JPH02240555A - Glucose sensor - Google Patents
Glucose sensorInfo
- Publication number
- JPH02240555A JPH02240555A JP1059521A JP5952189A JPH02240555A JP H02240555 A JPH02240555 A JP H02240555A JP 1059521 A JP1059521 A JP 1059521A JP 5952189 A JP5952189 A JP 5952189A JP H02240555 A JPH02240555 A JP H02240555A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- ferrocene
- resin film
- compd
- contg
- 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
- 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 title claims abstract description 18
- 239000008103 glucose Substances 0.000 title claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 108010015776 Glucose oxidase Proteins 0.000 claims abstract description 6
- 239000004366 Glucose oxidase Substances 0.000 claims abstract description 6
- 229940116332 glucose oxidase Drugs 0.000 claims abstract description 6
- 235000019420 glucose oxidase Nutrition 0.000 claims abstract description 6
- -1 ferrocene compound Chemical class 0.000 claims description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 11
- 239000010931 gold Substances 0.000 abstract description 8
- 229910052737 gold Inorganic materials 0.000 abstract description 8
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011521 glass Substances 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 5
- 229910021607 Silver chloride Inorganic materials 0.000 abstract description 3
- 239000012153 distilled water Substances 0.000 abstract description 3
- 229910052709 silver Inorganic materials 0.000 abstract description 3
- 239000004332 silver Substances 0.000 abstract description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 230000002093 peripheral effect Effects 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 238000005259 measurement Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YVXDRFYHWWPSOA-BQYQJAHWSA-N 1-methyl-4-[(e)-2-phenylethenyl]pyridin-1-ium Chemical group C1=C[N+](C)=CC=C1\C=C\C1=CC=CC=C1 YVXDRFYHWWPSOA-BQYQJAHWSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- GPRSOIDYHMXAGW-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopentanecarboxylic acid iron Chemical compound [CH-]1[CH-][CH-][C-]([CH-]1)C(=O)O.[CH-]1C=CC=C1.[Fe] GPRSOIDYHMXAGW-UHFFFAOYSA-N 0.000 description 1
- WGZWXARAMMXBKD-UHFFFAOYSA-N cyclopenta-1,3-diene iron(2+) N,N,5-trimethylcyclopenta-1,3-dien-1-amine Chemical compound [Fe++].c1cc[cH-]c1.CN(C)[c-]1cccc1C WGZWXARAMMXBKD-UHFFFAOYSA-N 0.000 description 1
- VGBAECKRTWHKHC-UHFFFAOYSA-N cyclopenta-1,3-diene;1-ethenylcyclopenta-1,3-diene;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.[CH2-]C=C1C=CC=C1 VGBAECKRTWHKHC-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 150000002303 glucose derivatives Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- YTOVAWUSMUMHIM-UHFFFAOYSA-N iron(2+);5-methylcyclopenta-1,3-diene Chemical compound [Fe+2].C[C-]1C=CC=C1.C[C-]1C=CC=C1 YTOVAWUSMUMHIM-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、グルコースセンサに関する。更に詳しくは、
フェロセン化合物を作用極に付着せしめたグルコースセ
ンサに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a glucose sensor. For more details,
The present invention relates to a glucose sensor in which a ferrocene compound is attached to a working electrode.
フェロセン化合物を電極面に付着せしめて作用極とした
グルコースセンサが、Diabstologia第29
巻第817頁(1986)に記載されている。かかるグ
ルコースセンサは、以下の如き原理によって作動す極
[COD ニゲルコースオキシダーゼ]即ち、グルコー
ス1分子が酸化されるのに、2電子の作用極への移動が
行われるので、これを電流値として検出することができ
る。この際、フェロセン化合物は、電子メデイエータと
して作用する。A glucose sensor with a ferrocene compound attached to the electrode surface as a working electrode was published in Diabstologia No. 29.
Volume 817 (1986). Such a glucose sensor operates on the following principle: when one molecule of glucose is oxidized, two electrons are transferred to the working electrode, and this is detected as a current value. can do. At this time, the ferrocene compound acts as an electron mediator.
しかしながら、上記方法では、フェロセン化合物の作用
極への付着は、単なる吸着法によっているので、測定が
長時間に及んだりすると、付着フェロセン化合物が測定
溶液中へ溶出し、それの正確な測定を不可能とさせるよ
うな事態に至ることがある。However, in the above method, the adhesion of the ferrocene compound to the working electrode is based on a simple adsorption method, so if the measurement continues for a long time, the adhering ferrocene compound will elute into the measurement solution, making it impossible to accurately measure it. This can lead to situations that seem impossible.
このような流出を妨げる措置として、フェロセン化合物
を何らかの手段で作用極表面に結合さセることが考えら
れるが、その場合には感度の低下を免れることができな
い。即ち、フェロセン化合物は、遊離な状態で存在する
ことが感度の点からは望ましいといえる。As a measure to prevent such outflow, it is conceivable to bind a ferrocene compound to the surface of the working electrode by some means, but in that case, a decrease in sensitivity cannot be avoided. That is, it can be said that it is desirable from the viewpoint of sensitivity that the ferrocene compound exists in a free state.
本発明は、フェロセン化合物の測定溶液中への溶出とい
った事態を避けてセンサとしての耐久性を付与せしめ、
かつ感度の点でもすぐれたグルコースセンサを提供する
ことを目的としている。The present invention provides durability as a sensor by avoiding the elution of a ferrocene compound into a measurement solution,
The present invention aims to provide a glucose sensor that is also excellent in sensitivity.
かかる目的を達成せしめる本発明のグルコースセンサで
は、作用極を一つの電極とするグルコースセンサにおい
て、電極面にフェロセン化合物含有光硬化樹脂膜および
タルコースオキシダーゼ含有光硬化樹脂膜を順次形成せ
しめた作用極が用いられる。The glucose sensor of the present invention that achieves the above object includes a working electrode in which a photocurable resin film containing a ferrocene compound and a photocurable resin film containing talcose oxidase are sequentially formed on the electrode surface. is used.
このグルコースセンサでは、作用極以外に、対極あるい
は対極と参照極とがいずれも線状体などの電極として用
いられる0作用極材料としては金、チタン、カーボンな
どが用いられ、対極材料としては白金、金などが用いら
れ、また参照極としては、銀/塩化銀電極などが用いら
れる。In this glucose sensor, in addition to the working electrode, the counter electrode or both the counter electrode and the reference electrode are used as electrodes such as linear bodies.The working electrode material is gold, titanium, carbon, etc., and the counter electrode material is platinum. , gold, etc., and as a reference electrode, a silver/silver chloride electrode or the like is used.
フェロセン化合物としては、フェロセン[ビス(シクロ
ペンタジェニル)鉄(■)]、]1.1’−ジメチルフ
ェロセンビニルフェロセン、フェロセンカルボン酸、ジ
メチルアミノメチルフェロセンなどが用いられ、好まし
くはl、1′−ジメチルフェロセンが用いられる。As the ferrocene compound, ferrocene [bis(cyclopentadienyl)iron (■)], ]1,1'-dimethylferrocene vinylferrocene, ferrocenecarboxylic acid, dimethylaminomethylferrocene, etc. are used, preferably l, 1' -dimethylferrocene is used.
フェロセン化合物含有光硬化樹脂膜の形成は、これらの
フェロセン化合物をアセトン、メチルエチルケトンなど
のそれの可溶性溶媒0.2m(lに約1〜10鵬g、好
ましくは約5■程度添加して溶解させた後、スチルバゾ
リウム基などを光硬化性基として含有する水溶性光硬化
性樹脂約0.O1〜0.5g、好ましくは約0.1g程
度をそこに添加し、このようにして調製された溶液を電
極面に塗布、乾燥させ、光照射して硬化させることによ
り行われる。The ferrocene compound-containing photocurable resin film was formed by adding and dissolving these ferrocene compounds in a soluble solvent such as acetone or methyl ethyl ketone by adding about 1 to 10 g, preferably about 5 μg, to 0.2 m (l) of the ferrocene compound. After that, about 0.01 to 0.5 g, preferably about 0.1 g, of a water-soluble photocurable resin containing a stilbazolium group or the like as a photocurable group is added thereto, and the solution thus prepared is mixed. This is done by coating the electrode surface, drying it, and curing it by irradiating it with light.
次いで行われるグルコースオキシダーゼ含有光硬化樹脂
膜の形成は、フェロセン化合物含有光硬化樹脂膜上に、
蒸留水0.4mmに約10〜50■、好ましくは約30
■程度のグルコースオキシダーゼおよび約0.1〜1g
、好ましくは約0.5g程度の光硬化性樹脂を添加した
水溶液を塗布し、乾燥、光硬化させることにより行われ
る。Next, the formation of the glucose oxidase-containing photocurable resin film is performed by depositing, on the ferrocene compound-containing photocurable resin film,
About 10 to 50 cm, preferably about 30 cm to 0.4 mm of distilled water
■Glucose oxidase and about 0.1-1g
This is preferably carried out by applying an aqueous solution containing about 0.5 g of a photocurable resin, drying, and photocuring.
本発明に係るグルコースセンサにあっては、樹脂膜内部
におけるフェロセン化合物の自由度が確保されかつフェ
ロセン化合物が作用極表面の近傍に担持されているので
、感度の点ですぐれている。The glucose sensor according to the present invention has excellent sensitivity because the degree of freedom of the ferrocene compound inside the resin membrane is ensured and the ferrocene compound is supported near the surface of the working electrode.
しかも、フェロセン化合物含有樹脂膜の上に、更にグル
コースオキシダーゼを含有する樹脂膜を形成せしめてい
るので、フェロセン化合物の流出が有効に防止され、セ
ンサとしての耐久性も高められている。Moreover, since the resin film containing glucose oxidase is further formed on the resin film containing the ferrocene compound, leakage of the ferrocene compound is effectively prevented, and the durability of the sensor is improved.
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
実施例
長さ3011鳳、直径0.2mmの金線2本を3m間隔
でガラス板上に並べ、それぞれの端部3■を残してエポ
キシ樹脂でガラス板上に接着した。Example Two gold wires each having a length of 3011 mm and a diameter of 0.2 mm were arranged on a glass plate at 3 m intervals and adhered to the glass plate with epoxy resin, leaving 3 inches at each end.
この中の1本の金線のガラス板上に接着されなかった端
部の外周面に、次のようにしてフェロセン化合物含有光
硬化樹脂膜を形成させた。即ち、1.1′−ジメチルフ
ェロセン5aIgをアセトン0.2+*Rに溶解し、そ
こにスチルバゾリウム基含有ポリビニルアルコール系光
硬化性樹脂0.1gを添加して調製した溶液を、上記金
線端部に塗布し、室温で1時間乾燥させた後、紫外線(
波長4000人)を30秒間照射した。A photocurable resin film containing a ferrocene compound was formed on the outer peripheral surface of the end of one of the gold wires that was not bonded to the glass plate in the following manner. That is, a solution prepared by dissolving 1.1'-dimethylferrocene 5aIg in acetone 0.2+*R and adding thereto 0.1 g of a stilbazolium group-containing polyvinyl alcohol photocurable resin was added to the end of the gold wire. After drying at room temperature for 1 hour, apply ultraviolet light (
4000 wavelength) was irradiated for 30 seconds.
このようして、形成されたフェロセン化合物含有光硬化
樹脂膜上に、グルコースオキシダーゼ301Ig、上記
光硬化性樹脂0.5gおよび蒸留水0.4ra Qから
調製された水溶液を塗布し、室温で1時間乾燥させた後
、紫外線照射を30秒間行った。An aqueous solution prepared from glucose oxidase 301Ig, 0.5 g of the above photocurable resin and 0.4 raQ of distilled water was coated on the ferrocene compound-containing photocurable resin film thus formed, and the mixture was kept at room temperature for 1 hour. After drying, ultraviolet rays were irradiated for 30 seconds.
このようにして得られた1、1’−ジメチルフェロセン
含有、グルコースオキシダーゼ固定化金電極を作用極と
し、未処理の金線を対極とし、更に銀/塩化銀電極を参
照極とするグルコースセンサについて、ポテンショスタ
ット、ファンクションジェネレータを用いて、その特性
を測定した。Regarding a glucose sensor using the thus obtained 1,1'-dimethylferrocene-containing glucose oxidase-immobilized gold electrode as a working electrode, an untreated gold wire as a counter electrode, and a silver/silver chloride electrode as a reference electrode. , a potentiostat, and a function generator to measure its characteristics.
参照極−作用極間の電位差を200mV、また作用極一
対極間の電位差を50mVとし、50mMリン酸緩衝液
(PH7,0,25℃)中で反応を行った。その結果、
グルコース最終濃度100B/dQに対し、定常値で3
0n^の電流が検出された。The potential difference between the reference electrode and the working electrode was 200 mV, and the potential difference between the working electrode and the opposite electrode was 50 mV, and the reaction was carried out in a 50 mM phosphate buffer (pH 7, 0, 25° C.). the result,
For a final glucose concentration of 100B/dQ, the steady value is 3
A current of 0 n^ was detected.
このような測定を行った後、4℃の空気中に保存し、所
定日数経過後測定−保存をくり返し、1100ta/
dt!濃度のグルコースに対する定常値(3回の平均値
)を測定し、それの耐久性を確認した。After performing such measurements, it was stored in the air at 4°C, and after a predetermined number of days had passed, the measurement and storage were repeated until it reached 1100ta/
dt! The steady-state value (average value of three measurements) of the glucose concentration was measured to confirm its durability.
1遵則致 定11玩柱 全く応答を示さなかった。1 Compliance with 11 standards There was no response at all.
Claims (1)
て、電極面にフェロセン化合物含有光硬化樹脂膜および
グルコースオキシダーゼ含有光硬化樹脂膜を順次形成せ
しめた作用極が用いられたグルコースセンサ。1. A glucose sensor using a working electrode as one electrode, in which a photocurable resin film containing a ferrocene compound and a photocurable resin film containing glucose oxidase are sequentially formed on the electrode surface.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1059521A JP2748516B2 (en) | 1989-03-14 | 1989-03-14 | Glucose sensor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1059521A JP2748516B2 (en) | 1989-03-14 | 1989-03-14 | Glucose sensor |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02240555A true JPH02240555A (en) | 1990-09-25 |
JP2748516B2 JP2748516B2 (en) | 1998-05-06 |
Family
ID=13115652
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1059521A Expired - Lifetime JP2748516B2 (en) | 1989-03-14 | 1989-03-14 | Glucose sensor |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2748516B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6547954B2 (en) | 1996-03-12 | 2003-04-15 | Matsushita Electric Industrial Co., Ltd. | Biosensor and method for quantitating biochemical substrate using the same |
JP2007506968A (en) * | 2003-09-26 | 2007-03-22 | エージェンシー フォー サイエンス,テクノロジー アンド リサーチ | Sensor array integrated electrochemical chip, formation method thereof, and electrode coating |
US7348128B2 (en) | 2002-12-10 | 2008-03-25 | Toyo Gosei Co., Ltd. | Photosensitive resin based on saponified polyvinyl acetate photosensitive resin composition, method of forming aqueous gel from the same, and compound |
US7408002B2 (en) | 2002-11-14 | 2008-08-05 | Toyo Gosei Co., Ltd | Photosensitive resin composition and process for the formation of hydrogel |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5769667A (en) * | 1980-10-16 | 1982-04-28 | Matsushita Electric Ind Co Ltd | Electrode |
JPS62235557A (en) * | 1986-04-05 | 1987-10-15 | Omron Tateisi Electronics Co | Enzyme electrode |
-
1989
- 1989-03-14 JP JP1059521A patent/JP2748516B2/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5769667A (en) * | 1980-10-16 | 1982-04-28 | Matsushita Electric Ind Co Ltd | Electrode |
JPS62235557A (en) * | 1986-04-05 | 1987-10-15 | Omron Tateisi Electronics Co | Enzyme electrode |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6547954B2 (en) | 1996-03-12 | 2003-04-15 | Matsushita Electric Industrial Co., Ltd. | Biosensor and method for quantitating biochemical substrate using the same |
US7408002B2 (en) | 2002-11-14 | 2008-08-05 | Toyo Gosei Co., Ltd | Photosensitive resin composition and process for the formation of hydrogel |
US7348128B2 (en) | 2002-12-10 | 2008-03-25 | Toyo Gosei Co., Ltd. | Photosensitive resin based on saponified polyvinyl acetate photosensitive resin composition, method of forming aqueous gel from the same, and compound |
JP2007506968A (en) * | 2003-09-26 | 2007-03-22 | エージェンシー フォー サイエンス,テクノロジー アンド リサーチ | Sensor array integrated electrochemical chip, formation method thereof, and electrode coating |
Also Published As
Publication number | Publication date |
---|---|
JP2748516B2 (en) | 1998-05-06 |
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