in that a proper amount of calcium ion carrier, polymer and plasticizer are added into a proper solvent to be fully and uniformly mixed, and the calcium ion sensitive film is obtained after the solvent is slowly volatilized at room temperature.
In one aspect, the present invention provides a calcium ion-selective response electrode sensitive membrane for calcium ion detection, comprising: a plurality of solutes and one or more solvents, wherein the plurality of solutes are dissolved in the one or more solvents and are sufficiently stirred to form a mixed solution, and the calcium ion selective response electrode sensitive membrane is formed after the solvents in the mixed solution are slowly volatilized; wherein the plurality of solutes consist of a calcium ion selective active carrier, a polymer and a plasticizer, and the total mass of the three solutes accounts for 15-25% of the mixed solution.
Preferably, the plurality of solutes are composed of 28 to 40% of polymer, 3 to 12% of calcium ion selective active carrier and 62 to 75% of plasticizer.
Preferably, the polymer is high molecular weight polyvinyl chloride.
Preferably, the calcium ion selective active carrier is calcium ditetradecyl phosphate or calcium bis (2-ethylhexyl) phosphate.
Preferably, the plasticizer is one or more of trioctyl phosphate, 2-ethylhexyl diphenyl phosphate and triphenyl phosphate.
Preferably, the solvent is tetrahydrofuran or a mixture of tetrahydrofuran and dichloromethane.
The second aspect of the present invention is to provide a method for preparing a calcium ion-selective response electrode-sensitive film, comprising:
s1, sequentially dissolving the calcium ion selective active carrier, the polymer and the plasticizer in one or more solvents, and fully stirring for a first time to form a mixed solution;
s2, treating the mixed solution to enable the solvent in the mixed solution to naturally volatilize for a second time period, and then forming the calcium ion selective response electrode sensitive film.
Preferably, the first duration is 4 hours; the second period of time is 48 hours.
Preferably, the treatment of the mixed liquor comprises pouring the mixed liquor into a flat bottom container, covering filter paper or a film with holes, and covering a glass sheet.
The third aspect of the invention provides an application of the calcium ion selective response electrode sensitive film in industrial and agricultural water quality detection.
The electrode sensitive film, the preparation method and the application provided by the invention have the following beneficial technical effects:
(1) The preparation method is simple and easy to realize.
(2) The electrode sensitive film has good performance, and the slope is close to the theoretical slope.
(3) The electrode sensitive film has quick response and response time of less than 2 minutes.
(4) The electrode sensitive film has good reproducibility and long stable service time.
Drawings
FIG. 1 is a schematic illustration of a formulation of six solute and solvent examples of a calcium ion selective responsive electrode sensitive membrane according to a preferred embodiment of the present invention;
FIG. 2 is a graph showing slope, indication error and 24 hour potential drift for corresponding tests of 6 embodiments and one comparative electrode according to a preferred embodiment of the present invention;
FIG. 3 is a flow chart of a method for preparing the calcium ion selective response electrode sensitive film.
Detailed Description
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The effect of the plasticizer is not only to change the film performance, but also to the sensitive film electrode, mainly in two aspects: firstly, the electrode slope is more similar to the theoretical Nernst response by being matched with a calcium carrier as a second electroactive substance; secondly, plasticizers may influence the selectivity of the calcium carrier for other ions by affecting the formation constant and partition coefficient. The theoretical slope of the calcium ion-selective electrode is 29.58mV at 25℃, whereas the actual slope is typically 80% to 110% of the theoretical slope.
Six solute and solvent examples of a calcium ion selective responsive electrode sensitive membrane are shown in fig. 1. Wherein:
in example 1, the ion-selective carrier was 20mg of calcium ditetradecyl phosphate; the polymer was 120mg polyvinyl chloride; the plasticizer was 250mg of trioctyl phosphate; the solvents were 4ml THF and 2ml DCM.
In example 2, the ion-selective carrier was 20mg of calcium bis (2-ethylhexyl) phosphate; the polymer was 120mg polyvinyl chloride; the plasticizer was 250mg of trioctyl phosphate; the solvents were 4ml THF and 2ml DCM.
In example 3, the ion-selective carrier was 20mg of calcium ditetradecyl phosphate; the polymer was 120mg polyvinyl chloride; the plasticizer was 250mg of 2-ethylhexyl diphenyl phosphate; the solvent was 6ml THF.
In example 4, the ion-selective carrier was 20mg of calcium bis (2-ethylhexyl) phosphate; the polymer was 120mg polyvinyl chloride; the plasticizer was 250mg of 2-ethylhexyl diphenyl phosphate; the solvent was 6ml THF.
In example 5, the ion-selective carrier was 25mg of calcium ditetradecyl phosphate; the polymer was 120mg polyvinyl chloride; the plasticizer was 250mg of trioctyl phosphate; the solvents were 4ml THF and 2ml DCM.
In example 6, the ion-selective carrier was 20mg of calcium bis (2-ethylhexyl) phosphate; the polymer was 120mg polyvinyl chloride; the plasticizer was 250mg of trioctyl phosphate; the solvent was 6ml THF.
In examples 1 to 6, the above solutes were added to the solvent in a certain ratio under a fume hood, and stirred on a magnetic stirrer for 4 to 5 hours, so that the solutes and the solvent were sufficiently and uniformly mixed. And then the mixed solution is transferred into a glass instrument with a flat bottom surface, and a glass sheet is covered after the filter paper or the film with holes is covered on the glass instrument, so that the solvent is slowly volatilized and the film solution can be kept clean. And standing the solution for 48 hours, and obtaining the transparent and elastic calcium ion sensing membrane after the solvent is completely volatilized.
And assembling the calcium ion sensing membrane and other parts of the electrode together to form the calcium ion selective electrode. The performance of the electrodes was tested.
The slope, indication error and 24 hour potential drift of the corresponding tests for 6 examples and one comparative electrode are shown in fig. 2:
example 1: slope 29.84mV, indication error 1.03%,24 hours potential drift 0.90mV;
example 2: slope 30.29mV, error of indication 1.56%,24 hours potential drift 0.86mV;
example 3: slope 29.93mV, error of indication 1.42%,24 hours potential drift 0.63mV;
example 4: slope 30.51mV, indication error 1.53%,24 hours potential drift 0.71mV;
example 5: slope 30.21mV, indication error 1.21%,24 hours potential drift 0.51mV;
example 6: slope 29.65mV, indication error 1.03%,24 hours potential drift 0.52mV;
comparative example 1: the slope was 27.19mV, the error in the indication was 1.65%, and the 24-hour potential drift was 1.08mV.
In summary, the response slope of the electrode is about 30mV, which is similar to the theoretical slope, and the linear range of detection: 10 -5 ～10 - 1 The potential drift of mol/L and 24h is not more than 3mV, the response time is within 2 minutes, and the service life of the electrode is long.
The preparation method of the calcium ion selective response electrode sensitive film shown in fig. 3 comprises the following steps:
s1, sequentially dissolving the calcium ion selective active carrier, the polymer and the plasticizer in one or more solvents, and fully stirring for a first time to form a mixed solution;
s2, treating the mixed solution to enable the solvent in the mixed solution to naturally volatilize for a second time period to form the calcium ion selective response electrode sensitive film
The specific production scheme of the sensitive film in the embodiment comprises the following steps:
(1) In a clean glass container, firstly weighing a certain amount of ion selective carrier, then adding a proper amount of solvent, putting a magnet, keeping the stirring speed at 400-700 r/min, and then sequentially adding a polymer and a plasticizer, wherein the polymer needs to be added uniformly and slowly to prevent caking. Finally, a glass evaporation dish is covered above the solvent, and the mixture is stirred for 4 hours at room temperature;
(2) Pouring the mixed solution into a stainless steel plane container with proper size, covering filter paper or a film with holes, and covering a glass sheet.
(3) After 48h of solvent evaporation, a transparent and elastic sensitive film is obtained. The film thickness is between 0.3mm and 0.6 mm.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. A calcium ion-selective responsive electrode-sensitive membrane for use in calcium ion detection comprising: a plurality of solutes and one or more solvents, wherein the plurality of solutes are dissolved in the one or more solvents and are sufficiently stirred to form a mixed solution, and the calcium ion selective response electrode sensitive membrane is formed after the solvents in the mixed solution are slowly volatilized; wherein the plurality of solutes consist of a calcium ion selective active carrier, a polymer and a plasticizer, and the total mass of the three solutes accounts for 15-25% of the mixed solution.
2. A calcium ion-selective responsive electrode-sensitive membrane according to claim 1, wherein said plurality of solutes consists of 28% to 40% polymer, 3% to 12% calcium ion-selective active carrier and 62% to 75% plasticizer.
3. The calcium ion-selective responsive electrode-sensitive film of claim 1, wherein said polymer is high molecular weight polyvinyl chloride.
4. A calcium ion-selective responsive electrode-sensitive membrane according to claim 1, wherein the calcium ion-selective active carrier is calcium ditetradecyl phosphate or calcium bis (2-ethylhexyl) phosphate.
5. A calcium ion-selective responsive electrode-sensitive film according to claim 1, wherein the plasticizer is one or more of trioctyl phosphate, 2-ethylhexyl diphenyl phosphate and triphenyl phosphate.
6. A calcium ion-selective responsive electrode-sensitive film according to claim 1, wherein the solvent is tetrahydrofuran or a mixture of tetrahydrofuran and methylene chloride.
7. A method of preparing a calcium ion-selective responsive electrode-sensitive film according to any one of claims 1 to 6, comprising:
s1, sequentially dissolving the calcium ion selective active carrier, the polymer and the plasticizer in one or more solvents, and fully stirring for a first time to form a mixed solution;
s2, treating the mixed solution to enable the solvent in the mixed solution to naturally volatilize for a second time period, and then forming the calcium ion selective response electrode sensitive film.
8. The method of claim 7, wherein the first period of time is 4 hours; the second period of time is 48 hours.
9. The method of claim 7, wherein the treating the mixture comprises pouring the mixture into a flat bottom container, and capping a filter paper or a perforated film followed by capping a glass sheet.
10. Use of a calcium ion-selective response electrode sensitive membrane according to any one of claims 1-6 in industrial and agricultural water quality detection.
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Citations (4)
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|---|---|---|---|---|
| US3932233A (en) * | 1972-10-02 | 1976-01-13 | Radiometer A/S | Calcium electrode and membrane and composition for use therein |
| US4816118A (en) * | 1986-01-24 | 1989-03-28 | Terumo Corporation | Ion-sensitive FET sensor |
| CN104109170A (en) * | 2013-04-17 | 2014-10-22 | 北京电子科技职业学院 | Preparation method of didecyl calcium phosphate and application thereof |
| CN110734583A (en) * | 2019-09-05 | 2020-01-31 | 北京华科仪科技股份有限公司 | Induction film of calcium ion selective electrodes and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3932233A (en) * | 1972-10-02 | 1976-01-13 | Radiometer A/S | Calcium electrode and membrane and composition for use therein |
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