WO1985002017A1 - Sensor for chemical analysis - Google Patents
Sensor for chemical analysis Download PDFInfo
- Publication number
- WO1985002017A1 WO1985002017A1 PCT/SE1984/000374 SE8400374W WO8502017A1 WO 1985002017 A1 WO1985002017 A1 WO 1985002017A1 SE 8400374 W SE8400374 W SE 8400374W WO 8502017 A1 WO8502017 A1 WO 8502017A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- analysis
- membrane
- sensor
- liquid flow
- electrode
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
- C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
- C12Q1/001—Enzyme electrodes
Definitions
- the present invention relates to a system in which a measuring chamber has been brought into connection with the sensitive surface of an analysis electrode.
- the measuring chamber which together with the analysis electrode is submerged in the sample solution and is spaced from the latter by means of a membrane of a cer ⁇ tain permeability, is continuously flushed through by a liquid flow emanating from a specific outer reservoir.
- a membrane of a cer ⁇ tain permeability is continuously flushed through by a liquid flow emanating from a specific outer reservoir.
- the electrochemical analysis electrodes may be di- vided up into ion-selective and membrane electrodes, where the ion-selective ones measure a specific elect ⁇ rochemical reaction on their sensitive surface and the membrane electrodes have a gas-permeable membrane which only allows gas molecules to pass into the electrolyte solution.
- the ion-selective electrode type are pH and NH.
- -electrodes and examples of the membrane type are NH-. and O ⁇ -electrodes.
- In practice problems may arise with these electrode types when measuring in samples of wholly or partly undefined contents. The problem may be illustrated with an example. In determin ⁇ ing NH.
- a lon-selective NH. electrode cannot be used due to its sensitivity to K and other ions which are known to be present in the medium.
- a membrane electrode for deter- mining the percentage of NH_. cannot either be used since at pH 7.0 almost all NH-, is present as NH. according to the equation
- the present invention allows direct measuring of the NH. content in the sample by placing in connection with the gas-permeable membrane of a NH-. electrode a ion-permeable membrane and laying between these mem- branes a flow of a buffer solution which holds so high a pH that the desired part of the NH. ions diffusing into the measuring chamber are converted into NH, form.
- This principle may be used in all systems of the type
- HA H + A (g) where it is desired to change an environmental para ⁇ meter such as e.g. pH or buffer capacity from those prevailing in the sample but still perform a not sample- destroying analysis with a sensor placed in the sample.
- the present invention may also be applied to other ⁇ es of chemical reactions, e.g. redox reactions.
- An ⁇ other advantage is that, if it is desired to analyse percentages exceeding the measuring range of the elect- trode in question, it is possible by a suitable choice of flow rate of the external buffer to create a direct, continuous dilution of the analysis substance inside the membrane adjacent the sensor surface. Thus it is possible to obtain an optional measuring range in the instrument by adjustment of the liquid flow.
- the system can be used solely to create a vari ⁇ able measuring range in a certain electrode.
- other liquids and membranes than those mentioned above may be used in dependence upon the desired application.
- One may, for instance, let a reagent be contained in a constant percentage in the liquid flow in order to react with the analysis substance and form a measurable product.
- the principle for an electrochemical analysis electrode constructed according to the present inven ⁇ tion will appear from the following (see Fig. 1).
- (1) is an electrochemical sensor over the sensi- tive surface of which a membrane (2) has been mounted so that a liquid flow (F) is allowed to pass the mea ⁇ suring chamber (3) thus formed, through tubes (4) adap ⁇ ted therefor.
- An adjustable pump (5) drives the flow which comes from a specific reservoir (6).
- the analysis substance diffuses from the sample through the membrane (2) into the measuring chamber (3) where, after dilution and possibly chemical conversion, the percentage is measured with the sensor (1) and the re- suit is obtained with the aid of the electronics (7).
- Enzyme electrodes have been the object of great, interest during the last decade (ref). They consist (see Fig.
- Electrode (2) in principle of an electrochemical sensor of membrane or ion-selective type (1) on the sensitive surface of which one has mounted one or more immobi ⁇ lized enzymes in the form of a membrane or on a carrier (2) and separated this from the sample solution by means of a semi-permeable membrane (3).
- the electrode signals is recorded in the electronics (4).
- the electrode (1) is chosen so that one of the reactants or products of the enzyme reaction will form analysis substance for the electrode.
- An enzyme reaction follows the formula A + H 2 0 + 0 2 E Z > C + H 2 0 2 and the substance A is that which is of interest to determine.
- a and C are complicated organic substances which cannot be measured directly electro ⁇ chemically.
- 0- and H-0- being stoichiometri- cally related with A, can be measured with rescpect- ively a membrane and an ion-selected electrode. In this case therefore one of these electrodes are chosen as sensor ( (1) in Fig. 2).
- Certain disadvantages are en ⁇ tailed with enzyme electrodes: sensitivity to environ ⁇ mental parameters such as e.g. pH, sensitivity to de- naturating substances, product inhibition due to in ⁇ creased product percentages inside the enzyme layer etc.
- the present invention permits elimination of these disadvantages in that it makes it possible, by means of the flow system described above and an appropriate choice of liquid in the flow (F), to create optimum conditions for enzyme inside the measuring chamber even if the conditions in the sample are very unfavourable. Moreover, possibilities are provided, in the same way as described above, for simply varying the measuring range for the enzyme electrode.
- the principle for an enzyme electrode built ac ⁇ cording to the present invention appears from the fol ⁇ lowing (see Fig. 3).
- Fig. 3 A shows the build-up of the measuring chamber when the enzyme functions-as "active membrane", i.e. the analysis substance must diffuse -through a membrane with immobilized enzyme (1) while being transformed before it reaches the measuring chamber and the sensor ( (2) and (3) respectively).
- Fig. 3 B shows the situation when the enzyme (4) is contained immobilized in the chamber (2) and the sample is .. spaced from the measuring chamber by means of a membrane (1).
- the present invention may, in the same way as de ⁇ scribed above, also be applied to other electrode sys ⁇ tems with active and passive membranes, e.g. microbial electrodes and antigen-antibody- and carbohydrate-lec- tine electrodes etc.
- active and passive membranes e.g. microbial electrodes and antigen-antibody- and carbohydrate-lec- tine electrodes etc.
- a reagent accompany the liquid flow (F), which reagent takes part in the enzyme reaction while forming coloured or otherwise characteristic substances which then may be detected optically or in another way.
- Fig. 4 shows the electrode flow I as a function of the glucose concentration when the present invention has been applied to a glucose-sen ⁇ sitive enzyme electrode in 4 different flows (F) .
Abstract
An analysis electrode including a sensor on the sensitive surface of which a variable liquid flow has been applied into which the analysis substances diffuses through a semi-permeable membrane in connection with the electrode surface. By varying the composition and rate of the liquid flow it is gained, on one hand, that the analysis substance undergoes suitable modification, e.g., dissociation and, on the other hand, that the chemical environment around the sensor surface can be optimized, e.g. for an enzymatic reaction. In addition, the measuring range may be made variable by variation of the concentration of the analysis substance by changing the liquid flow rate.
Description
SENSOR FOR CHEMICAL ANALYSIS
The present invention relates to a system in which a measuring chamber has been brought into connection with the sensitive surface of an analysis electrode. The measuring chamber, which together with the analysis electrode is submerged in the sample solution and is spaced from the latter by means of a membrane of a cer¬ tain permeability, is continuously flushed through by a liquid flow emanating from a specific outer reservoir. Among existing analysis electrodes those which are noticed in the first place today are the electrochemi¬ cal ones, the so-called enzyme electrodes and the mic- robial electrodes. Also so-called solid-state electrodes are coming into use.
The electrochemical analysis electrodes may be di- vided up into ion-selective and membrane electrodes, where the ion-selective ones measure a specific elect¬ rochemical reaction on their sensitive surface and the membrane electrodes have a gas-permeable membrane which only allows gas molecules to pass into the electrolyte solution. Examples of the ion-selective electrode type are pH and NH. -electrodes and examples of the membrane type are NH-. and O^-electrodes. In practice problems may arise with these electrode types when measuring in samples of wholly or partly undefined contents. The problem may be illustrated with an example. In determin¬ ing NH. in a sample from a fermentation (pH = 7.0) a lon-selective NH. electrode cannot be used due to its sensitivity to K and other ions which are known to be present in the medium. A membrane electrode for deter- mining the percentage of NH_. cannot either be used since at pH 7.0 almost all NH-, is present as NH. according to the equation
NH.+ ==* NH., + H+ fpΛK: = 9.3.
The present invention allows direct measuring of the NH. content in the sample by placing in connection with the gas-permeable membrane of a NH-. electrode a ion-permeable membrane and laying between these mem- branes a flow of a buffer solution which holds so high a pH that the desired part of the NH. ions diffusing into the measuring chamber are converted into NH, form. This principle may be used in all systems of the type
HA+ -s≤ HA =*=* H+ + A~ and
HA H + A (g) where it is desired to change an environmental para¬ meter such as e.g. pH or buffer capacity from those prevailing in the sample but still perform a not sample- destroying analysis with a sensor placed in the sample. The present invention may also be applied to other ^ es of chemical reactions, e.g. redox reactions. An¬ other advantage is that, if it is desired to analyse percentages exceeding the measuring range of the elect- trode in question, it is possible by a suitable choice of flow rate of the external buffer to create a direct, continuous dilution of the analysis substance inside the membrane adjacent the sensor surface. Thus it is possible to obtain an optional measuring range in the instrument by adjustment of the liquid flow. In other words, the system can be used solely to create a vari¬ able measuring range in a certain electrode. Also other liquids and membranes than those mentioned above may be used in dependence upon the desired application. One may, for instance, let a reagent be contained in a constant percentage in the liquid flow in order to react with the analysis substance and form a measurable product. The principle for an electrochemical analysis electrode constructed according to the present inven¬ tion will appear from the following (see Fig. 1).
(1) is an electrochemical sensor over the sensi-
tive surface of which a membrane (2) has been mounted so that a liquid flow (F) is allowed to pass the mea¬ suring chamber (3) thus formed, through tubes (4) adap¬ ted therefor. An adjustable pump (5) drives the flow which comes from a specific reservoir (6). When the analysis substance diffuses from the sample through the membrane (2) into the measuring chamber (3) where, after dilution and possibly chemical conversion, the percentage is measured with the sensor (1) and the re- suit is obtained with the aid of the electronics (7). Enzyme electrodes have been the object of great, interest during the last decade (ref). They consist (see Fig. 2) in principle of an electrochemical sensor of membrane or ion-selective type (1) on the sensitive surface of which one has mounted one or more immobi¬ lized enzymes in the form of a membrane or on a carrier (2) and separated this from the sample solution by means of a semi-permeable membrane (3). The electrode signals is recorded in the electronics (4). The electrode (1) is chosen so that one of the reactants or products of the enzyme reaction will form analysis substance for the electrode.
Ex. An enzyme reaction follows the formula A + H20 + 02 E Z > C + H202 and the substance A is that which is of interest to determine. However, A and C are complicated organic substances which cannot be measured directly electro¬ chemically. However, 0- and H-0-, being stoichiometri- cally related with A, can be measured with rescpect- ively a membrane and an ion-selected electrode. In this case therefore one of these electrodes are chosen as sensor ( (1) in Fig. 2). Certain disadvantages are en¬ tailed with enzyme electrodes: sensitivity to environ¬ mental parameters such as e.g. pH, sensitivity to de- naturating substances, product inhibition due to in¬ creased product percentages inside the enzyme layer etc.
The present invention permits elimination of these disadvantages in that it makes it possible, by means of the flow system described above and an appropriate choice of liquid in the flow (F), to create optimum conditions for enzyme inside the measuring chamber even if the conditions in the sample are very unfavourable. Moreover, possibilities are provided, in the same way as described above, for simply varying the measuring range for the enzyme electrode. The principle for an enzyme electrode built ac¬ cording to the present invention appears from the fol¬ lowing (see Fig. 3). Fig. 3 A shows the build-up of the measuring chamber when the enzyme functions-as "active membrane", i.e. the analysis substance must diffuse -through a membrane with immobilized enzyme (1) while being transformed before it reaches the measuring chamber and the sensor ( (2) and (3) respectively). Fig. 3 B shows the situation when the enzyme (4) is contained immobilized in the chamber (2) and the sample is .. spaced from the measuring chamber by means of a membrane (1).
The present invention may, in the same way as de¬ scribed above, also be applied to other electrode sys¬ tems with active and passive membranes, e.g. microbial electrodes and antigen-antibody- and carbohydrate-lec- tine electrodes etc. One may let a reagent accompany the liquid flow (F), which reagent takes part in the enzyme reaction while forming coloured or otherwise characteristic substances which then may be detected optically or in another way. Fig. 4 shows the electrode flow I as a function of the glucose concentration when the present invention has been applied to a glucose-sen¬ sitive enzyme electrode in 4 different flows (F) .
Reference.
Guilbault, G.G.
Enz. Microb. Technol, 2, 258 (1980).
OAIP "
Claims
1. Analysis electrode including a sensor, c h a ¬ r a c t e r i z e d in that a variable liquid flow has been disposed in the vicinity of the sensitive sur¬ face thereof and that this liquid flow has been spaced from the sample solution by means of a membrane.
2. Analysis electrode according to claim 1, c h a r a c t e r i z e d in that said membrane is a semi-permeable or gas-permeable membrane.
3. Analysis electrode according to claim 1, c h a r a c t e r i z e d in that said membrane con¬ tains one or more of the following components: proteins, enzymes, other active substances, organelles or micro¬ organisms.
4. Analysis electrode according to claim 1, c h a r a c t e r i z e d in that said measuring cham¬ ber contains an immobilized preparation of one or more of the following components: proteins, enzymes, other active substances, organelles or micro-organisms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE8306050A SE8306050D0 (en) | 1983-11-03 | 1983-11-03 | SENSOR OF CHEMICAL ANALYSIS |
| SE8306050-9 | 1983-11-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1985002017A1 true WO1985002017A1 (en) | 1985-05-09 |
Family
ID=20353170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/SE1984/000374 WO1985002017A1 (en) | 1983-11-03 | 1984-11-02 | Sensor for chemical analysis |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0161299A1 (en) |
| JP (1) | JPS61500330A (en) |
| SE (1) | SE8306050D0 (en) |
| WO (1) | WO1985002017A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5278048A (en) * | 1988-10-21 | 1994-01-11 | Molecular Devices Corporation | Methods for detecting the effect of cell affecting agents on living cells |
| US5496697A (en) * | 1988-10-21 | 1996-03-05 | Molecular Devices Corporation | Methods and apparatus for detecting the effect of cell affecting agents on living cells |
| WO1996030751A1 (en) * | 1995-03-27 | 1996-10-03 | Coulter International Corp. | Apparatus for measuring analytes in a fluid sample |
| WO2011110517A1 (en) * | 2010-03-08 | 2011-09-15 | Octens Bvba | Conditioning apparatus and method for ion- selective electrode |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002330752A (en) * | 2001-05-08 | 2002-11-19 | Sanden Corp | Apparatus for counting number of microorganisms |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE397731B (en) * | 1975-03-27 | 1977-11-14 | Servochem | STERILIZABLE AND REGENERATABLE ENZYME ELECTRODE AND WAY TO PRODUCE THE SAME |
| DE2714379A1 (en) * | 1977-03-31 | 1978-10-05 | Eschweiler & Co | Gas partial pressure sensor - uses electrode enclosed by hollow sleeve with pervious membrane across its end |
| WO1983003006A1 (en) * | 1982-02-22 | 1983-09-01 | Beckman Instruments Inc | Method for measuring ionic concentration utilizing an ion-sensing electrode |
-
1983
- 1983-11-03 SE SE8306050A patent/SE8306050D0/en not_active Application Discontinuation
-
1984
- 1984-11-02 EP EP19840904205 patent/EP0161299A1/en not_active Withdrawn
- 1984-11-02 WO PCT/SE1984/000374 patent/WO1985002017A1/en not_active Application Discontinuation
- 1984-11-02 JP JP50419084A patent/JPS61500330A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE397731B (en) * | 1975-03-27 | 1977-11-14 | Servochem | STERILIZABLE AND REGENERATABLE ENZYME ELECTRODE AND WAY TO PRODUCE THE SAME |
| DE2714379A1 (en) * | 1977-03-31 | 1978-10-05 | Eschweiler & Co | Gas partial pressure sensor - uses electrode enclosed by hollow sleeve with pervious membrane across its end |
| WO1983003006A1 (en) * | 1982-02-22 | 1983-09-01 | Beckman Instruments Inc | Method for measuring ionic concentration utilizing an ion-sensing electrode |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5278048A (en) * | 1988-10-21 | 1994-01-11 | Molecular Devices Corporation | Methods for detecting the effect of cell affecting agents on living cells |
| US5496697A (en) * | 1988-10-21 | 1996-03-05 | Molecular Devices Corporation | Methods and apparatus for detecting the effect of cell affecting agents on living cells |
| WO1996030751A1 (en) * | 1995-03-27 | 1996-10-03 | Coulter International Corp. | Apparatus for measuring analytes in a fluid sample |
| US5607565A (en) * | 1995-03-27 | 1997-03-04 | Coulter Corporation | Apparatus for measuring analytes in a fluid sample |
| WO2011110517A1 (en) * | 2010-03-08 | 2011-09-15 | Octens Bvba | Conditioning apparatus and method for ion- selective electrode |
| US9645107B2 (en) | 2010-03-08 | 2017-05-09 | Pion Inc. | Conditioning apparatus and method for ion-selective electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| SE8306050L (en) | 1985-05-04 |
| JPS61500330A (en) | 1986-02-27 |
| SE8306050D0 (en) | 1983-11-03 |
| EP0161299A1 (en) | 1985-11-21 |
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