EP1869439A1 - Procede d'analyse electrochimique par voltametrie et dispositif pour sa mise en oeuvre - Google Patents
Procede d'analyse electrochimique par voltametrie et dispositif pour sa mise en oeuvreInfo
- Publication number
- EP1869439A1 EP1869439A1 EP06725372A EP06725372A EP1869439A1 EP 1869439 A1 EP1869439 A1 EP 1869439A1 EP 06725372 A EP06725372 A EP 06725372A EP 06725372 A EP06725372 A EP 06725372A EP 1869439 A1 EP1869439 A1 EP 1869439A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- analysis
- electrode
- sample
- measurements
- solution
- 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.)
- Withdrawn
Links
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
Definitions
- the field of the invention is that of chemistry and more specifically methods for electrochemical analysis of liquid solutions or gases for the detection and / or assay of chemical species.
- a technique for qualitative and quantitative analysis of electrochemical species commonly used is voltammetry. This technique is based on the measurement of the current flow resulting from the reduction or oxidation of the species present under the effect of a controlled variation of the potential difference between two electrodes.
- a large number of species can thus be analyzed, whether organic or inorganic compounds, cations or anions.
- a voltammetric analyzer is thus composed of an electrochemical analysis cell based on a three-electrode system immersed in the solution to be analyzed.
- the three electrodes are:
- a working electrode also called indicator electrode
- a reference electrode a reference electrode
- a counter-electrode also called auxiliary electrode
- the voltammetric analyzer is also composed of a potentiostat making it possible to impose a potential difference between the working electrode and the counter-electrode, and to impose a specific and constant potential on the reference electrode so that the potential imposed on the working electrode is precisely defined.
- Different voltametric analysis techniques can be implemented depending on the variation of the imposed potential, which can be linear or modulated.
- a first known technique is the step scan voltammetry, also called potential jump voltammetry (SCV: Staircase Voltammetry).
- SCV potential jump voltammetry
- a series of regularly increasing value (constant jump height) and constant duration (staircase step) steps is applied, and the current is measured by sampling after a certain duration of the step.
- LSV Linear Scan Voltammetry
- NPV normal impulse voltammetry
- a series of potential pulses is imposed and the intensity of the current is measured after a certain time "t" after the jump. After each pulse, the potential returns to its initial value and the height of each pulse is varied regularly so as to carry out a scanning potential exploration.
- a third known technique is differential voltage voltammetry, also known as Differential Pulse Voltammetry (DPV).
- DUV Differential Pulse Voltammetry
- a series of potential pulses is imposed and the current difference before and after the jump is measured.
- Each impulse is of constant height, but the return potential is different from the potential before impulse, which allows a potential evolution and a potential exploration.
- electrochemical analysis methods use different types of electrodes, and in particular, different types of working electrodes.
- a solid working electrode is immersed in the solution to be analyzed. It may be of different natures, that is to say made in different conductive materials, such as
- non-metallic materials graphite or vitreous carbon, for example
- the working electrode used for the analysis can then be chosen in particular according to the oxidation or reduction potential of a particular species that it is desired to analyze.
- this method has two major disadvantages. First, during measurements, adsorption phenomena, deposition, or even corrosion of the electrode are likely to occur and modify the surface of the electrode by disturbing the current response.
- the concentration of the substrate or chemical species studied with the variation of the potential.
- the concentration of the substrate on the surface of the electrode decreases with respect to its initial concentration in the solution, far from the electrode. This phenomenon is at the origin of a concentration gradient and the appearance of a diffusion layer whose thickness is generally a few microns on the surface of the electrode.
- Hi 0 is the material transport coefficient of the oxidant.
- techniques known from the prior art provide for various alternatives such as stirring the solution during the measurements by a magnetic stirrer for example, or the use of a rotating electrode.
- the rotating electrode consists of a disk-forming electrode, which can for example be made of platinum, silver or vitreous carbon, and driven by a rotational movement.
- Another known technique of the prior art makes it possible to ensure the renewal of the surface of the working electrode with each measurement.
- This is the mercury drop electrode.
- polarography a drop of mercury grows at the end of a capillary fed with mercury continuously. The size of the drop increases until it breaks off under the effect of its weight. A new drop is then formed at the end of the capillary. The drop is thus renewed at each measurement and is substantially identical to the previous one.
- the current is measured at a specific time during the lifetime of the drop or is a value averaged over the entire life of the drop.
- this technique effectively ensures the renewal of the active surface of the electrode. Moreover, the drop of the drop ensures the agitation of the solution and cancels out the effect of depletion in the substrate. So, each new drop begins its growth in a solution corresponding to the initial solution.
- a first disadvantage of this technique is that it requires the use and handling of mercury which is a toxic compound and which therefore requires special and restrictive conditions of use to meet the current standards of hygiene, safety and security. environmental.
- the mercury electroactivity range is between +0.2 V and -2 V, depending on the pH of the solution.
- This field allows a study of electroactive species up to a cathodic value not reached by other metals.
- this area is very limited on the anodic side (+0.2 V), unlike other materials (for example +1.5 V for platinum and gold, +1.8 V for carbon, etc.)
- the invention particularly aims to overcome these disadvantages of the prior art.
- an object of the invention is to provide a new technique for a simple and rapid analysis of a solution, and in particular the detection and / or rapid assay of one (or more) chemical species.
- Another objective of the invention is to propose a powerful technique making it possible to overcome the phenomenon of depletion in species of the solution which has reacted in the vicinity of the working electrode, as well as to avoid surface alteration. activates the working electrode during measurements, so that the measurements made are rigorous and precise.
- Yet another particular object of the invention is to propose a technique offering a good modularity as to the oxidation-reduction potential of the species to be analyzed and which is simple to implement by the method. 'user.
- These objectives, as well as others, which will become clearer later, are achieved by an electrochemical analysis method. voltammetry of a liquid solution, allowing detection and / or dosage in said solution of at least one chemical species.
- the method comprises the steps of:
- each analysis cell further comprising a counter-electrode and a test electrode; reference;
- the invention consists in analyzing a solution by means of a single analysis support having a plurality of working electrodes, each of them being used only for the realization of a single measurement, independent potentials being applied.
- An analysis cell for performing a measurement comprises:
- the working electrode of each analysis cell is located on the analysis support.
- the counter-electrode and / or the reference electrode completing an analysis cell can, for their part, be located on the same analysis medium or, on the contrary, be carried on a second support
- a counter-electrode and / or a reference electrode may, on the other hand, be common to several or all the analysis cells.
- the chemical species present in the solution and analyzed by this process can be ionic, molecular or gaseous (in the form of a dissolved gas).
- the same sample of the solution is in contact
- the analysis support may for example be immersed in the sample of the test solution.
- the measurements are carried out simultaneously by each of the analysis cells.
- the independent potentials are then applied simultaneously to the working electrodes of the different cells.
- the composition of the sample is identical at the level of each electrode and corresponds to the initial composition. In addition, this makes it possible to reduce as much as possible the time required for the establishment of the voltammogram (s) and therefore for the analysis of the sample.
- the measurements are carried out successively by the analysis cells.
- the duration separating two successive measurements will be less than a maximum duration. Limitation of the delay between two measurements ensures that the current response in a cell is not impaired by electrochemical reactions taking place in neighboring cells. At the moment when a measurement is made, the composition of the sample in the vicinity of the cell is not modified by the previous measurement or measurements and is therefore not depleted in the chemical species reacted during the measurement.
- a counter-electrode and / or a reference electrode are common to at least two analysis cells. Indeed, it will then be possible to provide that a same counter-electrode and / or the same reference electrode is used for making measurements by different cells, the measurements being carried out successively, and these electrodes not risking to not alter during measurements.
- the reference electrode and / or the counter-electrode common to different analysis cells may be located on the analysis support carrying the working electrodes, or on a complementary support.
- the technique of the invention allows rapid analysis of a sample insofar as the different measurements can be performed simultaneously.
- One or more different voltammograms can thus be established and exploited from the measurements made.
- said measurements allow the implementation of at least one voltametric analysis belonging to the group comprising: voltammetry by potential jump; normal impulse voltammetry; differential pulse voltammetry.
- the method according to the invention can be implemented prior to further study and more accurate sample. It will thus be possible to use a support having a reduced number of working electrodes for the establishment of a voltammogram, so as to rapidly determine the presence or absence of a particular chemical species in the solution for example.
- At least ten measurements can be used from ten working electrodes to establish a voltammogram.
- the invention also relates to an analysis support for the implementation of an electrochemical analysis method as described above.
- a support has at least two working electrodes each belonging to a separate electrochemical analysis cell, and it furthermore has at least one electrical connection network allowing application of an independent potential to each of the working electrodes.
- An analysis support may also be called “analysis plate” or “plate” or “chip”.
- the different working electrodes of an analysis support are of the same dimensions.
- the working electrodes belonging to the cells used for the establishment of the same voltammogram are of the same dimensions. It is indeed important during the measurements that the working electrodes making it possible to carry out measurements making it possible to establish a voltammogram have a substantially identical active surface.
- at least two of the analysis cells comprise a working electrode made of different materials. It may indeed be provided that the working electrodes of the same analysis medium (or chip) are made with different materials.
- all the working electrodes are not necessarily adapted, in particular as a function of the material in which the working electrode and the oxidation-reduction potential of the electrode are produced. the species to be analyzed, or the pH conditions of the solution.
- said working electrodes of the analysis cells are made of at least one material belonging to the group comprising metals and non-conducting metals.
- the metals used may for example be gold, platinum, silver, copper, chromium, zinc, tin, nickel or lead or alloys.
- Non-metallic and conductive materials may for example be the graphite, vitreous carbon, doped silicon or organic materials such as conductive polymers (polypyrrole, polythiophene or polyanaline for example).
- the working electrodes may also be chemically modified electrodes. Such modified electrodes thus have a mediator for reacting in the presence of one or more particular chemical species of a solution to be analyzed.
- the mediator can be covalently attached to the working electrode or by adsorption phenomena.
- a modified electrode may in particular allow the detection and / or the determination of non-electroactive substances.
- the modification of the surface of the electrode can be done by immobilization for example of organic compounds, organometallic or ionic fragments, strands of DNA, enzymes or other molecules of high molecular weight.
- voltammetric analysis can be difficult in the case of solutions comprising several different chemical species. In fact, a measurement by an analysis cell may then be due to several compounds and not be characteristic of a single chemical species.
- a support having working electrodes of different natures may thus allow a discriminant analysis of the different species by comparison of the different voltammograms obtained with each of the different electrodes. Indeed, the behavior of the chemical species is variable depending on the working electrode used.
- the working electrodes used for producing the same voltammogram are of the same dimensions.
- the working electrodes of the different analysis cells are distributed on the same face of the analysis support.
- the sample of the solution to be analyzed may for example be deposited on this side of the analysis support.
- the working electrodes are at least 100 ⁇ m apart.
- the method according to the invention can be implemented prior to further study and more accurate sample.
- a reduced number of measurements and therefore a reduced number of working electrodes
- an analysis support having one hundred working electrodes. These may for example be divided into ten lines of ten.
- the higher the number of measurements taken to establish a voltammogram the more precise the analysis will be.
- the larger the number of working electrodes of different natures is used the more precise the analysis will be in that it will allow analysis of very different chemical species of oxidation-reduction potentials.
- the working electrodes of the different cells are of the same shapes and dimensions and therefore have a substantially identical active surface.
- an analysis cell is composed of: - a working electrode
- each counter-electrode and each reference electrode are specific to an analysis cell.
- the potentials being applied simultaneously to the different working electrodes.
- the different electrodes composing an analysis cell are specific to it and located close to each other, they can be grouped together on an area measuring 100 ⁇ m to 1000 ⁇ m for example, each of the zones then defining a cell. analysis, and the different zones can be separated by a distance of 10 microns to 1 mm.
- a counter electrode and / or a reference electrode is common to several analysis cells.
- the analysis support carrying the working electrodes also comprises a counter-electrode in the vicinity of each working electrode, and that the counter-electrodes are electrically connected to each other.
- each working electrode to be spatially close to the common counter electrode.
- the use of common counter-electrodes and / or of common reference electrodes during measurements carried out successively in particular makes it possible to limit the number of electrical connections on the analysis support. This simplifies and limits the costs of manufacturing them.
- the invention also relates to a complementary support, intended to cooperate with an analysis support as presented, having at least one counter-electrode and / or at least one reference electrode belonging to the analysis cells.
- a complementary support intended to cooperate with an analysis support as presented, having at least one counter-electrode and / or at least one reference electrode belonging to the analysis cells.
- the complementary support may for example be placed facing the analysis support, parallel to it, a small distance separating them.
- the distance separating the two supports may for example be 5 mm.
- the counter electrodes and / or the reference electrodes may then be placed on the complementary support so that they are directly opposite the working electrode with which they form an analysis cell.
- the space between the two supports will then preferably comprise the sample of the solution to be analyzed so that it is in contact simultaneously with the two supports (that is to say with the different electrodes carried by the supports) .
- each reference electrode and each counter-electrode is specific to each analysis cell. This will be the case, especially when measurements are performed simultaneously by each analysis cell.
- a single counter-electrode and / or a single reference electrode common to the different cells of analysis, as described above. This may in particular be the case when the measurements are carried out successively, that is to say when the potentials are successively applied to the different working electrodes.
- a single reference electrode and / or a single counter electrode located on the complementary support can then be common to the different working electrodes.
- the complementary support carrying the common counter electrode and / or the common reference electrode may for example be in the form of a ribbon. It is indeed advantageous for the accuracy of the measurements that the reference electrode and / or the counter-electrode are common to the different working electrodes of the analysis support.
- a complementary support carrying the counter-electrode or electrodes and / or the reference electrode or electrodes when used, it may then be reused for later analyzes, after have been properly washed.
- the one or more counter-electrodes and / or the reference electrode or electrodes have no risk of tampering when used, unlike working electrodes.
- successive measurements using the same complementary support does not therefore risk to alter the accuracy of the measurements.
- the invention also relates to a device for implementing an electrochemical analysis method as described above.
- a device for implementing an electrochemical analysis method as described above.
- Such a device comprises: first means for receiving at least one analysis medium as described above, second means for receiving at least one sample; means for contacting said at least one analysis support and said sample; means for applying an independent potential to each of said working and measuring electrodes of said sample in each of said analysis cells.
- the device thus comprises receiving means at which the analysis support is placed for each analysis.
- Each support being used for only one analysis. It may also be provided that the device is designed to receive several analysis media, içzier to simultaneously perform the analysis of different samples may come from different solutions.
- the device comprises means for establishing at least one voltammogram from the measurements.
- the device may also comprise third means for receiving a complementary support as described above, comprising at least one counter-electrode and / or at least one reference electrode, as well as means for contacting said sample. and said complementary support.
- a complementary support as described above, comprising at least one counter-electrode and / or at least one reference electrode, as well as means for contacting said sample. and said complementary support.
- the analysis support carrying the working electrodes of the analysis cells does not bear, on the other hand, the electrodes of reference and / or counter electrodes. It has already been indicated previously that one and / or the other of these may be located on a complementary support.
- the device also comprises means for deducing from said at least one voltammogram information relating to the detection and / or the assay of said at least one chemical species in the sample.
- Such a device thus makes it possible to quickly establish one or more voltammograms and the analysis of the species present in a sample of a solution.
- the device is portable (or portable). It is of course understood that it is advantageous to enable the production of a portable device in relation to the methods known in the prior art and allowing a rigorous voltammetric analysis, such as polarography using a mercury drop electrode, which implement a equipment voluminous and expensive, and therefore difficult to move.
- the device according to the invention can thus be transported and used directly where the solution to be analyzed is located, in order to determine, for example, whether further analysis is necessary and then to carry it out in the laboratory.
- FIG. 1 shows a voltammogram obtained by a technique known from the prior art for a solution of Fe 3+ at a concentration of 10 -2 mol / l in sulfuric acid H 2 SO 4 at 0.5 moLL "1 ;
- FIGS. 2A, 2B and 2C are simplified and schematic views of an analysis support according to the invention;
- FIGS. 2A, 2B and 2C are simplified and schematic views of an analysis support according to the invention
- 3A and 3B respectively show the current measurements for an analysis cell and a voltammogram obtained by Voltammetry by potential jump from a process according to the invention for a solution of Fe 3+ at a concentration of 10 -2 mol. L “1 in sulfuric acid H 2 SO 4 at 0.5 moLL "1 ;
- FIG. 4 illustrates a voltammetry obtained by voltammetry by potential jump from a method according to the invention for a solution of
- FIGS. 5A and 5B respectively show the current measurements obtained for an analysis cell and a voltammogram obtained from a process according to the invention by differential pulse voltammetry for a Fe 3+ solution at a concentration of 10 ". 3 mMll -1 in sulfuric acid H 2 SO 4 at 0.5 mol. L "1 ;
- FIGS. 6A, 6B and 6C respectively illustrate the voltammograms obtained for a Cu 2+ solution on a gold and copper electrode, a Cu 2+ solution and an Fe 3+ solution on an electrode. of gold, and a solution of Cu 2+ and Fe 3+ on a copper electrode.
- the invention thus has a new technique for analyzing a sample of a solution by voltammetry, ensuring the renewal of the sample on the surface of the working electrode so that it corresponds to the initial composition, and which also ensures the renewal of the surface of the working electrode during the measurements necessary for the establishment of a voltammogram.
- the method uses a support having a plurality of working electrodes each belonging to a separate electrochemical analysis cell in contact with the sample, each of the working electrodes being used only for the realization of a single measurement of the sample.
- the solution analyzed is a solution of Fe 3+ at a concentration of 10 -2 moLL "1 in sulfuric acid H 2 SO 4 at 0.5 rnoLL " 1 .
- the applied potentials evolve automatically in a step of 1 mV and a speed of variation of the potential equal to 20 mV / s.
- the Iiimi you corresponds to the difference of the intensity between the lower and upper levels of the curve, and the half wave potential Ey 2 corresponds to the value of the potential at the point of inflection of the curve.
- This value of the half-wave potential of 0.06 V is characteristic of the Fe 2+ ZFe 3+ couple under such analysis conditions (solvent: H 2 SO 4 at 0.5 mol -1 " , gold working electrode saturated calomel reference electrode).
- FIG. 2A is a schematic, deliberately schematic and simplified view of an analysis support 10 according to the invention, presenting twenty distinct zones 11 each comprising a working electrode, divided into four lines of five and distant from one another .
- the number of working electrodes distributed on an analysis support 10 can of course vary according to the degree of accuracy of the voltammograms that one wishes to establish.
- the dimensions of a working electrode can be variable.
- the dimensions of the working electrodes of the same support, or at least the working electrodes belonging to analysis cells allowing the establishment of a same voltammogram, will be of the same shapes and dimensions.
- the dimensions of the surface of the working electrode affect the values of the currents during the measurements.
- the distance between the different electrodes, and especially between different working electrodes, may also be variable, taking care however to avoid short circuits.
- the risk of short circuit is in fact a limit to the increase of the surface density of the working electrodes on the analysis support.
- all the electrodes (working electrode, counter-electrode and reference electrode) of an analysis cell are present on the analysis support, it is the density of these different electrodes that will be limiting.
- FIG. 2B represents a zone 11 of the analysis support 10 shown in FIG. 2A. This has a working electrode 12 and a counter electrode 13 of the same analysis cell. According to this embodiment, the counter-electrode 13 surrounds the working electrode 12, made of gold for example.
- the analysis support 10 thus carries the working electrode 12 and the counter-electrode 13 of each analysis cell.
- FIG. 2C illustrates a cross section of the zone 11 of the analysis support 10 according to FIG. 2B.
- Like reference numerals designate identical elements in FIGS. 2A to 2C.
- the width 14 of the zone 11 comprising the working electrode 12 and the counter-electrode 13 may for example be 740 ⁇ m, the diameter of the working electrode 500 ⁇ m, and the distance separating the working electrode 12 and the counter-electrode 13 of about 30 microns.
- the zones 11 comprising electrodes of different analysis cells can be separated by approximately 500 ⁇ m.
- the analysis support 10 may be produced according to conventional techniques relating to microelectronics (for example vacuum metallization). This may for example be made of a plastic material, a resin or silicon.
- the presence of a single electrode can be predicted.
- a saturated calomel electrode has been used, and is placed directly in the sample of the solution to be analyzed, facing the working electrodes.
- the counter-electrodes 13 of the different cells can be connected together. This simplifies the manufacturing process of the analysis support by reducing the number of necessary connections.
- the solution analyzed is, as in the previous case illustrated by FIG. 1, a solution of Fe 3+ at a concentration of 10 -2 mol -1 in sulfuric acid H 2 SO 4 at 0.5 mol -1 "1 .
- the method used is voltammetry by potential jump on a gold electrode with a saturated calomel electrode as the reference electrode.
- FIG. 3B illustrates the voltammogram obtained after carrying values of the current obtained for the twenty different cells at a constant "t" time from a twenty-cell analysis support as shown in FIGS. 2A-2C.
- the points represented by a square correspond to the measurements obtained for the solution containing the iron, and the curve whose points are represented by circles corresponds to the "white", that is to say to the measurements obtained for the same solution containing no iron.
- Figure 4 shows a voltammogram obtained according to the process of the invention under the same experimental conditions as above, with a ten times less concentrated solution to Fe 3+, that is to say Fe 3+ at 10 "3 moll” 1 in sulfuric H 2 SO 4 to 0.5 acid moll "1. a value for the Iumi you 2.1 uA was obtained from this curve.
- a starting potential is imposed on a working electrode of a 400 mV analysis cell for 6 s, followed by a pulse ( ⁇ E) of 50 mV for 1 s.
- the starting potential imposed on the different working electrodes is gradually decreased by 20 mV for each of the analysis cells.
- the current response over time of an analysis cell is illustrated in FIG. 5A.
- the method according to the invention thus allows the analysis of chemical species of a liquid solution or a gas making it possible to quickly obtain one or more voltammograms of a sample.
- the independent potentials can be applied simultaneously to the different cells and the measurements can therefore all be made simultaneously.
- the voltammogram (s) can be established very quickly.
- performing a single measurement for each analysis cell ensures the renewal of the working electrode and the sample at each measurement.
- the working electrodes of the different cells are of different natures.
- the same support may allow the analysis of species of oxidation-reduction potentials very different.
- a working electrode in copper may allow the analysis of compounds whose oxidation-reduction potential is within a range of -0.8 to 0 V, and a gold working electrode is suitable for analysis in a range of -0, 4 to 0.8 V.
- the reactivity of the species is related to the interaction they have with the surface of the working electrode (more or less strong adsorption, metallic or covalent bonding, etc ...) - Therefore, the reactivity of the different chemical species is variable depending on the nature of the working electrode.
- FIG. 6A represents the voltammograms obtained for a solution of Cu 2+ at 10 -3 mol. L 1 by voltammetry by potential jump on a copper electrode and a gold electrode, with a saturated calomel electrode as the reference electrode.
- FIG. 6B shows the voltammograms obtained for a solution of Cu 2+ at 10 -3 mol- 1 and a Fe 3+ solution at 10 -3 mol- 1 by voltammetry by potential jump on a gold electrode, with a saturated calomel electrode as the reference electrode.
- FIG. 6C shows the voltammograms obtained for a solution of Cu 2+ at 10 -2 moLL “1 and a solution of Fe 3+ at 10 " 2 mol ⁇ "1 by voltammetry by potential jump on a copper electrode, with an electrode saturated calomel as the reference electrode.
- the two curves obtained show that the iron response on the copper electrode is comparable to that of copper.
- the potential The initial reduction of iron is about -50 mV while that of copper is about -300 mV.
- the comparison of the different voltammograms obtained allows a better determination and analysis of the voltammograms and species present.
- a voltammogram is simultaneously established with a gold electrode for example, it will be easy to determine whether the first voltammogram obtained characterized the copper or iron present in the sample.
- the technique according to the invention thus allows the realization of rigorous measurements with renewal of the electrode and the sample at each measurement and also offers a great modularity. Indeed, it will be possible to refine the analyzes by increasing the number of cells used to establish a voltammogram, to simultaneously study several potential domains, to apply several methods of voltametric analysis simultaneously, and to vary the nature of the electrodes working cells of the same analysis support.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0503654A FR2884318B1 (fr) | 2005-04-12 | 2005-04-12 | Procede d'analyse electrochimique par voltametrie, support d'analyse et dispositif pour sa mise en oeuvre. |
PCT/EP2006/061112 WO2006108759A1 (fr) | 2005-04-12 | 2006-03-28 | Procede d'analyse electrochimique par voltametrie et dispositif pour sa mise en oeuvre |
Publications (1)
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EP1869439A1 true EP1869439A1 (fr) | 2007-12-26 |
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EP06725372A Withdrawn EP1869439A1 (fr) | 2005-04-12 | 2006-03-28 | Procede d'analyse electrochimique par voltametrie et dispositif pour sa mise en oeuvre |
Country Status (6)
Country | Link |
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US (1) | US20080190782A1 (fr) |
EP (1) | EP1869439A1 (fr) |
CN (1) | CN101184992A (fr) |
CA (1) | CA2608080A1 (fr) |
FR (1) | FR2884318B1 (fr) |
WO (1) | WO2006108759A1 (fr) |
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WO2012019980A1 (fr) | 2010-08-10 | 2012-02-16 | Endress+Hauser Conducta Gesellschaft Für Mess- Und Regeltechnik Mbh+Co. Kg | Système de mesure et procédé de détection d'une concentration de substance à analyser dans un fluide de mesure |
IT202000027546A1 (it) * | 2020-11-17 | 2022-05-17 | Cardiovascular Lab S P A | Metodo per rilevare e/o quantificare un elemento metallico in un liquido biologico |
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DE4136779A1 (de) * | 1991-11-08 | 1993-05-13 | Bayer Ag | Vorrichtung zum simultanen nachweis verschiedener gaskomponenten |
US5389215A (en) * | 1992-11-05 | 1995-02-14 | Nippon Telegraph And Telephone Corporation | Electrochemical detection method and apparatus therefor |
ATE227844T1 (de) * | 1997-02-06 | 2002-11-15 | Therasense Inc | Kleinvolumiger sensor zur in-vitro bestimmung |
US6818110B1 (en) * | 1997-09-30 | 2004-11-16 | Symyx Technologies, Inc. | Combinatorial electrochemical deposition and testing system |
US20010042693A1 (en) * | 2000-03-07 | 2001-11-22 | Elina Onitskansky | Electrochemical sensor for detection and quantification of trace metal ions in water |
US6664776B2 (en) * | 2001-12-18 | 2003-12-16 | Otre Ab | Method and system for voltammetric characterization of a liquid sample |
AU2003259038A1 (en) * | 2002-06-19 | 2004-01-06 | Becton, Dickinson And Company | Microfabricated sensor arrays |
US20040099531A1 (en) * | 2002-08-15 | 2004-05-27 | Rengaswamy Srinivasan | Methods and apparatus for electrochemically testing samples for constituents |
US7341834B2 (en) * | 2003-12-15 | 2008-03-11 | Geneohn Sciences, Inc. | Multiplexed electrochemical detection system and method |
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2005
- 2005-04-12 FR FR0503654A patent/FR2884318B1/fr not_active Expired - Fee Related
-
2006
- 2006-03-28 US US11/911,456 patent/US20080190782A1/en not_active Abandoned
- 2006-03-28 EP EP06725372A patent/EP1869439A1/fr not_active Withdrawn
- 2006-03-28 CA CA002608080A patent/CA2608080A1/fr not_active Abandoned
- 2006-03-28 WO PCT/EP2006/061112 patent/WO2006108759A1/fr active Application Filing
- 2006-03-28 CN CNA2006800188353A patent/CN101184992A/zh active Pending
Non-Patent Citations (1)
Title |
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See references of WO2006108759A1 * |
Also Published As
Publication number | Publication date |
---|---|
CN101184992A (zh) | 2008-05-21 |
FR2884318A1 (fr) | 2006-10-13 |
FR2884318B1 (fr) | 2007-12-28 |
WO2006108759A1 (fr) | 2006-10-19 |
US20080190782A1 (en) | 2008-08-14 |
CA2608080A1 (fr) | 2006-10-19 |
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