EP0394411A1

EP0394411A1 - An electrochemical sensor

Info

Publication number: EP0394411A1
Application number: EP19890911745
Authority: EP
Inventors: Karl Harnoncourt; Gerald BRANDSTÄTTER
Original assignee: Individual
Current assignee: Individual
Priority date: 1988-10-25
Filing date: 1989-10-25
Publication date: 1990-10-31
Also published as: AT392848B; ATA264988A; WO1990004777A1

Abstract

L'élément de mesure d'un détecteur électrochimique présente une électrode-support inerte, dont les parties exemptes d'une gaine électriquement isolante, sont recouvertes d'un conducteur électronique formé d'une couche polymère stable en milieu aqueux. L'élément de mesure peut dès lors, en vue de réaliser une électrode au CO2, être disposé à l'intérieur d'une enveloppe (17) remplie d'un tampon H2CO3/HCO3-, dont l'ouverture (18) située du côté de l'échantillon est obturée par une membrane (19) perméable au CO2, appliquée sur la couche polymère (3) de l'élément de mesure (1), ou encore, le cas échéant, en vue de réaliser une électrode de référence, être disposé à l'intérieur d'une enveloppe (13) remplie d'un électrolyte et dont l'ouverture (14) située du côté de l'échantillon présente un diaphragme (15).The measuring element of an electrochemical detector has an inert support electrode, the parts of which are free from an electrically insulating sheath, are covered with an electronic conductor formed by a polymer layer stable in an aqueous medium. The measuring element can therefore, in order to produce a CO2 electrode, be placed inside an envelope (17) filled with an H2CO3 / HCO3- buffer, the opening (18) of which is located side of the sample is closed by a membrane (19) permeable to CO2, applied to the polymer layer (3) of the measuring element (1), or alternatively, if necessary, in order to produce a reference electrode , be placed inside an envelope (13) filled with an electrolyte and whose opening (14) located on the side of the sample has a diaphragm (15).

Description

Electrochemical sensor

The invention relates to an electrochemical sensor for detecting chemical and physicochemical parameters of an aqueous sample with a measuring element which has an inert carrier electrode, the parts of which are free from an electrically insulating coating and are covered by an electron conductor from a polymer layer which is stable in aqueous media .

The signal acquisition in conventional electrochemical sensors takes place, for example, with metal / metal salt derivatives (for example calomel electrodes, Ag / AgCl electrodes, etc.) which are immersed in ion-stable aqueous solutions which, together with the selective element (pH-selective glass membrane, ion-selective membranes of all kinds, etc.) form the actual measuring element or establish a connection to the sample or measurement solution that is as electrically neutral as possible when they are used as part of a reference electrode.

For example, the H ~ -selective membrane in conventional pH glass electrodes consists of a special glass. Swelling in the aqueous sample medium leads to the incorporation of H ~ or OH ^_ ions into the glass framework.

In the case of the ion-selective membranes, plastics are used as carrier elements on or in which the substances responsible for the selectivity are fixed.

Limiting boundary conditions for these selective sensors are given by the need to keep the aqueous connection solution for discharge absolutely stable (it must be protected from drying out), by the time limitation of the selective properties of the membranes from their manufacture.

REPLACEMENT LEAF Position, by the need for their conditioning in aqueous solutions on the surface provided for the measurement, and by the production costs. Depending on the sensor, problems such as high impedance, fragility, chemical resistance, etc. arise.

With conventional reference electrodes, an electrical signal derivative, e.g. a calomel electrode, is immersed in the aqueous connection solution, preferably saturated KCl solution. The filling electrolyte is connected to the sample to be measured via an opening or a diaphragm, for example a glass frit. This electrode must also be protected from drying out and takes several days until a stable potential is set again after it has been filled again. When biological liquids are measured, there is a denaturation (coagulation) of protein on the contact surface of the filling electrode and the measuring solution, which closes the channels of the membrane and thus leads to disturbing membrane potentials in the measuring section. However, these reference electrodes are not sufficiently stable in blood isotonic solutions. A further disadvantage of these reference electrodes is the contamination, which arises from the open electrolyte bridge, especially in stand-by mode, with drying-out KCl solution escaping.

An electrochemical sensor of the type mentioned at the outset has become known, for example, from EP-A 0 056 283. The pH sensor described there has an electrically conductive element, preferably made of platinum, as the carrier electrode, which is insulated with a Teflon layer and the free part of which is covered by an electrically conductive polymer layer. The polymer layer, which is immobilized directly on the carrier electrode, consists of at least one aromatic compound in the form of nitrogen-containing aromatic compounds, such as, for example, aniline and pyrrole, or aromatic hydroxy compounds, such as e.g. Phenol.

The polymer layer is designed for low impedance and can be polymerized by electrochemical oxidation on the surface of the carrier electrode. Furthermore, it is known from EP-A 0 228 969, by attaching an ion-selective layer which covers the polymer layer, to produce ion sensors which, depending on the ion-selective substance incorporated, can be used to determine the concentration of different ions i nen.

The conductive polymers mentioned can be regarded as solid redox systems which form a constant electrochemical potential in a corresponding charge state. This can be used as a reference potential for electrochemical potential measurements.

Conductive polymers with basic or acidic groups (e.g. basic nitrogen in polyaniline) have a characteristic potential / pH dependence in certain pH ranges, which largely corresponds to that of the classic glass electrode.

The positive properties of the measuring element described above are briefly summarized:

1) The polymer layer of the measuring element which is present as a solid is an electron conductor.

2) The polymer layer can be applied directly to an inert electrode.

3) The measuring element has a stable potential in relation to many, especially biological electrolyte solutions.

4) The measuring element is not damaged by drying out.

5) The surfaces of the measuring element are easy to clean.

6) Because of the cheap mass production, disposable electrodes or sensors can be produced.

The low layer thickness of the polymer layer of only 0.1 to 500 / um ensures that the sensor responds quickly to changing parameters in the sample.

Proceeding from this, the object of the present invention is also others with the disadvantages described at the outset Affected electrochemical sensors, in particular reference electrodes and electrodes for measuring C0 _{2, are} easier, more robust and cheaper to manufacture.

According to the invention, this object is achieved in that the measuring element for realizing a C0 ₂ electrode is arranged in a housing filled with an H ₂ C0 ₃ / HC0 ₃ ^_ buffer, the sample-side opening of which is connected to a C0 ₂ - resting on the polymer layer of the measuring element. permeable membrane is closed.

The measurement of the CO ₂ concentration is carried out as follows. C0 ₂ passes through a gas-permeable membrane into an electrolyte space which is filled with bicarbonate buffer solution. There are C0 ₂ / H ₂ C0 ₃ / HC0 ₃ ^_ in equilibrium, which is shifted by the penetration of carbon dioxide. The shift in the equilibrium leads to a change in pH, which can be measured with the aid of the measuring element according to the invention.

A major advantage of this CO ₂ electrode is that the polymer layer itself can be designed so that the CO ₂ permeable membrane lies directly above it. The polymer layer not only serves as a sensor layer, but also as a spacer, since its interior is electrolyte-swollen. The advantageous construction also achieves better geometric stability of the measuring layer.

In a further development of the invention it is provided that a further measuring element, essentially designed like the first measuring element and in contact with the H ₂ C0 ₃ / HC0 ₃ ^_ buffer, is provided in the housing, the second of the C0 ₂ permeable membrane being provided uncovered measuring element acts as a reference electrode. By arranging an inner reference electrode, certain signs of aging of the measuring element can be compensated for.

An embodiment variant of the C0 ₂ electrode with internal reference electrode provides that the carrier electrode of the reference electrode is sleeve-shaped and includes the insulation of a signal lead leading away from the measuring element, and that the outer surface of the sleeve-shaped carrier electrode is covered with the polymer layer . In all versions, the C0 ₂ permeable membrane can consist of a Teflon film.

In an advantageous embodiment of the invention, it is provided that the polymer layer of the measuring element consists of medium-oxidized polyaniline. In acidic electrolytes the existence of three different oxidation levels of the polymer is observed (reduced I, medium oxidized II and fully oxidized III). In the neutral pH range, however, only two different oxidation states should be possible (reduced IV and oxidized V). By producing Form II in the acidic medium, a defined mixture of Forms IV and V can be achieved in neutral solution.

Some conductive polymers are listed below. Oxidation levels and their protonated state are also given for polyaniline:

1) POLYANILINE:

Starting material: aniline (as hydroperchlorate) ^C 6 ^H 5 ^NH 2 ^or " ^C 6 ^H 5 ^NH 3 ^{- C10} 4

The polymer shows three states in acid; above pH 5-6, only two oxidation states can be distinguished.

pH <2 pH> 6

-H, ©

reduced: m- () - m) ^~ [τ _V ]

medium oxidized:

REPLACEMENT LEAF oxidized [III]

2) Other starting materials:

a) Methyl anilines: CHgC ₆ H ₄ NH ₂

b) * <- Naphtyl amine: C _lfJ H ₇ NH ₂

c) pyrrole

Polypyrrole

The potential of the polyaniline layer is essentially determined by the degree of oxidation caused by the production and by the pH of the electrolyte.

A further advantageous embodiment of the invention is given in that the measuring element for realizing a reference electrode is arranged in a housing filled with an electrolyte, the sample-side opening of which has a diaphragm. Conductive polymers require a constant electrochemical environment in order to provide a stable potential, but different ions have little influence on the potential. It is therefore also possible according to the invention to use a physiological saline solution (Ringer's solution) as a filling electrolyte for the reference electrode. The denaturing problems mentioned at the beginning are thus solved.

There is also the possibility of producing the polymer layer of such measuring electrodes in such a way that the formation of selective potentials for the constituents of the sample solution is avoided. Measuring elements equipped with such polymer layers can then come into direct contact with the test samples and be used as so-called "dry reference electrodes". This eliminates the entire effort required for the filling electrolyte.

Finally, according to the invention it is provided that an enzyme is immobilized on or in the polymer layer of the measuring element in order to implement a biochemical electrode. By immobilizing enzymes which catalyze redox reactions in which electrochemically active species are converted or generated, biochemical electrodes can be produced which are superior to the enzyme electrodes which have been customary hitherto, inter alia due to their more compact design. This creates the possibility of developing very efficient, stable enzyme electrodes for biochemical analysis.

The production of a measuring element with a polyaniline layer is given as an example:

The polymerization takes place, for example, on a gold electrode in a potentiodynamically controlled manner. This means that the potential of the working electrode is checked against a non-polarizable reference electrode via a three-electrode circuit. The current flows through a polarizable electrode (counter-electrode).

Description of the arrangement:

Potentiostat (A. JAISSLE Electronics Laboratory, IMP 83) Electrolyte: 70 ml standard electrolyte (1 M HC10 ₄ , 0.1 M NaClO ^)

+ 5 ml aniline (C _e H _B -NH ₂ ) - electrode 1 + 3 ml aniline <C _e H _B -NH ₂ ) - electrode 2 reference electrode: SCE (Hg / Hg ₂ Cl _E / KCl, _β -c) counter -Electrode: Pt sheet (about 5 cm ² ) measuring electrode: gold (0.78 m ² surface)

The electrode potential is varied in the form of a triangular voltage over 25 cycles between -200 and +800 mV (voltage feed lOmV / sec.). At the end of the polymerization, a constant potential of +400 mV is kept constant for a long time in order to produce the medium-oxidized polyaniline form.

REPLACEMENT LEAF The electrodes covered with a thin polyaniline film are then rinsed with triple-distilled water and stored in a 1 M KCl solution, so that the environment was able to balance in pH. It is assumed that in the polyaniline layer, which must always also contain anions, the perchlorate is completely replaced by chloride. Furthermore, a pH balance must take place, since the -NH- and -N = groups of the polymer chain are present in the acidic medium as -NH ₂ ~ - or -NH ~ =, but are largely deprotonated between pH 3 and 5.

The invention is explained in more detail below with reference to drawings. Show it:

1 shows a measuring element according to the prior art, FIG. 2 shows a reference electrode according to the invention with a measuring element according to FIG. 1,

3 shows a measuring arrangement with a pH and a reference electrode according to the invention, FIG. 4 shows a C0 ₃ electrode according to the invention, FIG. 5 shows a detail from FIG. 4, and FIG. 6 shows an embodiment variant according to FIG. 4.

The measuring element 1 consists of an inert carrier electrode 2 to which the conductive polymer layer 3 made of polyaniline, poly-naphthylamine or one of its substituted derivatives is applied by electrochemical polymerization. The detection of the measurement signals takes place via the signal lead 4, which is electrically conductively connected to the carrier electrode 2. The parts of the carrier electrode 2 not covered by the polymer layer 3, and the signal lead 4, have an electrically insulating sheath 5. The layer thickness d of the polymer layer 2 is approximately 0.1 to 500 _μm .

As stated at the beginning, there are two different oxidation states of the polymer, a mixed state of these two components being prepared and an electoral chemical equilibrium being established.

The electrode potential is determined, for example, by the equilibrium between two solid phases, an oxidized (P ₀ ) and a reduced P _R. If:

REPLACEMENT LEAF n. e _c = P _F applies to the potential E

n.F.

E = E "In o RT ^a p

Where a _PO and a _{PB are} the corresponding activities of the oxidized and the reduced phase. However, since these are solid substances, the activities are constant. So the potential is constant until one of the phases Po or P _{R is} completely used up.

If the measuring element 1 is brought into contact with the sample, the side 6 of the polymer layer 3 facing away from the carrier electrode 2 being immersed directly in the sample to be measured, an extremely simple, compact pH electrode is already implemented.

In the reference electrode shown in FIG. 2, the measuring element 1 is arranged in a housing 13 filled with an electrolyte, which has an opening 14 with a diaphragm 15 on the sample side. Both the housing 13 and the U-cladding 5 of the measuring element 1 can be made of plexiglass, glass or the like, for example. The diaphragm 15 separating the electrolyte, for example a Ringer's solution, from the sample can be a membrane provided with pores or a glass frit.

3 shows a measuring arrangement for pH measurement in biological media, a known pH electrode and a reference electrode according to FIG. 2 being used. The measuring circuit is closed by a high-resistance voltmeter 16.

With a C0 ₂ electrode shown in FIG. 4, the measuring element 1 is arranged ange¬ in a container filled with a buffer solution housing 17. As shown in detail in FIG. 5, the sample-side opening 18 of the housing 17 is closed with a C0 ₂ -permeable membrane 19 lying against the polymer layer 3 of the measuring element 1. At a distance from the membrane 19, a further measuring element 1, which is in contact with the buffer solution, is arranged in the housing 17 as a reference electrode 20. The signal leads 4, 4 'lead to a voltmeter 16. In measuring operation, CO ₂ dissolved in the sample diffuses through the CO ₂ permeable membrane 19 into the electrolyte film of the swollen polymer layer 3 and shifts the equilibrium

HCO ^" + H ⁺ £ ■■? H ₂ C0 ₃

H ₂ 0 + C0 ₂

in the buffer solution. The changing potential on the measuring element leads together with the signal of the reference electrode 20 to the measuring signal.

According to the detailed drawing in FIG. 6, the carrier electrode 2 of the reference electrode 20 can be sleeve-shaped and comprise the insulation 21 of the signal lead 4 leading away from the measuring element 1, thereby shielding it. The outer surface 22 of the sleeve-shaped carrier electrode 2 is covered with the polymer layer 3.

REPLACEMENT LEAF

Claims

PATENT CLAIMS

1. Electrochemical sensor for detecting chemical and physical-chemical parameters of an aqueous sample with a measuring element which has an inert carrier electrode, the parts of which are free from an electrically insulating sheath and are covered by an electron conductor from a polymer layer which is stable in aqueous media, characterized . that the measuring element (1) for realizing a C0 ₂ electrode is arranged in a housing (17) filled with an H ₂ C0 ₃ / HC0 ₃ buffer, the sample-side opening (18) of which is connected to the polymer layer (3 ) of the measuring element (1) adjacent C0 ₂ permeable membrane (19) is closed.

2. Sensor according to claim 1, characterized in that in the Ge¬ housing (17) another, essentially like the first measuring element (1) designed, with the H ₂ C0 ₃ / HC0 ₃ ^~ buffer in contact measuring element is provided , wherein the second measuring element uncovered by the CO _a permeable membrane (19) acts as a reference electrode (20).

3. Sensor according to claim 2, characterized in that the carrier electrode (2) of the reference electrode (20) is sleeve-shaped and the insulation (21) of the measuring element (1) leading signal lead (4), and that the outer surface ( 22) of the sleeve-shaped carrier electrode (2) is covered with the polymer layer (3).

4. Sensor according to one of claims 1 to 3, characterized ge indicates that the C0 ₂ permeable membrane consists of a Tef¬ lon film

5. Electrochemical sensor for detecting chemical and physical-chemical parameters of an aqueous sample with a measuring element which has an inert carrier electrode, the parts of which are free from an electrically insulating sheath and are covered by an electron conductor from a polymer layer which is stable in aqueous media, characterized in that the measuring element (1) for realizing a reference electrode in one with an electrolyte

REPLACEMENT LEAF Filled housing (13) is arranged, the sample-side opening (14) has a diaphragm (15).

6. Sensor according to claim 5, characterized by a physiological saline solution as an electrolyte.

7. Electrochemical sensor for detecting chemical and physical-chemical parameters of an aqueous sample with a measuring element which has an inert carrier electrode, the parts of which are free from an electrically insulating sheath and are covered by an electron conductor from a polymer layer which is stable in aqueous media, characterized in that an enzyme is immobilized on or in the polymer layer (3) of the measuring element (1) to implement a biochemical electrode.

8. Sensor according to one of claims 1 to 7, characterized ge indicates that the polymer layer (3) of the measuring element (1) consists of medium-oxidized polyaniline.

REPLACEMENT LEAF