CN117949515B - Potassium ion selective electrode, preparation method thereof and electrolyte analyzer - Google Patents
Potassium ion selective electrode, preparation method thereof and electrolyte analyzer Download PDFInfo
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- CN117949515B CN117949515B CN202410357937.8A CN202410357937A CN117949515B CN 117949515 B CN117949515 B CN 117949515B CN 202410357937 A CN202410357937 A CN 202410357937A CN 117949515 B CN117949515 B CN 117949515B
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- potassium ion
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- ion selective
- potassium
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- 239000000463 material Substances 0.000 claims description 22
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 21
- 125000000524 functional group Chemical group 0.000 claims description 21
- 229910052700 potassium Inorganic materials 0.000 claims description 21
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- 239000007788 liquid Substances 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
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- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
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- 230000035790 physiological processes and functions Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000003308 potassium ionophore Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- WVPHWBRDLWLAEZ-UHFFFAOYSA-N potassium;platinum(2+) Chemical compound [K+].[Pt+2] WVPHWBRDLWLAEZ-UHFFFAOYSA-N 0.000 description 1
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- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
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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
- G01N27/416—Systems
- G01N27/4166—Systems measuring a particular property of an electrolyte
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
Abstract
The invention belongs to the technical field of electrochemical sensors, solves the technical problem of poor stability and selectivity of a potassium ion selective electrode in the prior art, and provides the potassium ion selective electrode, a preparation method thereof and an electrolyte analyzer. The potassium ion selective electrode comprises a potassium ion selective membrane, wherein the potassium ion selective membrane comprises a crown ether compound, a fat-soluble salt, a plasticizer and a thermoplastic resin, the crown ether compound comprises two crown ether units connected through a bridging unit, the crown ether units are benzo-15 crown-5 ether, the first group is a cycloalkyl group or an aromatic group, and the second group is an aromatic group or an amide group. The potassium ion selective electrode increases the hydrophobicity of the whole molecule through the benzene ring part of the benzo-15 crown-5, has higher selectivity, is beneficial to improving the overall hydrophobicity of an electrode film, and enhances the selectivity and the service life of the electrode.
Description
Technical Field
The invention relates to the field of electrochemical sensors, in particular to a potassium ion selective electrode, a preparation method thereof and an electrolyte analyzer.
Background
Potassium ion (K +) is one of the most important electrolytes in the human body and other organisms, and plays a key role in maintaining cellular functions and whole body physiological processes, and in human vital activities, potassium ion is closely related to neural activity, kidney health and heart activity. In human sweat, the concentration range of potassium ions is 1-24 mmol/L, in human blood, the concentration range of potassium ions is 3.8-5.4 mmol/L, and abnormal potassium ion concentration can cause a plurality of diseases, when the concentration of potassium ions is increased, abnormal heartbeat and arrhythmia can be caused, and the concentration of potassium ions is reduced, muscle weakness and spasm can be caused, and heart functions can be influenced seriously, especially in patients with cardiovascular diseases, so that the method has important significance for measuring the concentration of potassium ions.
At present, an electrolyte analyzer based on an electrochemical method is mainly used for detecting the concentration of potassium ions, and a potassium ion carrier of a potassium ion selective electrode is the core of the electrolyte analyzer for detecting the potassium ions. In the prior art, japanese patent publication No.62-70452 discloses a cyclic polyether composition composed of crown ether compound having 12-crown-4 as skeleton and thermoplastic resin, wherein the composition of these compounds is formed into a film as potassium ion selective film, but the cavity diameter of 12-crown-4 crown ether is smaller than the size of potassium ion, so that the potassium ion cannot be effectively "wrapped" and the compounding ability is insufficient; and the 12-crown-4 crown ether has relatively good hydrophilicity, which makes it stable in aqueous solution, but excessive hydrophilicity may cause the mechanical properties of the membrane to be reduced, affecting the service life and stability of the electrode, the electrode of the electrolyte analyzer usually needs to be soaked in a sample or standard solution for a long time, and thus the used material must have good chemical stability;
As another example, chinese patent with application number 20130374373.0 discloses a card-type potassium ion sensor and a method for preparing the same, according to the description of the embodiments, the potassium ion active carrier used is valinomycin, which has lower sensitivity as the potassium ion active carrier, and requires higher potassium ion concentration to achieve reliable detection result, and the valinomycin has relatively poor stability, is easily affected by environmental conditions, such as light, humidity, temperature, etc., and may cause performance fluctuation or decrease of the sensor; examples also describe potential potassium ion active carriers such as 4-tert-butyl-2,2,14,14-tetraco-2 a,14a, di-oxa [4] aryltetra-tert-butyl tetraacetate, which have large molecular volumes and complex structures, which may lead to complex preparation processes, high costs, and furthermore their stability under specific environmental conditions needs to be further verified.
Disclosure of Invention
In view of the above, the embodiment of the invention provides a potassium ion selective electrode, a preparation method thereof and an electrolyte analyzer, which are used for solving the problems of poor stability and selectivity of the potassium ion selective electrode in the prior art.
In a first aspect, an embodiment of the present invention provides a potassium ion-selective electrode, including: a potassium ion selective membrane, wherein the potassium ion selective membrane comprises a crown ether compound, a fat-soluble salt, a plasticizer, and a thermoplastic resin;
a crown ether compound, wherein the crown ether compound has the structural formula shown below: ；
In the structural formula, A is a first group, B is a second group, the first group and the second group are different, the first group is a cycloalkyl group or an aromatic group, the second group is an aromatic group or an amide group, and the potential response value of the crown ether compound to potassium ions has correlation with the first group and the second group;
The structural formula of the fat-soluble salt is as follows: ；
In the structural formula, X 1、X2、X3、X4 is one or more of a hydrogen atom, a halogen atom, an alkyl group or a halogenated alkyl group, Y1, Y2, Y3 and Y4 are integers of 1 to 5, and M is an alkali metal.
As a preferred embodiment of the present invention, the structural formula of the first group is one of the following structural formulas:
，/>，/>，；
Wherein R1 to R4 are hydrogen atoms or alkyl groups.
As a preferred embodiment of the present invention, the structural formula of the second group is one of the following structural formulas:
，/>，/>。
As a preferred embodiment of the present invention, the fat-soluble salt includes at least one of potassium tetraphenylborate, potassium tetrakis (4-chlorophenyl) borate, potassium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, sodium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, potassium tetrakis- (4-t-butylphenyl) borate, potassium tetrakis- (4-isopropylphenyl) borate, sodium tetrakis (4-isopropylphenyl) borate, lithium tetrakis (p-fluorophenyl) borate, or lithium tetrakis (pentafluorophenyl) borate.
As a preferred embodiment of the invention, the potassium ion selective membrane comprises the following components in percentage by mass: 0.1% -5% of the crown ether compound, 0.1% -5% of the fat-soluble salt, 15% -30% of the thermoplastic resin and 60% -84.8% of the plasticizer.
As a preferred embodiment of the present invention, the fat-soluble salt is potassium tetraphenylborate, and the structural formula of the first group is as follows:
；
Wherein R1-R4 are hydrogen atoms or alkyl groups, and the structural formula of the second group is shown as follows:
。
in a second aspect, an embodiment of the present invention further provides a method for preparing the potassium ion selective electrode according to the first aspect, where the preparation method includes:
Dissolving 0.1% -5% of crown ether compound, 0.1% -5% of fat-soluble salt, 15% -30% of thermoplastic resin and 60% -84.8% of plasticizer in a preset organic solvent to obtain a mixed solution, wherein the organic solvent comprises tetrahydrofuran, chloroform, 1, 2-dichloroethane, dichloromethane, dimethylformamide, dimethyloxyamine, benzene or toluene;
coating the mixed solution on the upper surface of a flat plate, and evaporating the organic solvent to obtain a potassium ion selective membrane;
And fixing the potassium ion selective membrane on the electrode body to obtain the potassium ion selective electrode.
As an alternative embodiment of the present invention, the fixing the potassium ion selective membrane on the electrode body to obtain a potassium ion selective electrode includes:
cleaning the surface of the electrode body to remove impurities on the surface;
performing frosting treatment on the surface of the electrode body after cleaning so that the surface of the electrode body has preset roughness, wherein the preset roughness is determined based on the material of the electrode body;
Immersing the electrode body into an activating agent for chemical activation treatment, wherein the activating agent comprises one of an acidic activating agent and an alkaline activating agent, and/or an oxidizing agent;
cleaning and drying the electrode body after the activation treatment through deionized water and nitrogen;
And fixing the potassium ion selective membrane on the cleaned and dried electrode body to obtain the potassium ion selective electrode.
As an alternative embodiment of the present invention, the fixing the potassium ion selective membrane on the cleaned and dried electrode body to obtain the potassium ion selective electrode includes:
Dissolving a self-assembled monolayer modifier into a corresponding solvent to obtain a modified solvent, wherein the self-assembled monolayer modifier has specific functional groups, and the specific functional groups are determined based on potassium ions and/or the material of the electrode body;
immersing the electrode body in the modification solvent to form a modification layer on the surface of the electrode body;
And fixing the potassium ion selective membrane on the modification layer of the electrode body to obtain the potassium ion selective electrode.
In a third aspect, an embodiment of the present invention provides an electrolyte analyzer, including the potassium ion selective electrode described in the first aspect.
In summary, the beneficial effects of the invention are as follows:
The potassium ion carrier, the potassium ion selective electrode and the electrolyte analyzer provided by the embodiment of the invention improve the stability and the selectivity of the potassium ion selective electrode by improving the structure of the crown ether compound, particularly by introducing two benzo-15 crown-5 ether units connected through a bridging unit, the size and the three-dimensional structure of the benzo-15 crown-5 can be matched with the size of potassium ions relatively well, so that the potassium ion selective electrode can form a complex with potassium ions efficiently, and smaller crown ethers such as 12-crown-4 and benzo-15 crown-5 are more suitable for complexing with potassium ions because the cavity diameter of the crown ether compound is closer to the optimal matching size of potassium ions, and the benzo-15 crown-5 has higher selectivity, thereby reducing the cross response with other ions such as sodium ions;
Furthermore, the benzene ring part of the benzo-15 crown-5 increases the hydrophobicity of the whole molecule, is beneficial to improving the overall hydrophobicity of the electrode film, thereby reducing the interference of water molecules, enhancing the stability and the service life of a potassium ion selective electrode, and the chemical structure of the benzo-15 crown-5 provides higher chemical stability, so that crown ether compounds are not easy to decompose in the process of storage or use, and the stability and the reliability of the electrode are further improved;
Finally, the structure of benzo-15 crown-5 allows to further adjust its properties by introducing functional groups on the benzene ring, the potential response of crown ether compounds to potassium ions being related to the properties of the introduced functional groups, allows to adjust the response range and sensitivity of the electrode by selecting different groups, adapting to different measurement requirements.
Drawings
In order to more clearly illustrate the technical solution of the embodiments of the present invention, the drawings required to be used in the embodiments of the present invention will be briefly described, and it is within the scope of the present invention to obtain other drawings according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a structural formula of a crown ether compound according to an embodiment of the present invention.
FIG. 2 is a structural formula of a fat-soluble salt according to an embodiment of the present invention.
FIG. 3 is a schematic flow chart of a method for preparing a potassium ion selective electrode according to an embodiment of the invention.
Detailed Description
Features and exemplary embodiments of various aspects of the present invention will be described in detail below, and in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely configured to illustrate the invention and are not configured to limit the invention. It will be apparent to one skilled in the art that the present invention may be practiced without some of these specific details. The following description of the embodiments is merely intended to provide a better understanding of the invention by showing examples of the invention.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
Example 1
Referring to fig. 1, an embodiment of the present invention provides a potassium ion carrier, including:
a crown ether compound, wherein the crown ether compound has the structural formula shown below:
；
In the above structural formula, a is the first group, B is the second group, the first group and the second group are different, the first group is a cycloalkyl group or an aromatic group, the second group is an aromatic group or an amide group, and the potential response value of the crown ether compound to potassium ions has a correlation with the first group and the second group.
In particular, it can be seen from the above formula that the crown ether compound comprises two crown ether units connected by a bridging unit;
The crown ether unit is benzo-15 crown-5, the crown ether unit has high selectivity to potassium ions, the cavity diameter of the benzo-15 crown-5 is suitable for forming a stable complex with the potassium ions, and the crown ether can 'trap' the potassium ions in a solution, so that potential change related to the concentration of the potassium ions is generated in an electrode, and the potassium ion detection with high selectivity and sensitivity is provided;
The two crown ether units are connected through a bridging unit, the bridging unit can enhance the stability of the whole structure of the molecule and can introduce additional functionality or change the physical and chemical properties of the compound, so that the selectivity and the potential response of potassium ions are influenced, the bridging unit comprises a first group and a second group, the first group and the second group are different, the potential response value of the crown ether compound to the potassium ions is related to the first group and the second group, the first group and the second group can be in various different chemical structures, such as alkyl chains, aromatic groups or nitrogen-containing groups, if the first group is a cycloalkyl group, the introduction of cycloparaffin can indirectly influence the coordination environment of the potassium ions by changing the three-dimensional structure and the flexibility of the compound, the cycloparaffin group increases the hydrophobicity of the compound, the solubility of the compound in water environment is reduced, and when the first group and the second group are aromatic groups, the first group and the second group are different aromatic groups;
The size and spatial arrangement of the first group a and the second group B may limit the flexibility of the crown ether, reducing the number of stereoisomers thereof. This conformational restriction helps to stabilize the specific morphology of the crown ether, which has a higher selectivity and binding affinity for potassium ions. Suitable first groups a and second groups B may make the cavity size and shape of the crown ether compound more suitable for specific ions, such as potassium ions, thereby improving selectivity.
If the first group is an aromatic group, the aromatic group increases the selectivity to potassium ions through pi-pi interaction or through an aromatic group with a polar functional group, and the aromatic group has a functional group capable of forming hydrogen bonds, the interaction between potassium ions and the compound is increased, so that the selectivity to potassium ions is increased.
If the second group is an amide group, this has a positive effect on the potassium ion selectivity because its polar carbonyl group (c=o) and amino group (-NH 2) can form hydrogen bonds with potassium ions. The polarity of the amide groups may also provide additional coordination sites with potassium ions; amide groups are less hydrophobic than aromatic groups because they contain carbonyl and amino groups that can form hydrogen bonds. However, the overall hydrophobicity may be affected by other components in the compound, especially if the number of amide groups is large or the structure is large, and the overall hydrophobicity may still be increased.
As an alternative embodiment of the present invention, the structural formula of the first group is one of the following structural formulas:
First structural formula 1: ；
First structural formula 2: ；
first structural formula 3: ；
First structural formula 4: ；
Wherein R1 to R4 are hydrogen atoms or alkyl groups.
The group shown in the first structural formula 1 is a cyclohexane group, and the cyclohexane group can increase the hydrophobicity of the whole crown ether compound, so that the solubility of the compound in an aqueous medium is reduced; the cyclohexane group does not directly enhance the selectivity of potassium ions because it does not provide a functional group coordinated with potassium ions, but it can indirectly affect the coordination environment of potassium ions by affecting the overall three-dimensional structure of the compound.
The group represented by the first structural formula 2 is a naphthalene group, which is a polycyclic aromatic hydrocarbon formed by fusing two benzene rings together. When R1 and R2 are hydrogen atoms, the structure is naphthalene, if R1 and R2 are alkyl, the structure is an alkyl derivative of naphthalene, the aromaticity and rigidity of the naphthalene group help the crown ether compound and potassium ions form a more stable complex, because the aromatic group can provide additional pi-pi interaction, and the naphthalene group can obviously increase the overall hydrophobicity of the compound due to the larger aromatic area, so that the solubility of the compound in an aqueous solution is influenced;
the group shown in the first structural formula 3 is an anthracene group, anthracene is polycyclic aromatic hydrocarbon formed by fusing three benzene rings together, and when R1-R3 are all hydrogen atoms, the structure is anthracene; when R1-R3 are alkyl, the structure is an alkyl derivative of anthracene;
The aromaticity and large conjugated system of the anthracene group helps the crown ether compound to form a more stable complex with potassium ions, the aromatic group can provide additional pi-pi interactions, thereby stabilizing the complexation of potassium ions, and the anthracene group can significantly increase the overall hydrophobicity of the crown ether compound due to its large aromatic area, thereby enhancing the response and stability of the electrode to potassium ions.
The group represented by the first structural formula 4 is an azobenzene group, which is a compound containing two benzene rings linked by an azo bond (-n=n-), and the introduction of azobenzene changes the three-dimensional configuration of crown ether, thereby affecting its coordination ability with potassium ions, and it increases the hydrophobicity of the whole compound, so that its solubility in an aqueous medium is reduced.
As an alternative embodiment of the present invention, the structural formula of the second group is one of the following structural formulas:
the second structural formula 1: ；
the second structural formula 2: ；
the second structural formula 3: ；
The second group shown in the structural formula 1 is a benzoate structure, and comprises a benzene ring connected with an ester group through an oxygen atom, if the benzoate group is used as the second group of the crown ether compound, the selectivity of the crown ether to potassium ions is not directly enhanced unless the position or the interaction with other functional groups can influence the coordination environment of the crown ether center, but the polarity of the ester group can influence the charge distribution of the whole crown ether compound, so that the combination of potassium ions is indirectly influenced; the presence of benzene rings increases the hydrophobicity of the entire compound, which is more hydrophobic due to its larger pi-electron system.
The second group represented by structural formula 2 is an anisole group, which is composed of one benzene ring and one methoxy, anisole is generally chemically stable and does not easily participate in most types of chemical reactions, which helps to enhance the overall stability of crown ether compounds and increase the hydrophobicity of crown ether compounds, thereby affecting the solubility of compounds and the behavior in biological membranes, and helping the stability and intercalation of compounds in hydrophobic environments.
The second group of formula 3 is an amide group, which is a common functional group consisting of one amino group (-NH 2) and one carbonyl group (c=o). In particular, this amide group is the simplest form of amide, i.e., formamide, which is formed by the combination of the carbonyl group of formic acid with an amino group.
If the amide group is used as the B group of the crown ether compound, the amide group may provide an additional coordination point, interacting with potassium ions through hydrogen bonds, thereby enhancing the selectivity to potassium ions.
In a preferred embodiment, the first group is a group of formula 1 and the second group is a group of formula 1, the hydrophobicity of the cyclohexane group contributing to the stability of the compound in a hydrophobic environment, such as in a biofilm or in an organic phase; although cyclohexane groups do not provide direct selectivity of potassium ions per se, coordination of crown ether centers and potassium ions can be indirectly influenced by adjusting the spatial structure of the compound, selectivity is enhanced, and the polarity of benzoate groups indirectly improves the binding affinity of potassium ions by influencing the charge distribution of crown ether; a specific experimental verification procedure is set forth in example 2, which is not repeated here;
In summary, the potassium ion carrier provided in the embodiment of the invention includes a crown ether compound with a specific structure, wherein the first group a may be a cycloalkyl group or an aromatic group, and the second group B may be an aromatic group or an amide group, and the three-dimensional structure and the electronic properties of the crown ether compound may be adjusted by reasonably selecting the groups a and B, so as to optimize the coordination interaction with potassium ions. For example, aromatic groups may enhance coordination through pi-pi interactions, while amide groups may form more stable complexes with potassium ions through hydrogen bonds;
The choice of groups a and B can affect the solubility of the entire compound. For example, cycloalkyl groups can increase hydrophobicity, while amide groups can provide hydrophilicity, thereby enabling the crown ether compound to be both stably present in an aqueous environment and effectively operate in a hydrophobic environment. There is a correlation between the potential response value of the crown ether compound and the properties of the selected groups a and B, which means that the sensitivity and response speed of the compound to changes in potassium ion concentration can be adjusted by changing these groups. These properties of potassium ionophores make them suitable for a wide range of applications, from environmental monitoring to biomedical detection, and for accurate measurement of potassium ions in industrial process control.
Example 2
Based on the potassium ion carrier provided in embodiment 1, embodiment 2 of the present invention further provides a potassium ion selective electrode, wherein the potassium ion selective electrode comprises a potassium ion selective membrane, and the components of the potassium ion selective membrane comprise:
crown ether compound, fat-soluble salt, thermoplastic resin and plasticizer in example 1.
In particular, the potassium ion selective membrane used for the potassium ion selective electrode is a key component of the electrode because it is directly involved in the selective recognition of potassium ions, and the potassium ion selective membrane comprises the crown ether compound described in example 1, which has a specific three-dimensional structure and can form a stable complex with potassium ions, and the crown ether structure is designed to be highly selective to potassium ions, which means that it can distinguish potassium ions from other similar ions such as sodium ions from a sample;
The thermoplastic resin provides mechanical strength and structural support to the selective membrane, and is also the matrix of the selective membrane in which both the crown ether compound and the fat-soluble salt are dispersed; specifically, thermoplastic resins include, but are not limited to, halogenated ethylene monomers or copolymers, such as polyvinyl chloride (PVC), polyvinyl bromide, polyvinylidene chloride, polytetrafluoroethylene (PTFE), and the like; styrene and its substitutes, such as Polystyrene (PS), polychloroprene, polybrominated styrene, etc.; acrylate or methacrylate monomers or copolymers, such as polymethyl methacrylate (PMMA), polyethyl acrylate, and the like; diene polymers such as polybutadiene, polyisoprene, and copolymers thereof with styrene, acrylonitrile, and the like; silicone polymers or copolymers, such as Polydimethylsiloxane (PDMS), and the like. Key factors to be considered in selecting thermoplastic resins for use in making potassium ion selective membranes include chemical compatibility of the resin, handling properties, and physical and chemical stability of the final membrane. For example, polyvinyl chloride is widely used in the manufacture of ion selective membranes due to its good mechanical properties, chemical stability, and compatibility with plasticizers and other additives, the choice of other resins will depend on the intended application conditions and performance requirements.
Plasticizers, including but not limited to phthalates such as dimethyl phthalate, diethyl phthalate, dioctyl phthalate, are used to increase the flexibility of the resin so that the film may be more easily handled and applied to the electrode, which may also affect the physical properties of the film, such as permeability and softening point, thereby affecting the performance of the electrode; fatty acid esters such as dioctyl adipate, dioctyl pimelate; o-nitrophenylalkyl ethers, such as o-nitrophenyloctyl ether.
Liposoluble salts, including but not limited to potassium complexing agents such as tetrabutylammonium salts, tetraphenylborates, or organometallic salts such as potassium copper (II) tetrachloroate ([ CuCl4] 2-) or potassium platinum (II) tetrachloroate ([ PtCl4] 2-), play a key role in the function of the electrode because they, together with crown ether compounds, enhance the selectivity for potassium ions; the selection of an appropriate fat-soluble salt is critical to ensure the selectivity and sensitivity of the electrode. The choice of salts depends on the target analyte (here potassium ions) and the properties that the electrode is desired to exhibit in a particular measurement environment;
In a specific embodiment, the potassium ion selective electrode comprises a reference electrode, a filling solution, a shell, an electrode body and the like in addition to the potassium ion selective membrane, and the design of the potassium ion selective electrode can be different according to the application and the required measurement range, and the components can work together, so that the potassium ion selective electrode can reliably measure the concentration of potassium ions in the solution.
As an alternative embodiment of the present invention, referring to fig. 2, the fat-soluble salt has the structural formula:
；
wherein X 1、X2、X3、X4 is one or more of a hydrogen atom, a halogen atom, an alkyl group or a haloalkyl group, Y1, Y2, Y3 and Y4 are integers of 1 to 5, and M is an alkali metal.
In particular, the fat-soluble salt represented by the above formula is a general organometallic complex in which M represents an alkali metal, and may be lithium, sodium, potassium, or the like. X1, X2, X3 and X4 represent different atoms or groups which may be substituted on the benzene ring and may be a hydrogen atom, a halogen atom (e.g., chlorine, bromine or iodine), an alkyl group (e.g., methyl, ethyl, etc.), or a haloalkyl group (e.g., chloromethyl, etc.). Y1, Y2, Y3 and Y4 represent the number of these substituents on the benzene ring and are integers from 1 to 5, and such fat-soluble salts can form complexes with potassium ions (K +) to promote the transmission of potassium ions in the selective membrane; specific organometallic complexes can be designed to preferentially interact with potassium ions, thereby increasing the electrode selectivity for potassium ions over other ions (e.g., sodium or lithium); the nature of the fat-soluble salt affects the potential response of the electrode and thus the tuning of the electrode response curve can be achieved by selecting an appropriate organometallic complex.
The particular chemical nature of such fat-soluble salts (e.g., solubility, stability, lipophilicity, etc.) will depend on the particular choice of X and Y. For example, the introduction of a halogen atom may increase the hydrophobicity of the compound, while the introduction of an alkyl group may provide some flexibility and solubility. The choice of alkali metal M (e.g., potassium) will directly affect its application in potassium ion selective electrodes.
As an alternative embodiment of the present invention, the fat-soluble salt includes one or more of potassium tetraphenylborate, potassium tetrakis (4-chlorophenyl) borate, potassium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, sodium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, potassium tetrakis- (4-t-butylphenyl) borate, potassium tetrakis- (4-isopropylphenyl) borate, sodium tetrakis (4-isopropylphenyl) borate, lithium tetrakis (p-fluorophenyl) borate, or lithium tetrakis (pentafluorophenyl) borate.
In particular, potassium tetraphenylborate is a commonly used fat-soluble salt, providing good potassium ion selectivity and stable potential response;
The potassium tetrakis (4-chlorophenyl) borate and the potassium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate are halogen-containing fat-soluble salts, so that the hydrophobicity is increased, and the performance of the electrode is improved in a hydrophobic environment;
Sodium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate and lithium tetrakis (p-fluorophenyl) borate, salts of sodium and lithium may be used for specific applications, such as when operating within a specific potential window, or under specific ionic strength conditions;
Potassium tetrakis- (4-t-butylphenyl) borate and potassium tetrakis- (4-isopropylphenyl) borate, which lipid-soluble salts having larger alkyl substituents may increase the flexibility and mechanical stability of the electrode film;
These salts of sodium tetrakis (4-isopropylphenyl) borate and lithium tetrakis (pentafluorophenyl) borate can provide specific potential responses suitable for electrodes operating over a wide temperature range or in environments with special requirements.
Key parameters considered in the selection of these fat-soluble salts include their solubility, stability of the potential response, and synergy with crown ether compounds. The use of these salts in the potassium ion selective electrode helps to increase the electrode selectivity to potassium ions while maintaining good potential stability and proper mechanical properties.
As an optional embodiment of the present invention, the components respectively comprise the following mass percentages: 0.1% -5% of the crown ether compound, 0.1% -5% of the fat-soluble salt, 15% -30% of the thermoplastic resin and 60% -84.8% of the plasticizer.
Specifically, crown ether compounds are used as main active components and are responsible for forming complexes with potassium ions, so the content of the crown ether compounds directly affects the sensitivity and the selectivity of an electrode, and the proportion of crown ether compounds in a selective membrane is usually low because of the high activity of the crown ether compounds and the capability of providing the required selectivity with a small mass percentage, so the mass percentage of crown ether compounds in the components is 0.1% -5%;
The fat-soluble salt enhances the selectivity of the electrode to potassium ions and participates in forming potential response, and the content of the fat-soluble salt is low, because the high concentration can cause the increase of the background potential of the selective membrane, the sensitivity of the electrode is affected, so that the mass percentage of the fat-soluble salt in the components is 0.1% -0.5%;
The thermoplastic resin provides a structural matrix for the selective membrane in an amount sufficient to ensure mechanical stability and overall strength of the selective membrane, and the thermoplastic resin accounts for 15% -30% by mass of the components in order to ensure processability and final physical properties of the potassium ion selective membrane;
The plasticizer is used for improving the flexibility of the resin, so that the potassium ion selective membrane is easier to process and apply, the high-proportion plasticizer is used for enabling the potassium ion selective membrane to have better flexibility and ductility, meanwhile, the dispersion of the crown ether compound and the fat-soluble salt in the thermoplastic resin matrix is facilitated, and the high content of the plasticizer is also facilitated for optimizing the electrochemical performance of the electrode, such as potential stability and response time, so that in the embodiment, the mass percentage of the plasticizer in the components is 60% -84.8%.
In one embodiment, the mass percentages of the components are as follows:
crown ether compound: 0.1%
Fat-soluble salts: 0.1%
Thermoplastic resin: 15%
And (3) a plasticizer: 84.8%
In this example, the content of crown ether compound and fat-soluble salt is low, and the content of thermoplastic resin and plasticizer is high. This may result in a potassium ion selective membrane that is better flexible and stable, but may sacrifice some selectivity.
In yet another embodiment, the mass percentages of the components are as follows:
Crown ether compound: 2.5%
Fat-soluble salts: 2.5%
Thermoplastic resin: 22.5%
And (3) a plasticizer: 72.5%
In this example, the contents of the components are relatively balanced. Moderate levels of crown ether compounds and fat-soluble salts can provide good ion selectivity and sensitivity, and moderate levels of thermoplastic resins and plasticizers can provide suitable film mechanical properties and stability.
As an alternative embodiment of the invention, the ratio of the fat-soluble salt to the crown ether compound is 0.01-0.5.
In the design of potassium ion selective electrodes, the molar ratio of the fat-soluble salt to the crown ether compound is one of the key factors affecting the electrode performance. This ratio determines the selectivity and sensitivity of the electrode to potassium ions, as well as the useful life of the electrode.
Specifically, the proper molar ratio can optimize the response of the electrode to the change of the concentration of potassium ions, so that the measurement is more sensitive, and the proper ratio of the fat-soluble salt and the crown ether compound is also beneficial to improving the stability of the electrode, thereby prolonging the service life of the electrode; if the amount of the fat-soluble salt exceeds the optimum molar ratio range, the electrode selectivity and sensitivity may be lowered. This is because too much of the fat-soluble salt interferes with the potassium ion coordination environment of the crown ether compound or causes phase separation in the selective membrane, thereby affecting the performance of the electrode.
Therefore, the molar ratio of the fat-soluble salt to the crown ether compound is 0.01-0.5, and sufficient combination of the fat-soluble salt and the crown ether compound can be ensured, so that the selectivity of the electrode to potassium ions is improved. This means that the electrodes are better able to distinguish potassium ions from other similar ions (such as sodium ions);
In a preferred embodiment, the ratio of the liposoluble salt to the crown ether compound is 0.02-0.4. The excess of the fat-soluble salt can interfere with the coordination of the crown ether composition with potassium ions, thereby weakening the specific binding to potassium ions, leading to the electrode also responding to other ions and reducing the selectivity; the response of the electrode to potassium ion concentration changes becomes less sensitive, requiring larger ion concentration changes to detect potential changes, and the decrease in selectivity and sensitivity accelerates degradation of the electrode performance, resulting in more frequent calibration or replacement of the electrode.
As an alternative embodiment of the present invention, the plasticizer is 30% to 300% by weight of the thermoplastic resin.
In the formulation of potassium ion selective membranes, plasticizers are added to improve the processability of the thermoplastic resin and the physical properties of the final product. Plasticizers can lower the glass transition temperature of the resin, making the material softer and more flexible at room temperature.
The greater the amount of plasticizer, the better the flexibility of the film. This is because the plasticizer molecules intercalate between the molecular chains of the resin, reducing intermolecular forces, and higher plasticizer content can reduce the melt viscosity of the resin, making the mixture easier to process into films at lower temperatures. In an embodiment of the present invention, the plasticizer is present in an amount of 30% to 300% by weight of the thermoplastic resin, allowing the proportion of plasticizer to be adjusted according to the intended use of the film-like material. For example, if a film is desired to have a relatively high flexibility, a high proportion of approximately 300% or more may be selected; if a higher mechanical strength is desired, a lower proportion, approaching 30%, may be selected. The selection of this range allows optimizing the performance of the membrane to suit different application requirements and operating conditions.
In the preparation of potassium ion selective membranes, the exact proportions of the components need to be optimized experimentally to ensure optimal performance of the membrane. These proportions may be adjusted depending on the particular application and the type of raw material used. The experimental results will determine the optimum ratio of these components to achieve high selectivity, high sensitivity, good mechanical properties and stable potential response.
As an alternative embodiment of the present invention, the molecular weight of the thermoplastic resin is between 1000 and 1000000;
In particular, when selecting thermoplastic resins for molding into films, it is critical to consider their molecular weight, and lower molecular weight thermoplastic resins are generally easier to process and shape because they soften and flow at lower temperatures. Resins with molecular weights in this range, particularly those near the lower limit, generally have lower melting points and higher flowability, making them suitable for film production; as the molecular weight increases, the mechanical strength of the resin generally increases. Higher molecular weight means more intermolecular forces between the chains, thereby improving the toughness and durability of the material. Resins with molecular weights approaching or exceeding 1000000 may exhibit excellent strength and chemical resistance, but may require higher processing temperatures.
The thermoplastic resin is selected in the molecular weight range of 1,000 to 1,000,000 to find a balance between the ease of plasticity and the mechanical strength. This ensures that the resin is easy to handle during the manufacturing process, while the resulting film has sufficient strength to withstand the stresses of practical use. The thermoplastic resin having a molecular weight of between 1,000 and 1,000,000 is selected to ensure ease of handling and shaping of the film during manufacture while exhibiting good mechanical stability and durability in use. Such a selection helps to optimize the overall performance of the film and to accommodate the needs of different application scenarios.
As an alternative embodiment of the present invention, in the potassium ion selective membrane, the crown ether compound is used in an amount of 0.1 to 40 parts by weight for 100 parts by weight of the thermoplastic resin;
In particular, when the amount of crown ether compound is less than 0.1 part, it may be insufficient to provide the desired potassium ion selectivity. Crown ether compounds play a key role in the selective membranes, their main function being to form stable complexes with potassium ions, thereby increasing the selectivity for potassium ions. Too low an amount may result in a decrease in the ability of the film to recognize potassium ions. When the amount of the crown ether compound exceeds 40 parts, uneven dispersion in the thermoplastic resin matrix, even precipitation, may be caused. This can disrupt the uniformity of the selective membrane, affecting its overall performance. Too much crown ether compound may not be completely dissolved in the resin matrix, resulting in uneven areas in the film, which may reduce the performance and reliability of the electrode.
In a preferred embodiment, the crown ether compound is used in an amount of 0.1 to 10 parts by weight for 100 parts by weight of the thermoplastic resin;
The amount of crown ether compound is kept within the range of 1-10 parts, so that the membrane can be ensured to have good potassium ion selectivity, and unnecessary material waste and cost increase can be avoided. This range provides the best cost performance, ensures the performance of the membrane while taking into account economic benefits.
In one embodiment, as shown in fig. 3, the preparation method of the potassium ion selective electrode includes the following steps:
S1, dissolving 0.1% -5% of crown ether compound, 0.1% -5% of fat-soluble salt, 15% -30% of thermoplastic resin and 60% -84.8% of plasticizer into a preset organic solvent to obtain a mixed solution, wherein the organic solvent comprises tetrahydrofuran, chloroform, 1, 2-dichloroethane, dichloromethane, dimethylformamide, dimethyloxyamine, benzene or toluene;
Specifically, the crown ether compound, the fat-soluble salt, the thermoplastic resin and the plasticizer in the above examples are weighed into a container according to the ratio, and an appropriate organic solvent such as tetrahydrofuran, chloroform, 1, 2-dichloroethane, methylene chloride, dimethylformamide, dimethylamine, benzene or toluene is selected. These solvents may provide solubility and handleability during the preparation process; adding the pre-weighed crown ether compound, the fat-soluble salt, the thermoplastic resin and the plasticizer into an organic solvent, and stirring or heating for dissolution until a uniform mixed solution is obtained.
S2, smearing the mixed solution on the upper surface of a flat plate, and evaporating the organic solvent to obtain a potassium ion selective membrane;
A flat plate, typically a flat surface made of glass, quartz or a polymeric material, is prepared to ensure that the surface of the plate is clean and free of dust or impurities. Uniformly coating the mixed solution prepared in the step S1 on the upper surface of a flat plate by using a proper coating tool such as a spin coater, a scraper coater and the like, placing the mixed solution coated on the surface of the flat plate on a fume hood or a heating plate, and slowly volatilizing the mailing solvent at a preset temperature until a uniform and continuous film is formed; the preset temperature is determined according to the selected organic solvent and the solvent volatilization rate required in the preparation process, and is not particularly limited herein; during the experiment, it was possible to try to run the experiment at different temperatures, observe the film formation and select the most suitable temperature conditions.
And S3, fixing the potassium ion selective membrane on an electrode body to obtain the potassium ion selective electrode.
Specifically, a suitable electrode body is first prepared, the material of the electrode body may be glass, ceramic, metal or conductive polymer, so as to ensure that the surface of the electrode is clean, no greasy dirt or impurities are generated, the potassium ion selective membrane prepared in step S2 is fixed on the upper surface of the electrode body, the membrane can be fixed on the electrode by using an adhesive or pressure, and if necessary, the membrane fixed on the electrode can be further processed, such as baking, ultraviolet exposure and the like, so as to ensure firm combination of the membrane and the electrode.
Through the steps, the potassium ion selective electrode with good performance can be successfully prepared and used in the application of electrolyte analysis and the like.
In one embodiment, the step S3 specifically includes:
s31, cleaning the surface of the electrode body to remove impurities on the surface;
Specifically, deionized water and an organic solvent (such as ethanol or acetone) are used to thoroughly clean the electrode surface to remove impurities, greasy dirt and oxides on the surface. The purpose of this is to ensure clean electrode surfaces, reduce the effect of impurities on subsequent steps, and improve the stability and reliability of the potassium ion selective electrode.
S32, carrying out frosting treatment on the surface of the electrode body after cleaning so that the surface of the electrode body has preset roughness;
Specifically, the surface of the electrode is slightly frosted by using grinding paper or a grinding rod, the surface area and the adhesive force can be increased by roughening the surface, and the frosting treatment can adopt mechanical grinding, chemical etching or sand blasting and other methods to form a tiny concave-convex structure on the surface of the electrode, so that the surface area of the electrode can be increased, the bonding force between a potassium ion selective membrane and an electrode body can be improved, and meanwhile, the contact between the electrode and an electrolyte to be detected can be enhanced, so that the sensitivity and the response speed of the electrode can be improved; in addition, the surface roughening can form a microscopic concave-convex structure, so that the diffusion path of substances on the surface of the electrode can be increased, the transfer and exchange of the substances are promoted, and the sensing performance of the electrode is improved.
The setting of the preset roughness needs to be determined according to the material of the electrode body, and is not particularly limited herein, and the electrode bodies of different materials have different surface characteristics and properties, so that it is necessary to select an appropriate preset roughness for a specific material, for example, but not limited thereto, and if the electrode body is a metal material such as platinum, gold or carbon, a lower preset roughness is generally required because the surface of these materials itself is relatively smooth. In this case, the preset roughness may be on the order of micrometers or less. However, if the electrode body is a non-metallic material such as glassy carbon, a higher predetermined roughness may be required to ensure good bonding between the potassium ion selective membrane and the electrode body due to the relatively rough surface itself. Therefore, the setting of the preset roughness should be adjusted according to the material characteristics of the electrode body and the requirements of the subsequent process steps to ensure that the finally prepared potassium ion selective electrode has excellent performance and stability.
S33, soaking the electrode body into an activating agent, and performing chemical activation treatment, wherein the activating agent comprises one of an acidic activating agent and an alkaline activating agent, and/or an oxidizing agent;
specifically, the electrode body is immersed in an activator to perform chemical activation treatment. Chemical activation can improve the chemical property of the electrode surface, increase the density of active sites, thereby improving the electrochemical performance and stability of the electrode, the type of the activator is determined according to the material of the electrode body and the required activation effect, and acid activators such as sulfuric acid and hydrochloric acid are suitable for the metal electrode body, can remove surface oxides or other impurities, and improve the conductivity and activity of the electrode; alkaline activators such as sodium hydroxide, potassium hydroxide are commonly used in nonmetallic electrode bodies to clean surfaces and enhance their activity. Oxidizing agents such as hydrogen peroxide and potassium permanganate can be used for metallic and non-metallic electrode bodies, and can oxidize surface substances and change surface chemical properties, thereby improving the catalytic activity of the electrode. In selecting the activator, factors such as the material of the electrode body, the desired activation effect, and the subsequent use environment need to be considered. In addition, the conditions such as the concentration of the activator, the treatment time and the temperature are also required to be adjusted according to the specific conditions so as to achieve the optimal activation effect.
Furthermore, the activation treatment can change the charge distribution or chemical property of the electrode surface, so that the interaction between the electrode and ions to be detected is more effective and specific, and the selectivity and detection performance of the electrode are improved. Through the activation treatment, the surface of the electrode is more stable, the unstable factors of the surface are reduced, and the durability and reusability of the electrode are improved, so that the service life of the electrode is prolonged.
S34, cleaning and drying the electrode body after the activation treatment through deionized water and nitrogen;
and cleaning and drying the electrode body after the activation treatment by deionized water and nitrogen. The purpose of this step is to remove chemical agents and impurities that may remain during the activation process, to ensure the purity of the electrode surface and to ensure its stability in subsequent use.
S35, fixing the potassium ion selective membrane on the cleaned and dried electrode body to obtain a potassium ion selective electrode;
Specifically, the potassium ion selective membrane is fixed on the electrode body after cleaning and drying, and the potassium ion selective electrode is obtained. The step is to tightly combine the prepared potassium ion selective membrane with the pretreated electrode body to ensure the stability and reliability of the membrane, thereby improving the performance and service life of the potassium ion selective electrode.
In one embodiment, the step S35 specifically includes:
s351, dissolving the self-assembled monolayer modifier into a corresponding solvent to obtain a modified solvent;
In particular, the self-assembled monolayer modifications are usually in solid form, and need to be dissolved in a suitable solvent in order to modify the electrode in a subsequent step, and dissolving the self-assembled monolayer modifications can cause the molecules thereof to dissociate and disperse in the solution, thus preparing for modifying the electrode surface, and by dissolving the modifications, the concentration and uniformity of the modifications can be better controlled, thus contributing to the uniformity and stability of the modification layer.
Wherein the self-assembled monolayer modification has specific functional groups, which are determined based on potassium ions and/or the material of the potassium ion-selective electrode, in particular, the specific functional groups should be selected such that the electrode has good affinity and selectivity for potassium ions, and further, the chemical nature of the functional groups should be compatible with the electrode surface and be able to stably bind to the electrode surface under desired conditions;
for example, but not limited to, for the potassium ion selection electrode, a functional group having a high affinity for potassium ions, such as crown ether compounds, which can form a stable coordination complex with potassium ions to achieve efficient selective recognition of potassium ions;
The self-assembled monolayer modifier may also be a sulfur-based compound, which has good metal surface binding properties and is capable of stably modifying the electrode surface. Sulfur-based compounds generally form strong metal-sulfur bonds and thus can provide higher stability and durability when modifying the electrode surface;
The self-assembled monolayer modifications may also be functional groups containing nucleophilic substitution reactivity: for example, haloalkyl, ester, and the like. These functional groups can form chemical bonds with the electrode surface during the modification process, thereby achieving a stable connection of the modification layer.
The self-assembled monolayer modifications may also be functional groups with stability and durability: for example, an ether bond, a thioether bond, etc. These functional groups are stable under electrochemical conditions and are well tolerated by temperature, solvents and other environmental factors.
S352, soaking the electrode body into the modification solvent to form a modification layer on the surface of the electrode body;
Specifically, the electrode body after the activation treatment is soaked in a modification solvent for a certain time, and modifier molecules dissolved in the modification solvent are adsorbed on the surface of the electrode and self-assembled into a single-layer structure to form a modification layer, so that the electrode has specific functions and performances, the electrode specificity can be enhanced by forming the modification layer, the selectivity of the electrode to specific ions is improved, and the stability and reusability of the electrode are enhanced.
And S353, fixing the potassium ion selective membrane on the modification layer of the electrode body to obtain the potassium ion selective electrode.
The potassium ion selective membrane prepared in advance is fixed on the surface of the modified electrode, the membrane is covered on the surface of the electrode usually in a coating or sticking mode, the potassium ion selective membrane can be fully contacted with the modification layer and firmly attached to the surface of the electrode, effective transfer and detection of ions are ensured, the potassium ion selective membrane can be fixed to enable the electrode to have higher selectivity and sensitivity, the application performance of the electrode in potassium ion analysis is enhanced, and the stability and reusability of the electrode are improved.
In another embodiment, the method for preparing the potassium ion selective electrode comprises the steps of:
s01, mixing a crown ether compound, thermoplastic resin, a plasticizer and fat-soluble salt to obtain a mixture;
S02, heating the mixture at a temperature higher than the softening or melting temperature of the thermoplastic resin to melt the mixture;
S03, preparing a molten mixture into a film-shaped product by using an extrusion or hot-press molding method to obtain a potassium ion selective membrane;
and S04, fixing the potassium ion selective membrane on an electrode body to obtain the potassium ion selective electrode.
In order to test the slope, accuracy and precision of the electrode assembled by the potassium ion selective membranes with different components and ratios, the components are weighed according to the ratios shown in table 1 and dissolved in a solvent to prepare an induction membrane liquid, and the table 1 is as follows:
TABLE 1 Potassium ion Selective Membrane component proportion Table
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In table 1, crown ether 1 has a group of the first formula 1 as a first group and a group of the second formula 1 as a second group; crown ether 2 has a group of the first structural formula 1 as a first group and a group of the second structural formula 2 as a second group; crown ether 3 has a group of the first structural formula 1 as a first group and a group of the second structural formula 3 as a second group;
crown ether 4 has a group of the first structural formula 2 as a first group and a group of the second structural formula 1 as a second group; crown ether 5 has a group of the first structural formula 2 as a first group and a group of the second structural formula 2 as a second group; crown ether 6 has a group of the first formula 2 as a first group and a group of the second formula 3 as a second group;
Crown ether 7 has the group of the first structural formula 3 as a first group and the group of the second structural formula 1 as a second group; crown ether 8 has a group of formula 3 as a first group and a group of formula 2 as a second group; crown ether 9 has a group of the first structural formula 3 as a first group and a group of the second structural formula 3 as a second group;
crown ether 10 has a group of formula 4 as a first group and a group of formula 1 as a second group; crown ether 11 has a group of formula 4 as a first group and a group of formula 2 as a second group; crown ether 12 has a group of formula 4 as a first group and a group of formula 3 as a second group;
In a specific experiment, the steps for preparing the potassium ion sensing membrane comprise:
Accurately weighing crown ether compound, fat-soluble salt, thermoplastic resin and plasticizer according to the proportion shown in table 1, and dissolving the components in a selected organic solvent; adding a solvent to the solute at room temperature under a fume hood; adding clean magnons, and sealing the container by using a sealing film; placing the container on a magnetic stirrer, stirring the solution at a speed of 500-600 rpm for 12 hours to ensure that the components are fully and uniformly mixed; pouring the uniformly stirred solution into a flat dish made of Polytetrafluoroethylene (PTFE) material to ensure that the solution can be volatilized slowly under clean conditions, volatilizing the solvent in the solution at room temperature for 48 hours until a membranous substance is formed, and obtaining a membrane after volatilizing, namely the required potassium ion selective membrane;
then, the potassium ion selective membranes prepared in different proportions are assembled into an electrode, the slope, the accuracy and the precision are tested, and in the process of evaluating the electrode performance of the membrane material prepared by the composition, the following equipment and method are adopted:
Test conditions:
The measurement experiments were performed in aqueous solutions containing potassium chloride to simulate the behavior of potassium ions in an aqueous environment.
The test covers a range of potassium chloride concentrations from 10 -1 M to 10 ^- M to evaluate the performance of the electrodes at different concentrations.
All measurements were performed at constant temperature, with the exact temperature being controlled at 25 ℃, to ensure consistency and comparability of the experimental data.
Performance evaluation parameters:
Slope: the Nernst slope of the electrode response was measured and this is an indicator of the sensitivity of the electrode to concentration changes. Ideally, this value is close to the theoretical value 59.16 mV/decade.
Accuracy: the deviation, expressed as a percentage, between the estimated electrode reading and the actual value of the known concentration is higher, indicating that the electrode reading is closer to the true value.
Precision: the repeatability of the electrode readings was tested. Lower precision values indicate better uniformity and reliability of the electrodes.
Testing according to the test conditions, and obtaining test results shown in Table 2;
Table 2 test results table
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Tables 1 and 2 show a plurality of experiments from experimental example 1 to experimental example 37, each of which corresponds to a different composition ratio, and by comparing tables 1 and 2, it can be seen that the effect of the different composition ratios on the electrode performance, the slope indicates the sensitivity of the electrode to the change in potassium ion concentration. The theoretical slope predicted by the Nernst equation is about 59.16 mV/decade at 25 ℃;
Accuracy represents the deviation of the electrode reading from the actual potassium ion concentration. Ideally, the accuracy is close to 0%, while the values in the table are typically below 1.5%, indicating that the electrodes produced by the potassium ion selective membranes described above have better accuracy;
precision indicates repeatability of electrode readings, lower precision values indicate high repeatability, values in the table are typically below 1.5%, indicating that the readings of electrodes prepared by the potassium ion selective membranes described above are reliable;
In table 2, the slope values of experimental examples 8, 10, 17, 21, 29 and 30 were 59, which are quite close to the theoretical values. The accuracy and precision of these experimental examples were very low, showing good performance, but the performance of the electrode was considered not only for slope, but also for accuracy and precision, the slope of experimental example 1 was close to 59.16 mV/decade, and had better accuracy and precision.
In summary, the potassium ion-selective electrode provided in example 2 was designed to optimize the selectivity for potassium ions, meaning that it can more effectively distinguish potassium ions from other ions, such as sodium ions, in the sample. The addition of the fat-soluble salt and the thermoplastic resin increases the hydrophobicity of the membrane, which helps to prevent dissolution of the membrane in an aqueous or water-containing environment, thereby improving the durability and stability of the electrode; due to the stability of the material and the high selectivity for potassium ions, the effective lifetime of the electrode may be significantly extended, which is particularly important in case of long-term monitoring or continuous use.
Example 3
Based on the potassium ion-selective electrode of embodiment 2, embodiment 3 of the present invention also provides an electrolyte analyzer including any one of the potassium ion-selective electrodes.
Since the electrode of example 2 has high selectivity for potassium ions, it can provide accurate potassium measurement, which is critical for medical diagnosis and research requiring high-precision monitoring of potassium levels, the design of the electrode allows for rapid response to changes in potassium ions, which means that the electrolyte analyzer can monitor potassium ion concentration changes in a sample in real time; the hydrophobicity and chemical stability of the electrodes ensure reliability in long-term continuous monitoring, reducing the need for frequent replacement due to electrode damage or performance degradation.
In summary, the potassium ion carrier, the potassium ion selective electrode and the electrolyte analyzer provided by the embodiments of the present invention improve the stability and selectivity of the potassium ion selective electrode by improving the structure of the crown ether compound, especially by introducing two benzo-15 crown-5 ether units connected by a bridging unit, the size and three-dimensional structure of the benzo-15 crown-5 can be matched with the size of the potassium ion relatively well, so that it can form a complex with the potassium ion efficiently, and smaller crown ethers such as 12-crown-4, benzo-15 crown-5 are more suitable for complexing with the potassium ion because the cavity diameter thereof is closer to the optimal matching size of the potassium ion, and the benzo-15 crown-5 has higher selectivity, thereby reducing the cross response with other ions such as sodium ion;
Furthermore, the benzene ring part of the benzo-15 crown-5 increases the hydrophobicity of the whole molecule, is beneficial to improving the overall hydrophobicity of the electrode film, thereby reducing the interference of water molecules, enhancing the stability and the service life of a potassium ion selective electrode, and the chemical structure of the benzo-15 crown-5 provides higher chemical stability, so that crown ether compounds are not easy to decompose in the process of storage or use, and the stability and the reliability of the electrode are further improved;
Finally, the structure of benzo-15 crown-5 allows to further adjust its properties by introducing functional groups on the benzene ring, the potential response of crown ether compounds to potassium ions being related to the properties of the introduced functional groups, which may allow to adjust the response range and sensitivity of the electrode by selecting different groups, adapting to different measurement requirements.
It should be understood that the invention is not limited to the particular arrangements and instrumentality described above and shown in the drawings. For the sake of brevity, a detailed description of known methods is omitted here. In the above embodiments, several specific steps are described and shown as examples. The method processes of the present invention are not limited to the specific steps described and shown, but various changes, modifications and additions, or the order between steps may be made by those skilled in the art after appreciating the spirit of the present invention.
It should also be noted that the exemplary embodiments mentioned in this disclosure describe some methods or systems based on a series of steps or devices. The present invention is not limited to the order of the above-described steps, that is, the steps may be performed in the order mentioned in the embodiments, or may be performed in a different order from the order in the embodiments, or several steps may be performed simultaneously.
In the foregoing, only the specific embodiments of the present invention are described, and it will be clearly understood by those skilled in the art that, for convenience and brevity of description, the specific working processes of the systems, modules and units described above may refer to the corresponding processes in the foregoing method embodiments, which are not repeated herein. It should be understood that the scope of the present invention is not limited thereto, and any equivalent modifications or substitutions can be easily made by those skilled in the art within the technical scope of the present invention, and they should be included in the scope of the present invention.
Claims (6)
1. A potassium ion selective electrode comprising: a potassium ion selective membrane, wherein the potassium ion selective membrane comprises a crown ether compound, a fat-soluble salt, a plasticizer, and a thermoplastic resin;
the structural formula of the crown ether compound is shown as follows:
In the structural formula, A is a first group, B is a second group, the first group and the second group are different, the first group is a cycloalkyl group or an aromatic group, the second group is an aromatic group or an amide group, and the potential response value of the crown ether compound to potassium ions has correlation with the first group and the second group;
The structural formula of the first group is one of the following structural formulas:
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Wherein R1 to R4 are hydrogen atoms or alkyl groups;
the structural formula of the second group is one of the following structural formulas:
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The structural formula of the fat-soluble salt is as follows:
In the structural formula, X 1、X2、X3、X4 is one or more of a hydrogen atom, a halogen atom, an alkyl group or a halogenated alkyl group, Y1, Y2, Y3 and Y4 are integers of 1 to 5, and M is an alkali metal;
The fat-soluble salt includes at least one of potassium tetraphenylborate, potassium tetrakis (4-chlorophenyl) borate, potassium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, sodium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, potassium tetrakis- (4-t-butylphenyl) borate, potassium tetrakis- (4-isopropylphenyl) borate, sodium tetrakis (4-isopropylphenyl) borate, lithium tetrakis (p-fluorophenyl) borate, or lithium tetrakis (pentafluorophenyl) borate;
The potassium ion selective membrane comprises the following components in percentage by mass: 0.1% -5% of the crown ether compound, 0.1% -5% of the fat-soluble salt, 15% -30% of the thermoplastic resin and 60% -84.8% of the plasticizer.
2. The potassium ion-selective electrode according to claim 1, wherein the fat-soluble salt is potassium tetraphenylborate, and the first group has the structural formula:
Wherein R1-R4 are hydrogen atoms or alkyl groups, and the structural formula of the second group is shown as follows:
。
3. A method for producing a potassium ion selective electrode for use in the potassium ion selective electrode according to any one of claims 1 to 2, comprising:
Dissolving 0.1% -5% of crown ether compound, 0.1% -5% of fat-soluble salt, 15% -30% of thermoplastic resin and 60% -84.8% of plasticizer in a preset organic solvent to obtain a mixed solution, wherein the organic solvent comprises tetrahydrofuran, chloroform, 1, 2-dichloroethane, dichloromethane, dimethylformamide, dimethyloxyamine, benzene or toluene;
coating the mixed solution on the upper surface of a flat plate, and evaporating the organic solvent to obtain a potassium ion selective membrane;
And fixing the potassium ion selective membrane on the electrode body to obtain the potassium ion selective electrode.
4. The method according to claim 3, wherein the fixing of the potassium ion selective membrane to the electrode body gives a potassium ion selective electrode, comprising:
cleaning the surface of the electrode body to remove impurities on the surface;
performing frosting treatment on the surface of the electrode body after cleaning so that the surface of the electrode body has preset roughness, wherein the preset roughness is determined based on the material of the electrode body;
Immersing the electrode body into an activating agent for chemical activation treatment, wherein the activating agent comprises one of an acidic activating agent and an alkaline activating agent, and/or an oxidizing agent;
cleaning and drying the electrode body after the activation treatment through deionized water and nitrogen;
And fixing the potassium ion selective membrane on the cleaned and dried electrode body to obtain the potassium ion selective electrode.
5. The method according to claim 4, wherein the fixing of the potassium ion selective membrane to the cleaned and dried electrode body gives a potassium ion selective electrode, comprising:
Dissolving a self-assembled monolayer modifier into a corresponding solvent to obtain a modified solvent, wherein the self-assembled monolayer modifier has specific functional groups, and the specific functional groups are determined based on potassium ions and/or the material of the electrode body;
immersing the electrode body in the modification solvent to form a modification layer on the surface of the electrode body;
And fixing the potassium ion selective membrane on the modification layer of the electrode body to obtain the potassium ion selective electrode.
6. An electrolyte analyzer comprising the potassium ion-selective electrode of any one of claims 1-2.
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Citations (6)
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| US4361473A (en) * | 1981-10-28 | 1982-11-30 | Nova Biomedical Corporation | Potassium ion-selective membrane electrode |
| US4523994A (en) * | 1982-06-30 | 1985-06-18 | Shimadzu Corporation | Bis-crown-ether derivatives and their use |
| CN85102668A (en) * | 1985-04-01 | 1986-09-17 | 四川大学 | Ion selected electrode of film-painted carbon rod |
| CA1215062A (en) * | 1982-07-19 | 1986-12-09 | Jeno Havas | Crown ether compounds, process for the preparation of the crown ether complex forming agents and ion- selective membrane electrodes containing the same |
| JPH08327584A (en) * | 1995-06-02 | 1996-12-13 | Tokuyama Corp | Ion-selective electrode and method for measuring ion concentration |
| CN110161102A (en) * | 2018-02-15 | 2019-08-23 | 爱科来株式会社 | Ion selective electrode, test film |
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| US4361473A (en) * | 1981-10-28 | 1982-11-30 | Nova Biomedical Corporation | Potassium ion-selective membrane electrode |
| US4523994A (en) * | 1982-06-30 | 1985-06-18 | Shimadzu Corporation | Bis-crown-ether derivatives and their use |
| CA1215062A (en) * | 1982-07-19 | 1986-12-09 | Jeno Havas | Crown ether compounds, process for the preparation of the crown ether complex forming agents and ion- selective membrane electrodes containing the same |
| CN85102668A (en) * | 1985-04-01 | 1986-09-17 | 四川大学 | Ion selected electrode of film-painted carbon rod |
| JPH08327584A (en) * | 1995-06-02 | 1996-12-13 | Tokuyama Corp | Ion-selective electrode and method for measuring ion concentration |
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