JP6827047B2 - 導電性ダイヤモンド電極で微量金属を検出するための装置および方法 - Google Patents
導電性ダイヤモンド電極で微量金属を検出するための装置および方法 Download PDFInfo
- Publication number
- JP6827047B2 JP6827047B2 JP2018526617A JP2018526617A JP6827047B2 JP 6827047 B2 JP6827047 B2 JP 6827047B2 JP 2018526617 A JP2018526617 A JP 2018526617A JP 2018526617 A JP2018526617 A JP 2018526617A JP 6827047 B2 JP6827047 B2 JP 6827047B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- chamber
- analysis
- passage
- electrodes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 112
- 239000002184 metal Substances 0.000 title claims description 112
- 239000010432 diamond Substances 0.000 title claims description 67
- 229910003460 diamond Inorganic materials 0.000 title claims description 65
- 150000002739 metals Chemical class 0.000 title claims description 45
- 238000000034 method Methods 0.000 title description 66
- 238000004458 analytical method Methods 0.000 claims description 70
- 239000012530 fluid Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 238000004891 communication Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000012491 analyte Substances 0.000 description 22
- 239000002253 acid Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 19
- 238000003950 stripping voltammetry Methods 0.000 description 18
- 238000004140 cleaning Methods 0.000 description 17
- 238000003968 anodic stripping voltammetry Methods 0.000 description 16
- 229910021654 trace metal Inorganic materials 0.000 description 15
- 230000008901 benefit Effects 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 238000009713 electroplating Methods 0.000 description 12
- 230000035945 sensitivity Effects 0.000 description 12
- 238000001514 detection method Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 230000002441 reversible effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- 230000007246 mechanism Effects 0.000 description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 10
- 229910052753 mercury Inorganic materials 0.000 description 10
- 238000002032 lab-on-a-chip Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000005416 organic matter Substances 0.000 description 9
- 239000011133 lead Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 241000894007 species Species 0.000 description 8
- 238000004365 square wave voltammetry Methods 0.000 description 8
- 238000010790 dilution Methods 0.000 description 7
- 239000012895 dilution Substances 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- 238000004752 cathodic stripping voltammetry Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 229910052785 arsenic Inorganic materials 0.000 description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 238000001903 differential pulse voltammetry Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 229910000497 Amalgam Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000003842 bromide salts Chemical class 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 244000052769 pathogen Species 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- 230000000153 supplemental effect Effects 0.000 description 2
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- 150000003567 thiocyanates Chemical class 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241001439061 Cocksfoot streak virus Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004186 food analysis Methods 0.000 description 1
- -1 food analysis Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000004904 long-term response Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
- G01N27/42—Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
- B01L3/502707—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by the manufacture of the container or its components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
- B01L3/502715—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by interfacing components, e.g. fluidic, electrical, optical or mechanical interfaces
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
-
- 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
- G01N27/302—Electrodes, e.g. test electrodes; Half-cells pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes
-
- 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
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- 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
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
- B01L2300/06—Auxiliary integrated devices, integrated components
- B01L2300/0627—Sensor or part of a sensor is integrated
- B01L2300/0645—Electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
- B01L2300/08—Geometry, shape and general structure
- B01L2300/0809—Geometry, shape and general structure rectangular shaped
- B01L2300/0816—Cards, e.g. flat sample carriers usually with flow in two horizontal directions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
- B01L2300/08—Geometry, shape and general structure
- B01L2300/0861—Configuration of multiple channels and/or chambers in a single devices
- B01L2300/0864—Configuration of multiple channels and/or chambers in a single devices comprising only one inlet and multiple receiving wells, e.g. for separation, splitting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
- B01L2300/08—Geometry, shape and general structure
- B01L2300/0861—Configuration of multiple channels and/or chambers in a single devices
- B01L2300/087—Multiple sequential chambers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
- B01L2300/08—Geometry, shape and general structure
- B01L2300/0887—Laminated structure
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46147—Diamond coating
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1813—Specific cations in water, e.g. heavy metals
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Dispersion Chemistry (AREA)
- Hematology (AREA)
- Clinical Laboratory Science (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Sampling And Sample Adjustment (AREA)
- Carbon And Carbon Compounds (AREA)
Description
本願は、2015年8月7日に出願された米国仮出願連続番号第62/202,422号の利益を主張する。当該仮出願はその全体がここに援用される。
1.発明の分野
本発明は、さまざまなサンプル中の金属を検出するように構成された導電性ダイヤモンド材料を含む微量金属分析検出器に向けられる。本発明は、陽極および陰極ストリッピングボルタンメトリーで使用される従来の電極では検出が非常に困難な微量金属の正確で精密で反復可能な検出を可能にするとともに、ドープダイヤモンド電極、具体的にはホウ素ドープダイヤモンド材料の薄膜を含む電極の使用を含む従来の検出器を用いて検出が困難な分析物を検出するための感度の向上を可能にする、装置および方法を提供する。
多くの装置および方法が、サンプル中の特定の分析物を検出するために存在する。通常のサンプルは、地下水、食品分析、産業廃棄物、製品サンプル、飲料水、および、陽極または陰極ストリッピングボルタンメトリーにおいて電極を使用して特定の分析物を検出することが望ましい任意のサンプルを含む。より具体的には、陽極および陰極ストリッピングボルタンメトリーは、析出ステップ中に1つ以上の分析物を作用電極上に電気めっきするかまたは析出させ、場合によってはストリッピングステップ中に分析物を酸化させるかまたは電極から除去することにより、特定のイオン種の定量的判断のために使用されてきた。より具体的には、ストリッピングステップ中、具体的には陽極ストリッピングボルタンメトリー中に電流が測定され、種の酸化が、電極からの電流信号におけるピークとして、すなわち、イオン種が酸化され始める電位として検知される。
本発明は一般に、サンプル中の金属イオンなどのイオン種、またはある有機分子を検出するための検出器装置および方法に向けられる。検出器は一般に、サンプル中の選択されたイオン種の量を判断するための陽極または陰極ストリッピングボルタンメトリーに関連して使用される。
本発明の他の利点は、添付図面に関連して以下の詳細な説明を参照することによってよりよく理解されるため、容易に理解されるであろう。
本発明は一般に、サンプル中の金属イオンなどのイオン種、またはある有機分子を検出するための検出器装置10および方法に向けられる。検出器20とコントローラ110とを有する検出器装置10は一般に、サンプル中の選択されたイオン種の量を判断するための陽極または陰極ストリッピングボルタンメトリーに関連して使用される。検出器20は主として、陽極ストリッピングボルタンメトリー(anodic stripping voltammetry:ASV)法において使用されるように、以下におよび明細書全体にわたって説明されるであろう。しかしながら、検出器20は代わりに、わずかな変更で、陰極ストリッピングボルタンメトリー(cathodic stripping voltammetry:CSV)法を用いて容易に使用され得る、ということが認識されるべきである。したがって、陽極ストリッピングボルタンメトリーへのどの言及も、陰極ストリッピングボルタンメトリーと置換えられてもよく、その時に印加される正電流および負電流を取り替える変更、および他のわずかな変更を加えてもよい。
1) 作用電極40の表面46を整える/洗浄するために、正電位を保持する;
2) 第1の対象金属(最も正のめっき電位の金属)を電気めっきするために、予め定められた第1の電気めっき用電位を印加する;
3) 第1の金属を定量化するために、作用電極40上で正電位まで逆走査(LV、SWVまたはDPV)を実行する;
4) 作用電極40の表面46を整える/洗浄するために、正電位を保持する;
5) 第1および第2の金属をともに作用電極40上に電気めっきするために、第1の電気めっき用電位よりも負である予め定められた第2の電気めっき用電位を印加する;
6) 第1および第2の金属をともに定量化するために、作用電極40上で正電位まで逆走査(LV、SWVまたはDPV)を実行する;
7) 作用電極40の表面46を整える/洗浄するために、正電位を保持する;
8) 第1、第2および第3の金属をともに作用電極40上に電気めっきするために、第1および第2の電気めっき用電位よりも負である予め定められた第3の電気めっき用電位を印加する;
9) 第1、第2および第3の金属をともに定量化するために、作用電極40上で正電位まで逆走査(LV、SWVまたはDPV)を実行する;
10) 作用電極40の表面46を整える/洗浄するために、正電位を保持する;
11) 追加の望ましい金属をめっきして定量化するために、追加のより負である電気めっき用電位について、上述のステップを何回でも好きなだけ繰り返す。
1) すべての作用電極40の表面46を同時に整える/洗浄するために、正電位を保持する;
2) 対象金属を電気めっきするために、予め定められた電気めっき用電位を各作用電極40に同時に、重複して順次、または間隔をあけて順次(またはその変形)印加する。各作用電極40は、その特定の作用電極に関連してどの金属が分析されるかに依存して、異なる電位で保持される;
3) 各作用電極40上の金属を定量化するために、各作用電極40上で正電位まで逆走査(LV、SWVまたはDPV)を同様に同時に、重複して順次、または間隔をあけて順次(またはその変形)実行する;および
4) 次の測定のためにすべての作用電極40の表面46を整える/洗浄するために、正電位を保持する。設定全体は、3電極設定を有する複数のセンサチップと、分析を実行し、データを収集し、データを有線または無線でコンピュータ、スマートフォン、またはタブレットへ転送する読出しユニットを含む多重ポテンショメータとを含んでいてもよい。
Claims (15)
- 第1の入力チャンバを含む少なくとも1つの入力チャンバと、前記第1の入力チャンバから延在する第1の通路を含む少なくとも1つの通路とにおいて、流体サンプルを受けるように構成された検出器と、
ホウ素ドープダイヤモンド電極と、
参照電極と、
対極と、
流体のpHを修正するように構成されたpH電極とを含み、
前記検出器は、分析チャンバを有するチップであり、
前記ホウ素ドープダイヤモンド電極は、前記分析チャンバの近傍に位置し、pHメータが、前記分析チャンバと前記少なくとも1つの通路のうちの少なくとも1つに位置する、流体中の微量金属を検出するためのシステム。 - 前記ホウ素ドープダイヤモンド電極は、前記少なくとも1つの通路のうちのある通路内に位置する、請求項1に記載のシステム。
- 前記検出器は、前記少なくとも1つの通路において、複数のホウ素ドープダイヤモンド電極を含む、請求項2に記載のシステム。
- 前記検出器は、通路およびチャンバを形成するために協働する基板、ガスケットおよび上部層を有するチップである、請求項1に記載のシステム。
- 前記入力チャンバと前記分析チャンバとの間に延在する第2の通路をさらに含み、
前記pH電極は、前記第2の通路を通過する前記流体のpHを修正するように構成される、請求項1に記載のシステム。 - 前記分析チャンバにおいてpHメータをさらに含み、
前記pH電極は、前記第2の通路にのみ位置する、請求項5に記載のシステム。 - 第2の入力チャンバと、
前記第2の入力チャンバから前記第1の通路または前記分析チャンバのうちの1つまで延在する第2の通路とを含み、
前記pH電極は、前記第2の通路を通過し、前記第1の通路または前記分析チャンバのいずれかに入る前記流体のpHを修正するように構成される、請求項1に記載のシステム。 - 前記分析チャンバは、pHメータを含む、請求項7に記載のシステム。
- 前記流体サンプルとは異なるpHを有する流体を前記分析チャンバへ供給するように構成されたpH修正チャンバをさらに含み、
前記分析チャンバは、pHメータを含む、請求項1に記載のシステム。 - 前記入力チャンバと前記分析チャンバとの間に位置する前処理電極を有する前処理エリアをさらに含む、請求項1に記載のシステム。
- 前記第1の通路および前記分析チャンバと各々並列である複数の通路および分析チャンバをさらに含み、
各分析チャンバは、少なくとも1つの作用電極を含む、請求項1に記載のシステム。 - 前記第1の通路および前記分析チャンバと直列に配置された少なくとも1つの追加の通路および少なくとも1つの追加の分析チャンバをさらに含む、請求項1に記載のシステム。
- 少なくとも1つの前記分析チャンバと流体連通する体積調節チャンバをさらに含む、請求項12に記載のシステム。
- 前記第1の通路および前記分析チャンバと並列に配置された少なくとも1つの追加の通路および1つの追加の分析チャンバと、直列に配置された少なくとも1つ以上の追加の通路および少なくとも1つ以上の追加の分析チャンバとをさらに含む、請求項1に記載のシステム。
- 少なくとも1つの追加の通路および1つの分析チャンバをさらに含み、
前記流体は、前記分析チャンバを通って周期的に繰り返し循環される、請求項1に記載のシステム。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201562202422P | 2015-08-07 | 2015-08-07 | |
US62/202,422 | 2015-08-07 | ||
PCT/US2016/046063 WO2017027477A1 (en) | 2015-08-07 | 2016-08-08 | Apparatus and method for detecting trace metals with electrically conductive diamond electrodes |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2019182481A Division JP6861255B2 (ja) | 2015-08-07 | 2019-10-02 | 導電性ダイヤモンド電極で微量金属を検出するための装置および方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2018529981A JP2018529981A (ja) | 2018-10-11 |
JP6827047B2 true JP6827047B2 (ja) | 2021-02-10 |
Family
ID=57983598
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2018526617A Active JP6827047B2 (ja) | 2015-08-07 | 2016-08-08 | 導電性ダイヤモンド電極で微量金属を検出するための装置および方法 |
JP2019182481A Active JP6861255B2 (ja) | 2015-08-07 | 2019-10-02 | 導電性ダイヤモンド電極で微量金属を検出するための装置および方法 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2019182481A Active JP6861255B2 (ja) | 2015-08-07 | 2019-10-02 | 導電性ダイヤモンド電極で微量金属を検出するための装置および方法 |
Country Status (6)
Country | Link |
---|---|
US (2) | US11073494B2 (ja) |
EP (1) | EP3332247A4 (ja) |
JP (2) | JP6827047B2 (ja) |
CN (1) | CN108139349B (ja) |
SG (1) | SG10201909836UA (ja) |
WO (1) | WO2017027477A1 (ja) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11255811B2 (en) | 2017-04-25 | 2022-02-22 | Case Western Reserve University | Sensor for lead detection |
US10532356B2 (en) * | 2017-11-09 | 2020-01-14 | International Business Machines Corporation | pH control for analyte detection |
WO2019099855A1 (en) * | 2017-11-17 | 2019-05-23 | Siemens Healthcare Diagnostics Inc. | Sensor assembly and method of using same |
FR3086554B1 (fr) * | 2018-09-28 | 2021-05-28 | Klearia | Procede de nettoyage et/ou de regeneration d'un capteur microfluidique en verre pour l'analyse de metaux |
JP7272565B2 (ja) * | 2018-11-01 | 2023-05-12 | 慶應義塾 | 参照電極として導電性ダイヤモンド電極を有する三極電極、装置及び、電気化学的測定方法 |
US11592373B2 (en) | 2018-11-30 | 2023-02-28 | Board Of Trustees Of Michigan State University | Electrochemical methods for sample pretreatment for metals determination and related apparatus |
US20210341418A1 (en) * | 2020-05-01 | 2021-11-04 | Hach Company | Detection of oxidant in seawater |
JP7249049B2 (ja) * | 2021-02-02 | 2023-03-30 | 株式会社ファーストスクリーニング | 電気化学センサ |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0769792A (ja) * | 1993-08-30 | 1995-03-14 | Canon Inc | ダイヤモンド結晶のエピタキシャル成長法及び選択エピタキシャル成長法 |
EP0961919A1 (en) * | 1996-09-24 | 1999-12-08 | Case Western Reserve University | Device for optical and electrochemical measurements in microliter size samples |
US5873986A (en) * | 1997-03-19 | 1999-02-23 | Cpac, Inc. | Metal recovery apparatus |
GB0318215D0 (en) * | 2003-08-04 | 2003-09-03 | Element Six Ltd | Diamond microelectrodes |
US7144753B2 (en) * | 2003-11-25 | 2006-12-05 | Board Of Trustees Of Michigan State University | Boron-doped nanocrystalline diamond |
US7394103B2 (en) * | 2004-09-13 | 2008-07-01 | Uchicago Argonne, Llc | All diamond self-aligned thin film transistor |
KR100590573B1 (ko) * | 2004-12-17 | 2006-06-19 | 삼성전자주식회사 | 전기분해 장치를 포함하는 미세유동장치를 이용한 pH조절 방법 |
JP4639334B2 (ja) * | 2005-03-11 | 2011-02-23 | 独立行政法人物質・材料研究機構 | ダイヤモンド膜、その製造方法、電気化学素子、及びその製造方法 |
US7625469B1 (en) * | 2005-03-16 | 2009-12-01 | Sandia Corporation | Nanoelectrode array for electrochemical analysis |
KR100647328B1 (ko) * | 2005-06-21 | 2006-11-23 | 삼성전자주식회사 | 미세유동 장치 내의 유체의 pH를 전기적으로 조절하기위한 미세유동 장치 및 그를 이용하여 pH를 조절하는방법 |
CN101622532B (zh) | 2007-04-27 | 2013-08-14 | 爱科来株式会社 | 分析芯片以及分析装置 |
KR100987510B1 (ko) * | 2008-04-30 | 2010-10-12 | 한국기초과학지원연구원 | 유기물 함유 시료에 대한 중금속 분석용 전기화학적측정장치 |
GB2479587A (en) * | 2010-04-16 | 2011-10-19 | Diamond Detectors Ltd | Diamond microelectrode |
JP2012225770A (ja) * | 2011-04-20 | 2012-11-15 | Horiba Ltd | 電気化学的測定装置 |
GB201108339D0 (en) * | 2011-05-18 | 2011-06-29 | Element Six Ltd | Electrochemical sensors |
US9810688B2 (en) * | 2013-03-15 | 2017-11-07 | Robert Bosch Gmbh | Smart glass slide for microarrays |
EP2885633B1 (en) * | 2012-08-16 | 2020-02-12 | CSEM Centre Suisse d'Electronique et de Microtechnique SA - Recherche et Développement | Method of measuring ion concentration of an analyte using a micro machined chip of an ion-selective sensor |
EP2936133A2 (en) | 2012-12-20 | 2015-10-28 | King Abdullah University Of Science And Technology | Sensor for metal detection |
JP2014232052A (ja) * | 2013-05-29 | 2014-12-11 | 学校法人慶應義塾 | セレンの電気化学的分析方法及び装置 |
GB201312106D0 (en) | 2013-07-05 | 2013-08-21 | Element Six Ltd | Diamond based electrochemical sensors |
CN203484166U (zh) * | 2013-08-13 | 2014-03-19 | 青岛中一监测有限公司 | 一种环境监测用微流控芯片 |
US9233859B2 (en) * | 2013-09-30 | 2016-01-12 | Uchicago Argonne, Llc. | Microfluidic process monitor for industrial solvent extraction system |
FR3011727B1 (fr) * | 2013-10-16 | 2018-03-02 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Microelectrodes a base de diamant structure pour des applications d'interfacage neuronale. |
-
2016
- 2016-08-08 CN CN201680058065.9A patent/CN108139349B/zh active Active
- 2016-08-08 EP EP16835763.0A patent/EP3332247A4/en active Pending
- 2016-08-08 US US15/751,133 patent/US11073494B2/en active Active
- 2016-08-08 SG SG10201909836U patent/SG10201909836UA/en unknown
- 2016-08-08 WO PCT/US2016/046063 patent/WO2017027477A1/en active Application Filing
- 2016-08-08 JP JP2018526617A patent/JP6827047B2/ja active Active
-
2019
- 2019-10-02 JP JP2019182481A patent/JP6861255B2/ja active Active
-
2021
- 2021-07-20 US US17/381,173 patent/US12061162B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
JP6861255B2 (ja) | 2021-04-21 |
US12061162B2 (en) | 2024-08-13 |
WO2017027477A4 (en) | 2017-05-11 |
US11073494B2 (en) | 2021-07-27 |
US20200088671A1 (en) | 2020-03-19 |
EP3332247A1 (en) | 2018-06-13 |
US20210349047A1 (en) | 2021-11-11 |
SG10201909836UA (en) | 2019-11-28 |
JP2020024211A (ja) | 2020-02-13 |
WO2017027477A1 (en) | 2017-02-16 |
EP3332247A4 (en) | 2019-05-01 |
JP2018529981A (ja) | 2018-10-11 |
CN108139349B (zh) | 2021-01-29 |
CN108139349A (zh) | 2018-06-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6861255B2 (ja) | 導電性ダイヤモンド電極で微量金属を検出するための装置および方法 | |
Punrat et al. | Method development for the determination of arsenic by sequential injection/anodic stripping voltammetry using long-lasting gold-modified screen-printed carbon electrode | |
Ordeig et al. | Trace detection of mercury (II) using gold ultra‐microelectrode arrays | |
Chuanuwatanakul et al. | Determination of trace heavy metals by sequential injection-anodic stripping voltammetry using bismuth film screen-printed carbon electrode | |
CN103534585B (zh) | 具有金刚石电极的电化学传感器 | |
KR100955710B1 (ko) | 전기화학분석법을 이용한 온라인 중금속 분석장치 | |
US20070278096A1 (en) | Method and apparatus for stripping voltammetric and potentiometric detection and measurement of contamination in liquids | |
JP4215132B2 (ja) | ホウ素ドープ導電性ダイヤモンド電極を用いた電気化学的分析方法 | |
WO2014165659A2 (en) | An electrochemical tongue | |
US8702957B2 (en) | Electrochemical detection of silica species | |
Muñoz et al. | A continuous flow system design for simultaneous determination of heavy metals in river water samples | |
Wonsawat et al. | Highly sensitive determination of cadmium and lead using a low-cost electrochemical flow-through cell based on a carbon paste electrode | |
JP2004520577A (ja) | オゾン検出器としての電子舌 | |
Superville et al. | An adaptable automatic trace metal monitoring system for on line measuring in natural waters | |
Olsson et al. | A self polishing electronic tongue | |
US6841053B2 (en) | Electronic tongue as ozone detector | |
KR20040009344A (ko) | 전기화학식 잔류염소센서 및 이를 이용한 측정장치 | |
JP2022114416A (ja) | 電気化学測定装置及び電気化学測定方法 | |
Gobet et al. | Microelectrode array sensor for water quality monitoring | |
Afonso et al. | Voltammetric studies on the electrochemical reduction of methylmercury in HCl aqueous medium at a carbon microelectrode | |
Punrat et al. | Determination of Arsenic (III) by Sequential Injection/Anodic Stripping Voltammetry (SI/ASV) Using In-situ Thin Film-Modified Screen-Printed Carbon Electrode (SPCE) Original Paper | |
EP1219957A1 (en) | Electronic tongue as ozone detector | |
Wang et al. | Determination of cadmium in a sequential injection lab-on-valve system with voltammetric detection using a morin modified electrode | |
Paukpol et al. | Bismuth coated screen-printed electrode platform for greener anodic stripping voltammetric determination of cadmium and lead | |
Duong et al. | Determination of inorganic arsenic As (III) in water by linear sweep anodic stripping voltammetry using gold ultra-microelectrode array |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A524 | Written submission of copy of amendment under article 19 pct |
Free format text: JAPANESE INTERMEDIATE CODE: A525 Effective date: 20180405 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180830 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180830 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20190529 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190702 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20191002 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200204 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20200428 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20200703 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200730 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20201222 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210118 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6827047 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |