DE2924117A1 - ELECTRODE SYSTEM WITH A REFERENCE ELECTRODE WITHOUT LIQUID TRANSITION FOR VOLTAMETER MEASUREMENTS - Google Patents
ELECTRODE SYSTEM WITH A REFERENCE ELECTRODE WITHOUT LIQUID TRANSITION FOR VOLTAMETER MEASUREMENTSInfo
- Publication number
- DE2924117A1 DE2924117A1 DE19792924117 DE2924117A DE2924117A1 DE 2924117 A1 DE2924117 A1 DE 2924117A1 DE 19792924117 DE19792924117 DE 19792924117 DE 2924117 A DE2924117 A DE 2924117A DE 2924117 A1 DE2924117 A1 DE 2924117A1
- Authority
- DE
- Germany
- Prior art keywords
- electrode
- reference electrode
- solution
- measurements
- voltameter
- 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.)
- Ceased
Links
- 238000005259 measurement Methods 0.000 title description 5
- 239000007788 liquid Substances 0.000 title description 4
- 230000007704 transition Effects 0.000 title description 2
- 230000002441 reversible effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 7
- 239000008103 glucose Substances 0.000 description 7
- 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
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229930027945 nicotinamide-adenine dinucleotide Natural products 0.000 description 5
- BOPGDPNILDQYTO-NNYOXOHSSA-N nicotinamide-adenine dinucleotide Chemical compound C1=CCC(C(=O)N)=CN1[C@H]1[C@H](O)[C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OC[C@@H]2[C@H]([C@@H](O)[C@@H](O2)N2C3=NC=NC(N)=C3N=C2)O)O1 BOPGDPNILDQYTO-NNYOXOHSSA-N 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 101710088194 Dehydrogenase Proteins 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000002255 enzymatic effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- WQZGKKKJIJFFOK-SVZMEOIVSA-N (+)-Galactose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-SVZMEOIVSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 2
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- POJWUDADGALRAB-UHFFFAOYSA-N allantoin Chemical compound NC(=O)NC1NC(=O)NC1=O POJWUDADGALRAB-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000006911 enzymatic reaction Methods 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229940116269 uric acid Drugs 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- KPGXRSRHYNQIFN-UHFFFAOYSA-N 2-oxoglutaric acid Chemical compound OC(=O)CCC(=O)C(O)=O KPGXRSRHYNQIFN-UHFFFAOYSA-N 0.000 description 1
- 101150116940 AGPS gene Proteins 0.000 description 1
- POJWUDADGALRAB-PVQJCKRUSA-N Allantoin Natural products NC(=O)N[C@@H]1NC(=O)NC1=O POJWUDADGALRAB-PVQJCKRUSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229930195714 L-glutamate Natural products 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- YJZATOSJMRIRIW-UHFFFAOYSA-N [Ir]=O Chemical compound [Ir]=O YJZATOSJMRIRIW-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- -1 alcohol aldehyde Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229960000458 allantoin Drugs 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229960003681 gluconolactone Drugs 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 210000002768 hair cell Anatomy 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229940116871 l-lactate Drugs 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- KHPXUQMNIQBQEV-UHFFFAOYSA-N oxaloacetic acid Chemical compound OC(=O)CC(=O)C(O)=O KHPXUQMNIQBQEV-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 239000012086 standard solution Substances 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
-
- 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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Description
Istituto Sieroterapicö e vaccinogeno Toscano "SCLAVO" S.p.A.Istituto Sieroterapicö e vaccinogeno Toscano "SCLAVO" S.p.A.
Siena / ItalienSiena / Italy
Elektrodensystem mit einer Bezugselektrode ohne flüssigen Übergang für VoltametermessungenElectrode system with a reference electrode without smooth transition for voltmeter measurements
Die "Erfindung betrifft ein neues Elektrodensystem, das es ermöglicht, polarograph!sehe oder Voltametermessungen in besonders vorteilhafter Weise durchzuführen. The invention relates to a new electrode system which enables polarographic or voltmeter measurements to be carried out in a particularly advantageous manner.
Das vorliegende Voltametersystem besteht aus einer .Arbeitselektrode, einet· Bezugselektrode und einer Hilf selektrode, eingetaucht in eine lösung mit konstanter Ionenkonzentration,The voltameter system at hand consists of a working electrode, a reference electrode and an auxiliary electrode, immersed in a solution with constant ion concentration,
bezüglich derer die Bezugselektrode reversibel ist. Die Bezugselektrode ist eine Elektrode zweiter Art oder ist vom Metall/Metalloxid-Typ.with respect to which the reference electrode is reversible. The reference electrode is an electrode of the second type or is of the metal / metal oxide type.
Es ist gut bekannt, daß das Aufzeichnen von Stromstärke/Spanmrags-DiagratiUün,
wie uie unter geeigneten Bedingungen erhalten werden, die Grundlage für ein wichtiges analytisches Verfahren
darateLlfc, das als polarographische oder Voltameteranalyse
bezeichnet wird, Dieses Verfahren gestattet nicht nur die gleichzeitige Bestimmung sowohl qualitativ als auch quantitativ
zahlreicher Kationen und Anionen und auch einer grousen
Anzahl von organischen Substanzen, die elektrochemisch
reduziert und oxidiert werden können, sondern ist auch in der Lage, verschiedene Probleme chemischer üatur zu lösen, wie diejenigen
einer Konstitucionsbestimraung bestimmter Substanzen,It is well known that the recording of current / span diagrams, as obtained under suitable conditions, forms the basis of an important analytical method called polarographic or voltameter analysis. This method not only allows simultaneous determination both qualitatively as well as quantitatively numerous cations and anions and also a large number of organic substances that are electrochemically
can be reduced and oxidized, but is also able to solve various problems of chemical nature, such as those of a constitutional determination of certain substances,
die Untersuchung von Reaktionsmechanismen, die Ermittlung von the investigation of reaction mechanisms, the identification of
Ö09851/087SÖ09851 / 087S
29?Λ11729? Λ117
Gleichgewichtskonstanten, die Bestimmung von Stabilitätskonstanten von Komplexen und zahlreiche andere.Equilibrium constants, the determination of stability constants of complexes and numerous others.
Die bei polarographisehen Messungen verwendeten Elektrodensysteme können im allgemeinen aus 2 oder 3 Elektroden bestehen.The electrode systems used in polarographic measurements can generally consist of 2 or 3 electrodes.
Im ersten Pail wird die elektromotorische Kraft zwischen der Arbeitselektrode und der Bezugselektrode angelegt und der zwischen den beiden Elektroden fließende Strom wird gemessen.The first pail is the electromotive force between the working electrode and the reference electrode are applied and the current flowing between the two electrodes is measured.
Im zweiten Pail wird unter Verwendung eines potentiostatischen Systems eine elektromotorische Kraft zv/ischen einer Hilfselektrode und der Arbeitselektrode derart angelegt, daß die gewünschte elektromotorische Kraft zwischen der Arbeitseiefctrode und der Bezugshalbzelle vorliegt.The second pail is made using a potentiostatic System applied an electromotive force zv / ischen an auxiliary electrode and the working electrode in such a way that the desired electromotive force between the working electrode and the reference half-cell is present.
Der durch die Arbeitselektrode fließende Strom wird in Abhängigkeit der vorgewählten elektromotorischen Kraft aufgezeichnet.The current flowing through the working electrode is dependent the preselected electromotive force is recorded.
In der Regel besteht ein Drei-Elektrodensystem aus:As a rule, a three-electrode system consists of:
1. der Arbeitselektrode (ein Quecksilbertropfen, Pt, Au, Graphit und andere)1. the working electrode (a drop of mercury, Pt, Au, graphite and others)
2. der Hilfselektrode (Pt)2. the auxiliary electrode (Pt)
3. der Bezugshalbzelle (Hg/Hg2Cl2/KCl)3. the reference half-cell (Hg / Hg 2 Cl 2 / KCl)
(Hg/Hg2SO4/K2SO4) (Ag/AgCl/KCl)(Hg / Hg 2 SO 4 / K 2 SO 4 ) (Ag / AgCl / KCl)
Die schwerwiegendsten von der Verwendung von Bezugshalbzellen mit einer Lösung im Inneren und einer flüssigen Verbindung stammenden Probleme sind:The most serious of the use of reference half-cells Problems arising with an inside solution and a fluid compound are:
Die phycikalisehen Dimensionen können nicht über bestimmte Frenzen hinaus reduziert v/erden, derart daß die Verwendung in kl el::: a System schwierig wird;The physical dimensions cannot be reduced beyond certain limits , so that the use in kl el ::: a system becomes difficult;
9098R 1 /08759098R 1/0875
y a / /. 117 y a / /. 117
die flüssige Verbindung zwischen der zu untersuchenden Lösung und der Lösung im Inneren der Halbzelle verursacht das sog. "flüssige Verbindungspotential", dessen Verminderung mühsam ist, wobei dieses Potential überdies in Abhängigkeit von der Natur der zu untersuchenden Lösung variiert; die Probe der zu untersuchenden Lösung wird durch die Lösung im Inneren der Halbzelle verunreinigt und umgekehrt; die Bezugshalbzelle erfordert vergleichsweise häufige Instandhaltungsmaßnahmen .the liquid connection between the solution to be examined and the solution inside the half-cell causes the so-called "liquid connection potential", which is laboriously reduced this potential also varies depending on the nature of the solution to be investigated; the sample of the solution to be examined is contaminated by the solution inside the half-cell and vice versa; the reference half-cell requires comparatively frequent maintenance measures.
Erfindungsgemäß wurde gefunden, daß es möglich ist, die herkömmliche Bezugshalbzelle durch eine feste Elektrode, beispielsweise eine solche der zweiten Art zu ersetzen, deren Potential durch eine konstante Ionenkonzentration (bezüglich derer die fragliche Elektrode rerersibel ist), die in die zu untersuchende Lösung eingebracht ist, stabilisiert ist.According to the invention it has been found that it is possible to use the conventional Replace the reference half-cell with a fixed electrode, for example one of the second type, its potential by a constant ion concentration (with respect to which the electrode in question is rerersible), which is introduced into the investigating solution is introduced, is stabilized.
Verwendbare Elektroden können die folgenden sein: Iridium/Iridiumoxid,
Palladiuta/Palladiuraoxid, Rhodium/Bhodiuraoxid (mit
einer konstanten H -Eonsentration in der zu untersuchenden Lösung); eine Fluoridelektrode (mit einer konstanten P~-Konzentration
in der zu untersuchenden Lösung); Ag/AgCl, Ag/AgJ und Ag/AgBr (mit einer konstanten Konsentration an Cl""-,J~"
bzw. Br~~Ionen in der zu untersuchenden Lösung); Ag/AgpS ( mit
einer Konzentrat!o:
suchenden Lösung).Usable electrodes can be the following: Iridium / Iridiumoxid, Palladiuta / Palladiuraoxid, Rhodium / Bhodiuraoxid (with a constant H 2 concentration in the solution to be examined); a fluoride electrode (with a constant P ~ concentration in the solution to be examined); Ag / AgCl, Ag / AgJ and Ag / AgBr (with a constant concentration of Cl "" -, J ~ "or Br ~~ ions in the solution to be examined); Ag / AgpS (with a concentrate! O:
seeking solution).
einer Konzentration an entweder Ag+ oder S~ in der zu unter-a concentration of either Ag + or S ~ in the
Unter Ausnutzung des erfindungsgemäßen Elektrodensystems, das z.B. eine Arbeitselektrode und eine Hilfselektrode beide aus Platin und eine Ir/Ir00-Bezugselektrode (wie in Pig. I gezeigt) enthalten kann, ist es möglich, beim Arbeiten in einer Pufferlösung eine elektrochemische Reaktion an der Arboitnelektrode su über:;;; 2'α·?ώ, die rr.ivor auf eine vorherbestimmte Spannung in Bezug auf die Bezugselektrode aufgeladen worden ist.Using the electrode system according to the invention, which can contain, for example, a working electrode and an auxiliary electrode both made of platinum and an Ir / Ir0 0 reference electrode (as shown in Pig. I ), it is possible to initiate an electrochemical reaction at the Arboitnel electrode when working in a buffer solution see below about: ;;; 2'α ·? Ώ, which rr.ivor has been charged to a predetermined voltage with respect to the reference electrode.
9098R1/08759098R1 / 0875
?c) -~> 4117 -5- ? c ) - ~> 4117 -5-
Das erfindungsgemäße Elektrodensystem besitzt den Vorteil, daß es nicht durch einen der zuvor aufgezählten Mangel für Systeme, die Bezugsharbzellen mit einer Lösung im Inneren verwenden, beeinträchtigt wird. Ein besonderer Vorteil beruht darauf, daß die 3 individuellen Elektroden rasch zu einer einzigen Gesamtheit angeordnet werden können, selbst wenn sie eine reduzierte Große besitzen und Messungen von Volumina im mikroskopischen Haßstab der zu untersuchenden Lösung angepaßt werden können.The electrode system according to the invention has the advantage that it is not affected by any of the deficiencies listed above for systems using reference hair cells with a solution inside will. A particular advantage is based on the fact that the 3 individual electrodes quickly become a single unit can be arranged even if they have a reduced size and measurements of volumes in the microscopic hate rod can be adapted to the solution to be investigated.
Figur 1 der beigefügten Zeichnungen zeigt lediglich beispielshalber eine mögliche Ausführungsform des vorliegenden Elektrodensystems. Figure 1 of the accompanying drawings shows only by way of example a possible embodiment of the present electrode system.
Es wird nun zuerst auf Figur 1 Bezug genommen. In dieser bedeutet die Zahl 1 die Ir/IrOg-Elektrode, 2 ist die Platiiiarbeitselektrode, 3 die Platinhilfselektrode, 4 eine Sonde (gegebenenfalls) zur Temperaturkontrolle, 5 ist der Körper des Elektrodensystems und 6 ist schließlich die Anordnung der Anschlußteila zum Anschließen des Heßinstruments. Das Elektrodensystem, wie es nun beschrieben wurde, kann zur Durchführung zahlreicher Analysen verwendet werden. Z.B. kann es für die folgenden Bestimmungen verwendet werden:Reference is now made first to FIG. In this means the number 1 is the Ir / IrOg electrode, 2 is the platinum working electrode, 3 the auxiliary platinum electrode, 4 a probe (if applicable) for temperature control, 5 is the body of the electrode system and 6 is finally the arrangement of the connection parts for connecting the measuring instrument. The electrode system, as now described, can be used to carry out several Analyzes are used. E.g. it can be used for the following determinations be used:
1. Bestimmung von Wasserstoffperoxid, z.B. in Verbindung mit der Entwicklung der folgenden enzymatischen Reaktionen:1. Determination of hydrogen peroxide, e.g. in connection with the development of the following enzymatic reactions:
1.1, O2 + a-D-Glucose1.1, O 2 + aD-glucose
1.2. O2 + Alkohol Aldeh7d + H 2°21.2. O 2 + alcohol aldehyde 7 d + H 2 ° 2
1.3. O2 + Harnsäure Pricase> Allantoin + CÖ2+H2O2 1.3. O 2 + uric acid P ricase > allantoin + CO 2 + H 2 O 2
1.4. O0 + D-Galaktose —r D-Galaktohexodialdo-2 Oxydase - se + H9O2 1.4. O 0 + D-galactose - r D-galactohexodialdo-2 oxidase - se + H 9 O 2
1.5. O0 + Cholesterin 4-Cholestan-3-on + iU 1.5. O 0 + cholesterol 4-cholestan-3-one + iU
1.6. O0 + H0O+ L-Amino3äure 2-Sefcosäure +1.6. O 0 + H 0 O + L-amino3 acid 2-sefco acid +
ά - uxyaase NH.,+H„0o ά - uxyaase NH., + H "0 o
9098 51/08 7 5 5 22 9098 51/08 7 5 5 22
?9M 1 17? 9M 1 17
2. Bestimmung von ΙΓΑΌ(Ρ)Η^==^ΐίΑΙ)(Ρ)+, beispielsweise in Verbindung mit der Entwicklung der folgenden enzymatischen Reaktionen: 2. Determination of ΙΓΑΌ (Ρ) Η ^ == ^ ΐίΑΙ) (Ρ) + , for example in connection with the development of the following enzymatic reactions:
2.1. Pyruvab + ITADH L-Lactat + ITAD+ 2.1. Pyruvab + ITADH L-lactate + ITAD +
TfehydrogenaseTefehydrogenase
2.2. L-GIutamat + HpO + HAD(P)+ 2-Ketoglutarat2.2. L-glutamate + H p O + HAD (P) + 2-ketoglutarate
Dehydrogenase +1TH,+IIAD(P)HDehydrogenase + 1TH, + IIAD (P) H
2.5. Alkohol + HAD(P)+ Aldehyd+ITADH2.5. Alcohol + HAD (P) + aldehyde + ITADH
DehydrogenaseDehydrogenase
2.4. Glycerin + ITAD+ ■—> Dihydroxy ac et on-f ITADH2.4. Glycerin + ITAD + ■ -> Dihydroxy ac et on-f ITADH
tfehydr ο genäsetfehydr ο genäse
2.5. L-Malat+irAD+ oxalacetat+UAIH2.5. L-malate + irAD + oxaloacetate + UAIH
DehydrogenaseDehydrogenase
2.6. ß-D-Glucose+ilAD(P)+ D-Gluconolacton +2.6. β-D-glucose + ilAD (P) + D-gluconolactone +
tfehydrogenase IiAD(P)H und anderetfehydrogenase IiAD (P) H and others
3. Bestimmung von biologischen Substanzen und nicht-biologischen Substanzen, die bereits in zu untersuchenden Flüssigkeiten vorliegen im Gegensatz zu solchen, die bei Reaktionen gebildet werden, wie die zuvor genannten, wie z.B.:3. Determination of biological and non-biological substances Substances that are already present in the liquids to be examined in contrast to those that are formed during reactions like the ones mentioned before, such as:
3.1. Harnsäure3.1. uric acid
3.2. Ascorbinsäure3.2. Ascorbic acid
4. Bestimmung von sämtlichen Substanzen, die gewöhnlich unter Verwertung herkömmlicher Elektrodensysteme nachgewiesen werden.4. Determination of all substances that are usually detected using conventional electrode systems.
Weitere Verfahrenseinzelheiten werden beim Studium der folgenden Beispiele ersichtlich, die die Erfindung näher erläutern.Further process details will become apparent from a study of the following examples which further illustrate the invention.
Bestimmung von Glucose gemäß dem vorstehend unter 1.1. angegebenen Reakfcionsschema.Determination of glucose according to the above under 1.1. specified Reaction scheme.
9 0 9 8 5 1 / 0 8 7 59 0 9 8 5 1/0 8 7 5
y ■/■ λ 117y ■ / ■ λ 117
1. Enzymatisches Reagens, enthaltend 75 mM Phosphat-Puffer, pH 7 und Glucose-Oaydase 50 E/ml1. Enzymatic reagent containing 75 mM phosphate buffer, pH 7 and glucose oaydase 50 U / ml
2. im Handel erhältliche Kontrollsera2. Commercially available control sera
3. Glucosestandardlösungen (5Ο-1ΟΟ-15Ο-2ΟΟ-3ΟΟ-5ΟΟ mg/dl) in gesättigter Benzoesäurelösung3. Glucose standard solutions (5Ο-1ΟΟ-15Ο-2ΟΟ-3ΟΟ-5ΟΟ mg / dl) in saturated benzoic acid solution
4. Meßzelle von Eigur 2, die mit den speziellen polarographischen Instrumenten verbunden ist.4. Eigur 2 measuring cell connected to the special polarographic instruments.
In Eigur 2 gibt die Bezugszahl 1 den Weg des Einbringens des enzymatischem Reagens über eine automatische Dosiervorrichtung an, 2 sind die mit dem Polarographen verbundenen Elektroden, 3 iet die Probenzufuhrpipette, 4 ist ein Rührer, 5 ist die mit einem Saugsystem verbundene Absenkung, 6 sind die Verbindungen der Sensoren mit dem Polarographen.In Figure 2, the reference number 1 indicates the way of introducing the enzymatic reagent via an automatic metering device on, 2 are the electrodes connected to the polarograph, 3 is the sample feed pipette, 4 is a stirrer, 5 is the one with lowering connected to a suction system, 6 are the connections between the sensors and the polarograph.
Methoden;Methods;
Van bringt 2 ml enzymatisches Reagens in die Meßseile ein und fibt 0,02 ml Serum oder einen Standard su. Der Polarograph wird njt einem Registriergerät für das Aufzeichnen des Reaktions-•verlaufs auf einem Diagramm verbunden. Man erhält Peaks wie nie in Eigur 3 dargestellt sind. Die Höhe eines jeden Peaks ißt proportional zur Konzentration der Glucose in der Probe (Figur4). Van brings 2 ml of enzymatic reagent into the measuring ropes and adds 0.02 ml of serum or a standard see below. The Polarograph is not connected to a recording device for recording the course of the reaction on a diagram. One obtains peaks like never shown in Figure 3. The height of each peak is proportional to the concentration of glucose in the sample (Figure 4).
'/-MT Überprüfung der Genauigkeit wurden acht kommerzielle Seren untersucht und die Ergebnisse sind in Tabelle I angegeben. '/ -MT check the accuracy were examined eight commercial sera and the results are given in Table I below.
Vergleich mit der enzymatisch-colorimetrisehen Methode (GOD-POD) ergab die folgenden Daten:Comparison with the enzymatic-colorimetric method (GOD-POD) resulted in the following data:
9098 5 1/08759098 5 1/0875
Anzahl der Proben Gleichung der RegresBionslinie Korrelationskoeffizient Mittel von χ Mittel von y Maximum von χ Maximum von y Minimum von χ Minimum von y Bereich von χ Bereich von yNumber of samples Equation of the regression line Correlation coefficient mean of χ mean of y maximum of χ Maximum of y Minimum of χ Minimum of y Area of χ Area of y
y = 0,94 x + 7,8 r = 0,985 128,5 mg/dl 128,0 mg/dl 325,0 mg/dl 341,0 mg/dl 57,0 mg/dly = 0.94 x + 7.8 r = 0.985 128.5 mg / dl 128.0 mg / dl 325.0 mg / dl 341.0 mg / dl 57.0 mg / dl
57,0 mg/dl 268,0 mg/dl 284,0 mg/dl57.0 mg / dl 268.0 mg / dl 284.0 mg / dl
909851/0875909851/0875
Iabelle IIabelle I
GlucoseSpecified
glucose
GlucoseFound
glucose
Bestimmung von NADH in Anwesenheit von ITAD+ Determination of NADH in the presence of ITAD +
Es wurde ein polarographisches System mit den folgenden Verfahrensparametern verwendet:A polarographic system was used with the following process parameters used:
Spannung : + 800 mVVoltage: + 800 mV
Wert bei voller Skala : 500 nA (Nanoampere)Full scale value: 500 nA (nanoampere)
Mechanisches Rühren : bei ca. 500 TJpMMechanical stirring: at approx. 500 TJpM
Reaktionsvolumen : 10 ml Phosphat-Puffer 0,05 M, pH 7,4Reaction volume: 10 ml phosphate buffer 0.05 M, pH 7.4
1 .zuder 1. To
Man gab zunehmende Mengen von 10 mcl bis 100 mcl (Millicentiliter J] Prob? von 0,1 mg/ml NADH und führte eine kontinuierliche Aufzeichnung der Stromstärke in Bezug auf die Oxidationsreaktion von NADH zu NAD+ durch.Increasing amounts of 10 mcl to 100 mcl (millicentiliter J) sample of 0.1 mg / ml NADH were given and a continuous recording of the current intensity in relation to the oxidation reaction of NADH to NAD + was carried out.
Die Anzeigen des Instruments waren proportional zur Zunahme der NADH-Konzentration in der Reaktionszelle bei einem 70 nA Signal für 0,14 mMol/ml NADH.The instrument's readings were proportional to the increase in NADH concentration in the reaction cell with a 70 nA signal for 0.14 mmol / ml NADH.
909851/0875909851/0875
Claims (2)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT24640/78A IT1158856B (en) | 1978-06-16 | 1978-06-16 | ELECTRODIC SYSTEM WITH REFERENCE ELECTRODE WITHOUT LIQUID JUNCTION FOR VOLTAMMETRIC MEASUREMENTS |
Publications (1)
Publication Number | Publication Date |
---|---|
DE2924117A1 true DE2924117A1 (en) | 1979-12-20 |
Family
ID=11214235
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19792924117 Ceased DE2924117A1 (en) | 1978-06-16 | 1979-06-15 | ELECTRODE SYSTEM WITH A REFERENCE ELECTRODE WITHOUT LIQUID TRANSITION FOR VOLTAMETER MEASUREMENTS |
DE19797917122U Expired DE7917122U1 (en) | 1978-06-16 | 1979-06-15 | MEASURING DEVICE FOR POLAROGRAPHIC OR VOLTAMETER MEASUREMENTS |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19797917122U Expired DE7917122U1 (en) | 1978-06-16 | 1979-06-15 | MEASURING DEVICE FOR POLAROGRAPHIC OR VOLTAMETER MEASUREMENTS |
Country Status (6)
Country | Link |
---|---|
JP (1) | JPS554591A (en) |
CA (1) | CA1141435A (en) |
DE (2) | DE2924117A1 (en) |
FR (1) | FR2428839A1 (en) |
GB (1) | GB2023846B (en) |
IT (1) | IT1158856B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3725597A1 (en) * | 1987-08-01 | 1989-02-09 | Siegert Gmbh | Ionometric sensor |
DE102010040057A1 (en) * | 2010-08-31 | 2012-03-01 | Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG | Electrochemical sensor, particularly pH-sensor, comprises measuring electrode and reference electrode for generating reference potential |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS507615A (en) * | 1973-05-28 | 1975-01-27 | ||
JPS5026614A (en) * | 1973-07-10 | 1975-03-19 | ||
BR8607043A (en) * | 1985-02-12 | 1988-02-23 | Commw Scient Ind Res Org | VOLTAMETRIC CELL |
DE3810186A1 (en) * | 1987-08-01 | 1989-10-05 | Siegert Gmbh | SENSOR FOR MEASURING THE ACTIVITY OF IONS AND METHOD FOR THE PRODUCTION THEREOF |
DE3937577A1 (en) * | 1989-11-11 | 1991-05-16 | Lutz Ehrlich | Voltametric analysis cell - with holder cavity holding oversize mercury droplet |
US5144247A (en) * | 1991-02-14 | 1992-09-01 | Westinghouse Electric Corp. | Method and apparatus for reducing IR error in cathodic protection measurements |
US5653864A (en) * | 1994-06-30 | 1997-08-05 | Nok Corporation | Protein biosensor and method for protein measurement with the same |
WO1999046586A1 (en) * | 1998-03-10 | 1999-09-16 | Micronas Gmbh | Reference electrode |
JP3982133B2 (en) * | 2000-01-25 | 2007-09-26 | 松下電器産業株式会社 | Measuring device using biosensor and biosensor and dedicated standard solution used therefor |
WO2015138690A2 (en) * | 2014-03-12 | 2015-09-17 | Glucovation, Inc. | Electrochemical sensing system |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
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FR1426514A (en) * | 1965-02-27 | 1966-01-28 | Apparatus for studying solids comprising several compounds | |
US3676321A (en) * | 1970-07-27 | 1972-07-11 | Honeywell Inc | Electrochemical oxygen demand system |
US3910830A (en) * | 1974-04-08 | 1975-10-07 | Petrolite Corp | Flush mounted probe assembly |
FR2331017A1 (en) * | 1975-11-07 | 1977-06-03 | Owens Illinois Inc | Determn. of glucose by oxidn. on supported glucose oxidase - and polarographic determn. of hydrogen peroxide formed, esp. for analysis of blood serum |
US4073053A (en) * | 1976-02-27 | 1978-02-14 | Honeywell Inc. | Method of making an ion responsive electrode |
JPS52126285A (en) * | 1976-04-16 | 1977-10-22 | New Cosmos Electric Co | Measuring method and apparatus for residual free chlorine concentration |
JPS52126286A (en) * | 1976-04-16 | 1977-10-22 | New Cosmos Electric Co | Measuring apparatus for residual chlorine |
FR2636943B1 (en) * | 1988-09-26 | 1991-04-12 | Rhone Poulenc Sante | PROCESS FOR THE PREPARATION OF SATURATED ALDEHYDES BY HYDROGENATION OF ALDEHYDES (ALPHA), (BETA) -UNSATURES |
-
1978
- 1978-06-16 IT IT24640/78A patent/IT1158856B/en active
-
1979
- 1979-06-05 CA CA000329156A patent/CA1141435A/en not_active Expired
- 1979-06-08 GB GB7920119A patent/GB2023846B/en not_active Expired
- 1979-06-15 JP JP7477779A patent/JPS554591A/en active Pending
- 1979-06-15 DE DE19792924117 patent/DE2924117A1/en not_active Ceased
- 1979-06-15 DE DE19797917122U patent/DE7917122U1/en not_active Expired
- 1979-06-15 FR FR7915476A patent/FR2428839A1/en active Granted
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3725597A1 (en) * | 1987-08-01 | 1989-02-09 | Siegert Gmbh | Ionometric sensor |
DE102010040057A1 (en) * | 2010-08-31 | 2012-03-01 | Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG | Electrochemical sensor, particularly pH-sensor, comprises measuring electrode and reference electrode for generating reference potential |
Also Published As
Publication number | Publication date |
---|---|
GB2023846B (en) | 1983-03-30 |
FR2428839B1 (en) | 1982-11-05 |
IT7824640A0 (en) | 1978-06-16 |
FR2428839A1 (en) | 1980-01-11 |
GB2023846A (en) | 1980-01-03 |
IT1158856B (en) | 1987-02-25 |
JPS554591A (en) | 1980-01-14 |
DE7917122U1 (en) | 1982-09-30 |
CA1141435A (en) | 1983-02-15 |
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