JPH0814541B2 - Optical fiber sensor - Google Patents
Optical fiber sensorInfo
- Publication number
- JPH0814541B2 JPH0814541B2 JP62082275A JP8227587A JPH0814541B2 JP H0814541 B2 JPH0814541 B2 JP H0814541B2 JP 62082275 A JP62082275 A JP 62082275A JP 8227587 A JP8227587 A JP 8227587A JP H0814541 B2 JPH0814541 B2 JP H0814541B2
- Authority
- JP
- Japan
- Prior art keywords
- optical fiber
- reaction chamber
- enzyme
- enzyme reaction
- fiber 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
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/7703—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、試料液中の特定物質の測定に用いられる光
ファイバーセンサーに関する。TECHNICAL FIELD The present invention relates to an optical fiber sensor used for measuring a specific substance in a sample liquid.
従来、例えば試料液中のグルコース濃度の、酵素反応
を利用した測定装置として酵素固定化膜を使用した電
極、半導体、サーミスター等が知られている。2. Description of the Related Art Conventionally, electrodes, semiconductors, thermistors and the like using an enzyme-immobilized membrane have been known as measuring devices utilizing the enzyme reaction, for example, the glucose concentration in a sample solution.
しかし、酵素固定化膜を使用した電極は液中のイオン
強度などにより測定が影響を受け易い、小型化が困難、
測定対象がせまい、電磁誘導の妨害を受け易い等の欠点
を有し、半導体、サーミスターも同様の欠点を一部有し
ている。However, an electrode using an enzyme-immobilized membrane is easily affected by measurement due to ionic strength in the liquid, etc.
There are drawbacks such as a small measurement object and easy interference with electromagnetic induction, and semiconductors and thermistors also have some similar drawbacks.
そこで、本発明は液のイオン強度などにより影響され
ず高精度の測定を短時間で行なうことができ、かつ小型
化が容易である光ファイバーセンサーを提供することに
ある。Therefore, the present invention is to provide an optical fiber sensor that can perform highly accurate measurement in a short time without being affected by the ionic strength of a liquid and can be easily downsized.
本発明は、前記の問題点を解決するものとして、酵素
反応及び該酵素反応の生成物を反応物とする発色反応を
利用する特定物質の光ファイバーセンサーであって、 前記酵素反応に関与する酵素を固定化した磁気微粒子
が媒体中に分散され、使用時に試料液と接触する底壁が
液透過性膜で形成されている酵素反応室と、 前記酵素反応室の上に、少なくとも上面が白色である
液透過性膜をはさんで設けられ、前記発色反応に必要な
前記生成物以外の反応成分を含有する室であって、上部
に光ファイバーが導入されている発色反応室と を備えてなる光ファイバーセンサーを提供するものであ
る。MEANS TO SOLVE THE PROBLEM This invention is an optical fiber sensor of a specific substance which utilizes an enzyme reaction and a color development reaction which makes the product of this enzyme reaction a reaction thing as what solves the said problem, Comprising: An enzyme reaction chamber in which the immobilized magnetic fine particles are dispersed in a medium, and a bottom wall which comes into contact with a sample solution at the time of use is formed of a liquid permeable membrane, and at least an upper surface of the enzyme reaction chamber is white. An optical fiber sensor provided with a liquid permeable membrane and containing a reaction component other than the product necessary for the color forming reaction, the color forming reaction chamber having an optical fiber introduced therein. Is provided.
本発明の光ファイバーセンサーに利用される酵素反応
及び発色反応としては種々のものが挙げられるが、以
下、グルコースオキシダーゼ（GOD）を用いて試料液中
のグルコースを測定するグルコースセンサーを例に、本
発明の光ファイバーセンサーを説明する。Examples of the enzymatic reaction and the color reaction used in the optical fiber sensor of the present invention include various ones. Hereinafter, the present invention will be described with reference to a glucose sensor that measures glucose in a sample solution using glucose oxidase (GOD). The optical fiber sensor of will be described.
本発明のセンサー（センサープローブ）は、測定の際
には試料液に浸漬されるが、酵素反応室の底壁は液透過
性であるため、試料液中にグルコースが存在すると、液
透過性膜を通って酵素反応室へ浸透する。酵素反応室内
にはグルコースオキシダーゼが固定化された磁気微粒子
が分散しているので、式： で表わされる酵素反応が進行し、過酸化水素（H2O2）が
生成する。生成した過酸化水素は拡散し、上方の液透過
性膜を通って発色反応室の中へ浸透して行く。発色反応
室にはオルトジアニシジンとペルオキシダーゼを含む溶
液が入っており、過酸化水素によるオルトジアニシジン
の酸化による発色反応が生起する。酸化オルトジアニシ
ジンは過酸化水素が液透過性膜を透過すると同時に生成
しその膜を着色する。酸化オルトジアニシジンは436nm
にピークをもつ吸光を有する。発色反応室上部に導入さ
れた入射用光ファイバーからの光を前記の膜に照射し反
射光を出射用光ファイバーにより導出し、外部で膜の着
色に伴なう吸光度変化を例えば電圧変化に変えて測定す
る。The sensor (sensor probe) of the present invention is immersed in the sample solution at the time of measurement, but since the bottom wall of the enzyme reaction chamber is liquid permeable, when glucose is present in the sample solution, the liquid permeable membrane is present. Permeate through to the enzyme reaction chamber. Since the magnetic particles having glucose oxidase immobilized thereon are dispersed in the enzyme reaction chamber, the formula: The enzymatic reaction represented by is progressed, and hydrogen peroxide (H 2 O 2 ) is produced. The produced hydrogen peroxide diffuses and permeates into the color reaction chamber through the upper liquid-permeable membrane. The color reaction chamber contains a solution containing orthodianisidine and peroxidase, and a color reaction occurs due to the oxidation of orthodianisidine by hydrogen peroxide. Orthodianisidine oxide forms at the same time as hydrogen peroxide permeates the liquid-permeable membrane, and colors the membrane. 436 nm for oxidized orthodianisidine
It has an absorbance with a peak at. Light from the incident optical fiber introduced to the upper part of the coloring reaction chamber is applied to the film, and the reflected light is led out by the outgoing optical fiber, and the change in the absorbance due to the coloring of the film is converted to, for example, the voltage change, and measured. To do.
以上が本発明の光ファイバーセンサーの機能及び測定
の概要であるが、このセンサーを構成する部材は次のよ
うなものである。The above is the outline of the function and measurement of the optical fiber sensor of the present invention. The members constituting this sensor are as follows.
酵素反応室に分散される酵素固定化用の磁気微粒子の
材料は、特に限定されず、例えば、Fe3O4、γ−Fe2O3、
Co−γ−Fe2O3、（NiCuZn）Ｏ・Fe2O3、（CuZn）Ｏ・Fe
2O3、（Mn・Zn）Ｏ・Fe2O3、（NiZn）Ｏ・Fe2O3、SrO・
6Fe2O3、BaO・6Fe2O3、SiO2で被覆したFe3O4（粒径約20
0Å）（Enzyme Microb.Technol.,vol.2,p.2−10（198
0）参照〕、各種の高分子材料（ナイロン、ポリアクリ
ルアミド等）とフェライトとの複合微粒子等が挙げられ
る。また、これらの磁気微粒子の粒径は、200Å〜10μ
ｍの範囲が好ましく、特に、200Å〜１μｍの範囲であ
ることが好ましい。磁気微粒子の粒径が小さすぎると後
述する外部磁場による撹拌が不可能となるか、もしくは
非常に強い磁場を要する。また、粒径が大きすぎると試
料液に良好に分散させることが困難となる。Material of the magnetic particles for enzyme immobilization, which is dispersed in the enzyme reaction chamber are not particularly limited, for example, Fe 3 O 4, γ- Fe 2 O 3,
Co-γ-Fe 2 O 3 , (NiCuZn) O · Fe 2 O 3 , (CuZn) O · Fe
2 O 3 , (Mn ・ Zn) O ・ Fe 2 O 3 , (NiZn) O ・ Fe 2 O 3 , SrO ・
6Fe 2 O 3 , BaO ・ 6Fe 2 O 3 , and Fe 3 O 4 coated with SiO 2 (particle size about 20
0Å) (Enzyme Microb.Technol., Vol.2, p.2-10 (198
0)], composite fine particles of various polymer materials (nylon, polyacrylamide, etc.) and ferrite, and the like. The particle size of these magnetic particles is 200Å ~ 10μ.
The range of m is preferable, and the range of 200 Å to 1 μm is particularly preferable. If the particle size of the magnetic fine particles is too small, stirring by an external magnetic field described later becomes impossible or a very strong magnetic field is required. Further, if the particle size is too large, it becomes difficult to disperse it well in the sample liquid.
上記の材料および粒径を有するものの中でも特に好ま
しいものとして、SiO2で被覆した粒径約200ÅのFe3O4粒
子、及び粒径200〜300Åのγ−Fe2O3粒子を挙げること
ができる。さらに、このような好ましい磁気微粒子とし
て、走磁性細菌から得られる磁鉄鉱（Fe3O4）からなる
微粒子（粒径約500Å）が挙げられる。前記走磁性細菌
は、例えば特願昭60−203129号に開示された方法および
採取器により淡水又は海水から容易に採取することがで
きる。Among the materials having the above-mentioned materials and particle diameters, particularly preferable are Fe 3 O 4 particles having a particle diameter of about 200Å coated with SiO 2 , and γ-Fe 2 O 3 particles having a particle diameter of 200 to 300Å. . Further, such preferable magnetic fine particles include fine particles (particle size of about 500Å) made of magnetite (Fe 3 O 4 ) obtained from magnetotactic bacteria. The magnetotactic bacterium can be easily collected from fresh water or seawater by, for example, the method and collector disclosed in Japanese Patent Application No. 60-203129.
磁気微粒子への酵素の固定化は公知の方法により行な
うことができ、例えばシランカップリング剤の利用が挙
げられる。Immobilization of the enzyme on the magnetic fine particles can be carried out by a known method, and examples thereof include the use of a silane coupling agent.
酵素反応室の底壁を構成する液透過性膜は、試料液中
のグルコースを透過するが酵素反応室中の磁気微粒子を
透過するものであってならず、したがって、通常、孔径
25Å〜100Å程度の多孔質の膜が用いられる。酵素反応
室と発色反応室との間の隔膜も、同様に、過酸化水素の
拡散を妨げないが磁気微粒子の透過を防止するものであ
る必要があるので、上記と同様の多孔質の膜が用いられ
る。このような液透過性膜の具体例としては、ニトロセ
ルロース膜、セルロース膜、ガラスフィルター、セラミ
ックフィルター等が挙げられる。The liquid-permeable membrane that constitutes the bottom wall of the enzyme reaction chamber does not allow the permeation of glucose in the sample solution but the magnetic fine particles in the enzyme reaction chamber.
A porous membrane of about 25Å to 100Å is used. Similarly, the membrane between the enzyme reaction chamber and the color reaction chamber also needs to prevent the permeation of magnetic fine particles without hindering the diffusion of hydrogen peroxide. Used. Specific examples of such a liquid-permeable membrane include a nitrocellulose membrane, a cellulose membrane, a glass filter and a ceramic filter.
酵素反応室と発色反応室との間の隔膜の上面は、光フ
ァイバーからの入射光の反射面として機能するので白色
である必要がある。使用した液透過性膜が白色でない場
合には、その膜の上面に反射用の白色膜を重ねるなどの
措置が必要である。The upper surface of the diaphragm between the enzyme reaction chamber and the color reaction chamber needs to be white because it functions as a reflection surface of the incident light from the optical fiber. If the liquid-permeable film used is not white, it is necessary to take measures such as overlaying a white film for reflection on the upper surface of the film.
本発明のセンサーを用いて測定を行なう際には、測定
中に酵素反応室内の磁気微粒子に外部から磁場を加える
ことが望ましく、これにより磁気微粒子を振動させ、撹
拌し、酵素と基質である被測定物質との接触を促進でき
る結果、より迅速な測定が可能である。When performing the measurement using the sensor of the present invention, it is desirable to apply a magnetic field from outside to the magnetic fine particles in the enzyme reaction chamber during the measurement, whereby the magnetic fine particles are vibrated and agitated, and the enzyme and the substrate which are the substrates are stirred. As a result of facilitating contact with the measurement substance, more rapid measurement is possible.
本発明のセンサーに用いられる、酵素及び発色反応成
分は被測定物質に応じて種々選択可能であり、前記のグ
ルコースの場合のほか下記表１の例が挙げられる。いず
れの場合も、発色物質としては、オルトジアニシジンの
ほか、４−アミノフェナジンとN,N−ジメチルアミン
（カラターゼ）;4−アミノフェナジンと3,5−ジクロロ
−２−ヒドロキシベンゼンスルホン酸（カタラーゼ）を
用いることができる。The enzyme and the color-forming reaction component used in the sensor of the present invention can be variously selected according to the substance to be measured, and in addition to the above-mentioned case of glucose, examples of Table 1 below can be mentioned. In any case, as the color-developing substance, in addition to orthodianisidine, 4-aminophenazine and N, N-dimethylamine (calatase); 4-aminophenazine and 3,5-dichloro-2-hydroxybenzenesulfonic acid (catalase ) Can be used.
〔実施例〕 次に、本発明の実施例である光ファイバーグルコース
センサーを第１図の概念図により説明する。 Example Next, an optical fiber glucose sensor which is an example of the present invention will be described with reference to the conceptual diagram of FIG.
このセンサー（センサープローブ）１は、下部の酵素
反応室２とその上の発色反応室３とからなり、発色反応
室３の上部には２本の光ファイバー4,5が導入されてい
る。２つの室の間の隔膜６はニトロセルロース膜（商品
名 メンブランフィルター）からなり、強度補助のため
に透析膜（セルロース膜）が下側に重ねられている。ニ
トロセルロース膜６は白色で光反射膜としても機能す
る。光ファイバー4,5は、ニトロセルロース膜６に対し
て垂直な方向で導入され、プローブ１のガラス製ケーシ
ングにエポキシ樹脂７で固定されている。酵素反応室２
の底壁８は透析膜（孔径27Å）で構成されている。酵素
反応室２（容積0.1ml）には、人工の平均粒径1000Åの
磁鉄鉱粒子にγ−アミノプロピルトリエトキシシランを
用いて常法によりグルコースオキシダーゼを固定化した
もの（固定化量7.6μg/ml）が5mgで分散されている。ま
た、発色反応室３には、オルトジアニシジン（0.066mg/
ml）及びペルオキシダーゼを含む溶液が入っている。This sensor (sensor probe) 1 is composed of an enzyme reaction chamber 2 at the bottom and a color reaction chamber 3 above it, and two optical fibers 4 and 5 are introduced above the color reaction chamber 3. The diaphragm 6 between the two chambers is composed of a nitrocellulose membrane (trade name: membrane filter), and a dialysis membrane (cellulose membrane) is laminated on the lower side to assist strength. The nitrocellulose film 6 is white and also functions as a light reflecting film. The optical fibers 4 and 5 are introduced in a direction perpendicular to the nitrocellulose film 6 and fixed to the glass casing of the probe 1 with an epoxy resin 7. Enzyme reaction chamber 2
The bottom wall 8 is composed of a dialysis membrane (pore diameter 27Å). In the enzyme reaction chamber 2 (volume 0.1 ml), artificial magnetite particles with an average particle size of 1000 Å were immobilized with glucose oxidase by a conventional method using γ-aminopropyltriethoxysilane (immobilization amount: 7.6 μg / ml). ) Is dispersed at 5 mg. In addition, orthodianisidine (0.066 mg /
ml) and a solution containing peroxidase.
上記センサーを第２図に示す装置系に組み試料液21中
のグルコース濃度を測定した。試料及びセンサー１はし
ゃへい体22で光をしゃ断した暗所内に置かれ、かつマグ
ネット撹拌装置23の上に配されている。センサー１に接
続された入射用光ファイバー４、出射用光ファイバー５
は、光源、検出器及び増幅器を備えた測定装置24に接続
されている。試料21中のグルコース濃度は波長436nmに
おける吸光度変化として検知され、電圧変化に変えて測
定された後レコーダー25に出力される。The sensor was assembled in the apparatus system shown in FIG. 2 and the glucose concentration in the sample liquid 21 was measured. The sample and the sensor 1 are placed in a dark place where light is shielded by a shield 22 and are arranged on a magnet agitator 23. Input optical fiber 4 and output optical fiber 5 connected to the sensor 1.
Is connected to a measuring device 24 equipped with a light source, a detector and an amplifier. The glucose concentration in the sample 21 is detected as a change in absorbance at a wavelength of 436 nm, converted into a voltage change, measured, and then output to the recorder 25.
この装置系を使用して、濃度4mg/mlでグルコースを含
む試料液を測定した。測定開始後の得られた電圧変化の
時間的推移を、マグネット撹拌装置23を動作させて測定
を行なった場合と、動作させないで行なった場合につい
て観測したところ、第３図に示す結果が得られた。マグ
ネット撹拌装置により、磁気微粒子に加わる磁場を変動
させることにより酵素反応が促進され、より迅速に測定
結果が得られることがわかる。Using this device system, a sample solution containing glucose at a concentration of 4 mg / ml was measured. The time course of the voltage change obtained after the start of measurement was observed with and without the magnet agitator 23 being operated, and the results shown in Fig. 3 were obtained. It was It can be seen that the enzyme reaction is promoted by changing the magnetic field applied to the magnetic fine particles by the magnetic stirrer, and the measurement result can be obtained more quickly.
同じ装置系を用い、種々の濃度でグルコースを含む試
料液について、測定時間８分で、波長436nmにおける吸
光度の変化を求めたところ、第４図に示す検量線が得ら
れ、短時間で正確な測定が可能であることがわかる。な
お、マグネット撹拌装置23は作動させて測定した。Using the same device system, the change in absorbance at a wavelength of 436 nm was obtained for sample liquids containing glucose at various concentrations at a measurement time of 8 minutes, and the calibration curve shown in Fig. 4 was obtained. It turns out that measurement is possible. In addition, the magnetic stirring device 23 was operated and measured.
本発明の光ファイバーセンサーは、試料のイオン強度
などに影響されないで測定対象を正確、迅速に測定で
き、小型化も容易である。INDUSTRIAL APPLICABILITY The optical fiber sensor of the present invention can accurately and quickly measure an object to be measured without being affected by the ionic strength of the sample, and can be easily downsized.
第１図は本発明の光ファイバーセンサー例を概略的に示
し、第２図はそれを使用した装置系を示し、第３図、第
４図は実施例における測定結果を示す。 ２……酵素反応室、３……発色反応室、４、５……光フ
ァイバー、21……試料液、23……マグネット撹拌装置FIG. 1 schematically shows an example of the optical fiber sensor of the present invention, FIG. 2 shows an apparatus system using the same, and FIGS. 3 and 4 show measurement results in Examples. 2 ... Enzyme reaction chamber, 3 ... Color development reaction chamber, 4, 5 ... Optical fiber, 21 ... Sample solution, 23 ... Magnet stirring device
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 Ａｎａｌ．Ｃｈｅｍ．，57，Ｐ．565, （1985) ─────────────────────────────────────────────────── ─── Continued Front Page (56) References Anal. Chem. , 57, p. 565, (1985)
Claims (1)
とする発色反応を利用する特定物質の光ファイバーセン
サーであって、 前記酵素反応に関与する酵素を固定化した磁気微粒子が
媒体中に分散され、使用時に試料液と接触する底壁が液
透過性膜で形成されている酵素反応室と、 前記酵素反応室の上に、少なくとも上面が白色である液
透過性膜をはさんで設けられ、前記発色反応に必要な前
記生成物以外の反応成分を含有する室であって、上部に
光ファイバーが導入されている発色反応室と を備えてなる光ファイバーセンサー。1. An optical fiber sensor for a specific substance utilizing an enzyme reaction and a color development reaction using a product of the enzyme reaction as a reactant, wherein magnetic fine particles having an enzyme involved in the enzyme reaction immobilized in a medium. An enzyme reaction chamber having a bottom wall formed of a liquid permeable membrane that is dispersed and comes into contact with a sample solution at the time of use, and a liquid permeable membrane having at least a white upper surface is provided on the enzyme reaction chamber. An optical fiber sensor, which comprises a chamber containing a reaction component other than the product necessary for the color forming reaction, and a color forming reaction chamber into which an optical fiber is introduced.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62082275A JPH0814541B2 (en) | 1987-04-03 | 1987-04-03 | Optical fiber sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62082275A JPH0814541B2 (en) | 1987-04-03 | 1987-04-03 | Optical fiber sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63247646A JPS63247646A (en) | 1988-10-14 |
| JPH0814541B2 true JPH0814541B2 (en) | 1996-02-14 |
Family
ID=13769943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62082275A Expired - Fee Related JPH0814541B2 (en) | 1987-04-03 | 1987-04-03 | Optical fiber sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0814541B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2747933B2 (en) * | 1989-05-11 | 1998-05-06 | 日本特殊陶業株式会社 | Concentration measuring method and concentration measuring device |
| AU2003266899B2 (en) | 2002-09-20 | 2008-02-28 | Queen's University At Kingston | Detection of biological molecules by differential partitioning of enzyme substrates and products |
| GB0612834D0 (en) * | 2006-06-28 | 2006-08-09 | Glysure Ltd | Sensor calibration |
| US8841105B2 (en) | 2009-03-27 | 2014-09-23 | National University Corporation Okayama University | Organic-inorganic composite material and process for producing same |
| US8746031B2 (en) | 2009-05-18 | 2014-06-10 | Lightship Medical Limited | Glucose sensor calibration |
| WO2011156915A2 (en) | 2010-06-18 | 2011-12-22 | Pathogen Detection Systems, Inc. | Method and system for detecting biological molecules in samples |
| WO2012090919A1 (en) * | 2010-12-27 | 2012-07-05 | ローム株式会社 | Chip for light sensor, light sensor, measurement system, and measurement method using same |
| GB201401878D0 (en) | 2014-02-04 | 2014-03-19 | Lightship Medical Ltd | Calibration method |
-
1987
- 1987-04-03 JP JP62082275A patent/JPH0814541B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| Ａｎａｌ．Ｃｈｅｍ．，５７，Ｐ．５６５，（１９８５） |
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| Publication number | Publication date |
|---|---|
| JPS63247646A (en) | 1988-10-14 |
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