JP3451517B2 - Planar type enzyme sensor - Google Patents
Planar type enzyme sensorInfo
- Publication number
- JP3451517B2 JP3451517B2 JP12418096A JP12418096A JP3451517B2 JP 3451517 B2 JP3451517 B2 JP 3451517B2 JP 12418096 A JP12418096 A JP 12418096A JP 12418096 A JP12418096 A JP 12418096A JP 3451517 B2 JP3451517 B2 JP 3451517B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- membrane
- polymer
- enzyme
- sensor
- 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.)
- Expired - Fee Related
Links
- 108090000790 Enzymes Proteins 0.000 title claims description 41
- 102000004190 Enzymes Human genes 0.000 title claims description 41
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 35
- 239000012528 membrane Substances 0.000 claims description 29
- 229920006254 polymer film Polymers 0.000 claims description 29
- 239000004417 polycarbonate Substances 0.000 claims description 23
- 108010093096 Immobilized Enzymes Proteins 0.000 claims description 17
- 229920005597 polymer membrane Polymers 0.000 claims description 15
- 102000009027 Albumins Human genes 0.000 claims description 7
- 108010088751 Albumins Proteins 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003014 ion exchange membrane Substances 0.000 claims description 4
- 229920006289 polycarbonate film Polymers 0.000 claims description 3
- 239000010408 film Substances 0.000 description 46
- 229940088598 enzyme Drugs 0.000 description 36
- 210000002700 urine Anatomy 0.000 description 16
- 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 12
- 239000008103 glucose Substances 0.000 description 12
- 230000002452 interceptive effect Effects 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 239000002313 adhesive film Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000006911 enzymatic reaction Methods 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 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 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 108010015776 Glucose oxidase Proteins 0.000 description 1
- 239000004366 Glucose oxidase Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229940116332 glucose oxidase Drugs 0.000 description 1
- 235000019420 glucose oxidase Nutrition 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Investigating Or Analysing Biological Materials (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、尿測定器等の生化
学測定器に液成分検出用のセンサとして使用されるプレ
ーナ型酵素センサに関する。TECHNICAL FIELD The present invention relates to a planar enzyme sensor used as a sensor for detecting a liquid component in a biochemical measuring instrument such as a urine measuring instrument.
【０００２】[0002]
【従来の技術】この種のプレーナ型酵素センサを使用す
る尿測定器としては、図２〔表側の外観斜視図（ａ）、
裏側の外観斜視図（ｂ）〕に示すようなものがある。こ
の尿測定器１は、酵素の働きを利用して尿成分（尿糖
等）を検出するものであり、測定器本体２にセンサ本体
３が着脱可能に取付けられ、測定器本体２の表側に測定
値（尿糖等）や各種の指示等を表示する表示部（ＬＣ
Ｄ）４が設けられ、測定器本体２の頭部に電池カバー５
が着脱可能に取付けられたものである。センサ本体３
は、プレーナ型酵素センサを内蔵するセンサホルダ６
と、このセンサホルダ６に挿嵌されたセンサキャップ７
とからなる。又、測定器本体２には、各種電子部品が実
装された回路基板や電池等が内蔵されている。このよう
な尿測定器１では、尿をセンサホルダ６の検出部（開口
部）６ａに掛ければ、自動的に測定値が表示部４に表示
されるようになっている。2. Description of the Related Art A urine meter using this type of planar enzyme sensor is shown in FIG.
An external perspective view of the back side (b)] is available. This urine measuring device 1 detects urine components (urine sugar, etc.) by utilizing the function of an enzyme, and a sensor main body 3 is detachably attached to a measuring device main body 2 and is attached to the front side of the measuring device main body 2. Display unit (LC for displaying measured values (urine sugar, etc.) and various instructions
D) 4 is provided, and a battery cover 5 is provided on the head of the measuring device main body 2.
Is detachably attached. Sensor body 3
Is a sensor holder 6 containing a planar enzyme sensor.
And the sensor cap 7 inserted into the sensor holder 6
Consists of. Further, the measuring device main body 2 has a built-in circuit board on which various electronic components are mounted, a battery, and the like. In such a urine measuring device 1, when urine is applied to the detecting portion (opening) 6a of the sensor holder 6, the measured value is automatically displayed on the display portion 4.
【０００３】プレーナ型酵素センサは、例えば図３（セ
ンサホルダ６の検出部６ａにおける横断面図）に示すよ
うな構造になっている。ここに示すプレーナ型酵素セン
サ３０は、絶縁基板としての絶縁性フィルム３１と、過
酸化水素電極として例えば白金、金又は銀の薄膜からな
る金属電極３２と、固定化酵素膜３３とからなる。更に
固定化酵素膜３３は、下部保護膜３４と、酵素膜３５
と、上部保護膜３６と、表面保護膜３７とからなる。The planar type enzyme sensor has a structure as shown in, for example, FIG. 3 (a cross-sectional view of the detecting portion 6a of the sensor holder 6). The planar enzyme sensor 30 shown here comprises an insulating film 31 as an insulating substrate, a metal electrode 32 made of a thin film of platinum, gold or silver as a hydrogen peroxide electrode, and an immobilized enzyme film 33. Further, the immobilized enzyme film 33 includes a lower protective film 34 and an enzyme film 35.
And an upper protective film 36 and a surface protective film 37.
【０００４】[0004]
【発明が解決しようとする課題】上記のようなプレーナ
型酵素センサ３０では、センサホルダ６の検出部６ａか
ら試料（尿）が入ってくると、尿中のグルコースが固定
化酵素膜３３の酵素膜３５に浸透する。ところで、試料
中の電極妨害物質が金属電極３２まで透過して電極表面
に付着すると、特性が劣化するため、高分子膜である下
部保護膜３４により試料中の電極妨害物質の透過が制限
されている。又、下部保護膜３４には、試料中の電極妨
害物質の透過を制限する役目の他に、酵素膜３５で酵素
反応により発生する過酸化水素を選択的に透過させる作
用が求められるため、下部保護膜３４としては、通常は
セルロース膜が使用されている。しかしながら、セルロ
ース膜のような高分子膜は、過酸化水素を選択的に透過
させることができるが、試料中の電極妨害物質の透過量
を十分に制限できない、という問題点がある。In the planar type enzyme sensor 30 as described above, when a sample (urine) enters from the detecting portion 6a of the sensor holder 6, glucose in the urine is converted into the enzyme of the immobilized enzyme membrane 33. Permeate the membrane 35. By the way, when the electrode interfering substance in the sample permeates to the metal electrode 32 and adheres to the electrode surface, the characteristics are deteriorated. Therefore, the lower protective film 34, which is a polymer film, limits the permeation of the electrode interfering substance in the sample. There is. In addition to the role of limiting the permeation of the electrode interfering substance in the sample, the lower protective film 34 is required to have a function of selectively permeating hydrogen peroxide generated by the enzyme reaction in the enzyme film 35. As the protective film 34, a cellulose film is usually used. However, although a polymer membrane such as a cellulose membrane can selectively permeate hydrogen peroxide, it has a problem that the permeation amount of an electrode interfering substance in a sample cannot be sufficiently limited.
【０００５】一方、固定化酵素膜３３の上部保護膜３６
及び表面保護膜３７も高分子膜からなり、その微小孔に
より酵素膜３５へのグルコースの透過量を制限する役目
を有する。しかしながら、通常の高分子膜では、微小孔
の大きさにバラツキがあるため、均一な透過量が得られ
難く、これを解決するために緻密な膜を形成しようとし
ても通常の高分子膜ではうまくいかない、という問題点
がある。On the other hand, the upper protective film 36 of the immobilized enzyme film 33.
The surface protection film 37 is also made of a polymer film, and its micropores serve to limit the amount of glucose permeated into the enzyme film 35. However, in a normal polymer film, it is difficult to obtain a uniform permeation amount because the size of the micropores varies, and even if an attempt is made to form a dense film to solve this problem, a normal polymer film does not work. , There is a problem.
【０００６】従って、本発明は、そのような問題点に着
目してなされたもので、過酸化水素電極に係る下部層が
試料中の電極妨害物質の透過制限及び過酸化水素の選択
的透過性に優れ、また酵素膜に係る上部層がグルコース
の均一な透過性に優れたプレーナ型酵素センサを提供す
ることを目的とする。Therefore, the present invention has been made by paying attention to such problems, and the lower layer related to the hydrogen peroxide electrode limits the permeation of the electrode interfering substance in the sample and the selective permeation of hydrogen peroxide. It is an object of the present invention to provide a planar-type enzyme sensor which is excellent in the above-mentioned property and whose upper layer related to the enzyme film is excellent in uniform glucose permeability.
【０００７】[0007]
【課題を解決するための手段】前記目的を達成するため
に、本発明の請求項１記載のプレーナ型酵素センサは、
絶縁基板上に過酸化水素電極を形成し、この過酸化水素
電極上に、高分子膜をコーティングし更に加熱して形成
し、この高分子膜上に固定化酵素膜を設け、この固定化
酵素膜上に、少なくとも一方面側を高分子膜で被覆した
ポリカーボネイト膜をその他方面側を固定化酵素膜側に
して設けてなることを特徴とする。In order to achieve the above object, a planar type enzyme sensor according to claim 1 of the present invention comprises:
A hydrogen peroxide electrode is formed on an insulating substrate, and a polymer film is coated on this hydrogen peroxide electrode and further heated to form
Then , an immobilized enzyme membrane was provided on this polymer membrane , and this immobilized
At least one side of the enzyme membrane was covered with a polymer membrane
The other side of the polycarbonate membrane is the immobilized enzyme membrane side
It is characterized by being provided .
【０００８】この酵素センサでは、過酸化水素電極上の
高分子膜がコーティングだけでなく、更に加熱により形
成されているため、過酸化水素の透過性を維持しつつ試
料中の電極妨害物質の透過を十分に制限できる。つま
り、高分子膜の性能が加熱処理により更に向上すること
になる。特に、高分子膜としてイオン交換膜を使用する
こと（請求項２記載）により、より一層良好な特性が得
られる。In this enzyme sensor, since the polymer film on the hydrogen peroxide electrode is formed not only by coating but also by heating, the permeation of the electrode interfering substance in the sample is maintained while maintaining the permeability of hydrogen peroxide. Can be sufficiently limited. That is, the performance of the polymer film is further improved by the heat treatment. In particular, by using an ion exchange membrane as the polymer membrane (claim 2 ), better characteristics can be obtained.
【０００９】また、この酵素センサでは、固定化酵素膜
上に少なくとも一方面側が高分子膜で被覆されたポリカ
ーボネイト膜（以下、ＰＣ膜と略す）が形成されている
ので、グルコースの透過量が均一になる。即ち、ＰＣ膜
は、均一な大きさの微小孔を有し、グルコースの透過量
のバラツキが改善される。 Further , in this enzyme sensor, the immobilized enzyme membrane is used.
Polycarbonate coated on at least one side with a polymer film
Carbonate film (hereinafter abbreviated as PC film) is formed
Therefore, the glucose permeation amount becomes uniform. That is, PC film
Has a uniform size of micropores and permeates glucose.
Variation is improved.
【００１０】但し、ＰＣ膜は、非常な微小孔を有するの
で、目詰まりを起こしてグルコースの透過量が変化（減
少）し易い。これを防ぐために、ＰＣ膜の少なくとも一
方面側（上面側）を高分子膜で被覆してある。特に、そ
の高分子膜として、アルブミンとグルタルアルデヒドか
らなる膜を使用すること（請求項４記載）により、より
一層良好な目詰まり防止とグルコースの透過性を示すこ
とになる。つまり、ＰＣ膜が本来持つ性能を保ったまま
目詰まり防止作用を一層向上させることができる。[0010] and However, PC film, because it has a very micropores, transmission amount of glucose clogged changes (decreases) easily. In order to prevent this, at least one surface side (upper surface side) of the PC film is covered with a polymer film. In particular, by using a film composed of albumin and glutaraldehyde as the polymer film (claim 4 ), more excellent clogging prevention and glucose permeability are exhibited. That is, it is possible to further improve the function of preventing clogging while maintaining the original performance of the PC film.
【００１１】[0011]
【発明の実施の形態】以下、本発明を実施の形態に基づ
いて説明する。実施形態に係るプレーナ型酵素センサの
横断面図を図１に示す。ここに示すプレーナ型酵素セン
サ１０は、従来と同様に図２に示すような尿測定器１の
センサホルダ６に内蔵される。尿測定器１は、前記した
ように、測定器本体２にセンサ本体３が着脱可能に取付
けられ、測定器本体２の表側に尿糖等の測定値や各種の
指示等を表示する表示部４が設けられ、測定器本体２の
頭部に電池カバー５が着脱可能に取付けられたものであ
る。センサ本体３は、プレーナ型酵素センサを内蔵する
センサホルダ６と、このセンサホルダ６に挿嵌されたセ
ンサキャップ７とからなる。又、測定器本体２の裏側に
は、酵素センサを校正するための校正スイッチ８が設け
られている。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below based on embodiments. A cross-sectional view of the planar type enzyme sensor according to the embodiment is shown in FIG. The planar enzyme sensor 10 shown here is built in the sensor holder 6 of the urine measuring device 1 as shown in FIG. As described above, in the urine measuring device 1, the sensor main body 3 is detachably attached to the measuring device main body 2, and the display unit 4 for displaying the measured value of urine sugar and the like and various instructions on the front side of the measuring device main body 2. Is provided, and the battery cover 5 is detachably attached to the head of the measuring device main body 2. The sensor main body 3 is composed of a sensor holder 6 containing a planar enzyme sensor, and a sensor cap 7 inserted into the sensor holder 6. A calibration switch 8 for calibrating the enzyme sensor is provided on the back side of the measuring device body 2.
【００１２】このプレーナ型酵素センサ１０は、絶縁基
板としてのポリイミドフィルム（ＰＩフィルム）１１
と、過酸化水素電極としての一対の金属電極１２と、２
層からなる高分子膜１３と、２層からなる固定化酵素膜
１４と、高分子接着剤膜１５と、高分子膜１７で被覆さ
れたポリカーボネイト膜（ＰＣ膜）１６とからなる。な
お、絶縁基板は、ＰＩフィルム１１の代わりに、セラミ
ックや他の樹脂フィルムを用いてもよい。This planar type enzyme sensor 10 comprises a polyimide film (PI film) 11 as an insulating substrate.
And a pair of metal electrodes 12 as hydrogen peroxide electrodes and 2
It is composed of a polymer film 13 composed of layers, an immobilized enzyme film 14 composed of two layers, a polymer adhesive film 15, and a polycarbonate film (PC film) 16 covered with a polymer film 17. The insulating substrate may use ceramics or other resin films instead of the PI film 11.
【００１３】ＰＩフィルム１１上に形成される一対の金
属電極１２は、酵素膜１４における酵素反応に伴う酸素
や過酸化水素の増減を酸化電流変化として捕らえるもの
である。電極としては、各種の金属が利用されるが、作
用極としては主に白金（Ｐｔ）を用い、参照極（対極）
には金（Ａｕ）、白金（Ｐｔ）、銀（Ａｇ）等を用い
る。The pair of metal electrodes 12 formed on the PI film 11 catches the increase and decrease of oxygen and hydrogen peroxide due to the enzymatic reaction in the enzyme film 14 as a change in oxidation current. Various metals are used as the electrode, but platinum (Pt) is mainly used as the working electrode, and the reference electrode (counter electrode) is used.
For this, gold (Au), platinum (Pt), silver (Ag), or the like is used.
【００１４】この金属電極１２上に形成される高分子膜
１３は、金属電極１２をコーティングして更に加熱する
ことにより形成されたものである。使用される高分子材
料としては、陽イオン交換膜が好ましい。その陽イオン
交換膜の中でも取り分けデュポン社製のｎａｆｉｏｎ
（商品名）が最適である。ｎａｆｉｏｎ等のイオン交換
膜は、セルロース膜等の高分子膜に比べて、試料中の電
極妨害物質の透過抑制や過酸化水素の選択的透過性に優
れている。The polymer film 13 formed on the metal electrode 12 is formed by coating the metal electrode 12 and further heating it. As the polymer material used, a cation exchange membrane is preferable. Among the cation exchange membranes, especially Nafion made by DuPont
(Product name) is most suitable. An ion exchange membrane such as Nafion is superior to a polymer membrane such as a cellulose membrane in suppressing permeation of an electrode interfering substance in a sample and selective permeation of hydrogen peroxide.
【００１５】このような高分子膜を金属電極１２上にコ
ーティングした後に加熱処理するわけであるが、例えば
高分子材料にｎａｆｉｏｎを用いた場合には、約１７０
℃で６０分程度加熱する。この加熱処理により、コーテ
ィングのみの場合に比べて材料が本来持つ特性が更に向
上する。又、高分子膜１３は図１では２層からなるが、
層数には制限はない。しかしながら、高分子膜１３の膜
厚が厚いほど、試料中の電極妨害物質の透過をより制限
できるので、１層でも複数層でも層数にかかわらず、酵
素センサ全体の厚さを考慮しつつ膜厚を厚くするほうが
好ましい。The polymer film is coated on the metal electrode 12 and then heat-treated. For example, when nafion is used as the polymer material, about 170 is used.
Heat at 60 ° C for about 60 minutes. This heat treatment further improves the inherent properties of the material as compared with the case of coating alone. The polymer film 13 is composed of two layers in FIG.
There is no limit to the number of layers. However, as the film thickness of the polymer film 13 is larger, the permeation of the electrode interfering substance in the sample can be more restricted. Therefore, regardless of the number of layers, whether it is one layer or a plurality of layers, the total thickness of the enzyme sensor is taken into consideration. It is preferable to increase the thickness.
【００１６】高分子膜１３上に形成される固定化酵素膜
１４は、通常のものでよく、官能基を有する架橋材を用
いる架橋法、ゲルの格子内や高分子で被覆する包括法等
を用いて形成される。例えば、酵素としてグルコース酸
化酵素を使用する場合は、酵素反応が、
Glucose ＋Ｏ2 →グルコン酸＋Ｈ2 Ｏ2
となり、グルコースの分解に伴って、酸素（Ｏ2 ）が消
費（減少）されて、過酸化水素（Ｈ2 Ｏ2 ）が発生（増
加）すると共に、グルコン酸が発生（ｐＨ減少）する。
なお、固定化酵素膜１４も、図１では２層からなるが、
これも適宜増減すればよい。The immobilized enzyme membrane 14 formed on the polymer membrane 13 may be an ordinary one, such as a cross-linking method using a cross-linking material having a functional group, an encapsulation method in which a gel lattice or a polymer is coated. Is formed using. For example, when glucose oxidase is used as the enzyme, the enzymatic reaction is Glucose + O 2 → gluconic acid + H 2 O 2 , and oxygen (O 2 ) is consumed (decreased) with the decomposition of glucose, resulting in excess. Hydrogen oxide (H 2 O 2 ) is generated (increased) and gluconic acid is generated (pH decreased).
Although the immobilized enzyme membrane 14 is also composed of two layers in FIG. 1,
This may also be increased or decreased as appropriate.
【００１７】固定化酵素膜１４上に設けられるＰＣ膜１
６は、高分子接着剤膜１５で酵素膜１４に固着されてい
る。ＰＣ膜１６の一方面側（上面側）及び他方面側（下
面側）、即ち全周面は、高分子膜１７で被覆されてい
る。高分子膜１７の材料としては、たんぱく質固定化膜
等があるが、アルブミンとグルタルアルデヒドを用いて
形成するのが好ましい。アルブミンは、ＰＣ膜１６の特
長である均一な大きさの微小孔の目詰まりを防止する一
方、尿成分の湿潤拡散やグルコースの透過に効果的であ
り、ＰＣ膜１６が本来持つ特長を活かしつつ目詰まりを
防止できる。PC film 1 provided on the immobilized enzyme film 14
6 is fixed to the enzyme film 14 by a polymer adhesive film 15. One side (upper surface side) and the other surface side (lower surface side) of the PC film 16, that is, the entire peripheral surface is covered with the polymer film 17. As a material for the polymer film 17, there is a protein immobilization film or the like, but it is preferable to form it by using albumin and glutaraldehyde. Albumin is effective for the wet diffusion of urine components and the permeation of glucose, while preventing the clogging of the uniformly sized micropores which is a characteristic of the PC membrane 16, while utilizing the original characteristics of the PC membrane 16. It can prevent clogging.
【００１８】又、アルブミン等の高分子膜１７を使用す
ることで、酵素センサの感度検査を行うことができる。
即ち、高分子膜１７によりＰＣ膜１６へのゴミの付着を
防げるので、酵素センサの感度チェックをしてから酵素
センサを乾燥状態で出荷し、使用者が検査時に尿で濡ら
せば出荷時と同じ感度で使用でき、酵素センサの全数チ
ェックを行え、信頼性が高まる。高分子膜１７で被覆さ
れたＰＣ膜１６は、高分子膜１７と同じ材料（例えばア
ルブミン）からなる接着剤膜１５により固定化酵素膜１
４に密着される。なお、高分子膜１７は、ＰＣ膜１６の
上面側にのみ設けてもよいが、下面側にも設けること
で、高分子膜１７の形成が容易になるだけでなく、接着
剤膜を兼ねさせることもでき、それだけ材料・工程の省
略化を実現できる。Further, by using the polymer film 17 such as albumin, the sensitivity test of the enzyme sensor can be conducted.
That is, since the polymer film 17 can prevent dust from adhering to the PC film 16, the sensitivity of the enzyme sensor is checked, and then the enzyme sensor is shipped in a dry state. It can be used with high sensitivity, and all the enzyme sensors can be checked, increasing reliability. The PC membrane 16 covered with the polymer membrane 17 is the immobilized enzyme membrane 1 with the adhesive membrane 15 made of the same material as the polymer membrane 17 (eg albumin).
It is in close contact with 4. The polymer film 17 may be provided only on the upper surface side of the PC film 16, but by providing it on the lower surface side, not only the formation of the polymer film 17 is facilitated but also the adhesive film is used. Therefore, it is possible to reduce the number of materials and processes.
【００１９】上記の各膜の形成には、ディップコート法
やスピンコート法を用いることで、薄く均一な膜を得る
ことができる。A thin and uniform film can be obtained by using a dip coating method or a spin coating method for forming each of the above films.
【００２０】[0020]
【発明の効果】以上説明したように、請求項１記載のプ
レーナ型酵素センサによれば、過酸化水素電極上の高分
子膜がコーティングだけでなく、更に加熱により形成さ
れているため、過酸化水素の透過性を維持しつつ試料中
の電極妨害物質の透過を十分に制限できる。つまり、高
分子膜の性能が加熱処理により更に向上することにな
る。特に、高分子膜としてイオン交換膜を使用すること
（請求項２記載）により、より一層良好な特性が得られ
る。As described above, according to the planar type enzyme sensor of claim 1, since the polymer film on the hydrogen peroxide electrode is formed not only by coating but also by heating, the peroxide It is possible to sufficiently limit the permeation of the electrode interfering substance in the sample while maintaining the hydrogen permeability. That is, the performance of the polymer film is further improved by the heat treatment. In particular, by using an ion exchange membrane as the polymer membrane (claim 2 ), better characteristics can be obtained.
【００２１】また、固定化酵素膜上に少なくとも一方面
側が高分子膜で被覆されたポリカーボネイト膜（ＰＣ
膜）が設けられているので、グルコースの透過量が均一
になるだけでなく、ＰＣ膜の目詰まりを防止できる。
又、高分子膜によりＰＣ膜へのゴミ等の付着を防げるの
で、酵素センサを全数チェックすることができ、酵素セ
ンサの信頼性が高まる。 Also, a polycarbonate membrane (PC) having at least one surface side coated with a polymer membrane on an immobilized enzyme membrane
Since the membrane is provided, not only the glucose permeation amount becomes uniform, but also the clogging of the PC membrane can be prevented.
Further, since the polymer film can prevent dust and the like from adhering to the PC film, all the enzyme sensors can be checked and the reliability of the enzyme sensors is enhanced.
【００２２】特に、ＰＣ膜を被覆する高分子膜として、
アルブミンとグルタルアルデヒドからなる膜を使用する
こと（請求項４記載）により、より一層良好な目詰まり
防止とグルコースの透過性を示すことになる。つまり、
ＰＣ膜が本来持つ性能を保ったまま目詰まり防止作用を
一層向上させることができる。In particular, as a polymer film covering the PC film,
By using a membrane composed of albumin and glutaraldehyde (claim 4 ), even better prevention of clogging and glucose permeability will be exhibited. That is,
It is possible to further improve the function of preventing clogging while maintaining the original performance of the PC film.
【図１】実施形態に係るプレーナ型酵素センサをセンサ
ホルダに内蔵した状態での検出部における横断面図であ
る。FIG. 1 is a cross-sectional view of a detection unit in a state where a planar enzyme sensor according to an embodiment is built in a sensor holder.
【図２】プレーナ型酵素センサを使用する尿測定器の表
側の外観斜視図（ａ）、及び裏側の外観斜視図（ｂ）で
ある。FIG. 2 is a front perspective view (a) and a rear perspective view (b) of a urine measuring instrument using a planar enzyme sensor.
【図３】従来例に係るプレーナ型酵素センサをセンサホ
ルダに内蔵した状態での検出部における横断面図であ
る。FIG. 3 is a transverse cross-sectional view of a detection unit in a state where a planar type enzyme sensor according to a conventional example is built in a sensor holder.
１ 尿測定器 ６ 測定器本体 １１ ＰＩフィルム（絶縁基板） １２ 金属電極（過酸化水素電極） １３ 高分子膜 １４ 固定化酵素膜 １５ 高分子接着剤膜 １６ ポリカーボネイト膜 １７ 高分子膜 1 urine meter 6 Measuring instrument body 11 PI film (insulating substrate) 12 Metal electrode (hydrogen peroxide electrode) 13 Polymer membrane 14 Immobilized enzyme membrane 15 Polymer adhesive film 16 Polycarbonate film 17 Polymer membrane
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田中 孝英 京都市右京区山ノ内山ノ下町24番地 株 式会社オムロンライフサイエンス研究所 内 (72)発明者 遠藤 英樹 京都市右京区山ノ内山ノ下町24番地 株 式会社オムロンライフサイエンス研究所 内 (72)発明者 稲上 三佐子 京都市右京区山ノ内山ノ下町24番地 株 式会社オムロンライフサイエンス研究所 内 (72)発明者 迫田 勇策 京都市右京区山ノ内山ノ下町24番地 株 式会社オムロンライフサイエンス研究所 内 (56)参考文献 特開 平４−194661（ＪＰ，Ａ) 特開 昭62−261952（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Takahide Tanaka 24, Yamanouchi-Yamanoshitamachi, Ukyo-ku, Kyoto Omron Life Science Research Institute Within (72) Inventor Hideki Endo 24, Yamanouchi-Yamanoshitamachi, Ukyo-ku, Kyoto Omron Life Science Research Institute Within (72) Inventor Misako Inoue 24, Yamanouchi-Yamanoshitamachi, Ukyo-ku, Kyoto Omron Life Science Research Institute Within (72) Inventor Yusaku Sakoda 24, Yamanouchi-Yamanoshitamachi, Ukyo-ku, Kyoto Omron Life Science Research Institute Within (56) Reference JP-A-4-194661 (JP, A) JP 62-261952 (JP, A)
Claims (4)
の過酸化水素電極上に、高分子膜をコーティングし更に
加熱して形成し、この高分子膜上に固定化酵素膜を設
け、この固定化酵素膜上に、少なくとも一方面側を高分
子膜で被覆したポリカーボネイト膜をその他方面側を固
定化酵素膜側にして設けてなることを特徴とするプレー
ナ型酵素センサ。1. A hydrogen peroxide electrode is formed on an insulating substrate , and a polymer film is coated on the hydrogen peroxide electrode.
It is formed by heating, and an immobilized enzyme membrane is provided on this polymer membrane.On this immobilized enzyme membrane, a polycarbonate membrane coated with a polymer membrane on at least one side is immobilized enzyme membrane side on the other side. A planar-type enzyme sensor characterized by being provided as.
分子膜は、イオン交換膜であることを特徴とする請求項
１記載のプレーナ型酵素センサ。2. The polymer membrane coating the hydrogen peroxide electrode is an ion exchange membrane.
1 Symbol placement planar type enzyme sensor.
分子膜で被覆されていることを特徴とする請求項１記載
のプレーナ型酵素センサ。Wherein the polycarbonate membrane is planar type enzyme sensor according to claim 1, wherein the other surface side is coated with a polymer film.
膜は、アルブミンとグルタルアルデヒドからなることを
特徴とする請求項１又は請求項３記載のプレーナ型酵素
センサ。4. A polymer film covering the polycarbonate film, planar-type enzyme sensor according to claim 1 or claim 3, wherein the consisting of albumin and glutaraldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12418096A JP3451517B2 (en) | 1996-05-20 | 1996-05-20 | Planar type enzyme sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12418096A JP3451517B2 (en) | 1996-05-20 | 1996-05-20 | Planar type enzyme sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09304330A JPH09304330A (en) | 1997-11-28 |
| JP3451517B2 true JP3451517B2 (en) | 2003-09-29 |
Family
ID=14878964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12418096A Expired - Fee Related JP3451517B2 (en) | 1996-05-20 | 1996-05-20 | Planar type enzyme sensor |
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| Country | Link |
|---|---|
| JP (1) | JP3451517B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002221508A (en) * | 2001-01-29 | 2002-08-09 | Toyota Central Res & Dev Lab Inc | Biosensor |
| SG11201406203UA (en) | 2012-04-19 | 2014-11-27 | Aytu Bioscience Inc | Multiple layer gel |
| CA2847665A1 (en) | 2012-10-23 | 2014-04-23 | Raphael Bar-Or | Methods and systems for measuring and using the oxidation-reduction potential of a biological sample |
| TWI706131B (en) * | 2019-08-26 | 2020-10-01 | 臺灣塑膠工業股份有限公司 | Urine testing strip and urine testing system |
-
1996
- 1996-05-20 JP JP12418096A patent/JP3451517B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09304330A (en) | 1997-11-28 |
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