# US 10,871,464 B2 · Ion-selective electrode, method of manufacture thereof, and cartridge > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,871,464 B2 - Document ID: US10871464B2 - Status: Granted - Kind: B2 - Application number: 15/754,450 - Filed: 2016-08-30 - Published: 2018-08-30 - Granted: 2020-12-22 - Earliest claimed: 2015-09-14 - Assignees: Hitachi High-Tech Corporation - Applicants: Hitachi High-Tech Corporation - Inventors: Yu Ishige; Wolfgang Schuhmann; Stefan Klink - Web page: https://patentgrep.com/patent/US10871464B2 ## CPC - G01N 27/333: Ion-selective electrodes or membranes (glass electrodes G01N27/36) - G01N 27/3335: {the membrane containing at least one organic component (G01N27/3271 takes precedence; aspects concerning the enzyme reagent in enzyme electrodes C12Q1/001)} - G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q) ## Abstract There is provided a solid-contact ion-selective electrode having a high potential stability and potential reproducibility. The ion-selective electrode includes an ion sensitive film having a Group-1 element ion, a Group-2 element ion, a hydronium ion or an ammonium ion as a target ion, an ion occluding material layer, and a conductive electrode, wherein the ion occluding material contained in the ion occludes material layer occluding the target ion, the ion occluding material being a Prussian blue analog represented by the structure formula AaMx[M′(CN)6]y□z.kH2O. Herein, A is one type or a plurality of types of Group-1 elements, Group-2 elements, hydronium, or ammonium; M and M′ are one type or a plurality of types of transition metals; M or M′ includes at least one of nickel, cobalt, copper, silver, and cadmium; □ is a vacancy in a porous coordination polymer; x and y are greater than zero; and a, z, and k are numbers equal to or greater than zero. ## Claims ### Claim 1 An ion-selective electrode comprising: an ion sensitive film having a Group-1 element ion, a Group-2 element ion, a hydronium ion or an ammonium ion as a target ion; an ion occluding material layer; and a conductive electrode, wherein an ion occluding material contained in the ion occluding material layer occludes the target ion, the ion occluding material being a Prussian blue analog represented by structure formula AaMx[M′(CN)6]y□zkH2O, wherein A is at least one of a Group-1 element, a Group-2 element, hydronium, or ammonium, M and M′ are at least one type of transition metals, M or M′ includes at least one of nickel, cobalt, copper, silver, and cadmium, □ is a vacancy in a porous coordination polymer, and x and y are greater than zero; and a, z, and k are numbers equal to or greater than zero. ### Claim 2 A cartridge comprising a plurality of ion-selective electrodes, wherein when one of the ion-selective electrodes is made as an ion-selective electrode A, and the other ion-selective electrode is made as an ion-selective electrode B, the ion-selective electrode A and the ion-selective electrode B comprising: an ion sensitive film having a Group-1 element ion, a Group-2 element ion, a Group-17 element ion, a hydronium ion or an ammonium ion as a target ion; an ion occluding material layer; and a conductive electrode, wherein an ion occluding material contained in the ion occluding material layer occludes the target ion, the ion occluding material is a porous coordination polymer, and the target ion of the ion-selective electrode A is different from the target ion of the ion-selective electrode B, the ion occluding material being a Prussian blue analog represented by structure formula AaMx[M′(CN)6]y□z.kH2O, wherein A is at least one type of Group-1 elements, Group-2 elements, hydronium, or ammonium, M and M′ are at least one type of transition metals, M or M′ includes at least one of nickel, cobalt, copper, silver, and cadmium, □ is a vacancy in a porous coordination polymer, and x and y are greater than zero; and a, z, and k are numbers equal to or greater than zero. ### Claim 3 A method of manufacturing an ion-selective electrode, wherein the ion-selective electrode includes an ion sensitive film having a Group-1 element ion, a Group-2 element ion, a Group-17 element ion, a hydronium ion or an ammonium ion as a target ion, an ion occluding material layer, and a conductive electrode, and the ion occluding material layer includes a porous coordination polymer, the method comprising: a step of manufacturing the porous coordination polymer including: a step of mixing Solution A containing a transition metal M with Solution B containing a transition metal M′; and a step of recovering the porous coordination polymer from a product of the mixture, the transition metal M and the transition metal M′ are the same or different, at least Solution A contains the transition metal M in at least two different ions that have different valences, and at least one of Solution A and Solution B contains an organic ligand; adhering the ion occluding material layer to the conductive electrode; and adhering the ion sensitive film to the ion occluding material layer. ### Claim 4 (depends on 3) The method of manufacturing the ion-selective electrode according to claim 3, comprising: a step of examining a state of the porous coordination polymer recovered from the product of the mixture; and a step of adjusting a mixing ratio of the different ions of the transition metal M contained in Solution A or the mixing ratio of Solution A and Solution B based on the state of the porous coordination polymer. ### Claim 5 (depends on 4) The method of manufacturing the ion-selective electrode according to claim 4, wherein elemental analysis is performed in the step of examining the state of the recovered porous coordination polymer. ### Claim 6 (depends on 4) The method of manufacturing the ion-selective electrode according to claim 4, wherein the step of examining the state of the porous coordination polymer includes measuring a voltage potential of the ion-selective electrode. ### Claim 7 (depends on 4) The method of manufacturing the ion-selective electrode according to claim 4, wherein absorbance is measured in the step of examining the state of the porous coordination polymer. ### Claim 8 (depends on 4) The method of manufacturing the ion-selective electrode according to claim 4, wherein the step of examining the state of the porous coordination polymer includes determining whether an ion occlusion ratio of the ion occluding material layer, which is a ratio of ions occluded by the ion occluding material to all ions in the porous coordination polymer, is in a range of 0.1 to 0.9. ### Claim 9 A method of manufacturing an ion-selective electrode, wherein the ion-selective electrode includes an ion sensitive film having a Group-1 element ion, a Group-2 element ion, a Group-17 element ion, a hydronium ion or an ammonium ion as a target ion, an ion occluding material layer, and a conductive electrode, the method comprising: a step of manufacturing the ion occluding material layer including: a step of dispersing an ion occluding material into a solution; a step of adding an oxidation-reduction substance to the solution in which the ion occluding material is dispersed; and a step of recovering the ion occluding material from the solution in which the oxidation-reduction substance is added, in which an ion occlusion ratio, which is a ratio of ions occluded by the ion occluding material to all ions in the oxidation-reduction substance, is adjusted by the addition of the oxidation-reduction substance; adhering the ion occluding material layer to the conductive electrode; and adhering the ion sensitive film to the ion occluding material layer. ### Claim 10 (depends on 9) The method of manufacturing the ion-selective electrode according to claim 9, wherein the ion occlusion rate of the ion occluding material layer is adjusted to a range of 0.1 to 0.9. ### Claim 11 A method of manufacturing an ion-selective electrode, wherein the ion-selective electrode includes an ion sensitive film having a Group-1 element ion, a Group-2 element ion, a Group-17 element ion, a hydronium ion or an ammonium ion as a target ion, an ion occluding material layer, and a conductive electrode, the method comprising: a step of manufacturing the ion occluding material layer including: a step of preparing a first ion occluding material in which an ion occlusion rate of the target ion is a first value; a step of preparing a second ion occluding material in which the ion occlusion rate of the target ion is a second value; and a step of mixing the first ion occluding material with the second ion occluding material; adhering the ion occluding material layer to the conductive electrode; and adhering the ion sensitive film to the ion occluding material layer. ### Claim 12 (depends on 11) The method of manufacturing the ion-selective electrode according to claim 11, wherein the ion occlusion ratio of the ion occluding material layer is adjusted to a range of 0.1 to 0.9.