EP0122009A2
Expired / Lapsed
EP
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Electrochemical detection system
Assignee: Magellan Diagnostics Inc
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Filing: 1984-03-02
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Granted: —
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Expires: 2004-03-02
Abstract
Abstract An improved apparatus for electrochemically analyzing a sample in solution is described. The apparatus comprises an electrochemical detector comprising a plurality of electrochemically isolated flow cells arranged in series so as to define at least one flow path. Each of the electrochemical flow cells in turn comprises at least one working electrode, at least one reference electrode, and at least one counter electrode. Electrical potentials are applied to the various working electrodes so that the sample solution is cyclically subjected to oxidation and reduction conditions whereby selected substances contained in the sample solution may be electrically screaned or modified prior to detection and measurement on a downstream sensing electrode.
Inventors
- 👤 Wayne R. Matson
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-10-31 19:02
CPC Classifications
G; G01; G01N; G01N33/00; G01N33/48; G01N33/50; G01N33/68; G01N33/6803; G01N27/00; G01N27/26; G01N27/27; G01N30/00; G01N30/02; G01N30/62; G01N30/64; G01N2800/00; G01N2800/28; G01N2800/2814; G01N2800/2821; G01N30/86; G01N30/8651; Y; Y10; Y10T; Y10T436/00; Y10T436/17; Y10T436/173845; Y10T436/25; Y10T436/25125
Claims Analysis
Total Claims: 15
Claim 1
Independent Claim
195 words
An electrochemical detection apparatus for electrochemically testing a sample containing reversible and irreversible electrochemically active materials in solution, said apparatus characterized by comprising: at least three coulometric electrochemical flow cells, each of said cells having therein at least one . working electrode, at least one counter electrode and at least one reference electrode, said plurality of electrochemical cells being arranged in series and defining collectively at least one flow channel for said sample solution; means for connecting each said reference electrode to a reference potential; means connecting each said counter electrode to a counter potential; and means connecting each said working electrode to a working potential, at least two of said cells constituting gate cells, each of said gate cells having means for maintaining its working electrode at a different potential from the other, one of said gate cells being at a potential to oxidize electrochemically active materials in said sample and another of said gate cells being at a potential to reduce electrochemically active materials in said sample a third of said cells having means for maintaining its working electode at a potential to detect and coulometrically measure electrochemically reversible materials in said sample.
Claim 2
Dependent Claim
195 words
An electrochemical detection apparatus for electrochemically testing a sample containing reversible and irreversible electrochemically active materials in solution, said apparatus characterized by comprising: at least three coulometric electrochemical flow cells, each of said cells having therein at least one . working electrode, at least one counter electrode and at least one reference electrode, said plurality of electrochemical cells being arranged in series and defining collectively at least one flow channel for said sample solution; means for connecting each said reference electrode to a reference potential; means connecting each said counter electrode to a counter potential; and means connecting each said working electrode to a working potential, at least two of said cells constituting gate cells, each of said gate cells having means for maintaining its working electrode at a different potential from the other, one of said gate cells being at a potential to oxidize electrochemically active materials in said sample and another of said gate cells being at a potential to reduce electrochemically active materials in said sample a third of said cells having means for maintaining its working electode at a potential to detect and coulometrically measure electrochemically reversible materials in said sample.
Claim 3
Dependent Claim
246 words
In apparatus for analyzing complex mixtures of electrochemically active fluids such as blood, cerebrospinal fluids and the like containing electrochemically irreversible materials and trace quantities of electrochemically reversible materials, comprising a liquid chromatographic column for achieving time spaced separation of the materials eluting from the column and an electrochemical detection apparatus for electrochemically testing a sample containing reversible and irreversible electrochemically active materials in solution, the improvement characterized in that said detection apparatus comprises at least three coulometric electrochemical flow cells, each of said cells having therein at least one working electrode, at least one counter electrode and at least one reference electrode, said plurality of electrochemical cells being arranged in series and defining collectively at least one flow channel for said sample solution; means for connecting each said reference electrode to a reference potential; means connecting each said counter electrode to a counter l potential; and means connecting each said working electrodes to a working potential, at least two of said cells constituting gate cells, each of said gate cells having means for maintaining its working electrode at a different potential from the other, one of said gate cells being at a potential to oxidize electrochemically active materials in said sample and another of said gate cells being at a potential to reduce electrochemically active materials in said sample a third of said cells having means for maintaining its working electode at a potential to detect and coulometrically measure electrochemically reversible materials in said sample.
Claim 4
Dependent Claim
246 words
In apparatus for analyzing complex mixtures of electrochemically active fluids such as blood, cerebrospinal fluids and the like containing electrochemically irreversible materials and trace quantities of electrochemically reversible materials, comprising a liquid chromatographic column for achieving time spaced separation of the materials eluting from the column and an electrochemical detection apparatus for electrochemically testing a sample containing reversible and irreversible electrochemically active materials in solution, the improvement characterized in that said detection apparatus comprises at least three coulometric electrochemical flow cells, each of said cells having therein at least one working electrode, at least one counter electrode and at least one reference electrode, said plurality of electrochemical cells being arranged in series and defining collectively at least one flow channel for said sample solution; means for connecting each said reference electrode to a reference potential; means connecting each said counter electrode to a counter l potential; and means connecting each said working electrodes to a working potential, at least two of said cells constituting gate cells, each of said gate cells having means for maintaining its working electrode at a different potential from the other, one of said gate cells being at a potential to oxidize electrochemically active materials in said sample and another of said gate cells being at a potential to reduce electrochemically active materials in said sample a third of said cells having means for maintaining its working electode at a potential to detect and coulometrically measure electrochemically reversible materials in said sample.
Claim 5
Dependent Claim
47 words
The apparatus of claim 2, characterized in that the working electrode in each gate cell has an area equal to at lest 50 half times, the area of the working electrode in the detection cell being less than 1/10 that of the preceding gate cell working electrode.
Claim 6
Dependent Claim
156 words
In apparatus for analyzing complex mixtures of electrochemically active fluids such as blood, cerebrospinal fluids and the like containing electrochemically irreversible materials and trace quantities of electrochemically materials, comprising a liquid chromatographic column for achieving time spaced separation of the materials eluting from the column and an electrochemical detection apparatus for electrochemically testing a sample containing reversible and irreversible electrochemically active materials in solution, the improvement characterized in that said detection apparatus comprises at least two gate cells arranged to change the oxidation state of electrochemically reversible and electrochemically irreversible materials and convert at least some of said materials to an electrochemically inactive state at the potential on a following coulometric measuring electode, at least one additional test cell following said two gate cells, arranged to coulometrically measure electrochemically reversible materials of interest in the eluant at a measuring electrode held at a potential adequate to detect and measure the quantity of said materials of interest.
Claim 7
Dependent Claim
156 words
In apparatus for analyzing complex mixtures of electrochemically active fluids such as blood, cerebrospinal fluids and the like containing electrochemically irreversible materials and trace quantities of electrochemically materials, comprising a liquid chromatographic column for achieving time spaced separation of the materials eluting from the column and an electrochemical detection apparatus for electrochemically testing a sample containing reversible and irreversible electrochemically active materials in solution, the improvement characterized in that said detection apparatus comprises at least two gate cells arranged to change the oxidation state of electrochemically reversible and electrochemically irreversible materials and convert at least some of said materials to an electrochemically inactive state at the potential on a following coulometric measuring electode, at least one additional test cell following said two gate cells, arranged to coulometrically measure electrochemically reversible materials of interest in the eluant at a measuring electrode held at a potential adequate to detect and measure the quantity of said materials of interest.
Claim 8
Dependent Claim
91 words
The apparatus of claim 2, characterized in that wherein said detection apparatus includes at least two measuring cells following said gate cells, the working electrodes of said measuring cells being at different potentials to provide different electrochemical measurements for electrochemically active species passing sequentially through said two measuring cells, said two measuring cells preferably being arranged to operate at progressively varying potentials along said flow path, said apparatus optionally including means for displaying said measurements so as to separate said measurements by measuring potential as well as by time of elution.
Claim 9
Dependent Claim
35 words
The apparatus of claim 5, characterized in that the measuring cells are sufficiently close along said channel that time of transit of eluant between measuring cells is in significant with respect to overall elution times.
Claim 10
Dependent Claim
53 words
The apparatus of claim 4, characterized by one or more of the following features: (a) said oxidizing gate cell precedes said reducing gate cell; (b) said reducing gate cell precedes said oxidizing gate cell; (c) said measuring cell reduced said electrochemically reversible species; and (d) said measuring cell oxidizes said electrochemically reversible species.
Claim 11
Independent Claim
180 words
The method for analyzing complex mixtures of electrochemically active fluids such as blood, cerebrospinal fluids and the like containing electrochemically irreversible materials, and trace quantities of electrochemically reversible materials characterized by the steps of passing said electrochemically active fluids sequentially through a liquid chromatographic column for achieving time spaced separation of the materials eluting from the column and then through an electrochemical detection apparatus for electrochemically testing a sample containing reversible and irreversible electrochemically active materials in solution, the detection apparatus comprising at least three coulometric cells arranged in series, maintaining the coulometric electodes of two of said cells at different potentials to change the oxidation state of electrochemically reversible and electrochemically irreversible materials and convert at least some of said materials to an electrochemically inactive state at the potential maintained on a following coulometric measuring electrode, providing at least one additional test cell following said two gate cells for coulometrically measuring electrochemically reversible materials of interest in the eluant at a measuring electrode held at a potential adequate to detect and measure the quantity of said materials of interest.
Claim 12
Independent Claim
180 words
The method for analyzing complex mixtures of electrochemically active fluids such as blood, cerebrospinal fluids and the like containing electrochemically irreversible materials, and trace quantities of electrochemically reversible materials characterized by the steps of passing said electrochemically active fluids sequentially through a liquid chromatographic column for achieving time spaced separation of the materials eluting from the column and then through an electrochemical detection apparatus for electrochemically testing a sample containing reversible and irreversible electrochemically active materials in solution, the detection apparatus comprising at least three coulometric cells arranged in series, maintaining the coulometric electodes of two of said cells at different potentials to change the oxidation state of electrochemically reversible and electrochemically irreversible materials and convert at least some of said materials to an electrochemically inactive state at the potential maintained on a following coulometric measuring electrode, providing at least one additional test cell following said two gate cells for coulometrically measuring electrochemically reversible materials of interest in the eluant at a measuring electrode held at a potential adequate to detect and measure the quantity of said materials of interest.
Claim 13
Independent Claim
270 words
The method for analyzing complex mixtures of electrochemically active fluids such as blood, cerebrospinal fluids and the like containing electrochemically irreversible materials and trace quantities of electrochemically reversible materials, characterized by the steps of passing said electrochemically active fluids sequentially through a liquid chromatographic column for achieving time spaced separation of the materials eluting from the column and an electrochemical detection apparatus for electrochemically testing a sample containing reversible and irreversible electrochemically active materials in solution, the detection apparatus comprising at least three coulometric cells arranged in series, maintaining the coulometric electodes of two of said cells at different potentials to change the oxidation state of electrochemically reversible and electrochemically irreversible materials and convert at least some of said materials to an electrochemically inactive state at the potential maintained on a following coulometric measuring electrode, providing at least one additional test cell following said two gate cells for coulometrically measuring electrochemically reversible materials of interest in the eluant at a measuring electrode held at a potential adequate to detect and measure the quantity of said materials of interest, connecting each said working electrodes to a working potential, at least two of said cells constituting gate cells, each of said gate cells having its working electrode at a different potential from the other, one of said gate cells being at a potential to oxidize electrochemically active materials in said sample and another of said gate cells being at a potential to reduce electrochemically active materials in said sample a third of said cells having its working electode at a potential to detect and coulometrically measure electrochemically reversible materials in said sample.
Claim 14
Independent Claim
270 words
The method for analyzing complex mixtures of electrochemically active fluids such as blood, cerebrospinal fluids and the like containing electrochemically irreversible materials and trace quantities of electrochemically reversible materials, characterized by the steps of passing said electrochemically active fluids sequentially through a liquid chromatographic column for achieving time spaced separation of the materials eluting from the column and an electrochemical detection apparatus for electrochemically testing a sample containing reversible and irreversible electrochemically active materials in solution, the detection apparatus comprising at least three coulometric cells arranged in series, maintaining the coulometric electodes of two of said cells at different potentials to change the oxidation state of electrochemically reversible and electrochemically irreversible materials and convert at least some of said materials to an electrochemically inactive state at the potential maintained on a following coulometric measuring electrode, providing at least one additional test cell following said two gate cells for coulometrically measuring electrochemically reversible materials of interest in the eluant at a measuring electrode held at a potential adequate to detect and measure the quantity of said materials of interest, connecting each said working electrodes to a working potential, at least two of said cells constituting gate cells, each of said gate cells having its working electrode at a different potential from the other, one of said gate cells being at a potential to oxidize electrochemically active materials in said sample and another of said gate cells being at a potential to reduce electrochemically active materials in said sample a third of said cells having its working electode at a potential to detect and coulometrically measure electrochemically reversible materials in said sample.
Claim 15
Dependent Claim
160 words
The method of claim 9, characterized by one or more of the following features: (a) said detection apparatus includes at least two measuring cells following said gate cells, the working electrodes of said measuring cells being at different potentials to provide different electrochemical measurements for electrochemically active species passing sequentially through said two measuring cells, said measuring cells (i) preferably operating at progressively varying potentials along said flow path, and (ii) preferably being arranged sufficiently close along said channel that time of transit of eluant between measuring cells is insignificant with respect to overall elution times. (b) including the additional step of displaying said measurements so as to separate said measurements by measuring potential as well as by time of elution; (c) said oxidizing gate cell precedes said reducing gate cell; (d) said reducing gate cell precedes said oxidizing gate cell; (e) said measuring cell reduces said electrochemically reversible species; and (f) said measuring cell oxidizes said electrochemically reversible species.
References Cited (Backward Citations)
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