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Numéro de publicationUS3260656 A
Type de publicationOctroi
Date de publication12 juil. 1966
Date de dépôt27 sept. 1962
Date de priorité27 sept. 1962
Numéro de publicationUS 3260656 A, US 3260656A, US-A-3260656, US3260656 A, US3260656A
InventeursRoss Jr James W
Cessionnaire d'origineCorning Glass Works
Exporter la citationBiBTeX, EndNote, RefMan
Liens externes: USPTO, Cession USPTO, Espacenet
Method and apparatus for electrolytically determining a species in a fluid
US 3260656 A
Résumé  disponible en
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Revendications  disponible en
Description  (Le texte OCR peut contenir des erreurs.)

July 12, 1966 J. w. R055. JR 3,260,656

METHOD AND APPARATUS FOR ELECTROLYTIGALLY DETERMINING A SPECIES IN A FLUID Fzled Sept. 27, 1962 2 Sheets-Sheet 1 LOCAL DEPLETION TEST MEMBRANE LAYER FLUID F G (PRIOR ART) F IG. 2

GEN. ELECTRO- ELEC MEM- TEST LYTE TRODE BRANE FLUID z 56 ss 9 I- E -62 62 z w 0 g 60 U INVENTOR 52 JAMES w R088, JR.

DISTANCE BY F G 3 Rmfimub ATTORNEYS July 12, 1966 J. w. R055. JR 3,260,656

METHOD AND APPARATUS FOR ELECTROLYTIGALLY DETERMINING A SPECIES IN A FLUID Filed Sept. 27, 1962 2 Sheets-Sheet 2 INVENTOR Rm & SW

ATTORNEYS JAMES W ROSS, JR.

United States Patent C) York Filed Sept. 27, 1962, Ser. No. 226,533 19 Claims. (Cl. 204-1) Newton, Mass, assignor to (Iorning N.Y., a corporation of New This invention relates to electrochemical apparatus and more particularly to improved devices for electrically measuring the concentration of electrochemically active materials in fluids.

The term fluids as used herein is intended to include gases, liquids, vapors and mixtures thereof. Heretofore, in the determination of the concentration in fluids of an electrochemically active species (i.e. a substance such as an ion which is capable of being either reduced oroxidized at an electrode), electrochemical devices have been used in which an electrical characteristic of the species is measured and correlated with the concentration. Polarographic devices, for example, usually measure a characteristic potential at which such a species is reduced, and a diflusion current proportional to the concentration. An improvement on the basic polarographic apparatus is the well-known Clark apparatus as disclosed in US. Patent No. 2,913,386 issued November 17, 1959. The latter employs a dual electrode structure immersed in an electrolyte and encased at least in part in a membrane which is permeable to a predetermined species, for instance, gaseous oxygen. Typically, when used for oxygen analysis, the cathode is formed of platinum and is located closely adjacent the membrane; the anode is formed of silversilver chloride; and the electrolyte is an aqueous alkali halide solution. In operation of such a device, oxygen in a test fluid outside of the membrane permeates the latter and is presumably reduced at the cathode to water in accordance with the overall equation 2H++1/2O2+2 H20 It will be apparent that the Clark device is intended to completely reduce the oxygen permeating the membrane. The current (2e) necessary to effect this reduction is a measure then of the oxygen concentration in the test fluid. In determining oxygen concentration this device typically employs the Ag-AgCl anode with a KCl electrolytic solution. Hence, the anode reaction is Ag+Cl- AgCl+e As the electrode operates, H+ is consumed at the cathode, changing the pI-I of the electrolyte in time. For prolonged operation, a buflFer is therefore required.

While devices of this type have proved satisfactory for many purposes, certain problems arise in some applications. For instance, referring to FIG. 1, there is shown graphically a concentration diagram for such devices. In this diagram, the ordinate 20 is the scale from zero of the relative concentration of oxygen, and the abscissa represents distance from the cathode-membrane interface toward a test fluid. The position of the cathode-membrane interface (neglecting any small displacement between the two) is at line 20. Line 22., parallel to the ordinate, then represents the membrane-test fluid interface. The distance between lines 20 and 22 is representative of the membrane thickness. Now it may be assumed that the concentration of oxygen in the test fluid adjacent the outer face of the membrane is constant, as shown by the horizontal portion of broken line 24, and that the consumption of oxygen at the cathode is complete so that the concentration of oxygen at the cathode-membrane interface is substantially zero. Under such circumstances,

the concentration gradient, represented by the remainder of broken line 24, across the membrane is approximately linear and its slope is an inverse function of the membrane thickness.

However, during actual operation of the device, as oxygen is consumed at the cathode, there is a continual flow of the gas from the test fluid through the membrane to replenish the oxygen supply being consumed or reduced. If the oxygen in the test fluid adjacent the outer surface of the membrane is not continually replenished so as to be maintained at a constant level, the concentration gradient will then extend out into the test fluid, and its slope will become non-linear and reduced as shown at broken line 26 in FIG. 1, due to the local depletion of oxygen in a layer shown between lines 22 and 28. With continued operation of the device and no replenishment of oxygen, the local depletion layer will continue to expand further out into the test fluid, distorting the concentration gradient more and more. The distortion of concentration gradient reduces the measurement sensitivity and changes the mass flow rate of oxygen through the membrane to the cathode, making measurement uncertain and even spurious over a period of time. In order to avoid such occurrence, it is customary to provide means for breaking up any depletion layer, as for instance by stirring.

Further, if the fluid under measurement is a minute sample to which access is restricted, as in biological cells for example, depletion will continue until all of the oxygen is consumed. Because access to the fluid is restricted by the cell walls which act as barriers, the consumed oxygen cannot readily be renewed; the measurements in a short time become inconclusive. Additionally, even assuming that local depletion layers on the outer membrane surface can be avoided, in order to maintain the gas concentration at the cathode substantially at zero with reasonable current consumption the input flow rate of the oxygen must be controlled. This is usually done by providing a relatively thick membrane which, however, acts to slow the response time of the device to changes in oxygen concentration in the test fluid.

Accordingly, the present invention contemplates the provision of improvements in electrochemical analytic devices by virtue of which the sensitivity and response time are enhanced, and which improvements minimize material changes in the concentration of the species in the fluid under measurement during the measurement time. A principal object of the present invention is therefore to prove an improved electrochemical analytical device.

Further objects of the present invention are to provide an electrochemical device including enclosure means (for an electrolytic medium, at least a portion of the enclosure means being formed of barrier means selectively permeable to a predetermined spaced relation to one another within the enclosure means, means *for impressing -a predetermined potential difterence across the electrode, the electrolytic medium being one from which the elect-ro-active species can be liberated by passage of electrical current between said electrodes, the electrolytic medium bridging the electrodes and being in contact with the barrier means; to provide such a device in which one electrode is adapted to consume said species and the other electrode is adapted to generate said species; to provide such a device in which the cathode is adapted for reduction of said species and the anode is adapted to generate said species; to provide such a device in which the cathode is adapted for reduction of said species and the anode is adapted to generate said species in dependence upon said reduction, said anode being adjacent the barrier means and between the latter and the cathode; to provide such a device in which the anodic current flow is maintained at the same absolute value as the cathodic current flow; and to provide such a device in which the cathodic current is dependent upon the equilibrium between the species generated at the appropriate electrode and the concentration of the species which is outside of the enclosure means and free to permeate the barrier means.

Other objects are to provide such a device including a reference electrode which is in contact with the electrolytic medium and provides a high stability to the potential at the consuming electrode; to provide such a device which does not substantially aifect or deplete the concentration of the electro-active species outside of the enclosure means except (briefly, at all, during transient changes in said concentration) for appreciable time periods and in restricted samples of fluid; and to provide such a device in which the sensitivity and response time to changes in the concentration of electro-active species in the test fluid are markedly improved. Yet other objects of the present invention are to provide an electrical circuit for use with an electrochemical analytic device of the type described; and to provide such an electrical circuit which includes a negative feedback loop for stabilizing the potential between a reference electrode and a consuming electrode.

Other objects of the invention will in part be obvious and will .in part appear hereinafter. The invention accordingly comprises the apparatus possessing the construction, combination of elements and arrangement of parts which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims. [For a fuller understanding of the nature and objects of the present invention, reference should be had to the following detailed description taken in connection with the accompanying drawings wherein:

FIG. -1 is a graphical representation of the concentration gradient across the selectively permeable membrane in prior art devices as hereinbef-ore described;

FIG. 2 is a diagrammatic cross-sectional view of one embodiment of the present invention;

FIG. 3 is a graphical representation of a concentration gradient across a portion of the electrode-membrane structure of the embodiment shown in FIG. 2;.

FIG. 4 is a graphical representation of the current-voltage relationship at the electrodes in the structure of FIG. 2;

FIG. 5 is a diagrammatic cross-sectional representation of another embodiment of the present invention; and

FIG. '6 is a diagram of an electrical measuring circuit particularly adapted for use with the electrode structure of FIG. 5.

To effect the objects heretofore set forth the present invention generally comprises a pair of electrodes electrically coupled through an electrolytic medium of predetermined fixed characteristics. The medium is isolate-d from the test fluid under measurement by barrier means selectively permeable to the electro-active species which is to be detected and measured in the test fluid. A first electrode is adapted to consume the desired electro-active species, while the other electrode is adapted to produce or generate said species in dependence on the consumption activity of the first electrode. Thus, in operation, there is a steady state equality established between consumption and generation within the electrolyte. The electrode-membrane structure is such that this steady state equality is in turn responsive to an equilibrium between relative concentrations of the species on both sides of the barrier means. It will be seen, therefore, that in the present invention, during steady state conditions, there is no net transfer of species through the barrier means; only during transient changes in the concentration of the species in the test fluid will there be a small net transfer which rapidly decays as an internal steady state is reestablished. Consequently, the consumption of the electro-active species is minimized and changes in the concentration of the species in the fluid under measurement which may be ascribed to the analytical activity of the apparatus, are minute and quickly and automatically compensated.

The term electro-active species as used herein is intended to mean any group of identical chemical entities such as ions, molecules, atoms, etc., which are capable of being electrically oxidized or reduced. Where the species is a gas e.g. oxygen, chlorine or the like, which is dissolved in or mixed with another fluid, rather than referring to concentration, it is perhaps more accurate to refer to the equilibrium partial pressure. This is so because a gas may exhibit different solubilities with respect to difrferent fluids. Hence, although the equilibrium partial pressure (hereinafter referred to as the tension) of the gas in one fluid may be precisely equal to the tension of the same gas in another fluid, the concentrations of gas with respect to each of the fluids are not necessarily the same. However, where the gas tensions on opposite sides of a gas-permeable membrane are in equilibrium, the tension on one side is proportional to the concentration on the other side.

Referring now to FIG. 2, there will be seen one embodiment of the present invention in which there is shown a structure comprising a first electrode or anode 30, a second electrode or cathode 32, an electrolytic medium 34 which electrolytically coupled the anode and cathode, and selectively permeable barrier means, such as membrane 36. Means, such as battery 38, are provided for applying an appropriate potential across the cathode and anode through respective leads 46 and 47. The invention also may include means shown schematically as meter 40, for measuring current flow in the cathode anode circuit. In order to encase the electrodes and the electrolytic medium there is provided enclosure means 42 which preferably incorporates membrane 36 as a Wall portion thereof.

Enclosure means 42 is preferably formed with a substantially hollow chamber 44 interiorly thereof, the chamber having at least one opening to the outside of the enclosure means. Membrane 36 is so disposed as to completely cover the opening in chamber 44. The electrolytic medium (i.e. a medium capable of providing both positive and negative ionic charge transport as by ions provided from a disassociatable compound in a polar solvent, or by ions provided by a molten salt or the like), for example an aqueous electrolyte, is disposed within the chamber in suflicient quantity to maintain a continuous electrical contract between electrodes. The enclosure means preferably then is formed as a liquid-tight container so that the electrolyte cannot leak out. The electrolyte is preferably selected to be one whose ions require a more negative potential for reduction than does hydrogen and require a more positive potential for oxidation than does water or hydroxyl ion. The dilference between these more negative and positive potentials is generally termed the decomposition voltage of the electrolyte.

The walls of chamber 44, other than membrane 36, are preferably made of a material, such as glass, ceramic, solid polymer or the like, which is substantially impermeable to fluids, is a high resistance material (i.e. an electrical insulator) and is substantially chemically inert to the electrolyte and decomposition products of the latter. Membrane 36, in the form of a sheet with a substantially uniform thickness, for example, not more than approximately 5 mils, is selected from materials which exhibit selective permeability to the electro-active species which one desires to measure. For instance, where the species is gaseous oxygen, membrane 36 may be of a polymer such as polyethylene, polyvinyl chloride, rubber, or other known substances which provide a solid barrier selectively pervious to the gas. Barrier materials are known which are selectively permeable to other electro-active species. Appropriate means (not shown) are provided for sealing the membrane across the opening to chamber 44, for instance, adhesives which are insoluble in the electrolyte and test fluid, an O-ring, or other known techniques or structures.

Anode 30 is formed as a substantially sheet-like element typically having a thickness of about 3 mils and being porous to both the electrolyte and electro-active species. The anode is made of an electrically conductive material, preferably a noble metal such as platinum, gold or the like. To provide porosity, the anode may be provided as a mesh or screen as shown, as a spongy mass, or in other known configurations. In the form shown, anode 30 is disposed within electrolyte 34 and is superposed adjacent membrane 36, i.e. arranged either in face-to-face contact with the latter, or, if the anode and membrane are in separated condition, then there is approximate parallelism of the adjacent surfaces of the anode and membrane with a stratum of electrolyte between them.

Cathode 32, in the form shown, is also a substantially sheet-like element which may be either porous or solid, preferably the latter, and its thickness is determined by cost and considerations of structural strength. The cathode is also preferably made of a noble metal, for instance the same metal used as the anode. Cathode 32 is also disposed within electrolyte 34 and is disposed in approximately parallel face-to-face relationship to the anode, but separated from the latter a short distance by appropriate nneans such as spacer 46.

In the preferred form, spacer 46 is a substantially sheetlike porous element, such as a woven fabric. The spacer is preferably formed of material which is electrically nonconductive, relatively chemically inert to the electrolyte and its decomposition products, and exhibits good dimensional stability with respect to variables such as temperature, pressure, solvents and the like, whereby the spacing between the anode and the cathode is maintained at a substantially constant value. Typical materials from which such spacer may be made are nylon, polytetrafluorethylene, and the like. It will be seen then that the electrode structure of FIG. 2 is that of a sandwich in which the anode is spaced from the cathode and retained in between the latter and the membrane, other portions of the volume between the membrane and cathode being substantially filled with electrolyte.

In describing the operation of the embodiment of FIG. 2, it will be exemplary to consider oxygen as the electroactive species. In such case, the electrolyte is preferably an aqueous solution of a base, such as KOH, because in the operation of the device it is desired to avoid evolution of gaseous hydrogen at the anode. Hence, the pH of the electrolyte should preferably be basic and generally not less than approximately pH 2 or 3. In selecting the cathode and anode in this instance, it is preferred to use materials which will respectively reduce oxygen and generate oxygen with maximum current efliciencies. Because of their low oxygen over-voltages and relative chemical inertness, the noble metals are thus preferred and both anode and cathode can be made of, for example, platinum. If the potential applied across the anode and cathode is established well below the decomposition voltage of the electrolyte, and there is no oxygen available in the electrolyte (as from diffusion into the electrolyte through the membrane, or from being dissolved in the latter), only a virtually constant, minute, residual current will flow in the cathode-anode circuit. If, however, a supply of oxygen is presented to the outer surface of membrane 36, as for instance, by contacting the latter with a liquid having a dissolved oxygen content or by contacting the latter with a gas which comprises oxygen, because of the selective permeability of the membrane some oxygen will diffuse through the latter to its inner face and thence into the electrolyte to the cathode. If the potential across the electrodes is above the reduction potential of oxygen, although below the decomposition potential of the electrolyte, oxygen present at the cathode will be reduced. The reduction process is believed to be according to the same equation heretofore used in describing the cathodic reduction in the Clark apparatus.

Referring now to FIG. 4 there is graphically shown the general current-voltage relationship in the present invention during operation. The ordinate is shown as the current axis, the voltage axis being the abscissa. While the curve 48 is shown as being symmetrical about the origin, this is only for purposes of illustration and is not actually the case. At a point where there is a predetermined negative voltage -E, the oxygen at the cathode is electrically reduced. This produces a current I whose amplitude is a function of the concentration of gaseous oxygen present in the electrolyte. With a negative current -I, equal in magnitude to I, now flowing at the anode, the latter is at a positive voltage +E, shown at point 51, predetermined by the nature of the anode material and electrolyte. With proper choice of parameters in the example described above, at the anode the current oxidizes the water in the electrolyte, generating oxygen according to the following:

Hence the system consumes the species at one electrode and tends to generate a like quantity thereof at the other electrode, without changing the electrolyte pH. This leads rapidly to an internal or interelectrode steady state condition between the consumption and generation of the species, and the current flow is therefore a measure of the 0 present in the system. The steady state equality between generation and consumption is, however, responsive to any change in concentration of the oxygen outside of the membrane. This is largely because of the geometry of the system wherein the generating electrode lies between the consuming electrode and membrane. The gas tensions on both sides of the membrane will tend to reach an equilibrium with one another inasmuch as a high tension outside the membrane will result in net diffusion of the gas throughout the latter toward the anode, and conversely a higher tension inside the membrane would result in net gaseous diffusion through the membrane from the anode to the test fluid. Thus, any change in gas tension outside the membrane will upset the internal steady state of the system, forcing it to a new steady state by either increase or decreased consumption of gas and a corresponding increase or decrease in gas generation. Each change in gas generation is thus in a direction tending to establish equilibrium between the gas tensions on opposite sides of and across the membrane. Every change in the internal steady state is, of course, accompanied by a chance in the current flowing between the electrodes. It will thus be seen that in the equilibrium condition of gas tension across the membrane, the current flow is constant and there is no net transfer of gas through the membrane. On the other hand, if the gas tension in the test fluid should change, a transient condition will exist until a new steady state is established internally which again provides a gas tension equivalency on both faces of the membrane. Hence, depletion of oxygen is minimized at points adjacent the outside surface of the membrane i.e. the surface contacting the test fluid.

Referring now to FIG. 3, there is shown graphically a concentration diagram taken across the electrode-membrane structure of the embodiment of FIG. 2. As in FIG. 1, the ordinate 52 represents the relative concentration of the particular electroactive species. The absicca 54 represents distance from the cathode-electrolyte interface which is at the origin of the graph and hence, in a sense, the latter interface is line 52. Lines 56 and 58 then represent the respective surfaces of the anode facing the cathode and the membrane; and line 60 is the outer surface of the membrane in contact with the test fluid. For the sake of clarity, no displacement between anode and membrane is shown, hence line 58 can also be considered the anode-membrane interface. The

distance between the various lines is representative of the thickness of the various elements but is not to be considered as necessarily showing the actual proper proportions. Using again the example of oxygen and assuming for simplicity, that the oxygen exhibits the same tension in both electrolyte and test fluid and the concentration of oxygen in the test fluid is constant, the latter concentration is indicated by the horizontal portion of broken line 62 which extends from the test fluid into the membrane. The concentration gradient, represented by the remainder of broken line 62, extends from the anode-membrane interface to the cathode-electrolyte interface. The slope and position of line 62 will not change during steady state operation because of the equilibria established as heretofore described which results in no net transfer of oxygen across the membrane. However, during a transient change in oxygen concentration in the test fluid, although the horizontal portion of line 62 extending into the test fluid from membrane surface 60 will shift its level, this only results in a temporaray departure from a zero slope of the concentration level across the membrane. This zero slope is quickly re-established by the corresponding change in generation of oxygen at the anode. Hence, substantially no depletion layer will be created in the test fluid.

If the membrane is made very thin, for example, in the nature of 0.5 mils, the response time is considerably reduced inasmuch as diffusion time through the membrane in enhanced. Presupposing constant diffusion coefficients for the membrane, electrolyte and anode, the steady state current is approximately where K is a constant depending, inter alia, on the diffusion coeflicients, C is the concentration of the species in the test fluid and H and L are respectively the anode (generating here) thickness and inter-electrode spacing.

It is apparent that the spacing between the cathode and anode affects the sensitivity and response time, hence should be as small as possible without creating a dead short circuit. Typically, a spacing of l to 10 mils has proved quite satisfactory. Similarly, the spacing between the anode and membrane, if any, will also affect the response time and can be minimized without concern for short circuits.

Referring now to FIG. there will be seen another embodiment of the present invention similar in many respects to the embodiment of FIG. 2, and wherein like numerals denote like parts. The device shown in FIG. 5 also includes, in a configuration similar to FIG. 2, enclosure means 42 having a hollow 44 therein open to the outside of the enclosure means, the opening being sealed by membrane 36. A generating electrode, such as anode 30, is disposed inside hollow 44 against the membrane. A consuming electrode, such as cathode 32, is also disposed within hollow 44 and separated, as by separator 46, from the anode 36. Appropriately fluid-sealed electrically conductive leads 46 and 47 are respectively attached to cathode 32 and anode 30 to provide electrical connection to the electrodes from the exterior of the enclosure means. An electrolytic medium, such as a fluid electrolyte 34, substantially occupies the remaining space within hollow 44. Contacting the electrolyte and spaced from the other electrodes and membrane is a third or reference electrode 66 to which another electrically conductive lead 68 is attached to provide an electrical connection between electrode 66 and the exterior of the enclosure means.

Where this latter embodiment is intended to measure concentration of, for example, oxygen, the elements thereof can be selected and formed in the manner and of the materials heretofore described in connection with the embodiment of FIG. 2, except that electrode 66 is preferably an Ag-AgO electrode.

.Referring now to FIG. 6 there will be seen an electronic circuit for use with the embodiment of FIG. 5 to determine the current flow between anode and cathode as well as to provide high stability to the operation of the system. The circuit of FIG. 6 comprises means for electrically connecting the circuit to electrodes of FIG. 5, and such means may comprise leads 68, 46 and 47 respectively adapted to be connected to reference electrode 66, cathode 32 and anode 30. Lead 68 is also connected to lead 46 through a series resistor 70 and an electrical power source, such as battery 72, the latter being poled so that lead 46 is negative. A point intermediate resistor 70 and the reference electrode is connected, as by lead 74, to the input of D.C. voltage amplifying device or amplifier 76, the output of the latter being coupled to the anode through lead 47. A measuring instrument such as ammeter 78 is located preferably in the circuit between the amplifier and anode. The amplifier and positive side of the battery should be appropriately grounded in order to avoid transient from extraneous phenomena.

In operation of the device shown in connection with FIGS. 5 and 6, the presence of a species in the electrolyte permits current flow between the cathode and reference electrode, creating a potential across resistor 70 due to the IR drop therein. The voltage across resistor 70 is amplified by the gain of amplifier 76 and applied to anode 30. It will thus be apparent that amplifier 76 is a D.C. inverting amplifier which preferably exhibits high gain (in the order of thousands) and is also preferably stabilized as by internal negative feedback, chopper-stabilization or the like, all as well known in the art. Thus the reference electrode is positive with respect to cathode 32, but negative with respect to anode 30. If the gain of amplifier 76 is sufficiently high, the coupling of its output through anode 30 to reference electrode 66 constitutes a negative feedback loop which will tend to create a virtual ground at the input of the amplifier. The potential of the reference electrode is therefore fixed at the virtual ground, and the potential between cathode 32 and the reference electrode is consequently maintained at a very stable level at which only oxgen will be reduced at the cathode.

The following example is illustrative of the construction and operation of a device of the type shown in connection with FIGS. 5 and 6. A hollow container was formed of polymethylmethacrylate. In the container was placed a cathode formed of 1 mil platinum metal foil of approximately 0.3 square centimeter per surface. a platinum metal anode formed of 80 mesh gauze, 3 mil diameter wire, and having a mean thickness of 5 mils, was placed in the container and spaced from the cathode with a nylon fabric spacer having a thickness of approximately 5 mils. In contact with the electrolyte there was also installed an Ag-AgO reference electrode in the form of a very short piece of No. 16 gauge Wire. The remainder of the container was filled with a 1M KOH aqueous solution, and the opening into the container was capped with a polytetrafluoroethylene membrane having a thickness of 0.5 mil. In operation, the cathode potential was set at 0.7 volt with respect to the Ag-AgO electrode, and the device was operated at a temperature of 20 C.

In order to establish the backgriund current, the device was first operated with pure helium disposed against the surface of the membrane opposite the surface contacting the electrolyte, and a steady state current of 4.3 microamperes was obtained. Subsequently the outer surface of the membrane of the device was exposed to a number of various oxygen-containing fluids in samples of 0.2 cc. each, with the following results:

Sample: Current in microamperes Air saturated water 17.3 Air 17.3 O 59.6

All readings reached a constant level within a maximum of one minute after exposure to the sample. Each reading stayed constant for more than 3 hours after the initial transient. Despite the dilferent mobilities of the oxygen in water and in air, the readings achieved with respect to air and air saturated water were nevertheless identical and remarkably stable, indicating that in fact there was no net oxygen dfilusion through the membrane during steady state operation.

If one uses a similarly constructed apparatus in which however the electrolyte is aqueous KCl and the cathode is Ag-AgCl (thereby ensuring that no oxygen generation would occur within the apparatus), after 40 minutes the concentration of oxygen in a sample of similar size will be reduced approximately 70%. On the other hand, in the present invention, when operated for the same period of time there was no detectable change in oxygen concentration in the test sample.

It will be apparent to those skilled in the art that many modifications of the invention as thus described can be made. For example, a large number of electrolytes may be used. Indeed, under some circumstances the electrolyte may be a molten salt, and the enclosure means a membrane selected accordingly to have appropriate temperature resistant characteristics. While the anode and cathode of the present invention have been shown as substantially flat plates, of course other configurations which preserve the relative positioning of the electrodes and membrane may also be used. For example, the device may be constructed with the anode and cathode as concentric cylinders, the membrane lying along a portion of the exterior cylindrical surface of the anode. It will also be apparent that where the species to be measured is reducible, the generating electrode is an anode and the consuming electrode is a cathode. However, if the species to be measured is oxidizable, the generating electrode will be a negative electrode placed adjacent the membrane and the consuming electrode will be an anode or positive electrode.

Since certain changes may be made in the above apparatus without departing from the scope of the invention herein involved it is intended that all matter contained in the above description or shown in the accompanying drawing shall be interpreted in an illustrative and not in a limiting sense.

What is claimed is:

1. An electrode assembly for measuring the concentration of a specific electro-chemically active species in a fluid, said assembly comprising in combination:

a liquid electrolyte;

first electrode means of a material electrochemically inert to both said electrolyte and said species and in contact with said medium;

barrier means for separating said electrolyte from said fluid, and being selectively permeable to said species, and in contact with said medium;

an electrical power source connected for biasing said first electrode means at a potential at which said species in said electrolyte will be consumed at said first electrode means; second electrode means of a material electrochemically inert to both said electrolyte and said species, said second electrode means being in contact with said medium and connected to said power source for completing a circuit in which a current from said source can flow through both said electrode means at a level which is a function of such consumption;

said electrolyte being one from which substantially only said species is electrolytically generable at said second electrode means at said current level, said second electrode means being biased by said power source at a potential at which said species is generable from said medium; and

said second electrode means being so positioned with respect to said first electrode means and said barrier means that said species as generated at said second electrode means is available for consumption at said first electrode means in quantity dependent upon a tendency of said species to establish an equilibrium condition across said barrier means between concentration of said species respectively in said electrolyte and in said fluid.

2. An assembly as defined in claim 1 including means for measuring said current.

3. An assembly as defined in claim 1 including container means enclosing said electrolyte and said electrode means, said container means having said barrier means as a wall portion thereof.

4. An assembly as defined in claim 1 wherein said barrier means comprises a membrane having opposite surfaces, one of which is in contact with said electrolyte and the other of which is adapted to contact said fluid.

5. An electrode assembly for measuring the concentration of a specific electrochemically reducible gas in a fluid, said assembly comprising, in combination:

a cathode of an electrochemically inert material;

an anode of an electrochemically inert material;

an electrolytic medium in contact with both said cathode and anode;

barrier means for separating said fluid and said medium, said barrier means being selectively permeable to said gas, and in contact with said medium;

an electrical power source connected to said cathode for establishing a cathodic potential at said first electrode, said cathode being adapted for reducing said gas in said medium at said cathodic potential, said source providing an electrical current flow at said cathode at a level which is a function of such reduction;

said medium being a medium from which only said gas is electrolytically generable at said anode at said current level, said anode being adapted for generating said gas from said medium at said current level and connected to said power source so as to complete a circuit between said anode and cathode and bias said anode at an anodic potential at which said gas can be generated from said medium;

said anode and cathode being positioned in spaced relation to one another and to said barrier means, and said potentials being established at magnitudes, such that said current flow tends to substantially steady state condition responsively to a tendency for an equilibrium condition to become established across said barrier means between the partial .pressures of said gas in said medium and said fluid.

6. An assembly as defined in claim 5 including means for maintaining the magnitude of said cathodic potential at said cathode at a substantially constant value.

7. An assembly as defined in claim 5 wherein said electrolytic medium comprises a first material from which said gas can be generated at said anode at said current level and anodic potential, and a second material which provides ionic charge transport;

said source being connected for maintaining the magnitude of said anodic potential below the decomposition potential of said second material and above the poten- {ial 1at which said gas can be generated at said current eve 8. An electrode assembly for measuring the concentration of a specific electrochemically active gas in a fluid according to the level of electrical current flowing at a polarographic cathode responsively to the availability at said cathode of said gas; said assembly comprising in combination;

a liquid medium electrolytically and anodically decomposable to generate only said gas;

barrier means for separating said fluid from said rifedium and being selectively permeable to said gas and in contact with said medium;

said polarographic cathode being of a material electrochemically inert to both said medium and said gas,

and having a surface in contact with said medium for electrolytically consuming said gas;

an anode in contact with said medium and being of a material electrochemically inert to both said medium and gas, said anode being positioned wholly between said surface of said polarographic cathode and said barrier means and capable of generating said gas from said medium with a current efliciency substantially the same as the current efiiciency of consumption of said gas at said polarographic cathode, so that said gas as generated at said anode is available for consumption at said cathode in quantity dependent upon a tendency of said gas to establish across said barrier means an equilibrium condition between concentrations of said gas respectively in said medium and said fluid.

9. An assembly as defined in claim 8 wherein said second electrode is positioned in contact with said barrier means, said second electrode being porous to both said electrolytic medium and said gas.

10. An assembly as defined in claim 9 wherein said second electrode is a mesh.

11. An assembly as defined in claim 8 including means for impressing on said polarographic electrode, a first potential above the polarization potential for said gas,

" and means for impressing on said second electrode a second potential which is above the potential required for generation of said gas from said medium by electrolytic decomposition.

12. As assembly as defined in claim 11 including a third electrode contacting said medium and spaced from said polarographic and second electrode, and means for maintaining said third electrode at a reference potential between said first and second potentials and fixed with respect to said first potential.

13. An electrode assembly for measuring the concentration of a specific electrochemically active gas in a fluid according to the level of electrical current flowing at a polarographic cathode responsively to the availability at said cathode of said gas; said assembly comprising in combination:

' a liquid medium electrolytically and anodically decomposable to generate only said gas;

barrier means for separating said fluid from said medium and being selectively permeable to said gas and in contact with said medium;

said polarographic cathode being of a material electrochemically inert to both said medium and said gas, and having a surface in contact with said medium for electrolytically consuming said gas;

an anode in contact with said medium and being of a material electrochemically inert to both said medium and gas, said anode being positioned wholly between said surface of said polarographic cathode and said barrier means, for electrolytically generating said gas; a third electrode in contact with said medium; means for impressing (1) at said polarographic cathode a first potential which is above the polarization potential for said gas, (2) at said anode, a second A potential which is above the decomposition potential for said medium and (3) at said third electrode, a third potential between said first and second potentials, said first potential being fixed with respect to said third potential, said first and second potentials providing a current flow at said anode when said gas is present at said cathode, which current flow is equal and opposite to the current flow at said cathode, so that said gas as generated at said anode is available for consumption at said cathode in quantity dependent upon a tendency of said gas to establish an equilibrium condition, across said barrier means, between concentrations of said gas respectively in said medium and said fluid.

14. An assembly as defined in claim 13 wherein said means ,for impressing said potentials comprises an electrical power source connected through a series resistance between said polarographic and third electrodes, and a DC. amplifier means having the potential drop across said resistance as the input signal thereto, the output of said amplifier being connected to said second electrode so as to tend to maintain said potential drop at a minimum,

15. An electrode assembly for measuring the concentration of gaseous oxygen in a fluid, said assembly comprising in combination:

means defining an electrolyte space and having as a wall portion thereof barrier means selectively per- :meable to oxygen and impermeable to said fluid;

a first electrode of an electrochemically inert material and adapted to polarographically reduce said oxygen and disposed within said space in contact with said medium;

a second electrode for electrolytically generating oxygen, and formed of an electrically conductive material substantially electrochemically inert to said medium and to oxygen, said second electrode being positioned between said first electrode and said' barrier means;

an electrolytic medium disposed within said space in contact with said electrodes and said barrier means, said electrolytic medium comprising a material from which said oxygen can be generated at said second electrode by passage of an electrical current therethrough; and

means for effecting a current between said electrodes through said medium for simultaneous and substantially equal consumption and generation of oxygen at the respective electrodes in dependence upon establishment of an equilibrium between the partial pressures of oxygen at each side of said barrier means when the side of said barrier means opposite said electrolytic medium is in contact with said fluid.

16. An electrode assembly for measuring the concentration of an electrochemically reducible gas, said assembly comprising, in combination:

a hollow container of electrically insulating material having an opening therein, a membrane sealing said opening and being selectively permeable to said gas and impermeable to liquids, a cathode of electrochemically inert metal disposed within said hollow of said container for electrolytically reducing said gas, a porous anode of electrochemically inert metal disposed in said hollow between said cathode and said membrane adjacent the latter for electrolytically gen erating said gas;

means spacing said cathode from said anode, an electrolytic medium so disposed within said hollow as to form an ionically conductive path between said cathode and anode while in contact with said membrane, said electrolytic medium being capable of being so oxidized by an electrical current at said anode as to produce only said gas which is therefore available for reduction at said cathode in quantity dependent upon a tendency of said gas to establish across said barrier means an equilibrium condition between concentrations of said gas respectively in said medium and said fluid.

17. An electrode assembly as defined in claim 16 including means for impressing at said cathode, a potential above the polarization potential for said gas and means for impressing at said anode a potential above the potential necessary to produce said gas from said medium.

18. Method of measuring the concentration of an electrochemically active gas in a fluid comprising the steps of:

providing a body of electrolytic medium from which 70 said gas can be electrolytically generated;

diffusing said gas between said fluid and said medium through barrier means selectively permeable to said gas, and impermeable to both said medium and fluid; impressing a first potential on a first electrochemically inert metal electrode immersed in said medium and a second potential on a second electrochemically inert metal electrode immersed in said medium so as to cause a flow of current at said electrodes;

positioning said electrodes in spaced relation to one another and to said barrier means, and maintaining said potentials at magnitude and values at which said current flow causes at said electrodes a redox reaction in said body so that there is electrolytic generation of said gas at one electrode tending to an equality with an electrolytic consumption of said gas at the other electrode according to a tendency of said gas to establish an equilibrium of the partial pressures of said gas on opposite sides of said barrier means and the net diffusion of said gas through said barrier means is minimized, and,

measuring the magnitude of said current flow.

19. Method of measuring the concentration of gaseous oxygen in a fluid, comprising the steps of:

providing a body of electrolytic medium from which oxygen can be electrolytically generated,

contacting opposite sides of a membrane, Which is selectively permeable to oxygen, respectively with said fluid and said medium so as to permit oxygen diifusion through said membrane;

impressing first and second potentials respectively on an anode and cathode, both of electrochemically inert metals, in contact with said body, said anode being positioned in spaced-apart relation to and between said cathode and said membrane;

maintaining said potentials at values at which current flows in said body between said anode and cathode to generate oxygen at said anode responsive to a simultaneous reduction of oxygen at said cathode, the rate of oxygen generation being responsive to a tendency of the partial pressures of oxygen in said fluid and medium to establish a substantially static equilibrium across said membrane; and measuring said current flow,

References Cited by the Examiner UNITED STATES PATENTS 2,370,871 3/1945 Marks 204-1 2,758,079 8/1956 Eckfeldt 204- 2,805,191 9/1957 Hersch 204-1 2,898,282 8/1959 Flock et a1 204-195 2,912,367 11/ 1959 Asendorf et al 204-1 3,000,805 9/1961 Carritt et al. 204-195 3,022,241 2/ 1962 Jessop 204-195 3,028,317 4/1962 Wilson et al. 204-1 3,038,848 6/1962 Brewer et al 204-195 3,070,539 12/1962 Arthur et al. 204-195 3,088,905 5/1963 Glover 204-195 3,098,813 7/1963 Beebe et a1 204-1 3,160,577 12/1964 Nolan 204-195 JOHN H. MACK, Primary Examiner.

MURRAY A. TILLMAN, WINSTON A. DOUGLAS,

Citations de brevets
Brevet cité Date de dépôt Date de publication Déposant Titre
US2370871 *7 févr. 19426 mars 1945Wallace & Tiernan IncChlorine detection by electrode depolarization
US2758079 *29 mars 19507 août 1956Leeds & Northrup CoElectrolytic determination of the concentration of a constituent in a fluid
US2805191 *14 oct. 19543 sept. 1957Int Nickel CoOxygen analysis of gases
US2898282 *20 juin 19564 août 1959Du PontElectrolytic oxygen analysis
US2912367 *12 nov. 195710 nov. 1959DegussaMeasurement of cyanide concentration
US3000805 *30 août 195719 sept. 1961Walter G FinchElectrode measuring device
US3022241 *11 févr. 195820 févr. 1962Cambridge Instr Company IncMethod and apparatus for measurement of dissolved oxygen
US3028317 *28 mai 19593 avr. 1962Beckman Instruments IncGalvanic cell
US3038848 *20 juin 195812 juin 1962Mast Dev CompanyMethod and apparatus for detecting and measuring trace constituents in air and othergases
US3070539 *25 janv. 196025 déc. 1962Beckman Instruments IncIonic transducer
US3088905 *13 oct. 19607 mai 1963British Oxygen Co LtdMethod of and apparatus for oxygen determination
US3098813 *6 févr. 195923 juil. 1963Beckman Instruments IncElectrode
US3160577 *24 mars 19618 déc. 1964Bendix CorpSensing unit
Référencé par
Brevet citant Date de dépôt Date de publication Déposant Titre
US3328277 *3 avr. 196427 juin 1967Honeywell IncOxygen sensor with a scavenger electrode
US3380905 *11 oct. 196330 avr. 1968Leland C. Clark Jr.Electrolytic sensor with anodic depolarization
US3429784 *13 janv. 196425 févr. 1969Yellow Springs InstrMethod and apparatus for measuring gas content
US3429796 *16 sept. 196525 févr. 1969Analytic Systems CoGas analyzer
US3503861 *16 mars 196731 mars 1970Volpe EmilioApparatus for electrochemical analyses
US3509034 *29 mai 196828 avr. 1970NasaPulse-activated polarographic hydrogen detector
US3526577 *13 déc. 19661 sept. 1970Yellow Springs InstrMethod and apparatus for gas measurement
US3668101 *22 juil. 19686 juin 1972Nat Res DevMembrane electrodes and cells
US3755125 *14 janv. 197128 août 1973Envirometrics IncElectrochemical gas analyzer
US3767552 *6 oct. 197123 oct. 1973Teledyne IndGas analyzer
US3782170 *22 mars 19721 janv. 1974Lowrance Electronics MfgOxygen analyzer
US3925183 *28 janv. 19749 déc. 1975Energetics ScienceGas detecting and quantitative measuring device
US3992267 *21 avr. 197516 nov. 1976Energetics Science, Inc.Electrochemical gas detection method
US4076596 *7 oct. 197628 févr. 1978Leeds & Northrup CompanyApparatus for electrolytically determining a species in a fluid and method of use
US4168220 *10 juil. 197818 sept. 1979Leeds & Northrup CompanyMethod for detecting the fouling of a membrane covered electrochemical cell
US4259165 *10 déc. 197931 mars 1981Hokushin Electric Works, Ltd.Dissolved oxygen probe
US4450064 *21 mars 198322 mai 1984Beckman Instruments, Inc.Electrochemical gas sensor and method for producing the same
US4457808 *16 mai 19833 juil. 1984General Signal CorporationMethod and means for recalibrating electrochemical cells in situ
US4459180 *16 mai 198310 juil. 1984General Signal CorporationMethod and means for compensating for IR voltage drop in electrochemical cells
US4521290 *16 mars 19844 juin 1985Honeywell Inc.Thin layer electrochemical cell for rapid detection of toxic chemicals
US4522690 *1 déc. 198311 juin 1985Honeywell Inc.Electrochemical sensing of carbon monoxide
US4563249 *10 mai 19837 janv. 1986Orbisphere Corporation Wilmington, Succursale De Collonge-BelleriveElectroanalytical method and sensor for hydrogen determination
US4571292 *12 août 198218 févr. 1986Case Western Reserve UniversityApparatus for electrochemical measurements
US4627906 *22 août 19859 déc. 1986The Regents Of The University Of CaliforniaElectrochemical sensor having improved stability
US4655880 *1 août 19837 avr. 1987Case Western Reserve UniversityApparatus and method for sensing species, substances and substrates using oxidase
US4695361 *19 mai 198622 sept. 1987Seatronics, Inc.Oxygen sensor
US4853091 *26 avr. 19881 août 1989Siemens AktiengesellschaftMethod and apparatus for the electrochemical determination of oxygen concentration
US4865717 *10 août 198812 sept. 1989Transducer Research, Inc.Electrochemical micro sensor
US5007424 *29 juin 199016 avr. 1991Hellige GmbhPolarographic/amperometric measuring sensor
US5030310 *19 janv. 19909 juil. 1991Miles Inc.Electrode for electrochemical sensors
US5228974 *11 déc. 199120 juil. 1993Dragerwerk AktiengesellschaftElectrochemical measuring cell for determining ammonia or hydrazine in a measuring sample
US5344546 *19 févr. 19936 sept. 1994Dragerwerk AktiengesellschaftElectrical measuring cell for determinging ammonia, amines, hydrazine amines, hydrazine and hydrazine derivatives
US5376244 *29 oct. 199227 déc. 1994Siemens AktiengesellschaftElectrochemical determination of oxygen concentration
US5387329 *9 avr. 19937 févr. 1995Ciba Corning Diagnostics Corp.Extended use planar sensors
US5401376 *11 mars 199428 mars 1995Ciba Corning Diagnostics Corp.Electrochemical sensors
US5489371 *25 mars 19936 févr. 1996Teknekron Sensor Development CorporationSensor for electrochemical measurements
US5503719 *9 mars 19942 avr. 1996Ciba Corning Diagnostics Corp.Extended use planar sensors
US5518601 *24 août 199521 mai 1996Ciba Corning Diagnostics Corp.Extended use planar sensors
US5595646 *24 août 199521 janv. 1997Ciba Corning Diagnostics Corp.Extended use planar sensors
US6068748 *25 août 199730 mai 2000Berger; JosephExtended use planar sensors
US6103033 *4 mars 199815 août 2000Therasense, Inc.Process for producing an electrochemical biosensor
US6120676 *4 juin 199919 sept. 2000Therasense, Inc.Method of using a small volume in vitro analyte sensor
US6134461 *4 mars 199817 oct. 2000E. Heller & CompanyElectrochemical analyte
US6143164 *16 déc. 19987 nov. 2000E. Heller & CompanySmall volume in vitro analyte sensor
US6162611 *3 janv. 200019 déc. 2000E. Heller & CompanySubcutaneous glucose electrode
US617575230 avr. 199816 janv. 2001Therasense, Inc.Analyte monitoring device and methods of use
US625126024 août 199826 juin 2001Therasense, Inc.Potentiometric sensors for analytic determination
US62844784 déc. 19964 sept. 2001E. Heller & CompanySubcutaneous glucose electrode
US632110120 oct. 199820 nov. 2001Pacesetter AbMethod and device for determination of concentration
US632916122 sept. 200011 déc. 2001Therasense, Inc.Subcutaneous glucose electrode
US633879021 avr. 199915 janv. 2002Therasense, Inc.Small volume in vitro analyte sensor with diffusible or non-leachable redox mediator
US644767020 oct. 199810 sept. 2002Pacesetter AbMethod and apparatus for compensating for drift in potential of a reference electrode in electrochemical measurements
US646149627 oct. 19998 oct. 2002Therasense, Inc.Small volume in vitro analyte sensor with diffusible or non-leachable redox mediator
US648404610 juil. 200019 nov. 2002Therasense, Inc.Electrochemical analyte sensor
US651471829 nov. 20014 févr. 2003Therasense, Inc.Subcutaneous glucose electrode
US65514946 avr. 200022 avr. 2003Therasense, Inc.Small volume in vitro analyte sensor
US656550921 sept. 200020 mai 2003Therasense, Inc.Analyte monitoring device and methods of use
US65761016 oct. 199910 juin 2003Therasense, Inc.Small volume in vitro analyte sensor
US659112527 juin 20008 juil. 2003Therasense, Inc.Small volume in vitro analyte sensor with diffusible or non-leachable redox mediator
US659274517 mai 200015 juil. 2003Therasense, Inc.Method of using a small volume in vitro analyte sensor with diffusible or non-leachable redox mediator
US66168194 nov. 19999 sept. 2003Therasense, Inc.Small volume in vitro analyte sensor and methods
US661893415 juin 200016 sept. 2003Therasense, Inc.Method of manufacturing small volume in vitro analyte sensor
US665462516 juin 200025 nov. 2003Therasense, Inc.Mass transport limited in vivo analyte sensor
US674974028 déc. 200115 juin 2004Therasense, Inc.Small volume in vitro analyte sensor and methods
US688155128 janv. 200319 avr. 2005Therasense, Inc.Subcutaneous glucose electrode
US694251828 déc. 200113 sept. 2005Therasense, Inc.Small volume in vitro analyte sensor and methods
US697370631 mars 200313 déc. 2005Therasense, Inc.Method of making a transcutaneous electrochemical sensor
US697589325 nov. 200313 déc. 2005Therasense, Inc.Mass transport limited in vivo analyte sensor
US700334011 nov. 200221 févr. 2006Abbott Diabetes Care Inc.Electrochemical analyte sensor
US705843717 avr. 20036 juin 2006Therasense, Inc.Methods of determining concentration of glucose
US722553512 sept. 20035 juin 2007Abbott Diabetes Care, Inc.Method of manufacturing electrochemical sensors
US73811845 nov. 20033 juin 2008Abbott Diabetes Care Inc.Sensor inserter assembly
US746226415 juil. 20059 déc. 2008Abbott Diabetes Care Inc.Subcutaneous glucose electrode
US755006912 sept. 200323 juin 2009Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US756335015 sept. 200321 juil. 2009Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US75820596 sept. 20071 sept. 2009Abbott Diabetes Care Inc.Sensor inserter methods of use
US762043831 mars 200617 nov. 2009Abbott Diabetes Care Inc.Method and system for powering an electronic device
US772141216 août 200525 mai 2010Abbott Diabetes Care Inc.Method of making an electrochemical sensor
US77668294 nov. 20053 août 2010Abbott Diabetes Care Inc.Method and system for providing basal profile modification in analyte monitoring and management systems
US781123126 déc. 200312 oct. 2010Abbott Diabetes Care Inc.Continuous glucose monitoring system and methods of use
US78605447 mars 200728 déc. 2010Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US786139730 oct. 20074 janv. 2011Abbott Diabetes Care Inc.Method of making an electrochemical sensor
US78698536 août 201011 janv. 2011Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US787921330 oct. 20071 févr. 2011Abbott Diabetes Care Inc.Sensor for in vitro determination of glucose
US78856996 août 20108 févr. 2011Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US790600930 juil. 200815 mars 2011Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US79099847 févr. 200822 mars 2011Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US79209077 juin 20075 avr. 2011Abbott Diabetes Care Inc.Analyte monitoring system and method
US79288508 mai 200819 avr. 2011Abbott Diabetes Care Inc.Analyte monitoring system and methods
US79483692 août 201024 mai 2011Abbott Diabetes Care Inc.Method and apparatus for providing dynamic multi-stage signal amplification in a medical device
US797677822 juin 200512 juil. 2011Abbott Diabetes Care Inc.Blood glucose tracking apparatus
US798884528 janv. 20082 août 2011Abbott Diabetes Care Inc.Integrated lancing and measurement device and analyte measuring methods
US799605420 févr. 20069 août 2011Abbott Diabetes Care Inc.Electrochemical analyte sensor
US80294426 sept. 20074 oct. 2011Abbott Diabetes Care Inc.Sensor inserter assembly
US80666394 juin 200429 nov. 2011Abbott Diabetes Care Inc.Glucose measuring device for use in personal area network
US806685831 oct. 200729 nov. 2011Abbott Diabetes Care Inc.Analyte sensor with insertion monitor, and methods
US808392429 sept. 200927 déc. 2011Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US808392829 sept. 200927 déc. 2011Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US808392929 sept. 200927 déc. 2011Abbott Diabetes Care Inc.Small volume in vitro sensor and methods of making
US808716229 sept. 20093 janv. 2012Abbott Diabetes Care Inc.Methods of making small volume in vitro analyte sensors
US809122031 oct. 200710 janv. 2012Abbott Diabetes Care Inc.Methods of making small volume in vitro analyte sensors
US810345629 janv. 200924 janv. 2012Abbott Diabetes Care Inc.Method and device for early signal attenuation detection using blood glucose measurements
US810547630 juil. 200731 janv. 2012Abbott Diabetes Care Inc.Integrated lancing and measurement device
US811224029 avr. 20057 févr. 2012Abbott Diabetes Care Inc.Method and apparatus for providing leak detection in data monitoring and management systems
US81142707 févr. 200814 févr. 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US811427129 sept. 200914 févr. 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US811773430 oct. 200721 févr. 2012Abbott Diabetes Care Inc.Method of making an electrochemical sensor
US811899229 sept. 200921 févr. 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US811899329 sept. 200921 févr. 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US81236861 mars 200728 févr. 2012Abbott Diabetes Care Inc.Method and apparatus for providing rolling data in communication systems
US812392929 sept. 200928 févr. 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US813622030 oct. 200720 mars 2012Abbott Diabetes Care Inc.Method of making an electrochemical sensor
US814264230 juil. 200827 mars 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US814264329 sept. 200927 mars 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US814910323 mai 20113 avr. 2012Abbott Diabetes Care Inc.Method and apparatus for providing dynamic multi-stage amplification in a medical device
US814911729 août 20093 avr. 2012Abbott Diabetes Care Inc.Analyte monitoring system and methods
US815306329 sept. 200910 avr. 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US816282930 mars 200924 avr. 2012Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US816316429 sept. 200924 avr. 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US816805130 oct. 20071 mai 2012Abbott Diabetes Care Inc.Sensor for determination of glucose
US81756739 nov. 20098 mai 2012Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US817771621 déc. 200915 mai 2012Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US818267029 sept. 200922 mai 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US818267129 sept. 200922 mai 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US818604413 avr. 200729 mai 2012Abbott Diabetes Care Inc.Method of manufacturing small volume in vitro analyte sensors
US818718311 oct. 201029 mai 2012Abbott Diabetes Care Inc.Continuous glucose monitoring system and methods of use
US818789529 sept. 200929 mai 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US819261129 sept. 20095 juin 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US821136329 sept. 20093 juil. 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US822168529 sept. 200917 juil. 2012Abbott Diabetes Care Inc.Small volume in vitro sensor and methods of making
US822441310 oct. 200817 juil. 2012Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US822655518 mars 200924 juil. 2012Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US822655728 déc. 200924 juil. 2012Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US822655827 sept. 201024 juil. 2012Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US822681529 sept. 200924 juil. 2012Abbott Diabetes Care Inc.Small volume in vitro sensor and methods of making
US822689131 mars 200624 juil. 2012Abbott Diabetes Care Inc.Analyte monitoring devices and methods therefor
US823153230 avr. 200731 juil. 2012Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US823589621 déc. 20097 août 2012Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US823624212 févr. 20107 août 2012Abbott Diabetes Care Inc.Blood glucose tracking apparatus and methods
US825503117 mars 200928 août 2012Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US82603929 juin 20084 sept. 2012Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US826299629 sept. 200911 sept. 2012Abbott Diabetes Care Inc.Small volume in vitro sensor and methods of making
US82657269 nov. 200911 sept. 2012Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US826814429 sept. 200918 sept. 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US826816329 sept. 200918 sept. 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US826824328 déc. 200918 sept. 2012Abbott Diabetes Care Inc.Blood glucose tracking apparatus and methods
US827212529 sept. 200925 sept. 2012Abbott Diabetes Care Inc.Method of manufacturing in vitro analyte sensors
US827302213 févr. 200925 sept. 2012Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US827322730 oct. 200725 sept. 2012Abbott Diabetes Care Inc.Sensor for in vitro determination of glucose
US827324129 sept. 200925 sept. 2012Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US82754399 nov. 200925 sept. 2012Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US828745427 sept. 201016 oct. 2012Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US83065989 nov. 20096 nov. 2012Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US833371410 sept. 200618 déc. 2012Abbott Diabetes Care Inc.Method and system for providing an integrated analyte sensor insertion device and data processing unit
US834633618 mars 20091 janv. 2013Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US834633730 juin 20091 janv. 2013Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US835382921 déc. 200915 janv. 2013Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US835709121 déc. 200922 janv. 2013Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US836290418 avr. 201129 janv. 2013Abbott Diabetes Care Inc.Analyte monitoring system and methods
US836661430 mars 20095 févr. 2013Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US837200521 déc. 200912 févr. 2013Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US837226129 sept. 200912 févr. 2013Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US837737829 sept. 200919 févr. 2013Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US838027311 avr. 200919 févr. 2013Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US839194517 mars 20095 mars 2013Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US84091317 mars 20072 avr. 2013Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US841474912 nov. 20089 avr. 2013Abbott Diabetes Care Inc.Subcutaneous glucose electrode
US841475029 sept. 20109 avr. 2013Abbott Diabetes Care Inc.Subcutaneous glucose electrode
US842574312 mars 201023 avr. 2013Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US842575829 sept. 200923 avr. 2013Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US84272982 avr. 201223 avr. 2013Abbott Diabetes Care Inc.Method and apparatus for providing dynamic multi-stage amplification in a medical device
US844975829 sept. 200928 mai 2013Abbott Diabetes Care Inc.Small volume in vitro analyte sensor and methods of making
US84563018 mai 20084 juin 2013Abbott Diabetes Care Inc.Analyte monitoring system and methods
US84619858 mai 200811 juin 2013Abbott Diabetes Care Inc.Analyte monitoring system and methods
US84633516 août 201011 juin 2013Abbott Diabetes Care Inc.Electrochemical analyte sensor
US846542530 juin 200918 juin 2013Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US847302131 juil. 200925 juin 2013Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US847322023 janv. 201225 juin 2013Abbott Diabetes Care Inc.Method and device for early signal attenuation detection using blood glucose measurements
US848058019 avr. 20079 juil. 2013Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US851223920 avr. 200920 août 2013Abbott Diabetes Care Inc.Glucose measuring device for use in personal area network
US851224330 sept. 200520 août 2013Abbott Diabetes Care Inc.Integrated introducer and transmitter assembly and methods of use
US85327318 mai 200910 sept. 2013Abbott Diabetes Care Inc.Methods of determining analyte concentration
US854540328 déc. 20061 oct. 2013Abbott Diabetes Care Inc.Medical device insertion
US857162429 déc. 200429 oct. 2013Abbott Diabetes Care Inc.Method and apparatus for mounting a data transmission device in a communication system
US858559110 juil. 201019 nov. 2013Abbott Diabetes Care Inc.Method and system for providing basal profile modification in analyte monitoring and management systems
US85888812 mars 200719 nov. 2013Abbott Diabetes Care Inc.Subcutaneous glucose electrode
US85931093 nov. 200926 nov. 2013Abbott Diabetes Care Inc.Method and system for powering an electronic device
US859328720 juil. 201226 nov. 2013Abbott Diabetes Care Inc.Analyte monitoring system and methods
US85971893 mars 20093 déc. 2013Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US859757523 juil. 20123 déc. 2013Abbott Diabetes Care Inc.Analyte monitoring devices and methods therefor
US86029917 juin 201010 déc. 2013Abbott Diabetes Care Inc.Analyte sensor introducer and methods of use
US861215916 févr. 200417 déc. 2013Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US861370329 mai 200824 déc. 2013Abbott Diabetes Care Inc.Insertion devices and methods
US861707121 juin 200731 déc. 2013Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US862290325 mai 20127 janv. 2014Abbott Diabetes Care Inc.Continuous glucose monitoring system and methods of use
US862290621 déc. 20097 janv. 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US8636881 *12 juil. 201028 janv. 2014Michael A. MayIntegrated electrochemical reactor and process therefor
US864161921 déc. 20094 févr. 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US864726920 avr. 200911 févr. 2014Abbott Diabetes Care Inc.Glucose measuring device for use in personal area network
US86498413 avr. 200711 févr. 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US865204320 juil. 201218 févr. 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US866062717 mars 200925 févr. 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US866509130 juin 20094 mars 2014Abbott Diabetes Care Inc.Method and device for determining elapsed sensor life
US866646916 nov. 20074 mars 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US86686453 janv. 200311 mars 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US867081530 avr. 200711 mars 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US867284427 févr. 200418 mars 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US867651321 juin 201318 mars 2014Abbott Diabetes Care Inc.Method and device for early signal attenuation detection using blood glucose measurements
US868818830 juin 20091 avr. 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US869861522 avr. 201315 avr. 2014Abbott Diabetes Care Inc.Method and apparatus for providing dynamic multi-stage signal amplification in a medical device
US870128229 sept. 200922 avr. 2014Abbott Diabetes Care Inc.Method for manufacturing a biosensor
US870618010 juin 201322 avr. 2014Abbott Diabetes Care Inc.Electrochemical analyte sensor
US872829713 avr. 200620 mai 2014Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US873218815 févr. 200820 mai 2014Abbott Diabetes Care Inc.Method and system for providing contextual based medication dosage determination
US873434630 avr. 200727 mai 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US873434817 mars 200927 mai 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US87381093 mars 200927 mai 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US87415903 avr. 20073 juin 2014Abbott Diabetes Care Inc.Subcutaneous glucose electrode
US87445453 mars 20093 juin 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US876465730 mars 20121 juil. 2014Abbott Diabetes Care Inc.Medical device inserters and processes of inserting and using medical devices
US876505927 oct. 20101 juil. 2014Abbott Diabetes Care Inc.Blood glucose tracking apparatus
US877118316 févr. 20058 juil. 2014Abbott Diabetes Care Inc.Method and system for providing data communication in continuous glucose monitoring and management system
US877488724 mars 20078 juil. 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US879517630 juil. 20075 août 2014Abbott Diabetes Care Inc.Integrated sample acquisition and analyte measurement device
US880853113 janv. 200519 août 2014Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US884055326 févr. 200923 sept. 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US885210130 sept. 20097 oct. 2014Abbott Diabetes Care Inc.Method and apparatus for providing analyte sensor insertion
US886219817 déc. 201214 oct. 2014Abbott Diabetes Care Inc.Method and system for providing an integrated analyte sensor insertion device and data processing unit
US888013718 avr. 20034 nov. 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US891585028 mars 201423 déc. 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US892031928 déc. 201230 déc. 2014Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US89302033 févr. 20106 janv. 2015Abbott Diabetes Care Inc.Multi-function analyte test device and methods therefor
US893366425 nov. 201313 janv. 2015Abbott Diabetes Care Inc.Method and system for powering an electronic device
US893754024 févr. 201420 janv. 2015Abbott Diabetes Care Inc.Method and apparatus for providing dynamic multi-stage signal amplification in a medical device
US89743861 nov. 200510 mars 2015Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US899333131 août 201031 mars 2015Abbott Diabetes Care Inc.Analyte monitoring system and methods for managing power and noise
US900092922 nov. 20137 avr. 2015Abbott Diabetes Care Inc.Analyte monitoring system and methods
US901133129 déc. 200421 avr. 2015Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US901133230 oct. 200721 avr. 2015Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US90147737 mars 200721 avr. 2015Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US90172595 août 201428 avr. 2015Abbott Diabetes Care Inc.Integrated sample acquisition and analyte measurement device
US903576730 mai 201319 mai 2015Abbott Diabetes Care Inc.Analyte monitoring system and methods
US90399752 déc. 201326 mai 2015Abbott Diabetes Care Inc.Analyte monitoring devices and methods therefor
US90429532 mars 200726 mai 2015Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US90666943 avr. 200730 juin 2015Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US906669512 avr. 200730 juin 2015Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US906669727 oct. 201130 juin 2015Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US906670917 mars 201430 juin 2015Abbott Diabetes Care Inc.Method and device for early signal attenuation detection using blood glucose measurements
US907247721 juin 20077 juil. 2015Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US907860717 juin 201314 juil. 2015Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US909529027 févr. 20124 août 2015Abbott Diabetes Care Inc.Method and apparatus for providing rolling data in communication systems
US917745610 juin 20133 nov. 2015Abbott Diabetes Care Inc.Analyte monitoring system and methods
US918609824 mars 201117 nov. 2015Abbott Diabetes Care Inc.Medical device inserters and processes of inserting and using medical devices
US921599224 mars 201122 déc. 2015Abbott Diabetes Care Inc.Medical device inserters and processes of inserting and using medical devices
US922670128 avr. 20105 janv. 2016Abbott Diabetes Care Inc.Error detection in critical repeating data in a wireless sensor system
US923486319 mai 201412 janv. 2016Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US923486419 août 201412 janv. 2016Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US925917523 oct. 200616 févr. 2016Abbott Diabetes Care, Inc.Flexible patch for fluid delivery and monitoring body analytes
US926545324 mars 201123 févr. 2016Abbott Diabetes Care Inc.Medical device inserters and processes of inserting and using medical devices
US927166927 avr. 20151 mars 2016Abbott Diabetes Care Inc.Method for integrated sample acquisition and analyte measurement device
US929159219 mai 201422 mars 2016Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US931419531 août 201019 avr. 2016Abbott Diabetes Care Inc.Analyte signal processing device and methods
US93141983 avr. 201519 avr. 2016Abbott Diabetes Care Inc.Analyte monitoring system and methods
US931660919 mai 201419 avr. 2016Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US932046129 sept. 201026 avr. 2016Abbott Diabetes Care Inc.Method and apparatus for providing notification function in analyte monitoring systems
US932389815 nov. 201326 avr. 2016Abbott Diabetes Care Inc.Method and system for providing basal profile modification in analyte monitoring and management systems
US932671429 juin 20103 mai 2016Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US93267165 déc. 20143 mai 2016Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US933293329 sept. 201410 mai 2016Abbott Diabetes Care Inc.Method and apparatus for providing analyte sensor insertion
US934159119 mai 201417 mai 2016Abbott Diabetes Care Inc.Small volume in vitro analyte sensor
US935166930 sept. 201031 mai 2016Abbott Diabetes Care Inc.Interconnect for on-body analyte monitoring device
US93809715 déc. 20145 juil. 2016Abbott Diabetes Care Inc.Method and system for powering an electronic device
US939888210 sept. 200626 juil. 2016Abbott Diabetes Care Inc.Method and apparatus for providing analyte sensor and data processing device
US94025441 févr. 20102 août 2016Abbott Diabetes Care Inc.Analyte sensor and apparatus for insertion of the sensor
US940257011 déc. 20122 août 2016Abbott Diabetes Care Inc.Analyte sensor devices, connections, and methods
US940258414 janv. 20152 août 2016Abbott Diabetes Care Inc.Method and apparatus for providing dynamic multi-stage signal amplification in a medical device
US947781123 juin 200525 oct. 2016Abbott Diabetes Care Inc.Blood glucose tracking apparatus and methods
US948042119 août 20131 nov. 2016Abbott Diabetes Care Inc.Integrated introducer and transmitter assembly and methods of use
US949815930 oct. 200722 nov. 2016Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US952196830 sept. 200520 déc. 2016Abbott Diabetes Care Inc.Analyte sensor retention mechanism and methods of use
US957253428 juin 201121 févr. 2017Abbott Diabetes Care Inc.Devices, systems and methods for on-skin or on-body mounting of medical devices
US95749143 mars 201421 févr. 2017Abbott Diabetes Care Inc.Method and device for determining elapsed sensor life
US96100349 nov. 20154 avr. 2017Abbott Diabetes Care Inc.Analyte monitoring device and methods of use
US962541319 mai 201518 avr. 2017Abbott Diabetes Care Inc.Analyte monitoring devices and methods therefor
US963606824 juin 20162 mai 2017Abbott Diabetes Care Inc.Analyte sensor and apparatus for insertion of the sensor
US964905711 mai 201516 mai 2017Abbott Diabetes Care Inc.Analyte monitoring system and methods
US966205717 févr. 201630 mai 2017Abbott Diabetes Care Inc.Integrated sample acquisition and analyte measurement method
US96686844 mars 20106 juin 2017Abbott Diabetes Care Inc.Self-powered analyte sensor
US966916216 mars 20166 juin 2017Abbott Diabetes Care Inc.Method and system for providing basal profile modification in analyte monitoring and management systems
US968718330 mars 201227 juin 2017Abbott Diabetes Care Inc.Medical device inserters and processes of inserting and using medical devices
US969371327 juin 20164 juil. 2017Abbott Diabetes Care Inc.Analyte sensor devices, connections, and methods
US973058410 févr. 201415 août 2017Abbott Diabetes Care Inc.Glucose measuring device for use in personal area network
US974386229 mars 201229 août 2017Abbott Diabetes Care Inc.Systems and methods for transcutaneously implanting medical devices
US97438631 juin 201629 août 2017Abbott Diabetes Care Inc.Method and system for powering an electronic device
US974386613 juil. 201629 août 2017Abbott Diabetes Care Inc.Method and apparatus for providing dynamic multi-stage signal amplification in a medical device
US97504398 avr. 20165 sept. 2017Abbott Diabetes Care Inc.Method and apparatus for providing notification function in analyte monitoring systems
US975044427 avr. 20165 sept. 2017Abbott Diabetes Care Inc.Interconnect for on-body analyte monitoring device
US20080076997 *31 août 200727 mars 2008Abbott Diabetes Care, Inc.Analyte monitoring device and methods of use
US20080139798 *20 sept. 200712 juin 2008Dharmacon, Inc.siRNA targeting myeloid cell leukemia sequence 1
US20090137889 *12 nov. 200828 mai 2009Adam HellerSubcutaneous Glucose Electrode
US20100012519 *29 sept. 200921 janv. 2010Feldman Benjamin JSmall Volume In Vitro Sensor and Methods of Making
US20100012526 *29 sept. 200921 janv. 2010Feldman Benjamin JSmall Volume In Vitro Sensor and Methods of Making
US20100076287 *29 sept. 200925 mars 2010Feldman Benjamin JSmall Volume In Vitro Analyte Sensor and Methods of Making
US20100087721 *30 sept. 20098 avr. 2010Abbott Diabetes Care Inc.Method and Apparatus for Providing Analyte Sensor Insertion
US20100312078 *18 août 20109 déc. 2010Abbott Diabetes Care Inc.Analyte Monitoring Device and Methods of Use
US20110021895 *29 sept. 201027 janv. 2011Abbott Diabetes Care Inc.Subcutaneous Glucose Electrode
US20120006689 *12 juil. 201012 janv. 2012May Michael AIntegrated electrochemical reactor and process therefor
USRE31914 *29 avr. 198118 juin 1985Becton Dickinson & CompanyElectrochemical gas detection method
DE3504498A1 *9 févr. 198514 août 1986Draegerwerk AgGassensor mit mehreren sensorelementen
DE3815004A1 *3 mai 198816 nov. 1989GimatVorrichtung zur polarographischen messung des sauerstoffgehalts in fluessigen und gasfoermigen medien
DE4335487C2 *18 oct. 199318 déc. 2003St Jude MedicalSauerstoffsensor
WO1985002465A1 *28 nov. 19846 juin 1985Honeywell Inc.Electrochemical sensing of carbon monoxide
WO1987002461A1 *3 oct. 198623 avr. 1987Beckman Industrial Corporation Process InstrumentsA method of fabricating rhodium foil-glass electrodes
WO1988009500A1 *26 mai 19881 déc. 1988Transducer Research, Inc.Electrochemical micro sensor
WO1999022229A1 *23 oct. 19986 mai 1999Ceramatec, Inc.Volume efficient acid based galvanic oxygen sensor
WO1999022230A1 *20 oct. 19986 mai 1999Pacesetter AbMethod and device for determination of concentration
WO1999022232A1 *20 oct. 19986 mai 1999Pacesetter AbMethod and device for sensing
Classifications
Classification aux États-Unis205/783, 204/415, 208/254.00R, 204/406, 204/412
Classification internationaleG01N27/49
Classification coopérativeG01N27/404
Classification européenneG01N27/404