JPH01136061A - Enzyme sensor - Google Patents
Enzyme sensorInfo
- Publication number
- JPH01136061A JPH01136061A JP62293958A JP29395887A JPH01136061A JP H01136061 A JPH01136061 A JP H01136061A JP 62293958 A JP62293958 A JP 62293958A JP 29395887 A JP29395887 A JP 29395887A JP H01136061 A JPH01136061 A JP H01136061A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- enzyme
- ion
- electrode
- potential
- 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
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 41
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 41
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims description 69
- 150000002500 ions Chemical class 0.000 claims description 31
- 108010093096 Immobilized Enzymes Proteins 0.000 claims description 16
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 7
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- -1 hydrogen ions Chemical class 0.000 claims description 2
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 239000010408 film Substances 0.000 abstract 7
- 239000013039 cover film Substances 0.000 abstract 2
- 229940088598 enzyme Drugs 0.000 description 32
- 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 5
- 239000008103 glucose Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 108010046334 Urease Proteins 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 108010015776 Glucose oxidase Proteins 0.000 description 2
- 239000004366 Glucose oxidase Substances 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940116332 glucose oxidase Drugs 0.000 description 2
- 235000019420 glucose oxidase Nutrition 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 235000006693 Cassia laevigata Nutrition 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 241000735631 Senna pendula Species 0.000 description 1
- 108010092464 Urate Oxidase Proteins 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005513 bias potential Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229940124513 senna glycoside Drugs 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は酵素センサ、特に複数のイオン感応性膜を有す
る酵素センサに関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an enzyme sensor, particularly an enzyme sensor having a plurality of ion-sensitive membranes.
［従来の技術］
従来、生体の基質等を測定する酵素センサとしては、酸
素電極や過酸化水素電極、さらに水素イオン電極上に固
定化酵素膜を形成した酵素センサが用いられてきた。さ
らに、よりセンナを微小にするものとしてｌ５ＦＥＴの
ゲート上に固定化酵素膜を形成した酵素ＦＥＴセンサが
考案された。これらの電極で特に、電位変化により測定
する水素イオン電極とｌ５ＦＥＴでは安定した基準の電
位を与える電極が必要であり、Ａｇ／ＡｇＣ１を用いた
電極を用いたり、ｌ５ＦＥＴを二つ用いＰｔ（白金）な
どを疑似基準電極とじた差動型のセンサが考えられた。[Prior Art] Conventionally, as enzyme sensors for measuring biological substrates, etc., enzyme sensors in which an immobilized enzyme membrane is formed on an oxygen electrode, a hydrogen peroxide electrode, or a hydrogen ion electrode have been used. Furthermore, an enzyme FET sensor was devised in which an immobilized enzyme film was formed on the gate of an 15FET to make senna even smaller. Among these electrodes, especially hydrogen ion electrodes that measure potential changes and l5FETs, electrodes that provide a stable reference potential are required. A differential sensor with a pseudo reference electrode was considered.
しかし、Ａｇ／ＡｇＣ１は電極の微小化が難しく、また
塩素濃度により影響を受ける。そして、ｌ５ＦＥＴを用
いた差動型では、二つのｌ５ＦＥＴのｐＨ感度とドリフ
ト特性を一致させることは難しいので、個々のセンサの
特性が異なり、また出力値が時間的に変化してしまう。However, with Ag/AgC1, it is difficult to miniaturize the electrode, and it is also affected by the chlorine concentration. In the differential type using 15FETs, it is difficult to match the pH sensitivity and drift characteristics of the two 15FETs, so the characteristics of each sensor differ and the output value changes over time.
［発明が解決しようとする問題点］
本発明の目的は、前記従来例の問題点を解決し、安定な
基準電極を有し且つセンサの特性にバラツキのない酵素
センサを提供することにある。[Problems to be Solved by the Invention] An object of the present invention is to solve the problems of the conventional example and to provide an enzyme sensor that has a stable reference electrode and has uniform sensor characteristics.
［問題点を解決するための手段］
この問題点を解決するための一手段として、本発明の酵
素センサは、被覆膜を持たない第１のイオン感応性膜と
、酵素を失活または含まない膜により表面を被覆された
第２のイオン感応性膜と、固定化酵素膜により表面を被
覆された第３のイオン感応性膜とがそれぞれ同一基板上
に併設されている。[Means for Solving the Problem] As a means for solving this problem, the enzyme sensor of the present invention includes a first ion-sensitive membrane that does not have a coating membrane, and a first ion-sensitive membrane that does not have a coating membrane, and a membrane that deactivates or contains an enzyme. A second ion-sensitive membrane whose surface is coated with an immobilized enzyme membrane and a third ion-sensitive membrane whose surface is coated with an immobilized enzyme membrane are respectively provided on the same substrate.
又、被覆膜を持たない第１のイオン感応性膜と、酵素を
失活または含まない膜により表面を被覆された第２のイ
オン感応性膜と、固定化酵素膜により表面を被覆された
第３のイオン感応性膜とがそれぞれ同一平面上に併設さ
れ、かつ、前記第１のイオン感応性膜の電位にに対する
、第２のイオン感応性膜の電位と、第３のイオン感応性
膜の電位との差を出力する電位差出力手段を備える。In addition, a first ion-sensitive membrane having no coating membrane, a second ion-sensitive membrane whose surface is coated with a membrane inactivated or containing no enzyme, and a second ion-sensitive membrane whose surface is coated with an immobilized enzyme membrane. a third ion-sensitive membrane, and the potential of the second ion-sensitive membrane and the third ion-sensitive membrane relative to the potential of the first ion-sensitive membrane; includes a potential difference output means for outputting a difference between the potential of
［作用］
かかる構成において、少なくとも３木のイオン感応性膜
により構成し、被覆膜を持たないイオン感応性膜を基準
電極とし、酵素を失活または含まない膜により表面を被
覆されたイオン感応性膜を対照電極とし、固定化酵素膜
により表面を被覆されたイオン感応性膜を作動電極とす
る。[Function] In this configuration, the ion-sensitive membrane is composed of at least three ion-sensitive membranes, the ion-sensitive membrane without a coating is used as a reference electrode, and the ion-sensitive membrane whose surface is coated with a membrane inactivated or containing no enzyme is used. The ion-sensitive membrane is used as a control electrode, and the ion-sensitive membrane whose surface is coated with an immobilized enzyme membrane is used as a working electrode.
又、基準電極に対する対照電極の電位と作動電極の電位
との差を出力して基質濃度を測定する。Further, the substrate concentration is measured by outputting the difference between the potential of the reference electrode and the potential of the working electrode with respect to the reference electrode.
［実施例コ
以下、添付図面を参照しながら本発明の一実施例を説明
する。[Example 1] Hereinafter, an example of the present invention will be described with reference to the accompanying drawings.
第１図は本実施例の酵素センサの構造を示す正面図及び
各位置での断面図である。FIG. 1 is a front view and sectional views at various positions showing the structure of the enzyme sensor of this example.
く酸化イリジウム電極の作成〉
本実施例でセンサを形成する基板１としては、サファイ
ヤ、アルミナ、ガラスなどが使用される一０基板１の表
面に酸化イリジウム（ＩｒＯｘ）の？Ｅ １４パターン
をフォトレジストを用いて形成し、その上からスパッタ
リングや電子ビーム蒸着によりイオン感応性膜としてＩ
ｒＯｘをのせ、その後フォトレジストを取り去りＩｒｅ
Ｘ膜電極パターン（膜厚１０００人）２ａ、２ｂ、２ｃ
を形成する。ＩｒＯｘのスパッタリング条件は、出力３
０ Ｗ、 ５ ｘ １０−３Ｔｏｒｒの０２中である
。Preparation of iridium oxide electrode> In this example, the substrate 1 forming the sensor is made of sapphire, alumina, glass, etc. Iridium oxide (IrOx) is coated on the surface of the substrate 1. 14 patterns are formed using a photoresist, and an ion-sensitive film is formed on the pattern by sputtering or electron beam evaporation.
Apply rOx, then remove the photoresist and remove Ire.
X membrane electrode pattern (film thickness 1000 people) 2a, 2b, 2c
form. IrOx sputtering conditions are output 3
0 W, 5 x 10-3 Torr in 02.
ＩｒＯｘの膜厚は１００人〜５０μｍの厚さが好ましく
、特に好ましくは８００人から１０００人である。１０
０Å以下では、抵抗が小さくなり、ノイズを発生させ、
５０μｍ以上では、膜が７１１流じやすくなる。ＩｒＯ
ｘの代わりに酸化ルテニウム、酸化ロジウムなどの導電
性膜を用いてもよい。The thickness of the IrOx film is preferably 100 to 50 μm, particularly preferably 800 to 1000 μm. 10
Below 0 Å, the resistance becomes small and noise is generated.
When the thickness is 50 μm or more, the film 711 tends to flow. IrO
A conductive film made of ruthenium oxide, rhodium oxide, or the like may be used instead of x.
次に、Ｃｕ ／ Ｃｒな°どの金属電極４をスパッタリ
ングや蒸着により形成した。さらに、Ａ １２０３ 、
Ｓ １３Ｎａ 、 ホ’）イミドナトｆ）絶縁膜３を
形成して、測定部以外が、被検疫に触れるのを防ぐ構造
とした。絶縁膜３は、スパッタリング、ＣＶＤ （化学
的気相蒸着）、蒸着などにより形成した。Next, a metal electrode 4 such as Cu/Cr was formed by sputtering or vapor deposition. Furthermore, A 1203,
S13Na, e') imidato f) An insulating film 3 was formed to prevent parts other than the measurement part from touching the quarantined part. The insulating film 3 was formed by sputtering, CVD (chemical vapor deposition), vapor deposition, or the like.
く固定化酵素膜の作成〉
固定化酵素膜５はグルタルアルデヒドにより固定法を用
いた。まず、フォトレジストにより膜のパターンを形成
した。Preparation of Immobilized Enzyme Membrane The immobilized enzyme membrane 5 was prepared using a fixation method using glutaraldehyde. First, a film pattern was formed using photoresist.
そこに、
■５０ ｍ ｇ ／ ｍ Ｉｌのグルコースオキシダー
ゼ、またはウレアーゼ水溶液、
■３００ ｍ ｇ ／ ｍ １１の牛アルブミン水溶液
、０２％グルタルアルデヒド水溶液を、
■：■：■：＝１：１：１で混合した溶液を滴下して固
定化酵素膜５を形成した。Then, ■ 50 mg/m Il glucose oxidase or urease aqueous solution, ■ 300 mg/m 11 bovine albumin aqueous solution, and 02% glutaraldehyde aqueous solution were added in a ratio of ■:■:■:=1:1:1. The mixed solution was dropped to form an immobilized enzyme membrane 5.
酵素固定化膜は４００人〜１００μｍが好ましく、１μ
ｍ〜０μｍが特に好ましい。４００Å以下では酸素を十
分に固定できず寿命が短くなり、１００μｍを越えると
応答速度が遅くなる。The enzyme-immobilized membrane preferably has a thickness of 400 to 100 μm, and has a thickness of 1 μm.
m to 0 μm is particularly preferred. If the thickness is less than 400 Å, oxygen cannot be fixed sufficiently and the lifetime will be shortened, and if it exceeds 100 μm, the response speed will be slow.
〈酵素失活または含まない膜の形成〉
酵素失活または含まない膜６は、上記の■溶液を加熱に
より酵素を失活させ、同じように膜を形成、又は■酵素
溶液を混合させないで膜形成を行なった。<Enzyme inactivation or formation of a membrane that does not contain the enzyme> Enzyme inactivation or the membrane 6 that does not contain the enzyme can be made by heating the solution described above to inactivate the enzyme and forming a membrane in the same manner, or ■ forming a membrane without mixing the enzyme solution. Formation was carried out.
このようにして作成された酵素センサ７のグルコース濃
度及び尿素濃度に対する特性を、第２図に示す測定回路
により測定した。第２図において、７は本実施例で作成
された酵素センサ、８は被検液、９はＦＥＴ、１０はオ
ペアンプ、１１は定電流源、１２は作ｒＭＪ〜アンプで
ある。The characteristics of the enzyme sensor 7 thus prepared with respect to glucose concentration and urea concentration were measured using the measurement circuit shown in FIG. 2. In FIG. 2, 7 is an enzyme sensor prepared in this example, 8 is a test liquid, 9 is an FET, 10 is an operational amplifier, 11 is a constant current source, and 12 is a manufactured rMJ~amp.
なお、この回路は一例であって、出力電位差を正確に計
れるものであれば限定されない。Note that this circuit is just an example, and is not limited to any circuit as long as it can accurately measure the output potential difference.
酵素センサの応答例を第３図に示す。１００ｍｇ／ｄｐ
のグルコース、または尿素を含む１０ｍＭのリン酸緩衝
液にこの酵素センサを入れた時の、作動アンプ１２より
の差出力をみたものである。An example of the response of the enzyme sensor is shown in FIG. 100mg/dp
This figure shows the differential output from the operating amplifier 12 when this enzyme sensor is placed in a 10 mM phosphate buffer containing 10 mM glucose or urea.
グルコースの場合はグルコースオキシダーゼによってグ
ルコン酸が形成されるため、固定化酵素１模５中のｐＨ
が減少する。また尿素ではウレアーゼにより水素イオン
が消費され、固定化酵素１１ｉ ５中のｐ）（が増加す
る。このため、固定化酵素膜５を形成した電極２ａの電
位を■２とし、酵素失活または含まない膜６を形成した
電極２ｃの電位をｖｌとして、差（Ｖ２ ｖｌ）を出
力として得ると、グルコースではプラスにまた尿素では
マイナスの出力か得られる。In the case of glucose, gluconic acid is formed by glucose oxidase, so the pH in the immobilized enzyme
decreases. In addition, in the case of urea, hydrogen ions are consumed by urease, and p) in the immobilized enzyme 11i5 increases. Therefore, the potential of the electrode 2a on which the immobilized enzyme membrane 5 is formed is set to 2, and the enzyme is deactivated or contained. If the potential of the electrode 2c on which the free membrane 6 is formed is vl, and the difference (V2 vl) is obtained as an output, a positive output will be obtained for glucose and a negative output will be obtained for urea.
このような酵素センサの構成により、以下のような効果
が得られる。With this configuration of the enzyme sensor, the following effects can be obtained.
（１）ＩｒＯｘの電位が安定しているため、高安定な他
の電極を必要としない。このため、Ａｇ／Ａｇｃｘのよ
うな基準電極を必要とせず、−木の電極としてセンサを
作成することが容易にできる。(1) Since the potential of IrOx is stable, other highly stable electrodes are not required. Therefore, it is possible to easily create a sensor using a -wood electrode without requiring a reference electrode such as Ag/Agcx.
（２）電位法で測定するため、電極面積を厳密にそろえ
る必要はなく、また、センサ自体を微小にすることがで
きる。(2) Since the measurement is performed using the potential method, it is not necessary to strictly align the electrode areas, and the sensor itself can be miniaturized.
（３）同一種類（Ｉ ｒｏＸ ）の電極を基準。(3) Based on electrodes of the same type (IroX).
対照９作動電極に用いているため、それぞれの電極の電
位がほぼ一致する。そのため、バイアス電位をかけるこ
とで各電極の電位を自由に設定することが容易である。Since the reference 9 is used as the working electrode, the potentials of each electrode are almost the same. Therefore, it is easy to freely set the potential of each electrode by applying a bias potential.
（４）被測定液のｐＨが変化しても基準の電極がｐＨに
応答するため、それによる対照と作動電極の電位は変化
したい。このため、ＦＥＴにより電極電位を増幅した場
合、疑似基準電極とｌ５ＦＥＴの場合のようばゲートに
加わる電位変化はなく、酵素膜に加わる電位も変化しな
い。(4) Even if the pH of the liquid to be measured changes, the reference electrode responds to the pH, so the potentials of the reference and working electrodes should change accordingly. Therefore, when the electrode potential is amplified by the FET, there is no change in the potential applied to the gate as in the case of the pseudo reference electrode and the 15FET, and the potential applied to the enzyme membrane also does not change.
（５）導電性の感応膜を用いているため、電解重合法な
どの方法で酵素膜などを形成することができる。(5) Since a conductive sensitive membrane is used, enzyme membranes and the like can be formed using methods such as electrolytic polymerization.
（６）ドリフト特性のそろったｌ５ＦＥＴを必要としな
い。また、ｌ５ＦＥＴなどに比べ容易にセンサを作成す
ることができ、微小化も容易である。(6) No need for 15FETs with uniform drift characteristics. Furthermore, compared to 15FETs, sensors can be manufactured more easily, and miniaturization is also easier.
（７）感応膜が導電性であるため、電解重合法などによ
り固定化酵素膜を形成することができる。(7) Since the sensitive membrane is electrically conductive, the immobilized enzyme membrane can be formed by electrolytic polymerization or the like.
（８）センサ出力を増幅するものとして、いろいろな入
力インピーダンスを持ったＦＥＴを使うことができ、目
的により、ＭＯＳＦＥＴのような高入力インピーダンス
にしたり、接合型−ＦＥＴ。(8) FETs with various input impedances can be used to amplify the sensor output; depending on the purpose, high input impedances such as MOSFETs or junction-type FETs can be used.
ショットキー型ＦＥＴのように人力インピーダンスを低
くすることもできる。これにより、生体中で使うことも
でき、また、雑音の少ない高感度の測定を行なうことも
できる。It is also possible to lower the human impedance like a Schottky FET. As a result, it can be used in living organisms, and high-sensitivity measurements with little noise can be performed.
尚、本実施例ではグルコースセンサについて説明したが
、本発明がウレアーゼ、ウリカーゼ、コレステロール、
オキシターゼ等を使用した他の酵素センサに通用される
のは明らかである。Although this example describes a glucose sensor, the present invention also applies to urease, uricase, cholesterol,
It is obvious that the present invention can be applied to other enzyme sensors using oxidase or the like.
［発明の効果］
本発明により、安定な基準電極を有し且つセンサの特性
にバラツキのない酵素センサを提供できる。[Effects of the Invention] According to the present invention, an enzyme sensor having a stable reference electrode and having uniform sensor characteristics can be provided.
第１図は本実施例の酵素センサの平面図と断面図、
第２図は本実施例の酵素センサの測定回路の例を示す図
、
第３図は本実施例の酵素センサの応答例を示す図である
。
図中、ｌ・・・基板、２ａ、２ｂ、２ｃ・・Ｉ ｒｏｘ
膜電極、３・・・絶縁膜、４・・・金属電極、５・・・
固定化酵素膜、６・・・酵素失活または含まない膜、７
・・・酵素センサ、８・・・被検液、９・・・ＦＥＴ、
１０・・・オペアンプ、１１・・・定電流源、１２・・
・作動アンプである。Fig. 1 is a plan view and a cross-sectional view of the enzyme sensor of this embodiment, Fig. 2 is a diagram showing an example of the measurement circuit of the enzyme sensor of this embodiment, and Fig. 3 is a response example of the enzyme sensor of this embodiment. FIG. In the figure, l...substrate, 2a, 2b, 2c...I rox
Membrane electrode, 3... Insulating film, 4... Metal electrode, 5...
Immobilized enzyme membrane, 6... Enzyme deactivated or enzyme-free membrane, 7
... Enzyme sensor, 8... Test liquid, 9... FET,
10... operational amplifier, 11... constant current source, 12...
・It is a working amplifier.
Claims (4)
２のイオン感応性膜と、 固定化酵素膜により表面を被覆された第３のイオン感応
性膜とがそれぞれ同一基板上に併設されていることを特
徴とする酵素センサ。(1) A first ion-sensitive membrane without a coating membrane, a second ion-sensitive membrane whose surface is coated with a membrane inactivated or containing no enzyme, and a second ion-sensitive membrane whose surface is coated with an immobilized enzyme membrane. and a third ion-sensitive membrane, each of which is provided on the same substrate.
性膜であることを特徴とする特許請求の範囲第１項記載
の酵素センサ。(2) The enzyme sensor according to claim 1, wherein the ion-sensitive membrane is a conductive membrane exhibiting sensitivity to hydrogen ions.
酸化ルテニウムからなる特許請求の範囲第２項記載の酵
素センサ。(3) The enzyme sensor according to claim 2, wherein the conductive film is made of iridium oxide, rhodium oxide, or ruthenium oxide.
２のイオン感応性膜と、 固定化酵素膜により表面を被覆された第３のイオン感応
性膜とがそれぞれ同一平面上に併設され、かつ、 前記第１のイオン感応性膜の電位にに対する、第２のイ
オン感応性膜の電位と、第３のイオン感応性膜の電位と
の差を出力する電位差出力手段を備えることを特徴とす
る酵素センサ。(4) a first ion-sensitive membrane without a coating membrane; a second ion-sensitive membrane whose surface is coated with a membrane inactivated or containing no enzyme; and a second ion-sensitive membrane whose surface is coated with an immobilized enzyme membrane. and a third ion-sensitive membrane are arranged on the same plane, and the potential of the second ion-sensitive membrane and the third ion-sensitive membrane with respect to the potential of the first ion-sensitive membrane are An enzyme sensor characterized by comprising a potential difference output means for outputting a difference between the potential of the membrane and the potential of the membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62293958A JPH01136061A (en) | 1987-11-24 | 1987-11-24 | Enzyme sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62293958A JPH01136061A (en) | 1987-11-24 | 1987-11-24 | Enzyme sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01136061A true JPH01136061A (en) | 1989-05-29 |
| JPH0515984B2 JPH0515984B2 (en) | 1993-03-03 |
Family
ID=17801387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62293958A Granted JPH01136061A (en) | 1987-11-24 | 1987-11-24 | Enzyme sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01136061A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0777511A (en) * | 1993-07-16 | 1995-03-20 | Gold Star Co Ltd | Biosensor for gas measurement and preparation thereof |
| JPH07198668A (en) * | 1993-11-04 | 1995-08-01 | Lg Electron Inc | Biosensor for measuring concentration of alcohol, manufacture thereof and drinking measuring instrument using biosensor thereof |
| KR100360774B1 (en) * | 1999-12-27 | 2002-11-13 | 한국전자통신연구원 | Enzyme electrode sensor and manufacturing method thereof |
| KR20210048131A (en) * | 2019-10-23 | 2021-05-03 | 동우 화인켐 주식회사 | Bio Sensor |
-
1987
- 1987-11-24 JP JP62293958A patent/JPH01136061A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0777511A (en) * | 1993-07-16 | 1995-03-20 | Gold Star Co Ltd | Biosensor for gas measurement and preparation thereof |
| JPH07198668A (en) * | 1993-11-04 | 1995-08-01 | Lg Electron Inc | Biosensor for measuring concentration of alcohol, manufacture thereof and drinking measuring instrument using biosensor thereof |
| KR100360774B1 (en) * | 1999-12-27 | 2002-11-13 | 한국전자통신연구원 | Enzyme electrode sensor and manufacturing method thereof |
| KR20210048131A (en) * | 2019-10-23 | 2021-05-03 | 동우 화인켐 주식회사 | Bio Sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0515984B2 (en) | 1993-03-03 |
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