JPH04223257A - Electrode for measurement - Google Patents
Electrode for measurementInfo
- Publication number
- JPH04223257A JPH04223257A JP2406929A JP40692990A JPH04223257A JP H04223257 A JPH04223257 A JP H04223257A JP 2406929 A JP2406929 A JP 2406929A JP 40692990 A JP40692990 A JP 40692990A JP H04223257 A JPH04223257 A JP H04223257A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- conductive
- supporting body
- conductive filaments
- filament
- 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.)
- Granted
Links
- 238000005259 measurement Methods 0.000 title claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 10
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 102000004190 Enzymes Human genes 0.000 abstract description 21
- 108090000790 Enzymes Proteins 0.000 abstract description 21
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 230000004043 responsiveness Effects 0.000 abstract description 5
- 239000004593 Epoxy Substances 0.000 abstract description 2
- 239000004642 Polyimide Substances 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 abstract description 2
- 150000004767 nitrides Chemical class 0.000 abstract description 2
- 229920001721 polyimide Polymers 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 2
- 238000006911 enzymatic reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000012209 glucono delta-lactone Nutrition 0.000 description 1
- 229960003681 gluconolactone Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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
- G01N27/28—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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は例えば酵素サンサーに用
いられる測定用電極に関し、さらに詳しくは、感度と応
答性とに優れた測定用電極に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a measuring electrode used, for example, in an enzyme sensor, and more particularly to a measuring electrode with excellent sensitivity and responsiveness.
【０００２】0002
【従来の技術】従来から、酵素を固定した高分子膜状物
と測定用電極とで電子移行を行なわせ、酵素反応を検出
する酵素センサーが開発されている。BACKGROUND OF THE INVENTION Enzyme sensors have been developed that detect enzymatic reactions by causing electron transfer between a polymer membrane on which an enzyme is immobilized and a measuring electrode.
【０００３】その測定用電極としては金属製や炭素材料
製の棒状体あるいは筒状体などが用いられているが、こ
のような電極を用いた酵素センサーには応答性や感度の
点で改良の余地が残されている。[0003] Rod-shaped or cylindrical bodies made of metal or carbon materials are used as measurement electrodes, but enzyme sensors using such electrodes require improvements in terms of response and sensitivity. There is room left.
【０００４】本発明は上記事情に鑑みてなされたもので
ある。The present invention has been made in view of the above circumstances.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、より
優れた感度と応答性とを有する測定用電極を提供するこ
とにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a measuring electrode having better sensitivity and responsiveness.
【０００６】[0006]
【前記課題を解決するための手段】前記目的を達成する
ための本発明は、非導電性の支持体中に複数の導電性フ
ィラメントが平行に埋設されるとともに、該複数の導電
性フィラメントが前記支持体の一端部より突出している
ことを特徴とする測定用電極である。[Means for Solving the Problems] In order to achieve the above object, the present invention includes a plurality of conductive filaments buried in parallel in a non-conductive support, and a plurality of conductive filaments that are This is a measurement electrode characterized by protruding from one end of a support.
【０００７】また、前記導電性フィラメントは、炭素繊
維のフィラメントまたは表面に金属膜を形成した炭素繊
維であるのが好適である。[0007] The conductive filament is preferably a carbon fiber filament or a carbon fiber having a metal film formed on its surface.
【０００８】[0008]
【作用】本発明の測定用電極は、非導電性の支持体中に
複数の導電性フィラメントが平行に埋設されるとともに
、該複数の導電性フィラメントが前記支持体の一端部よ
り突出している。[Operation] In the measuring electrode of the present invention, a plurality of conductive filaments are embedded in parallel in a non-conductive support, and the plurality of conductive filaments protrude from one end of the support.
【０００９】このような測定用電極は、いわば多数のフ
ィラメント状微小電極の集合体であり、例えば酵素セン
サーとして用いると、各導電性フィラメントが作用電極
として作用するので、高速応答性と優れた感度とを発揮
することができる。[0009] Such measurement electrodes are, so to speak, an assembly of many filament-like microelectrodes, and when used, for example, as an enzyme sensor, each conductive filament acts as a working electrode, resulting in high-speed response and excellent sensitivity. and can demonstrate.
【００１０】0010
【実施例】−測定用電極の構造−
本発明の測定用電極は、図１に示すように、基本的に非
導電性の支持体１中に複数の導電性フィラメント２を平
行に埋設し、かつ該複数の導電性フィラメント２を前記
支持体１の一端部１ａより突出させてなる。[Example] - Structure of measurement electrode - As shown in Fig. 1, the measurement electrode of the present invention has a plurality of conductive filaments 2 buried in parallel in a basically non-conductive support 1, The plurality of conductive filaments 2 are made to protrude from one end 1a of the support 1.
【００１１】各構成要素の詳細は以下の通りである。[0011] Details of each component are as follows.
【００１２】−支持体−本発明に用いる支持体としては
、絶縁性を備えている限りその材質に特に制限はなく、
例えばエポキシ、ポリイミド、ポリウレタン、ポリエチ
レン、ポリ塩化ビニルなどの樹脂；シリコン、アルミニ
ウム、チタンなどの酸化物、窒化物、炭化物；各種セラ
ミックスならびに各種サーメットなどを挙げることがで
きる。- Support - The material of the support used in the present invention is not particularly limited as long as it has insulating properties.
Examples include resins such as epoxy, polyimide, polyurethane, polyethylene, and polyvinyl chloride; oxides, nitrides, and carbides such as silicon, aluminum, and titanium; various ceramics, and various cermets.
【００１３】前記支持体の長さ、径、形状については、
測定用電極の使用目的に応じて適宜に設定されるもので
あり、特に制約はない。Regarding the length, diameter, and shape of the support body,
It is set appropriately depending on the purpose of use of the measurement electrode, and there are no particular restrictions.
【００１４】−導電性フィラメント−
前記支持体に端部を除いて埋設される導電性フィラメン
トとしては、導電性を備えている限り任意の材料のフィ
ラメントを用いることが可能である。-Conductive filament- As the conductive filament buried in the support except for its ends, a filament of any material can be used as long as it has conductivity.
【００１５】その材料を挙げると、炭素繊維；白金や金
、銀等に代表される金属；導電性高分子などがある。
これらのうちでも、炭素繊維が特に好ましい。Examples of such materials include carbon fiber; metals such as platinum, gold, and silver; and conductive polymers. Among these, carbon fiber is particularly preferred.
【００１６】炭素繊維が特に好ましい理由としては、導
電性が良好であることに加え、酵素センサーなどに用い
た場合に水素や酸素ガス発生の過電圧が大きいこと、電
極の先端表面から突出したフィラメント間に、酵素や電
子伝達物質等を含む機能性材料を保持・固定し易いこと
、繊維径を３μｍから１００ μｍと自由に選択するこ
とができること、任意の断面形状のものが選べること、
などを挙げることができる。[0016] The reasons why carbon fiber is particularly preferable are that in addition to its good conductivity, when used in enzyme sensors etc., the overvoltage of hydrogen and oxygen gas generation is large, and that the carbon fiber is It is easy to hold and fix functional materials including enzymes and electron transfer substances, the fiber diameter can be freely selected from 3 μm to 100 μm, and any cross-sectional shape can be selected.
etc. can be mentioned.
【００１７】なお、導電性フィラメントとして上記の金
属フィラメントが望ましい場合があるが、細い金属フィ
ラメントでは直径２０μｍ前後にすると、切れ易いとい
う問題がある。[0017] Although the above metal filament is desirable as the conductive filament in some cases, there is a problem in that a thin metal filament with a diameter of about 20 μm is easily broken.
【００１８】このような場合も、上記炭素繊維の表面に
目的とする金属膜を蒸着、電着あるいは無電解メッキな
どの手段により形成させれば、容易に金属フィラメント
を製作することができる。しかも、この金属フィラメン
トは下地フィラメントが金属である場合と異なり、目的
金属膜のピンホールの有無は問題とならない。Even in such a case, a metal filament can be easily produced by forming a desired metal film on the surface of the carbon fiber by means such as vapor deposition, electrodeposition, or electroless plating. Moreover, unlike the case where the base filament is metal, the presence or absence of pinholes in the target metal film does not matter with this metal filament.
【００１９】本発明に用いる導電性フィラメントは前述
したように、支持体の一端部より突出しているが、その
突出部分の長さ、導電性フィラメント同士の間隔、導電
性フィラメントの径を目的に応じて制御することが可能
である。As mentioned above, the conductive filaments used in the present invention protrude from one end of the support, and the length of the protruding portion, the spacing between the conductive filaments, and the diameter of the conductive filaments may be adjusted depending on the purpose. It is possible to control the
【００２０】例えば、図１および図３において、各導電
性フィラメントの径をｄ、導電性フィラメント同士の間
隔をＳ、突出部分の長さをｋとすれば、ｋおよびｄを被
測定物質の拡散層の厚さよりも小さく、Ｓを被測定物質
の拡散層の厚さよりも大きくすると、高速応答性（π方
向）が得られる。For example, in FIGS. 1 and 3, if the diameter of each conductive filament is d, the interval between the conductive filaments is S, and the length of the protruding portion is k, then k and d are the diffusion of the substance to be measured. When S is smaller than the thickness of the layer and larger than the thickness of the diffusion layer of the substance to be measured, high-speed response (in the π direction) can be obtained.
【００２１】また、ｋがｄに比べて大きければ大きい程
、より高い感度を得ることができる。Furthermore, the larger k is compared to d, the higher the sensitivity can be obtained.
【００２２】−測定用電極の応用−
本発明の測定用電極は、例えば酵素サンサーの作用電極
として好適に用いることができる。- Application of measurement electrode - The measurement electrode of the present invention can be suitably used, for example, as a working electrode of an enzyme sensor.
【００２３】例えば図４に示す酵素センサーは、作用電
極である本発明の測定用電極Ａと、この側面に形成した
対照電極３とを備えている。For example, the enzyme sensor shown in FIG. 4 includes a measuring electrode A of the present invention, which is a working electrode, and a reference electrode 3 formed on the side surface of the measuring electrode A.
【００２４】測定用電極Ａの先端部１ａから突出した導
電性フィラメント２は、機能性材料としての高分子膜状
物４に埋め込まれている。The conductive filament 2 protruding from the tip 1a of the measuring electrode A is embedded in a polymer film 4 as a functional material.
【００２５】高分子膜状物４は、例えば高分子マトリッ
クス中に酵素および／または酸化還元物質を固定してな
るもので、酸化還元物質および／または酵素は、そのま
ま高分子マトリックス中に添加してもよいが、好ましく
は高分子材料に共有結合により固定し、得られる固定粒
子を高分子マトリックス中に配合するのがよい。もちろ
ん、本発明の測定用電極の特徴として、上記酸化還元物
質および／または酵素を導電性フィラメントの表面に直
接固定することも可能である。The polymer membrane 4 is, for example, one in which an enzyme and/or a redox substance is immobilized in a polymer matrix, and the redox substance and/or enzyme is added to the polymer matrix as is. However, it is preferable to immobilize the particles to a polymeric material by covalent bonding and blend the resulting immobilized particles into a polymeric matrix. Of course, as a feature of the measurement electrode of the present invention, it is also possible to directly immobilize the redox substance and/or enzyme on the surface of the conductive filament.
【００２６】かかる酵素センサーによる測定では、まず
被検体中の生化学物質、例えば試料溶液中のグルコース
が前記高分子膜状物中の酸化型の酵素により酵素反応を
受け、グルコノラクトンと水素イオンとに変化する。こ
れにより酵素は還元型酵素に変わる。次に、この還元型
酵素は酸化型の酸化還元物質と反応して、再び酸化型酵
素に変化する一方、酸化型の酸化還元物質は還元型に変
化する。この還元型の酸化還元物質は作用電極に電子を
放出し、再び酸化型に変化する。その結果、作用電極と
対照電極との間にグルコース濃度に比例した電流が流れ
、この電流値によって間接的にグルコース濃度が決定さ
れる。In measurement using such an enzyme sensor, first, a biochemical substance in the specimen, such as glucose in a sample solution, undergoes an enzymatic reaction by an oxidized enzyme in the polymeric membrane, and is converted into gluconolactone and hydrogen ions. and change. This converts the enzyme into a reduced enzyme. Next, this reduced enzyme reacts with the oxidized redox substance and changes back into the oxidized enzyme, while the oxidized redox substance changes into the reduced form. This reduced redox substance releases electrons to the working electrode and changes back to its oxidized form. As a result, a current proportional to the glucose concentration flows between the working electrode and the reference electrode, and the glucose concentration is indirectly determined by this current value.
【００２７】[0027]
【発明の効果】本発明の測定用電極は、非導電性の支持
体中に複数の導電性フィラメントを平行に埋設し、該導
電性フィラメントを前記支持体の一端部より突出させる
ものであり、目的に応じてその形状を制御することが可
能であるので、例えば酵素センサーの作用電極として用
いた場合に、優れた感度と応答性とを発揮することがで
きる。[Effects of the Invention] The measurement electrode of the present invention has a plurality of conductive filaments buried in parallel in a non-conductive support, and the conductive filaments protrude from one end of the support, Since its shape can be controlled depending on the purpose, it can exhibit excellent sensitivity and responsiveness when used as a working electrode of an enzyme sensor, for example.
【図１】本発明の測定用電極の概略的説明図である。FIG. 1 is a schematic explanatory diagram of a measurement electrode of the present invention.
【図２】本発明の測定用電極の一例を示す斜視図である
。FIG. 2 is a perspective view showing an example of a measurement electrode of the present invention.
【図３】図２のＩＩＩ −ＩＩＩ 線に沿う断面図であ
る。FIG. 3 is a sectional view taken along line III-III in FIG. 2;
【図４】本発明の測定用電極を適用した酵素センサーの
一例を示す断面図である。FIG. 4 is a sectional view showing an example of an enzyme sensor to which the measurement electrode of the present invention is applied.
１ 支持体 １ａ 支持体の一端部 ２ 導電性フィラメント 1 Support 1a One end of the support 2 Conductive filament
Claims (2)
ィラメントが平行に埋設されるとともに、該複数の導電
性フィラメントが前記支持体の一端部より突出している
ことを特徴とする測定用電極。1. A measuring device characterized in that a plurality of conductive filaments are buried in parallel in a non-conductive support, and the plurality of conductive filaments protrude from one end of the support. electrode.
のフィラメントまたは表面に金属膜を形成した炭素繊維
である請求項１に記載の測定用電極。2. The measurement electrode according to claim 1, wherein the conductive filament is a carbon fiber filament or a carbon fiber with a metal film formed on its surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2406929A JP2812455B2 (en) | 1990-12-26 | 1990-12-26 | Measurement electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2406929A JP2812455B2 (en) | 1990-12-26 | 1990-12-26 | Measurement electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04223257A true JPH04223257A (en) | 1992-08-13 |
| JP2812455B2 JP2812455B2 (en) | 1998-10-22 |
Family
ID=18516547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2406929A Expired - Fee Related JP2812455B2 (en) | 1990-12-26 | 1990-12-26 | Measurement electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2812455B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995004928A1 (en) * | 1993-08-11 | 1995-02-16 | Commonwealth Scientific And Industrial Research Organisation | A microelectrode assembly |
| JP2000512743A (en) * | 1996-05-16 | 2000-09-26 | センデックス メディカル，インク． | Sensor having microminiature through-holes and method of manufacturing such a sensor |
| WO2004003538A2 (en) * | 2002-06-28 | 2004-01-08 | November Aktiengesellschaft | Multi-electrode device for detecting an analyte |
| JPWO2007086268A1 (en) * | 2006-01-24 | 2009-06-18 | 独立行政法人産業技術総合研究所 | Microelectrode and manufacturing method thereof |
| WO2010103174A1 (en) * | 2009-03-09 | 2010-09-16 | Oulun Yliopisto | A carbon fiber multichannel electrode for measuring electrical and chemical activity in biological tissue and a process for making the electrode |
| WO2011095313A1 (en) * | 2010-02-02 | 2011-08-11 | Roche Diagnostics Gmbh | Biosensor and methods for manufacturing |
| JP2013164375A (en) * | 2012-02-13 | 2013-08-22 | National Institute Of Advanced Industrial & Technology | Heat-proof pressure-resistant corrosion resistance microelectrode |
| WO2014139494A1 (en) * | 2013-03-12 | 2014-09-18 | Westfälische Wilhelms-Universität Münster | Micro electrode liquid measurement cell |
-
1990
- 1990-12-26 JP JP2406929A patent/JP2812455B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995004928A1 (en) * | 1993-08-11 | 1995-02-16 | Commonwealth Scientific And Industrial Research Organisation | A microelectrode assembly |
| JP2000512743A (en) * | 1996-05-16 | 2000-09-26 | センデックス メディカル，インク． | Sensor having microminiature through-holes and method of manufacturing such a sensor |
| WO2004003538A2 (en) * | 2002-06-28 | 2004-01-08 | November Aktiengesellschaft | Multi-electrode device for detecting an analyte |
| WO2004003538A3 (en) * | 2002-06-28 | 2004-04-22 | November Ag Molekulare Medizin | Multi-electrode device for detecting an analyte |
| JPWO2007086268A1 (en) * | 2006-01-24 | 2009-06-18 | 独立行政法人産業技術総合研究所 | Microelectrode and manufacturing method thereof |
| JP4982899B2 (en) * | 2006-01-24 | 2012-07-25 | 独立行政法人産業技術総合研究所 | Microelectrode and manufacturing method thereof |
| WO2010103174A1 (en) * | 2009-03-09 | 2010-09-16 | Oulun Yliopisto | A carbon fiber multichannel electrode for measuring electrical and chemical activity in biological tissue and a process for making the electrode |
| WO2011095313A1 (en) * | 2010-02-02 | 2011-08-11 | Roche Diagnostics Gmbh | Biosensor and methods for manufacturing |
| US8721850B2 (en) | 2010-02-02 | 2014-05-13 | Roche Diagnostics Operations, Inc. | Biosensor and methods for manufacturing |
| JP2013164375A (en) * | 2012-02-13 | 2013-08-22 | National Institute Of Advanced Industrial & Technology | Heat-proof pressure-resistant corrosion resistance microelectrode |
| WO2014139494A1 (en) * | 2013-03-12 | 2014-09-18 | Westfälische Wilhelms-Universität Münster | Micro electrode liquid measurement cell |
| DE202014010453U1 (en) | 2013-03-12 | 2015-09-10 | Westfälische Wilhelms-Universität Münster | Micro electrode fluid measuring cell (MDE) |
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| Publication number | Publication date |
|---|---|
| JP2812455B2 (en) | 1998-10-22 |
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