JPH0469564A - Enzyme electrode and production thereof - Google Patents
Enzyme electrode and production thereofInfo
- Publication number
- JPH0469564A JPH0469564A JP2182963A JP18296390A JPH0469564A JP H0469564 A JPH0469564 A JP H0469564A JP 2182963 A JP2182963 A JP 2182963A JP 18296390 A JP18296390 A JP 18296390A JP H0469564 A JPH0469564 A JP H0469564A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- enzyme
- prescribed
- immersed
- concn
- 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.)
- Pending
Links
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 48
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229940088598 enzyme Drugs 0.000 abstract description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 abstract description 19
- 239000001301 oxygen Substances 0.000 abstract description 19
- 238000005259 measurement Methods 0.000 abstract description 14
- 108010015776 Glucose oxidase Proteins 0.000 abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004366 Glucose oxidase Substances 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001718 carbodiimides Chemical class 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 229940116332 glucose oxidase Drugs 0.000 abstract description 4
- 235000019420 glucose oxidase Nutrition 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 abstract description 2
- 229940046892 lead acetate Drugs 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 3
- 239000002253 acid Substances 0.000 abstract 1
- 239000000872 buffer Substances 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 230000003100 immobilizing effect Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 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 8
- 239000008103 glucose Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 239000008280 blood Substances 0.000 description 5
- 210000004369 blood Anatomy 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 108010093096 Immobilized Enzymes Proteins 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000008351 acetate buffer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
Landscapes
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
この発明は、被測定検体中の生化学物ｉｉｍ度を酵素反
応を利用して電気化学的に測定する酵素電極に間し、詳
しく言えばきわめて低い酸素濃度溶液中でも測定可能な
酵素電極に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Industrial application field This invention is an enzyme electrode that electrochemically measures the degree of biochemical IIM in a sample to be measured using an enzymatic reaction. In particular, it relates to an enzyme electrode that can perform measurements even in solutions with extremely low oxygen concentrations.
（ロ）従来の技術
従来の酵素電極は、作用電極として白金電極、対照電極
として銀からなる下地電極の電極面近傍に薄膜状の固定
化酵素膜を形成あるいは装着してなるものである。例え
ばグルコースを測定するためには、酵素としてグルコー
スオキシダーゼ（ＣＯＤ）が、固定化酵素化膜に固定さ
れる。ＣＯＤは、固定化酵素膜内で以下の（１）弐〇こ
示される反応を生ぜしめる。(B) Prior Art A conventional enzyme electrode is constructed by forming or attaching a thin film-like immobilized enzyme membrane near the electrode surface of a base electrode consisting of a platinum electrode as a working electrode and a silver electrode as a reference electrode. For example, to measure glucose, the enzyme glucose oxidase (COD) is immobilized on an immobilized enzyme-coated membrane. COD causes the following reactions (1) in the immobilized enzyme membrane.
・・・（１）
この（１）弐の生成物である過酸化水素（Ｈ２Ｏ２）は
、作用電極である白金上で以下の（２）式のように酸化
される。...(1) Hydrogen peroxide (H2O2), which is the product of (1) 2, is oxidized on platinum, which is the working electrode, as shown in equation (2) below.
Ｈｚ Ｏｚ→Ｏｚ＋２Ｈ”＋２６− −−（２）この
時の酸化電流の変化を計測することにより、過酸化水素
（Ｈ２０□）、さらにはグルコースの濃度を知ることが
できる。Hz Oz→Oz+2H"+26- --(2) By measuring the change in the oxidation current at this time, the concentration of hydrogen peroxide (H20□) and further glucose can be determined.
（ハ）発明が解決しようとする課題
上記従来の酵素電極では、（１）弐に示すように酸素（
０□）が不可欠である。従って、被測定検体中の溶存酸
素の影響を大きく受け、低酸素状態では、酵素電極の出
力が極めて小さく、また応答が遅くなり、加えて再現性
が劣化して測定可能な濃度範囲が非常に狭くなる問題が
あった。(c) Problems to be solved by the invention In the above conventional enzyme electrode, (1) As shown in 2, oxygen (
0□) is essential. Therefore, it is greatly affected by dissolved oxygen in the sample to be measured, and in low oxygen conditions, the output of the enzyme electrode is extremely small and the response is slow.In addition, reproducibility deteriorates and the measurable concentration range is extremely limited. There was a problem with it becoming too narrow.
例えば、血液のグルコース濃度の測定において、生体よ
り採血して血液を固定化酵素膜上に付着させる場合には
、血液が空気に触れるため、溶存酸素濃度が極端に低く
なるようなことはなく、計測に支障が生じることは少な
い。これに対して、酵素電極を生体中において、血液の
グルコース濃度を測定する場合には、血液中の溶存酸素
レベルの変動の影響を受け、正確な計測は不可能であっ
た。For example, when measuring blood glucose concentration, when blood is collected from a living body and deposited on an immobilized enzyme membrane, the dissolved oxygen concentration does not become extremely low because the blood is exposed to air. Measurement is rarely hindered. On the other hand, when measuring blood glucose concentration using an enzyme electrode in a living body, accurate measurement has been impossible due to the influence of fluctuations in the dissolved oxygen level in the blood.
この発明は、上記に鑑みなされたもので、低酸素条件下
でも、計測が行なえる酵素電極及びその製造方法の提供
を目的としている。The present invention has been made in view of the above, and aims to provide an enzyme electrode and a method for manufacturing the same that can perform measurements even under low oxygen conditions.
（ニ）課題を解決するための手段及び作用上記課題を解
決するため、第１請求項の酵素電極は、電極感応面に酵
素を固定化してなるものにおいて、前記電極感応面を白
金黒で覆い、この白金黒に酵素を固定化してなることを
特徴とするものである。(d) Means and action for solving the problem In order to solve the above problem, the enzyme electrode according to the first aspect has an enzyme immobilized on the electrode sensitive surface, and the electrode sensitive surface is covered with platinum black. , is characterized by having an enzyme immobilized on this platinum black.
この酵素電極では、電極反応による酸素の自己供給量が
大きい〔上記（２）式の反応の亢進〕ため、低酸素条件
下でも電極出力が大きく、その反応速度の劣化を防止し
、広範な濃度範囲で測定が可能となる。そして、このよ
うに酸素依存性が回避できたので、検体中の溶存酸素レ
ベル変動の影響を受けず、正確な計測が可能となる。This enzyme electrode has a large self-supply amount of oxygen due to the electrode reaction [acceleration of the reaction in equation (2) above], so the electrode output is large even under low oxygen conditions, preventing deterioration of the reaction rate, and allowing a wide range of concentrations. Measurements can be made within this range. Since oxygen dependence can be avoided in this way, accurate measurements can be made without being affected by fluctuations in the dissolved oxygen level in the sample.
また、第２請求項の酵素電極の製造方法は、プラチナイ
ズドカーボンペーバ上の白金を電解処理により白金黒化
し、この白金黒に酵素を固定化するものであり、上記酵
素電極を容易にかつ低価格で量産することを可能とする
。In addition, the method for manufacturing an enzyme electrode according to the second claim is a method in which platinum on a platinized carbon paver is turned into platinum black by electrolytic treatment, and an enzyme is immobilized on this platinum black, so that the enzyme electrode can be easily manufactured. It also enables mass production at low cost.
（ホ）実施例
この発明の一実施例を第１図乃至第６図に基づいて以下
に説明する。(E) Embodiment An embodiment of the present invention will be described below with reference to FIGS. 1 to 6.
第１図及び第２図は、それぞれ実施例酵素電極１の外観
斜視図及び断面図を示している。この実施例ではプラチ
ナイズドカーボンペーパ（以下ＰＣＰと略称する）２を
用いており、その作用電極感応面２ａを除いて、エポキ
シ樹脂３でコーティングされている０作用電極感応面２
ａでは白金は白金黒化されており、グルコースオキシダ
ーゼが固定化されている。４は、接続用のリード線であ
る。FIG. 1 and FIG. 2 show an external perspective view and a sectional view of an example enzyme electrode 1, respectively. In this example, platinized carbon paper (hereinafter abbreviated as PCP) 2 is used, and the working electrode sensitive surface 2 is coated with epoxy resin 3, except for the working electrode sensitive surface 2a.
In a, platinum is blackened with platinum, and glucose oxidase is immobilized. 4 is a lead wire for connection.
次に、この酵素電極１の製造工程を説明する。Next, the manufacturing process of this enzyme electrode 1 will be explained.
まず、ｐｃｐ （米国Ｐｒｏ ｔｅｃｈ社製）を作業上
適切な大きさ（この実施例では５ＩＩＩ１１×１３ｆｆ
ｉＩ１１）に切断し、リード［４を例えば銀ペーストを
用いて接続する。そして、作用電極感応面２ａを除いて
ＰＧＥ１をエポキシ樹脂３でコーティングする。作用電
極感応面２ａの大きさは、例えば５■×５−とされる。First, use PCP (manufactured by Pro tech in the United States) in an appropriate size for the work (in this example, 5III11 x 13ff).
iI11) and connect the lead [4 using, for example, silver paste. Then, PGE 1 is coated with epoxy resin 3 except for working electrode sensitive surface 2a. The size of the working electrode sensitive surface 2a is, for example, 5.times.5.sup.-.
次に白金黒の形成が、以下に説明する定電流電解で行わ
れる。電解液として酢酸鉛（ＣＨ，Ｃ００Ｐｂ）を１０
■を３０ｄの水に溶解した水溶液を、塩化白金Ｍ Ｄｔ
ｚ ｐ ｔ Ｃｊ！＊ ） カ６ Ｘ １０−’Ｍの濃
度になるように調整する。この電解液中に上記電極工を
浸漬し、＋７．５＊Ａで１０分間、−７゜５＊Ａで２分
間、そして再び＋７．５■＾で１０分間の定電流電解を
行う。Formation of platinum black is then performed by constant current electrolysis as described below. 10% lead acetate (CH, C00Pb) as an electrolyte
Platinum chloride M Dt
Z p t Cj! *) Adjust to a concentration of 6 x 10-'M. The electrode was immersed in this electrolytic solution and subjected to constant current electrolysis at +7.5*A for 10 minutes, at -7°5*A for 2 minutes, and again at +7.5*A for 10 minutes.
定電流電解の終了した電極は、さらに０．２ Ｎの硫酸
（Ｈ，Ｓｏ、）中に浸漬し、同様に＋７．５＊Ａで１０
分間、−７，５＊Ａで２分間、再び＋７．５ｇｎＡで１
０分間電解研磨を行う。After constant current electrolysis, the electrode was further immersed in 0.2 N sulfuric acid (H, So,), and similarly heated at +7.5*A for 10
2 min at -7,5*A, then 1 min at +7.5gnA again.
Perform electrolytic polishing for 0 minutes.
このようにして白金黒化した作用電極感応面２ａには、
ＣＯＤが固定化される。The working electrode sensitive surface 2a, which has been blackened with platinum in this way, has
COD is fixed.
まず、作用電極感応面２ａを、エチルアルコール水溶液
で５分間洗浄する。次に、電極をカルボジイミド試薬溶
液に浸漬する。この実施例では、カルボジイミド試薬と
して、■−シクロヘキシルー３−（２−モルホリノエチ
ル）カルボジイミドメト−Ｐ−）ルエンスルホネート（
１−Ｃｙｃｌｏｈｐｘｙｌ−３−（２−ｗｏｒｐｈｏｌ
ｉｎｏｅｔｈｙ）ｃａｒｂｏｄｉｉｓ＋ｉｄｅ Ｍｅ
ｔｈ。First, the working electrode sensitive surface 2a is washed with an aqueous ethyl alcohol solution for 5 minutes. Next, the electrode is immersed in a carbodiimide reagent solution. In this example, the carbodiimide reagent is ■-cyclohexyl-3-(2-morpholinoethyl)carbodiimidometh-P-)luenesulfonate (
1-Cyclohpxyl-3-(2-worphol
inoethy) carbodiis+ide Me
Th.
−ｐ −ｔｏｌｕｅｎｅｓｕｌｆｏｎａｔｅ、略称Ｍｏ
ｒｐｈｏ −ＣＤ Ｉ ）を選定した。このＭｏｒｐｈ
ｏ−ＣＤ Ｉ ０． １３ ｇを、ｐＨ４，５の酢酸
緩衝液２ｍに溶解し、当該電極をこの溶液に９０分間浸
漬する。-p-toluenesulfonate, abbreviation Mo
rpho-CD I) was selected. This Morph
o-CD I 0. 13 g is dissolved in 2 m of acetate buffer at pH 4.5, and the electrode is immersed in this solution for 90 minutes.
次に、ＧＯＤＩＯ■をｐＪ（５，６の酢酸緩衝液２Ｍ１
溶解した酵素液に、上記電極ｌを９０分浸漬し、白金黒
にＣＯＤを固定化する。Next, add GODIO to pJ (5,6 acetate buffer 2M1
The electrode 1 is immersed in the dissolved enzyme solution for 90 minutes to immobilize COD on the platinum black.
このようにして製造された酵素電極１は、使用されるま
で、０．１Ｍの塩化カリウム（ＫＣｊｌりが含まれるｐ
Ｈ７，０のリン酸緩衝液中に浸漬し、４℃で使用するま
で保存される。The enzyme electrode 1 manufactured in this way is kept in a solution containing 0.1M potassium chloride (KCjl) until it is used.
Immerse in H7,0 phosphate buffer and store at 4°C until use.
第３図は、実施例酵素電極Ｉの使用例を説明する図であ
る。１０は恒温槽であり、その内部には０゜ＩＭＫＣｆ
が含まれるｐＨ７，０のリン酸緩衝液１１が貯溜され、
一定温度（この実施例では２５℃）に保持される。また
、恒温槽１０の内部には、回転子１２が設けられ、恒温
槽１０の下方にあるスターク１３により、この回転子１
２が回転駆動され、緩衝液１１が撹拌される。FIG. 3 is a diagram illustrating an example of use of the enzyme electrode I of the embodiment. 10 is a constant temperature chamber, inside of which there is a temperature of 0゜IMKCf.
A phosphate buffer solution 11 with a pH of 7.0 containing is stored,
It is maintained at a constant temperature (25° C. in this example). Further, a rotor 12 is provided inside the thermostatic oven 10, and a star 13 located below the thermostatic oven 10 allows the rotor to
2 is driven to rotate, and the buffer solution 11 is stirred.
前記酵素電極１は、対照電極８と共に測定電極７を構成
し、上記緩衝液１１中に浸漬される。この実施例では、
対照電極８として銀塩化銀（Ａｇ／ＡｇＣｆ）電極を使
用しているが、これに限定されるものではなく適宜変更
可能である。The enzyme electrode 1 constitutes the measurement electrode 7 together with the reference electrode 8, and is immersed in the buffer solution 11. In this example,
Although a silver-silver chloride (Ag/AgCf) electrode is used as the control electrode 8, the present invention is not limited to this and can be changed as appropriate.
酵素電極１及び対照電極８の各々のリード線４．９は、
エレクトロメータ１４に接続され、また、このエレクト
ロメータ１４はレコーダ１５に連結され、電極出力が記
録される。The lead wires 4.9 of each of the enzyme electrode 1 and the reference electrode 8 are
It is connected to an electrometer 14, which in turn is connected to a recorder 15 to record the electrode output.
第４図は、第３図の測定系を用いてレコーダ１５に記録
された電極出力を示している。すなわち、前記緩衝液１
１中にグルコースを含む被測定検体が、マイクロピペッ
ト（図示せず）により所定量に計量されて注入された時
の電極出力を示している（酸素濃度約８．３■／ｌ）。FIG. 4 shows the electrode output recorded on the recorder 15 using the measurement system shown in FIG. That is, the buffer solution 1
1 shows the electrode output when a sample to be measured containing glucose is injected into a predetermined amount using a micropipette (not shown) (oxygen concentration approximately 8.3 .mu./l).
９５％の応答を得るのに５秒以内と非常に速い応答であ
ることが確認できる。It can be confirmed that the response is extremely fast, within 5 seconds to obtain a 95% response.
第５図は、酵素電極１と対照電極８との間に印加される
電圧（対照電極８に対する酵素電極１の電位）と、電極
出力のグルコース濃度に対する直線濃度範囲（リニアレ
ンジ）との関係を図示したものである。この第５図より
、印加電圧０．７５Ｖが最もリニアレンジが広く、最適
であることが確認できる。FIG. 5 shows the relationship between the voltage applied between the enzyme electrode 1 and the reference electrode 8 (potential of the enzyme electrode 1 relative to the reference electrode 8) and the linear concentration range of the electrode output with respect to the glucose concentration. This is what is illustrated. From FIG. 5, it can be confirmed that the applied voltage of 0.75 V provides the widest linear range and is optimal.
第６図は、溶存酸素が極めて低濃度（１，８ｍｇ／ｌ）
の時の実施例酵素電極１の異なるグルコース濃度に対す
る電極出力を図示したもので（を掻出力は、電流密度ｓ
Ａ／ｃｍ”の形で示している）、図中の白丸（０）はこ
の実施例の電極出力を（印加電圧０．７５Ｖ）、図中黒
丸（・）は比較例の電極出力をそれぞれ示している。こ
の比較例はＰＣＰを白金黒化せずに、ＣＯＤを固定化し
たものであり、印加電圧が０．６５Ｖである点を除いて
は、実施例酵素電極１と同じである。Figure 6 shows extremely low concentration of dissolved oxygen (1.8 mg/l)
This diagram shows the electrode output for different glucose concentrations of the enzyme electrode 1 of the example (the scraping force is the current density s).
The white circle (0) in the figure indicates the electrode output of this example (applied voltage 0.75 V), and the black circle (·) in the figure indicates the electrode output of the comparative example. This comparative example is one in which COD is immobilized without platinum-blackening PCP, and is the same as Example Enzyme Electrode 1 except that the applied voltage is 0.65V.
実施例酵素電極！ （０）と比較例（・）とを比べてみ
ると、実施例の電極出力の大きさと、測定可能な濃度範
囲の広さを確認することができる。Example enzyme electrode! Comparing Example (0) with Comparative Example (•), it is possible to confirm the magnitude of the electrode output of Example and the breadth of the measurable concentration range.
なお、上記実施例には、酵素としてＣＯＤを用い、カル
ボジイミド試薬を用いて固定化する方法を説明している
が、これに限定されるものではなく、適宜設計変更可能
である。In addition, although the above-mentioned example describes a method in which COD is used as the enzyme and immobilized using a carbodiimide reagent, the method is not limited to this, and the design can be changed as appropriate.
また、この実施例ではＰＣＰを用いているが、例えば、
白金をスパッタもしくは真空蒸着したセラミック板もく
しはプラスチックフィルム、さらには白金をめっきした
金属板等、適宜設計変更可能である。Furthermore, although PCP is used in this embodiment, for example,
The design can be changed as appropriate, such as a ceramic plate sputtered or vacuum-deposited with platinum, a plastic film, or a metal plate plated with platinum.
（べ）発明の詳細
な説明したように、第１請求項の酵素電極は、電極感応
面を白金黒で覆い、゛この白金黒に酵素を固定化してな
ることを特徴とするものであるから、以下に列挙する効
果を有する。(v) As described in detail of the invention, the enzyme electrode of the first claim is characterized in that the electrode sensitive surface is covered with platinum black, and the enzyme is immobilized on the platinum black. , has the effects listed below.
ｉ：電極反応による酸素の自己供給能が大きし・ため、
低酸素条件下でも電極出力が大きく、応答速度も劣化せ
ず、また広範な濃度範囲での測定が可能となる。i: Because the self-supply ability of oxygen due to electrode reaction is large,
Even under low oxygen conditions, the electrode output is high, the response speed does not deteriorate, and measurements can be made over a wide range of concentrations.
ｉｉ：上述のように酸素依存性を回避することができた
ので、検体中の溶存酸素レベル変動の影響を受けずに、
正確な計測を行うことができる。ii: As mentioned above, oxygen dependence could be avoided, so it was not affected by fluctuations in the dissolved oxygen level in the sample.
Accurate measurements can be taken.
ｉｉｉ二表二接面積きな白金黒に酵素を固定化している
ため、感度（測定分解能）が優れている。iii) Since the enzyme is immobilized on platinum black, which has a large contact area between two surfaces, the sensitivity (measurement resolution) is excellent.
ｉＶ＝使用耐久性、保存性が良好である。iV=good durability in use and storage stability.
一方、第２請求項の酵素電極の製造方法は、プラチナイ
ズドカーボンペーバ上の白金を電解処理により白金黒化
し、この白金黒に酵素を固定化するものであるから以下
の効果を有している。On the other hand, the method for manufacturing an enzyme electrode according to the second claim is a method in which platinum on a platinized carbon paver is turned into platinum black by electrolytic treatment, and an enzyme is immobilized on this platinum black, so that it has the following effects. ing.
Ｖ：加工しやすいプラチナイズドカーボンペーバを用い
ているため、構造及び製造工程が簡単となり、量産化、
低価格化が容易である。V: Since platinized carbon paver is used, which is easy to process, the structure and manufacturing process are simple, allowing for mass production.
It is easy to reduce the price.
ｉ■：いわゆるペーパ状電極のため、任意の電極形態に
製造することができる。i■: Because it is a so-called paper-like electrode, it can be manufactured into any electrode shape.
第１図は、この発明の一実施例に係る酵素電極の外観斜
視図、第２図は、同酵素電極の第１回中ｕ−ｎ線におけ
る断面図、第３図は、同酵素電極に通用される測定系の
一例を説明する図、第４図は、同酵素電極の電極出力と
時間との関係を説明する図、第５図は、同酵素電極の印
加電圧とリニアレンジとの関係を説明する図、第６図は
、同酵素電極の電極出力とグルコース濃度との関係を説
明する図である。
１；酵素電極、 ２ ： ＰＣＰ、２ａ：作用電
極感応面。
特許出願人 オムロン株式会社代理人
弁理士 中 村 茂 信第
図
第
図
時ｒｉ’ｌ ｆが゛）
１：酵木電棒
２：ＰＣＰFIG. 1 is an external perspective view of an enzyme electrode according to an embodiment of the present invention, FIG. 2 is a cross-sectional view of the same enzyme electrode taken along line u-n during the first run, and FIG. 3 is a cross-sectional view of the same enzyme electrode. Figure 4 is a diagram explaining an example of a commonly used measurement system. Figure 4 is a diagram explaining the relationship between the electrode output of the enzyme electrode and time. Figure 5 is the relationship between the applied voltage and linear range of the enzyme electrode. FIG. 6 is a diagram illustrating the relationship between the electrode output of the same enzyme electrode and the glucose concentration. 1: Enzyme electrode, 2: PCP, 2a: Working electrode sensitive surface. Patent applicant OMRON Co., Ltd. agent
Patent Attorney Shigeru Nakamura
Claims (2)
いて、 前記電極感応面を白金黒で覆い、この白金黒に酵素を固
定化してなることを特徴とする酵素電極。(1) An enzyme electrode comprising an enzyme immobilized on an electrode sensitive surface, characterized in that the electrode sensitive surface is covered with platinum black, and the enzyme is immobilized on the platinum black.
理により白金黒化し、この白金黒に酵素を固定化する酵
素電極の製造方法。(2) A method for manufacturing an enzyme electrode, in which platinum on platinized carbon paper is turned into platinum black by electrolytic treatment, and an enzyme is immobilized on this platinum black.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2182963A JPH0469564A (en) | 1990-07-10 | 1990-07-10 | Enzyme electrode and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2182963A JPH0469564A (en) | 1990-07-10 | 1990-07-10 | Enzyme electrode and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0469564A true JPH0469564A (en) | 1992-03-04 |
Family
ID=16127391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2182963A Pending JPH0469564A (en) | 1990-07-10 | 1990-07-10 | Enzyme electrode and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0469564A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001079706A3 (en) * | 2000-04-13 | 2002-05-30 | Elan Pharma Int Ltd | Electrolytic cell |
| JP2003082727A (en) * | 2001-09-10 | 2003-03-19 | Takara Standard Co Ltd | Waterproof pan |
| JP2005241622A (en) * | 2004-01-28 | 2005-09-08 | Dkk Toa Corp | Electrochemical sensor and electric conductivity cell |
-
1990
- 1990-07-10 JP JP2182963A patent/JPH0469564A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001079706A3 (en) * | 2000-04-13 | 2002-05-30 | Elan Pharma Int Ltd | Electrolytic cell |
| JP2004538360A (en) * | 2000-04-13 | 2004-12-24 | エラン・フアルマ・インターナシヨナル・リミテツド | Improved electrolytic cell |
| JP2003082727A (en) * | 2001-09-10 | 2003-03-19 | Takara Standard Co Ltd | Waterproof pan |
| JP2005241622A (en) * | 2004-01-28 | 2005-09-08 | Dkk Toa Corp | Electrochemical sensor and electric conductivity cell |
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