JPS6159727B2 - - Google Patents

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Publication number
JPS6159727B2
JPS6159727B2 JP53147075A JP14707578A JPS6159727B2 JP S6159727 B2 JPS6159727 B2 JP S6159727B2 JP 53147075 A JP53147075 A JP 53147075A JP 14707578 A JP14707578 A JP 14707578A JP S6159727 B2 JPS6159727 B2 JP S6159727B2
Authority
JP
Japan
Prior art keywords
dye
optical fiber
detector
containing material
light
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
Application number
JP53147075A
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English (en)
Other versions
JPS5485588A (en
Inventor
Aiban Piitaason Jon
Richaado Goorudosutein Sesu
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.)
US Department of Energy
Original Assignee
US Department of Energy
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Filing date
Publication date
Application filed by US Department of Energy filed Critical US Department of Energy
Publication of JPS5485588A publication Critical patent/JPS5485588A/ja
Publication of JPS6159727B2 publication Critical patent/JPS6159727B2/ja
Granted legal-status Critical Current

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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
    • G01N21/78—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 producing a change of colour
    • G01N21/80—Indicating pH value
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration or pH-value ; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid or cerebral tissue
    • A61B5/14539—Measuring characteristics of blood in vivo, e.g. gas concentration or pH-value ; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid or cerebral tissue for measuring pH
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration or pH-value ; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid or cerebral tissue
    • A61B5/1455—Measuring characteristics of blood in vivo, e.g. gas concentration or pH-value ; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid or cerebral tissue using optical sensors, e.g. spectral photometrical oximeters
    • A61B5/1459—Measuring characteristics of blood in vivo, e.g. gas concentration or pH-value ; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid or cerebral tissue using optical sensors, e.g. spectral photometrical oximeters invasive, e.g. introduced into the body by a catheter
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G01N31/221—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating pH value

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  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Molecular Biology (AREA)
  • Biophysics (AREA)
  • Analytical Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Biochemistry (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Surgery (AREA)
  • Veterinary Medicine (AREA)
  • Optics & Photonics (AREA)
  • Biomedical Technology (AREA)
  • Plasma & Fusion (AREA)
  • Medical Informatics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Investigating Or Analysing Biological Materials (AREA)
  • Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Measuring And Recording Apparatus For Diagnosis (AREA)

Description

【発明の詳細な説明】 この発明は生理学的研究のために人間または動
物の体内に植込むのに適した光フアイバーPH探知
子に関している。さらに詳しくは、この発明は可
逆性染料指示薬を用いかつ22ゲージ皮下針を通過
するに充分な小ささで研究すべき対象体の組織内
に植込むことのできる一本の光フアイバーで構成
された微少PH探知子の形態の光フアイバーPH探知
子に関している。この装置は研究すべき対象体の
運転中に使用するのに特に適している。
PHの決定は広範囲の生物学的研求において望ま
れている。特に、血中酸素含有量の研究に対し、
PHは酸素―ヘモグロビン解離曲線の重要なパラメ
ーターである。ある種の疾病例えば鎌状赤球貧血
症では、この曲線を運動中に体内で決定するのが
望ましい。
従来のPH感知子は、例えばJ.D.Czaban他、
Analytical Chemistry，47．11，P.1787〜1792
（1975年９月）および同48，２，P.277〜281
（1976年２月）に記載のように、皮下針に組み込
まれたガラス電極PH感知子を含んでいた。このよ
うな電極はある目的には適していても、この剛性
の針構成はその刺激性のために例えば運動の研究
のような生理学的研究には好ましくなかつた。さ
らにこの電極は電気的危険のために固有のリスク
があつた。
他のPH測定装置は、例えばUSP4033330および
USP4041932に示されているが、これらは体外よ
りPHを測定するように設計されていて体内に容易
に植え込めるように構成されていなかつた。
この発明により、柔軟構造で針を残すことなく
体内または体外で筋肉または他の組織に入れるこ
とのできる植込み可能のPH測定装置を提供する。
この発明のPH探知子は組立容易で非常に低価格な
ので使い捨て用として大量に容易に製造できる。
このPH探知子は一対の光フアイバーの端部を包囲
するイオン透過性半透膜外被を含んでいる。PH感
受性染料指示薬組成物が外被内部に存在してい
る。探知子はPH感受性染料の色相変化を光学的に
検知するように作動する。
第１図に示す光フアイバーPH探知子１０は一対
の光フアイバー１２，１３の末端を包囲するイオ
ン透過性半透膜外被１１を有している。外被１１
はチユーブ状、即ち中空の細長い円筒で２本のフ
アイバー１２，１３の周囲に密に係合しているの
が好ましい。半透膜１１およびフアイバー１２，
１３の端部内部にあるのは、PH指示染料含有組成
物１４である。適当なシール材料例えば紫外線硬
化性セメントを用いて半透膜１１の末端１５を密
封する。このシール材料は組立物を強固に一体的
に保持するために光フアイバー１２，１３を半透
膜１１に入れるときにも用いる。
半透膜外被１１は内部に包囲されている部品の
保護鞘を与えるように充分な丈夫さとともに破損
することなく身体の種々の部位内に容易に取付け
られるように充分な柔軟性または非脆弱性の適当
な任意の材料である。半透膜に対する別の要求
は、水素イオンを通過させるには充分な大きさの
孔であるが、染料の通過を阻止するような充分な
小ささのものを有することである。
良好な結果を伴つて使用されている半透膜１１
の一つの材料は、第１表に示す特性を有する再生
セルロースであるキユプロフアンB4AHとして公
知の透析用チユーブである。
第１表 キユプロフアンB4AHの半透膜強度測定値 引張り強さ 破断伸び 300ｇ以上 20％以上 使用したキユプロフアンチユーブは内径300ミ
クロン、壁厚15ミクロンを有していた。
PH指示染料含有材料１４は、半透膜１１ととも
に用いたとき、半透膜１１を通つて拡散すること
なくその内部で可視領域内に保持され所定の範囲
内のPHを指示する任意の各種の材料である。
半透膜１１の壁を通して可視領域外に拡散しな
いのに充分な大きさであれば、用いるべき染料物
質１４は染料それ自体である。このような染料の
例は、植物例えばazolitminから得られる天然染
料である。この染料は容易には拡散しないような
大きさの分子のものでPH指示薬として用いられ
る。重合体に結合させたような大分子量組成物で
なく、染料それ自体を用いることで起きる一つの
問題は、このような比較的低分子量染料物質に用
いる対応する半透膜１１は水素イオン拡散速度が
PHの良好な応答速度を与えるには低過ぎるような
孔寸法を有することである。このことは研究する
患者の運動中のPHの急速な変化を測定しようとす
るとき特に問題である。
もし用いるべき染料が充分な分子サイズを有し
ていなければ、これに代る方法は例えば重合体の
ような他の材料に結合させた染料を用いることで
ある。一般に用いられる染料は、PH指示染料、例
えばフタレインおよびスルフオフタレイン染料で
ある。この染料を他の分子に結合させる方法はマ
ンニツヒ型反応、即ちコンプレクソン製造のよう
な染料とアミノ基のホルムアルデヒド縮合ような
公知の方法である。この種の反応は例えばR.O.
Cinneide.Nature 175，47（1955年１月１日
号），Ｒ，Prible，Analyst 83，188〜195
（1958），スイス特許第298194号，USP 2745720お
よびSchwartzenbach外，Complexometric
Titrationに記載されている。染料を重合体に結
合させる他の方法は、例えばアミノ基を重合体に
結合させて誘導体化し、染料を引き続き反応でき
るようにすることで、これは例えばJ.K.Inman
外，Biochemistry８，4072〜4082（1969）に記
載されている。この方法は予じめ重合体を形成し
てから染料を結合させる必要がある。
PH指示染料を他の材料に結合させる別の方法は
結合したイソシアネート基を有する染料を用いる
ことで、この染料は例えばUSP 2937186の方法で
合成できる。染料の例としてはEastman
Organic Chemical Co.より市販の５(6)ローダミ
ンＢ―CNSおよびフルオレツセン―CNSがあ
る。イソシアネート基を有する染料は、この基を
介して活性水素と反応するので多数のその他のタ
イプの残基に結合できる、例えばUSP3847745お
よびJ.J.Haaijman外Journal of Immunological
Methods５，359〜374（1974）参照。後者の文献
にはフルオレツセンイソシアネートおよびローダ
ンミンイソシアネートをThe Pharmacia Corp.
より発売の親水性ポリサツカライド重体である
Sephadexのビーズに結合させることが記載され
ている。
一般に染料を化学的に結合させる方法は、染料
のアミノ基と反応するシアヌル酸クロライド用い
次いで支持体のアミノ基またはヒドロキシ基と反
応させて染料を支持体に化学的に結合させること
である。この方法は例えばC.V.Stead，The
Chemistry of Reactive Dyes andits Relevance
to Intracellular Staining Techniques，P41〜59
およびS.B.Katen外、Intracellular Staining in
Neurobiology，Springer―Verlag（1973）に記
載されている。
PH指示薬用染料は、例えばScience193，134〜
137（1976年７月９日）記載の方法でマイクロカ
プセル化で作ることもできる。染料組成物製造の
別法は、単量体に官能性基例えばヒドロキシ，ア
ミノまたはアミド基を含むアクリレートのような
フリーラジカル重合性ゲルを作り、次いで重合の
前または後に染料を官能性基と反応させることで
ある。
染料を親水性重合体に結合させる方法も、この
発明のPH探知子に用いるに適した染料含有材料を
作る別法である。この方法では、適当な染料をア
クリル系単量体例えばアクリルアミド，メチルメ
タクリレートまたはヒドロキシメチルメタクレー
ト（Hydron）と共重合させてPH指示染料を結合
させた親水性共重合体を形成して非拡散性形態の
染料を作るようにしている。この方法で共重合で
きる特定の染料にはフエノールレツド，ブリリア
ントエロー（CI14890）およびロゾール酸（オー
リン）がある。
さらに染料―重合体結合物はエマルジヨン（油
中水型）重合によつても作られる。この方法は同
日付の同一出願人の特許出願明細書に記載されて
いる。
光フアイバー１２，１３は例えば長さ約６フイ
ートのもので光源および光感知子（ともに通常の
もので図示せず）に関して装置１０に適当な運動
の自由性を与えるようにする。一方のフアイバー
１２はその真中の端部で光源に接続し、他のフア
イバー１３はその真中の端部で光感知子に接続す
る。光フアイバー１２，１３は普通の構造のもの
で一方のフアイバーは光線を光源から探知子１０
に向つて伝達し、他のフアイバーは光線を探知子
１０から受けて感知子に伝達するのに用いられ
る。フアイバー１２，１３は例えば直径約1/8mm
を有するプラスチツク光フアイバーである。２本
のフアイバー１２，１３は機械的保護のために直
径１mmのテフロンチユーブでその長さに沿つて検
知子の外側に被包される。
指示薬染料即ちフエノールレツドは一種の有機
酸（HA）で次の平衝関係で水素イオン（H+）お
よびアニオン（A-）に解離する。
Ｋ＝（Ｈ＋）（Ａ−）／（ＨＡ）＝解離恒数 式中括弧内は溶液の活性度または濃度を示す。
PH＝log〔１／（H+）〕と定議されるので PH＝−logK＋log（Ａ−）／（ＨＡ） ＝pK−log（解離恒数／Ａの光学密度−１） である。
第２図に実験的に示す通り、（A-）はその濃度
の関数として560nmで光を吸収するが、（HA）は
（A-）無関係ではない。したがつてPHと560nmで
の光学密度とは独特の関係がある。485nmでの吸
収はPHの関数ではないので（第２図参照）この波
長は560nmの光線を標準化する対照として用いら
れる。さもなければ染料は600nm以上のスペクト
ル領域の光線を吸収しないので、PHと無関係の
600nm以上の波長の光を用いる。検知子１０にお
いて、光が一方のフアイバーから他のフアイバー
に染料を通つて後方に散乱する場合にこれが所定
のPH範囲で起きれば、PHおよび560nmでの強さと
485nmでの強さとの比の関係は第３図に示すよう
に直線関係である。
前記の通り、光源および光感知子は普通の構造
のものである。したがつて、例えば励起光線は
150Wの高出力タングステン投光ランプにより与
えられる。強制対流冷却および赤外線反射用鏡を
用いてプラスチツクフアイバーが過熱されるのを
防止するる。プラスチツクフアイバーの大きな口
径（約1.2ラジアンの全挾角）は有効な有効な集
光を助ける。回帰光の測定は固体フオトダイオー
ド作動増幅機次いで高利得増幅機で行はれる。中
心波長560nmおよび485nmを有する８枚の狭バン
ド干渉フイルター（約5nm幅のハーフパワーポイ
ント）を、回帰光の出口と光感知子との間に設け
たモーター駆動ホイールの上に交互に置く。別法
としては560nm光線用の一枚のフイルターおよび
845nm光線用（または赤色）の一枚のフイルター
を交互にステツパーモーターで取付ける。長い滞
留時間は電気シグナル平均化に対しより長い時間
を可能にしその結果ノイズを減退させる。フイル
ターホイールに適当に設けた孔を通して投光され
る光線を検知する。さらに２個のフオトダイオー
ドにより発生する同期パルスは(a)560nm光線、(b)
485nm光線（または赤色）および(c)光の入力なし
に対する感知子出力を測定する３個のサンプルア
ンドホールド（Sampl―and―hold）モジユール
をコントロールする。光シグナル比をアナログデ
イバイダーに入れる前に、温度感知暗時出力を周
囲光に基づく出力（励起光を切つたとき）ととも
に他の２つの出力から減算する。次いで利得およ
びレベルの調節を行つてPHを直接デジタルボルト
メーターに指示するようにする。
染料含有材料１４の製造に際し、光散乱性粒子
例えば直径約１ミクロンのポリスチレン微小球
が、染料材料を中空半透膜１１に入れる前に添加
できる。
第３図に示す基本的探知子での体外測定は、実
験室用スペクトロメーターで行はれ0.01PH単位の
標準偏差を有していた。感知子のダイナミツク応
答は、0.7分時間常数で特徴づけられ、その温度
効率は0.02PH単位／℃でイオン強度効率は37℃で
８％のイオン強度変動に対し0.01PH単位であつ
た。
上記説明よりこの発明およびその長所は理解で
き、この発明の精神および範囲を逸脱したりその
利点を損うことなく構成および部品の配置を変更
できることは明らかである。
【図面の簡単な説明】
第１図はこの発明のPH検知子の末端部の部分断
面図、第２図は指示薬染料の光吸収を示すグラ
フ、第３図はPHの関数として回帰光線強度比の実
験的決定を示すグラフである。 １０：感知子、１１：半透膜、１２，１３：光
フアイバー、１４：染料指示薬、１５：シーリン
グ。

Claims (1)

  1. 【特許請求の範囲】 １ 中空の細長いシリンダー状で末端がシールさ
    れたイオン透過性半透膜、相互に平行でかつ末端
    部で隣接させて設けたかつ末端両端部を中空半透
    膜内に位置させた一対の光フアイバーおよび中空
    半透膜内に設けたPH感受性染料含有材料よりなり
    しかもイオン透過性半透膜は水素イオンは通過さ
    せるに充分な大きさであるが染料含有材料は通過
    させないのに充分な小ささの孔を有している生理
    学的研究のために組織に植え込むのに適した光フ
    アイバーPH検知子。 ２ 一方の光フアイバーの中間端部に光源を接続
    し他の光フアイバーの中間端部に光感知手段を接
    続した特許請求の範囲第１項記載の光フアイバー
    PH検知子。 ３ 染料含有材料がアクリル系単量体および染料
    の共重合体である特許請求の範囲第１項記載の光
    フアイバーPH検知子。 ４ アクリル系単量体がアクリルアミド，メチル
    メタクリレートおよびヒドロキシメチルメタクリ
    レートよりなる群から選択される特許請求の範囲
    第３項記載の光フアイバーPH検知子。 ５ 染料がフエノールレツド，ブリリアントエロ
    ー（CI24890）およびロゾール酸よりなる群から
    選択される特許請求の範囲第３項記載の光フアイ
    バーPH検知子。 ６ 染料含有材料がマイクロビーズの形態で存在
    する特許請求の範囲第１項記載の光フアイバーPH
    検知子。 ７ 染料含有材料が光散乱性粒子を含有する特許
    請求の範囲第１項記載の光フアイバーPH検知子。 ８ 光散乱性粒子がポリスチレン微小球である特
    許請求の範囲第７項記載の光フアイバーPH検知
    子。
JP14707578A 1977-11-28 1978-11-28 Optical fiber ph detector Granted JPS5485588A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US05/855,384 US4200110A (en) 1977-11-28 1977-11-28 Fiber optic pH probe

Publications (2)

Publication Number Publication Date
JPS5485588A JPS5485588A (en) 1979-07-07
JPS6159727B2 true JPS6159727B2 (ja) 1986-12-17

Family

ID=25321113

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Application Number Title Priority Date Filing Date
JP14707578A Granted JPS5485588A (en) 1977-11-28 1978-11-28 Optical fiber ph detector

Country Status (7)

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US (1) US4200110A (ja)
JP (1) JPS5485588A (ja)
CA (1) CA1121242A (ja)
DE (1) DE2851138A1 (ja)
FR (1) FR2409743A1 (ja)
GB (1) GB2009394B (ja)
NL (1) NL7811372A (ja)

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