JPS6129458B2 - - Google Patents
Info
- Publication number
- JPS6129458B2 JPS6129458B2 JP53081392A JP8139278A JPS6129458B2 JP S6129458 B2 JPS6129458 B2 JP S6129458B2 JP 53081392 A JP53081392 A JP 53081392A JP 8139278 A JP8139278 A JP 8139278A JP S6129458 B2 JPS6129458 B2 JP S6129458B2
- Authority
- JP
- Japan
- Prior art keywords
- ligand
- electrode
- oxygen
- membrane
- composition according
- 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
Links
- 239000003446 ligand Substances 0.000 claims description 33
- 239000012528 membrane Substances 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 10
- -1 hydrogen ions Chemical class 0.000 claims description 7
- 238000005259 measurement Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 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 6
- 239000008103 glucose Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 108010015776 Glucose oxidase Proteins 0.000 description 3
- 239000004366 Glucose oxidase Substances 0.000 description 3
- 229940116332 glucose oxidase Drugs 0.000 description 3
- 235000019420 glucose oxidase Nutrition 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 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
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 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 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
Description
【発明の詳細な説明】
本発明は、参照電極、貴金属よりなる酸素に対
する還元電極、および酸素に対して透過性であり
水に対して不透過性であつてこの構成物を外雰囲
気に対して閉じる遮断膜よりなる酸素濃度を測定
するための構成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a reference electrode, a reducing electrode for oxygen made of a noble metal, and a structure that is permeable to oxygen and impermeable to water and is The present invention relates to a structure for measuring oxygen concentration consisting of a closed barrier membrane.
公知のこの種の構成物には、本質的に二つの欠
点がある。 Known arrangements of this type essentially have two drawbacks.
第一に、電極用の高純度の貴金属を選択した場
合においても、電極上への不純物の移入を阻止す
ることができず、それ故に電極の円滑な動作寿命
を妨げる変動現象（Drifterseheinugen）が起
る。第二に、測定の際の酸素の消費量自体が多
く、そのためたいてい重要な有機組織中の拡散領
域が阻害される。そのために、真の酸素濃度が得
られないか、あるいは非常に長い測定時間を必要
とする。 Firstly, even when selecting high-purity noble metals for the electrodes, it is not possible to prevent the migration of impurities onto the electrodes, thus causing fluctuation phenomena (Drifterseheinugen) that impede the smooth operating life of the electrodes. Ru. Secondly, the consumption of oxygen during the measurement itself is high, so that the diffusion zone in the organic tissue, which is often important, is inhibited. Therefore, either the true oxygen concentration cannot be obtained or a very long measurement time is required.
これらの欠点は、カチオンリガンドを含有し、
水素イオンおよび酸素に対して透過性のリガンド
膜を還元電極の前に位置させ、そしてリガンド膜
と遮断膜との間にリガンドカチオンを含有する電
解液を配置するという本発明の電極構成物によつ
て解消される。 These drawbacks include containing cationic ligands,
With the electrode composition of the present invention, a ligand membrane permeable to hydrogen ions and oxygen is placed in front of a reducing electrode, and an electrolyte containing a ligand cation is placed between the ligand membrane and the blocking membrane. It will be resolved.
本発明の電極構成物においては、リガンド膜の
選択作用によつて、反応物質のみが還元電極と接
触し、そして電解液あるいは対向電極
（Gegenelektrode）からの物質は、還元電極と接
触しない。それ故に還元電極上での物理的および
化学的諸変化は起らず、そしてそのために長時間
の一定状態が増大される。つまり、電極への不純
物の移動によつてこれまでのところ避けられない
汚染（電極表面の水和）が起こり、これが測定器
の感度を変化させる。感度のこの低下は従来の電
極では、数時間の期間で現われるが、本発明の配
置により上記の期間は数週間にまで拡張される。
これは本発明を臨床用に使用する際の大きな利点
である。また、酸素の微小流（Teilchenstrom）
が著しく減少するので、測定の間中酸素の濃度領
域（Konzentrationfeld）が損れることは非常に
僅かである。 In the electrode arrangement of the invention, due to the selective action of the ligand membrane, only the reactants come into contact with the reducing electrode, and no substances from the electrolyte or the counter electrode come into contact with the reducing electrode. Therefore, no physical and chemical changes occur on the reducing electrode, and the long-term constant state is thereby increased. This means that the migration of impurities to the electrodes causes a so far unavoidable contamination (hydration of the electrode surface), which changes the sensitivity of the measuring instrument. This decrease in sensitivity appears with conventional electrodes over a period of several hours, but with the arrangement of the present invention, this period is extended to several weeks.
This is a major advantage in clinical use of the present invention. Also, oxygen microflow (Teilchenstrom)
is significantly reduced, so that the concentration range of oxygen is only slightly impaired during the measurement.
この利点を利用するためには、信号測定用の増
巾器の入力抵抗は、約1012Ωの値を示す。特に好
ましい状態は、リガンドが、Na選択性である場
合である。 To take advantage of this advantage, the input resistance of the amplifier for signal measurement exhibits a value of approximately 10 12 Ω. A particularly preferred situation is when the ligand is Na selective.
すなわち、その場合に、容易に表示可能でかつ
酸素濃度に良く比例した信号が得られるというこ
とが明らかになつた。 That is, it has become clear that in that case, a signal that can be easily displayed and that is well proportional to the oxygen concentration can be obtained.
この場合には、リガンドとして、３・６−ジオ
キサオクタン二酸−ビス−ジフエルアミンが有効
である。 In this case, 3,6-dioxaoctanedioic acid-bis-dipheramine is effective as the ligand.
さらに、電解液は、10ｍＭのNaClと0.1nのHCl
よりなるものが有利である。 Furthermore, the electrolyte was 10mM NaCl and 0.1n HCl.
It is advantageous to have more.
本発明の他の実施例においては、参照電極は、
リガンド膜のカチオンリガンドとは異なるリガン
ド膜によつて覆われている。これにより、参照電
極に対する物理的あるいは化学的攻撃が阻止され
る。 In other embodiments of the invention, the reference electrode is
It is covered by a different ligand film than the cationic ligand in the ligand film. This prevents physical or chemical attack on the reference electrode.
本発明の構成物によれば、測定系中に一定の微
小電流を生ずる約106Ωの測定抵抗器によつて、
電流的にも、通常の方法で測定を行なうことがで
きる。さらに、このことによつて、電極が物理的
かつ化学的に保護されるという利点も生ずる。 According to the arrangement of the invention, by means of a measuring resistor of approximately 10 6 Ω, which produces a constant small current in the measuring system,
Current measurement can also be carried out using conventional methods. Furthermore, this has the advantage that the electrodes are protected both physically and chemically.
本発明の一具体的構成例を図面を参照しながら
説明する。 A specific configuration example of the present invention will be explained with reference to the drawings.
極性電圧源１は、例えば白金よりなる還元電極
２および好適には、リング状で還元電極２の周囲
に配置された参照電極３上に設置される。 A polar voltage source 1 is placed on a reduction electrode 2 made of, for example, platinum and a reference electrode 3 preferably arranged around the reduction electrode 2 in the form of a ring.
還元電極２の前面には、イオン選択性のカチオ
ンリガンドを含みそして水素イオンおよび酸素透
過性のポリ塩化ビニル（PVC）よりなる膜２０
が設けられ、そして参照電極３の前面には、リガ
ンド膜とは異なるリガンドを含む参照リガンド膜
３０が設けられている。この参照リガンド膜は、
省略することもできる。リガンド膜２０のリガン
ドとしては、３・６−ジオキサオクタン二酸−ビ
ス−ジフエニルアミンが好適である。電解液５
は、この構成物全体をカバーし、そしてこの構成
物は、外部雰囲気に対しては遮断膜６によつて遮
断されている。参照リガンド膜を設けない場合に
は、電解液は、10ｍＭのNaClと0.1nのHClよりな
るものが良い。参照リガンド膜が有る場合には、
電解液は、やはりこのリガンドのイオンを付加的
に含まなければならない。 In front of the reduction electrode 2 is a membrane 20 made of polyvinyl chloride (PVC) containing an ion-selective cation ligand and permeable to hydrogen ions and oxygen.
A reference ligand film 30 containing a different ligand from the ligand film is provided in front of the reference electrode 3. This reference ligand membrane is
It can also be omitted. As the ligand for the ligand film 20, 3,6-dioxaoctanedioic acid-bis-diphenylamine is suitable. Electrolyte 5
covers the entire arrangement, which is shielded from the external atmosphere by a barrier membrane 6. If no reference ligand film is provided, the electrolyte preferably consists of 10mM NaCl and 0.1N HCl. If a reference ligand membrane is available,
The electrolyte must also additionally contain ions of this ligand.
さて、外部雰囲気に、ある濃度の酸素７が存在
する場合には、この酸素は、ポリテトラフルオロ
エチレン（例えばデユポン社の商品名テフロン）
膜６を通して拡散し、そしてさらに電解液５から
の水素イオンと共にリガンド膜２０中へ拡散す
る。そこで、次式に従つて、その酸素が水素イオ
ンによつて還元されて水を生ずる。 Now, when a certain concentration of oxygen 7 is present in the external atmosphere, this oxygen is made of polytetrafluoroethylene (for example, Teflon, a product of Dupont).
It diffuses through the membrane 6 and further into the ligand membrane 20 along with hydrogen ions from the electrolyte 5. Then, the oxygen is reduced by hydrogen ions to produce water according to the following equation.
O2＋4e-＋4H+→2H2O
電極２−２０，２−３０、電解液５および極性
電圧源１よりなるポテンシヤル鎖
（Potentialkeffe）中のこの過程によつて生じた電
極２−２０のポテンシヤルの変化は、指示計を具
えた測定用増巾器４によつて測定される。測定用
増巾器４の初期低抗値は、約1012Ωである。 O 2 +4e - +4H + →2H 2 O The potential of electrode 2-20 caused by this process in the potential chain consisting of electrodes 2-20, 2-30, electrolyte 5 and polar voltage source 1 The change is measured by a measuring amplifier 4 equipped with an indicator. The initial low resistance value of the measurement amplifier 4 is approximately 10 12 Ω.
実施例
実施例は本発明の構成物をグルコースセンサー
に利用した場合を示すものである。このセンサー
においては、固定化されたグルコースオキシダー
ゼ（GOD）を含む酵素膜が位置する反応空間中
にグルコースが被覆膜を通過して血液または組織
から拡散し、これがGODの触媒作用により、
グルコースＧＯＤ Ｏ２→グルコン酸＋H2O2
のような変化を受け、このH2O2が親油性膜を通
過して拡散し、金のアノードで、
H2O2−2e-→2H+＋O2
のように酸化されるのである。Examples Examples show the use of the composition of the present invention in a glucose sensor. In this sensor, glucose diffuses from blood or tissue through a coated membrane into a reaction space in which an enzyme membrane containing immobilized glucose oxidase (GOD) is located, and this is caused by the catalytic action of GOD . This H 2 O 2 undergoes a change such as O2 → gluconic acid + H 2 O 2 , and this H 2 O 2 diffuses through the lipophilic membrane, and at the gold anode, changes as H 2 O 2 −2e − →2H + + O 2 It is oxidized to
第２図は８個の曲線から構成された補正曲線を
示す。この曲線から示されるように、グルコース
濃度が1/10になるときの曲線の勾配は59.0ｍＶで
ある。これは、理想的なネルンスト（Nernst）
挙動における勾配のほとんど200％に当る。 FIG. 2 shows a correction curve made up of eight curves. As shown from this curve, the slope of the curve when the glucose concentration becomes 1/10 is 59.0 mV. This is the ideal Nernst
Almost 200% of the gradient in behavior.
非常に小さい僅か１−20pA／cm2・秒という酸
化電流のため、このセンサーは、非常に大きなア
ノードを使用しても対流感度を示さない。 Due to the very small oxidation current of only 1-20 pA/cm 2 ·sec, this sensor shows no convective sensitivity even with very large anodes.
この結果、グルコース移動率は最少限しか必要
とされず、このことは、外部の包囲膜がグルコー
スに対し極めて低い透過性を持ちうるということ
を意味している。センサーのドリフトは１ｍＶ／
24時間未満に当る。 As a result, only a minimum glucose transfer rate is required, which means that the outer surrounding membrane can have very low permeability to glucose. The sensor drift is 1mV/
Less than 24 hours.
第１図は本発明の構成物のうちの一具体例の説
明図、第２図は本発明の一実施例により得られた
結果を示すグルコース電極の補正曲線のグラフで
ある。
２……還元電極、３……参照電極、５……電解
液、６……遮断膜、７……酸素、２０，３０……
リガンド膜。
FIG. 1 is an explanatory diagram of one specific example of the composition of the present invention, and FIG. 2 is a graph of a correction curve of a glucose electrode showing the results obtained by one embodiment of the present invention. 2... Reduction electrode, 3... Reference electrode, 5... Electrolyte, 6... Blocking membrane, 7... Oxygen, 20, 30...
Ligand membrane.
Claims (1)
電極、および酸素に対して透過性であり水に対し
て不透過性であつて構成物自体を外部雰囲気に対
して閉じる遮断膜よりなる酸素濃度を測定するた
めの構造物において、カチオンリガンドを含有
し、水素イオンおよび酸素に対して透過性である
リガンド膜２０が還元電極２の前に配置され、そ
して前記リガンド膜と遮断膜の間にリガンドカチ
オンを含有する電解液５が配置されていることを
特徴とする酸素測定用電極構造物。 ２ 電極構成物の信号を測定する増巾器４が約
1012Ωの入力抵抗を有することを特徴とする特許
請求の範囲第１項記載の構成物。 ３ リガンドがNa選択性であることを特徴とす
る特許請求の範囲第１項記載の構造物。 ４ リガンドが３・６−ジオキサオクタン二酸−
ビス−ジフエニルアミンであることを特徴とする
特許請求の範囲第３項記載の構造物。 ５ 電解液が10ｍＭ NaClと0.1n HClよりなる
ことを特徴とする特許請求の範囲第１項記載の構
成物。 ６ 参照電極３がリガンド膜のカチオンリガンド
と異なるリガンドを含有する参照リガンド膜３０
によつて覆れていることを特徴とする特許請求の
範囲第１項記載の構成物。 ７ リガンド膜２０および３０がポリ塩化ビニル
よりなることを特徴とする特許請求の範囲第１項
または第６項記載の構成物。[Claims] 1. A reference electrode, a reducing electrode for oxygen made of a noble metal, and a barrier membrane that is permeable to oxygen and impermeable to water and closes the composition itself to the external atmosphere. In the structure for measuring the oxygen concentration, a ligand membrane 20 containing a cationic ligand and permeable to hydrogen ions and oxygen is placed in front of the reduction electrode 2, and the ligand membrane and the blocking membrane are separated. An electrode structure for oxygen measurement, characterized in that an electrolytic solution 5 containing a ligand cation is arranged between them. 2 The amplifier 4 for measuring the signal of the electrode structure is approximately
Arrangement according to claim 1, characterized in that it has an input resistance of 10 12 Ω. 3. The structure according to claim 1, wherein the ligand is Na-selective. 4 The ligand is 3,6-dioxaoctanedioic acid-
4. A structure according to claim 3, characterized in that it is bis-diphenylamine. 5. The composition according to claim 1, wherein the electrolyte consists of 10mM NaCl and 0.1n HCl. 6 A reference ligand film 30 in which the reference electrode 3 contains a ligand different from the cationic ligand of the ligand film.
A composition according to claim 1, characterized in that it is covered by a. 7. The composition according to claim 1 or 6, wherein the ligand films 20 and 30 are made of polyvinyl chloride.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2730143A DE2730143C3 (en) | 1977-07-04 | 1977-07-04 | Oxygen measurement electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5440693A JPS5440693A (en) | 1979-03-30 |
| JPS6129458B2 true JPS6129458B2 (en) | 1986-07-07 |
Family
ID=6013122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8139278A Granted JPS5440693A (en) | 1977-07-04 | 1978-07-04 | Electrode for measuring oxygen |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | USRE31299E (en) |
| JP (1) | JPS5440693A (en) |
| AT (1) | AT381594B (en) |
| CH (1) | CH629305A5 (en) |
| DE (1) | DE2730143C3 (en) |
| DK (1) | DK150997C (en) |
| FR (1) | FR2396972A1 (en) |
| GB (1) | GB2000595B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5752918A (en) * | 1980-09-09 | 1982-03-29 | Toyota Motor Corp | Constant-speed running device |
| DE3120559A1 (en) * | 1981-05-23 | 1982-12-09 | Robert Bosch Gmbh, 7000 Stuttgart | REACTIVE SERVO DRIVE |
| JPS5896142A (en) * | 1981-12-01 | 1983-06-08 | Nippon Denso Co Ltd | Auto-driving apparatus for car |
| DE3332745A1 (en) * | 1983-09-10 | 1985-03-28 | Jens 8520 Erlangen Höper | ARRANGEMENT FOR MEASURING THE CONCENTRATION OF A SUBSTANCE |
| EP0205399B1 (en) * | 1985-06-10 | 1993-10-06 | ORBISPHERE CORPORATION Wilmington Succursale de Collonge-Bellerive | Amperometric cell and method |
| DE3537919A1 (en) * | 1985-10-24 | 1987-04-30 | Kessler Manfred | ARRANGEMENT FOR STABILIZING A GAS REFERENCE ELECTRODE |
| US5968340A (en) | 1997-04-07 | 1999-10-19 | Marine Biological Laboratory | Polarographic self-referencing probe and method for using |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH589096A5 (en) * | 1972-04-24 | 1977-06-30 | Moeller W Glasblaeserei | |
| US3985633A (en) * | 1972-11-11 | 1976-10-12 | Eschweiler & Co. | Device for the polarographic measurement of oxygen pressure |
| CH585907A5 (en) * | 1973-08-06 | 1977-03-15 | Hoffmann La Roche | |
| US3857777A (en) * | 1973-08-10 | 1974-12-31 | Environmental Protection Agenc | Ion exchange membrane for measuring orthophosphate |
| GB1506048A (en) * | 1974-06-28 | 1978-04-05 | Siemens Ag | Electrode assembly for polarographic investigation |
-
1977
- 1977-07-04 DE DE2730143A patent/DE2730143C3/en not_active Expired
-
1978
- 1978-07-03 GB GB7828668A patent/GB2000595B/en not_active Expired
- 1978-07-03 DK DK300678A patent/DK150997C/en not_active IP Right Cessation
- 1978-07-03 CH CH721178A patent/CH629305A5/en not_active IP Right Cessation
- 1978-07-03 FR FR7819815A patent/FR2396972A1/en active Granted
- 1978-07-04 JP JP8139278A patent/JPS5440693A/en active Granted
- 1978-07-04 AT AT0484378A patent/AT381594B/en not_active IP Right Cessation
-
1982
- 1982-03-12 US US06/357,563 patent/USRE31299E/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FR2396972B1 (en) | 1983-11-18 |
| CH629305A5 (en) | 1982-04-15 |
| AT381594B (en) | 1986-11-10 |
| GB2000595A (en) | 1979-01-10 |
| JPS5440693A (en) | 1979-03-30 |
| DK150997B (en) | 1987-10-05 |
| DK300678A (en) | 1979-01-05 |
| DE2730143C3 (en) | 1980-06-26 |
| DK150997C (en) | 1988-02-15 |
| GB2000595B (en) | 1982-01-13 |
| DE2730143A1 (en) | 1979-01-18 |
| USRE31299E (en) | 1983-07-05 |
| DE2730143B2 (en) | 1979-10-04 |
| FR2396972A1 (en) | 1979-02-02 |
| ATA484378A (en) | 1986-03-15 |
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