JPH0222552A - Stylus electrode - Google Patents

Stylus electrode

Info

Publication number
JPH0222552A
JPH0222552A JP63171826A JP17182688A JPH0222552A JP H0222552 A JPH0222552 A JP H0222552A JP 63171826 A JP63171826 A JP 63171826A JP 17182688 A JP17182688 A JP 17182688A JP H0222552 A JPH0222552 A JP H0222552A
Authority
JP
Japan
Prior art keywords
recessed part
annular recessed
needle
stylus
electrode
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
Application number
JP63171826A
Other languages
Japanese (ja)
Inventor
Masao Goto
正男 後藤
Ichiro Takatsu
高津 一郎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nok Corp
Original Assignee
Nok Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nok Corp filed Critical Nok Corp
Priority to JP63171826A priority Critical patent/JPH0222552A/en
Publication of JPH0222552A publication Critical patent/JPH0222552A/en
Pending legal-status Critical Current

Links

Abstract

PURPOSE:To improve the characteristics of a glucose sensor by providing an annular recessed part at the intermediate position of a stylus body, forming a selective transmission film and a lift active material fixed film in order, and insulating the surface of the stylus body except at the annular recessed part. CONSTITUTION:An annular recessed part 2 is formed at the intermediate position of the stylus body 1 and the surface of the stylus body is coated with insulating films 3 and 3' except at the annular recessed part 2. The selective transmission film 4 and the life active material fixed film 5 are formed on the annular recessed part 2 in order. This stylus electrode is used as an anode and a stylus electrode having no annular recessed part is used as a cathode; and they are dipped in liquid to be measured and a potential is applied between the electrodes to obtain linear relation between the concentration of the liquid to be measured and the output current. At this time, the influence of a disturbing material such as uric acid and ascorbic acid is eliminated by controlling the difference in affinity to the selective transmission film 4 between an object material and the disturbing material and a hole diameter, so the glucose value in blood and urine is accurately measured and the characteristics of the glucose sensor are improved.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、針状電極に関する。更に詳しくは、選択透過
性を有し、グルコースセンサなどに有効に用いられる針
状電極に関する。
DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a needle electrode. More specifically, the present invention relates to a needle-like electrode that has permselectivity and is effectively used in glucose sensors and the like.

〔従来の技術〕および〔発明が解決しようとする課題〕
従来、選択透過性を有する針状電極というものは、未だ
検討されていない。これに類似したものとしては、ワイ
ヤの表面に生理活性物質を固定化したワイヤ型電極が知
られているが、この電極の場合にも選択透過性を保持さ
せることについての検討はなされていない。
[Prior art] and [Problem to be solved by the invention]
Hitherto, needle-shaped electrodes having permselectivity have not been studied yet. Although a wire-type electrode in which a physiologically active substance is immobilized on the surface of a wire is known as something similar to this, there has been no study on maintaining permselectivity in the case of this electrode as well.

こうした選択透過性を有しない電極を用いて。using electrodes that do not have such permselectivity.

例えば血中や尿中などのグルコース値を定量しようとす
ると、それらに含まれるアスコルビン酸、尿酸などが妨
害物質となり、正確にグルコース値を定量できないとい
う問題がみられる。
For example, when attempting to quantify glucose levels in blood or urine, ascorbic acid, uric acid, and the like contained therein act as interfering substances, making it impossible to accurately quantify glucose levels.

本発明の目的は、このような妨害物質の影響を排除し、
グルコースセンサなどの特性を改善せしめる針状電極を
提供することにある。
The purpose of the present invention is to eliminate the influence of such interfering substances,
An object of the present invention is to provide a needle-like electrode that improves the characteristics of a glucose sensor or the like.

〔課題を解決するための手段〕[Means to solve the problem]

かかる本発明の目的は、針状体の中間位置に設けられた
環状凹部に1選択透過膜および生理活性物質固定化膜を
順次形成させると共に、前記環状凹部以外の針状体表面
を絶縁せしめた針状電極によって達成される。
An object of the present invention is to sequentially form a selectively permeable membrane and a physiologically active substance immobilization membrane in an annular recess provided at an intermediate position of a needle-like body, and to insulate the surface of the needle-like body other than the annular recess. Achieved by needle-like electrodes.

電極本体を形成するのに用いられる針状体としては、白
金、銀、金、チタンなどの金属製であって、その直径が
約0.2〜2+mのものが、一般に約1〜51の長さで
用いられる。これらの針状体の中間位置には、幅約0 
、5〜10 m、深さ約0.05〜0.5mの任意横断
面形状の環状凹部が切削法、鋳型法。
The needle-shaped body used to form the electrode body is made of metal such as platinum, silver, gold, titanium, etc., and has a diameter of about 0.2 to 2+ m, and generally has a length of about 1 to 5 mm. It is used in At the intermediate position of these needle-like bodies, there is a width of approximately 0.
, 5 to 10 m, and a depth of approximately 0.05 to 0.5 m with an arbitrary cross-sectional shape.

レーザ光線法などを用いて設けられる。It is provided using a laser beam method or the like.

この環状凹部および端子部をテープなどでマスキングし
た後、残りの針状体面をエポキシ系樹脂など任意の絶縁
性樹脂を用いての絶縁処理が行われる。
After masking the annular recess and the terminal portion with tape or the like, the remaining surface of the needle-like body is insulated using an arbitrary insulating resin such as an epoxy resin.

マスキングが除去された環状凹部には、選択透過膜がま
ず形成される。膜形成材料としては1例えば酢酸セルロ
ースなどのセルロース類、ポリビニルブチラール、ポリ
スルホンなどの合成高分子物質、あるいはセルロース、
キチン、アルブミン、アルギン酸ナトリウム、アガロー
ス、カラギーナンなどの天然高分子物質が用いられ、そ
れらを可溶性溶媒に溶解させたドープ液として調製した
後、浸漬法、ドロップ法、スピナ法などにより環状凹部
に適用し、−旦乾燥させてから不溶性溶媒中に浸漬する
ことにより選択透過膜の形成が行われる。
A selectively permeable membrane is first formed in the annular recess from which the masking has been removed. Examples of membrane forming materials include celluloses such as cellulose acetate, synthetic polymer substances such as polyvinyl butyral and polysulfone, or cellulose,
Natural polymeric substances such as chitin, albumin, sodium alginate, agarose, and carrageenan are used, and after preparing a dope solution by dissolving them in a soluble solvent, it is applied to the annular recess by the dipping method, drop method, spinner method, etc. A selectively permeable membrane is formed by first drying the membrane and then immersing it in an insoluble solvent.

また、膜形成材料として1分子中に光架橋性基としてス
チルバゾリウム基、ジアゾ基などの感光性基を有するポ
リビニルアルコールなどの水溶性光架橋性重合体なども
水溶液として用いることができる。
Further, as a film-forming material, a water-soluble photocrosslinkable polymer such as polyvinyl alcohol having a photosensitive group such as a stilbazolium group or a diazo group in one molecule as a photocrosslinkable group can also be used in the form of an aqueous solution.

このようにして環状凹部の一部を占有するように選択透
過膜を形成させたら、次に生理活性物質固定化膜をその
上面に形成させる。固定化される生理活性物質としては
、各種酵素、抗原抗体、抗生物質、ホルモン、レセプタ
、オルガネラ、チャンネル、微生物(放線菌、糸状菌、
酵母、バクテリアなど)、更には人工物であるフタロシ
アニン金属錯体などが例示される。これらの物質の固定
化法としては、グルタルアルデヒド、カルボジイミドな
どを用いる共有結合法、イオン結合法、吸着法、架橋法
など一般的に用いられている方法が。
After the permselective membrane is formed so as to occupy a part of the annular recess in this manner, the physiologically active substance immobilized membrane is then formed on its upper surface. Physiologically active substances to be immobilized include various enzymes, antigens and antibodies, antibiotics, hormones, receptors, organelles, channels, microorganisms (actinomycetes, filamentous fungi,
(yeast, bacteria, etc.), as well as artificial phthalocyanine metal complexes. Commonly used methods for immobilizing these substances include covalent bonding using glutaraldehyde, carbodiimide, etc., ionic bonding, adsorption, and crosslinking.

浸漬法、ドロップ法、スピナ法などによって適用される
It can be applied by dipping method, drop method, spinner method, etc.

第1図には、本発明に係る針状電極の一態様が部分縦断
面図として示されており、針状体1の中間位置には環状
凹部2が設けられており、環状凹部以外の針状体面は絶
縁膜3.3′によって被覆されている。また、環状凹部
2には、選択透過膜4および生理活性物質固定化膜5が
順次形成されている。
FIG. 1 shows one embodiment of the needle-shaped electrode according to the present invention as a partial vertical cross-sectional view, in which an annular recess 2 is provided at an intermediate position of the needle-shaped body 1, and a needle other than the annular recess is provided. The surface of the body is covered with an insulating film 3.3'. Further, in the annular recess 2, a permselective membrane 4 and a physiologically active substance immobilization membrane 5 are sequentially formed.

〔作用〕および〔発明の効果〕 本発明の針状電極を陽極とし、環状凹部を設けない針状
電極を陰極として被測定液中に浸漬し。
[Function] and [Effects of the Invention] The needle-shaped electrode of the present invention is used as an anode, and the needle-shaped electrode without an annular recess is used as a cathode and immersed in a liquid to be measured.

これらの電極間に電位をかけると、被測定液濃度と出力
電流との間に直線的な関係が得られる。
When a potential is applied between these electrodes, a linear relationship is obtained between the concentration of the liquid to be measured and the output current.

この際、針状電極の環状凹部の生理活性物質固定化膜と
電極面との間に選択透過膜を設置すると。
At this time, a selectively permeable membrane is installed between the physiologically active substance immobilized membrane in the annular recess of the needle electrode and the electrode surface.

選択透過膜に対する対象物質と妨害物質との親和性の差
および孔径制御作用などにより、尿酸、アスコルビン酸
などの妨害物質の影響を殆んど排除し、血中、尿中など
のグルコース値などを正確に測定することができ、グル
コースセンサなどのセンサ特性を改善することができる
Due to the difference in affinity between target substances and interfering substances for the selectively permeable membrane and the pore size control effect, the effects of interfering substances such as uric acid and ascorbic acid are almost eliminated, and glucose levels in blood and urine are reduced. Accurate measurements can be made, and sensor characteristics such as glucose sensors can be improved.

グルコースセンサ以外には、コレステロールセンサ、ア
ルコールセンサ、乳酸センサなどへの利用を図ることが
できる。
In addition to glucose sensors, the present invention can be used for cholesterol sensors, alcohol sensors, lactate sensors, and the like.

〔実施例〕〔Example〕

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 直径1 m、長さ2aIlの白金製針状体の針先から1
0国の位置に、幅5mm、深さ0.2mの環状凹部を第
1図の形状の如くに形成させた。このようにして形成さ
せた環状凹部および端子部をテープでマスキングした後
、残りの針状体面にエポキシ樹脂系接着剤を全面塗布し
、硬化後マスクを外した。
Example 1 from the needle tip of a platinum needle with a diameter of 1 m and a length of 2 aIl
An annular recess with a width of 5 mm and a depth of 0.2 m was formed at the position of country 0 as shown in FIG. After masking the annular recess and terminal portion thus formed with tape, an epoxy resin adhesive was applied to the entire surface of the remaining needle-shaped body, and after curing, the mask was removed.

次いで、酢酸セルロース10gをアセトン−シクロヘキ
サノン(容積比1:1)混合溶媒100m1llに溶解
させたドープ液中に、上記絶縁膜形成針状体を10秒間
浸漬し、引き上げて1時間室温に放置した後。
Next, the insulating film-forming needle was immersed for 10 seconds in a dope solution in which 10 g of cellulose acetate was dissolved in 100 ml of acetone-cyclohexanone (volume ratio 1:1) mixed solvent, and then pulled out and left at room temperature for 1 hour. .

n−ヘキサン中に室温下で2時間浸漬し、引き上げて凹
部からはみ出した部分を除去した。この状態では、形成
された選択透過膜は、凹部を完全に埋めることはなかっ
た。
It was immersed in n-hexane at room temperature for 2 hours, and pulled up to remove the portion protruding from the recess. In this state, the formed permselective membrane did not completely fill the recesses.

11111のリン酸緩衝液(pH7,0)中に、グルコ
ースオキシダーゼ5■、ヒト血清アルブミン40■、5
0%グルタルアルデヒド水溶液20μQを添加して溶解
させ、溶液調製1分後の溶液中に、上記選択透過膜形成
針状電極を室温下に撹拌しながら1分間浸漬し、引き上
げてから4℃で保存した。
11111 phosphate buffer (pH 7.0), glucose oxidase 5■, human serum albumin 40■, 5
Add and dissolve 20 μQ of 0% glutaraldehyde aqueous solution, and after 1 minute of solution preparation, immerse the selectively permeable membrane-forming needle electrode in the solution for 1 minute while stirring at room temperature, and then remove and store at 4°C. did.

このようにして形成された選択透過膜およびグルコース
固定化膜形成針状電極を陽極とし、また直径1oa、長
さ2】の銀製針状体を陰極として、その間に電極電位を
0.7v設定した。
The selectively permeable membrane and glucose-immobilized membrane formed needle electrode thus formed was used as an anode, and a silver needle with a diameter of 1 oa and a length of 2] was used as a cathode, and an electrode potential of 0.7 V was set between them. .

測定溶媒として、37℃のリン酸緩衝液(pH7,0)
を用い、出力電流が安定した後、それぞれ200゜40
0、600.800または1000■/dil濃度とな
る量のグルコース(○印)、尿酸(Δ印)またはアスコ
ルビン酸(・印)をそれぞれ添加し、出力電流値を測定
した。
Phosphate buffer (pH 7.0) at 37°C as measurement solvent
200°40 after the output current stabilizes.
Glucose (○ mark), uric acid (Δ mark), or ascorbic acid (· mark) was added in an amount to give a concentration of 0, 600.800 or 1000 μ/dil, and the output current value was measured.

第2図のグラフに示されるように、尿酸およびアスコル
ビン酸には殆んど応答がみられなかった。
As shown in the graph of FIG. 2, almost no response was observed to uric acid and ascorbic acid.

なお、グルコースオキシダーゼ(COD)のグルコース
への反応は、次の如くに行われ、 発生したH、 O,が陽極で酸化されるのに伴ない、電
流が流れるようになるので、その出力電流が測定される
The reaction of glucose oxidase (COD) to glucose is carried out as follows. As the generated H and O are oxidized at the anode, a current begins to flow, so the output current is be measured.

比較例 実施例において、選択透過膜の形成を行わないと、第3
図のグラ、フに示されるように、尿酸およびアスコルビ
ン酸にも応答がみられ、このグルコースセンサには選択
性がないことが分る。
Comparative Example In the example, if the selectively permeable membrane is not formed, the third
As shown in the graphs in the figure, responses were also observed to uric acid and ascorbic acid, indicating that this glucose sensor has no selectivity.

【図面の簡単な説明】[Brief explanation of the drawing]

第1図は1本発明に係る針状電極の部分縦断面図である
。また、第2〜3図は、それぞれ実施例および比較例に
おける被測定液濃度と出方電流との関係を示すグラフで
ある。 (符号の説明) 1・・・・・針状体 2・・・・・環状凹部 3・・・・・絶縁膜 4・・・・・選択透過膜 5・・・・・生理活性物質固定化膜
FIG. 1 is a partial longitudinal sectional view of a needle-like electrode according to the present invention. Moreover, FIGS. 2 and 3 are graphs showing the relationship between the concentration of the liquid to be measured and the output current in Examples and Comparative Examples, respectively. (Explanation of symbols) 1...Acicular body 2...Annular recess 3...Insulating film 4...Selective perms membrane 5...Physiologically active substance immobilization film

Claims (1)

【特許請求の範囲】[Claims] 1、針状体の中間位置に設けられた環状凹部に、選択透
過膜および生理活性物質固定化膜を順次形成させると共
に、前記環状凹部以外の針状体表面を絶縁してなる針状
電極。
1. A needle-like electrode formed by sequentially forming a permselective membrane and a physiologically active substance immobilization film in an annular recess provided at an intermediate position of the needle, and insulating the surface of the needle other than the annular recess.
JP63171826A 1988-07-12 1988-07-12 Stylus electrode Pending JPH0222552A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP63171826A JPH0222552A (en) 1988-07-12 1988-07-12 Stylus electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP63171826A JPH0222552A (en) 1988-07-12 1988-07-12 Stylus electrode

Publications (1)

Publication Number Publication Date
JPH0222552A true JPH0222552A (en) 1990-01-25

Family

ID=15930460

Family Applications (1)

Application Number Title Priority Date Filing Date
JP63171826A Pending JPH0222552A (en) 1988-07-12 1988-07-12 Stylus electrode

Country Status (1)

Country Link
JP (1) JPH0222552A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007502162A (en) * 2003-08-14 2007-02-08 アイセンス コーポレーション Method for building a biosensor
JP2023134639A (en) * 2020-07-29 2023-09-27 バイオリンク インコーポレイテッド Continuous analyte monitoring system with microneedle array
US11857344B2 (en) 2021-05-08 2024-01-02 Biolinq Incorporated Fault detection for microneedle array based continuous analyte monitoring device

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007502162A (en) * 2003-08-14 2007-02-08 アイセンス コーポレーション Method for building a biosensor
JP4790612B2 (en) * 2003-08-14 2011-10-12 アイセンス コーポレーション Indwelling analytical sensor
JP2023134639A (en) * 2020-07-29 2023-09-27 バイオリンク インコーポレイテッド Continuous analyte monitoring system with microneedle array
US11872055B2 (en) 2020-07-29 2024-01-16 Biolinq Incorporated Continuous analyte monitoring system with microneedle array
US11857344B2 (en) 2021-05-08 2024-01-02 Biolinq Incorporated Fault detection for microneedle array based continuous analyte monitoring device

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