US4233031A
Expired / Lapsed
US
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Electrochemical testing system and method
Assignee: Magellan Diagnostics Inc
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Filing: 1978-12-11
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Granted: 1980-11-11
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Expires: 1998-12-11
Abstract
Abstract An electrochemical measuring system which effects, measures and sorts charge transfer reactions of selected substances in a sample solution is provided. The system includes a novel electrode which is adapted to measure simultaneously on at least two electrodes at least two electolytic potentials with reference to a reference potential. In a preferred form the electrode comprises a hollow, cylindrical body formed of an electrically insulating material. The electrode is open at least at one end and has a generally smooth cylindrical inner surface. A plurality of electrically discrete active electrode segments are mounted on the inner surface of the electrode with their active surfaces substantially flush with the generally smooth cylindrical inner surface. Completing the electrochemical measuring system are a stirring means for creating a relatively high degree of mixing adjacent the electrode active surfaces, means for charging liquid samples to the cell, and means connecting at least two of the electrically discrete active electrode segments to different electrical potentials. In use a sample to be tested is charged to the cell, and stirring is commenced. One of the electrically discrete active electrode sgements is held at a potential at which a selected substance of interest and also one or more interferring substances responds, while another of the electrode segments is held at a potential at which only the interferring substances respond. The presence of a substance of interest can be determined by subtracting the signals from the one and another electrode segments, and its quantity determined by integrating the signal difference.
Inventors
- 👤 Wayne R. Matson
- 👤 Ronald Vitukevich
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-26 00:47
CPC Classifications
G; G01; G01N; G01N33/00; G01N33/48; G01N33/483; G01N33/487; G01N33/49; G01N33/492
Claims Analysis
Total Claims: 53
Claim 1
Independent Claim
131 words
In serum iron testing, a method of electrochemical testing compatible with micro sized samples of serum comprising: preparing a substantially iron-free matrix including a lower aliphatic alcohol and between about 51/2 Formal and about 81/2 Formal HCl; introducing a predetermined quantity of serum into said matrix to provide an electrolytic sample, and adding a measured quantity of said sample containing a measured quantity of serum to an electrolytic cell; applying to a first electrode in said cell a potential to measure the quantity of copper and iron in said cell; applying to a second electrode in said cell a potential to measure a different quantity selected from copper and iron; obtaining signals corresponding to current flow at each of said electrodes; and comparing said signals to measure the quantity of iron.
Claim 2
Dependent Claim
131 words
In serum iron testing, a method of electrochemical testing compatible with micro sized samples of serum comprising: preparing a substantially iron-free matrix including a lower aliphatic alcohol and between about 51/2 Formal and about 81/2 Formal HCl; introducing a predetermined quantity of serum into said matrix to provide an electrolytic sample, and adding a measured quantity of said sample containing a measured quantity of serum to an electrolytic cell; applying to a first electrode in said cell a potential to measure the quantity of copper and iron in said cell; applying to a second electrode in said cell a potential to measure a different quantity selected from copper and iron; obtaining signals corresponding to current flow at each of said electrodes; and comparing said signals to measure the quantity of iron.
Claim 3
Dependent Claim
37 words
The method of claim 1, wherein the potential applied to said first electrode is between about 0.4 and about 0.5 volts and the potential applied to said second electrode is between about 0.2 and about 0.3 volts.
Claim 4
Dependent Claim
17 words
The method of claim 2, wherein the second electrode signal is subtracted from the first electrode signal.
Claim 5
Dependent Claim
30 words
A composition for releasing iron from serum for electrochemical testing comprising a substantially iron-free mixture of a lower aliphatic alcohol, and HCl between about 51/2 Formal and about 81/2 Formal.
Claim 6
Dependent Claim
30 words
A composition for releasing iron from serum for electrochemical testing comprising a substantially iron-free mixture of a lower aliphatic alcohol, and HCl between about 51/2 Formal and about 81/2 Formal.
Claim 7
Dependent Claim
11 words
A composition according to claim 4, wherein said alcohol comprises isopropanol.
Claim 8
Dependent Claim
14 words
A composition according to claim 5, wherein said HCl concentration is about 7 Formal.
Claim 9
Dependent Claim
195 words
Apparatus for electrochemical testing of serum iron comprising: (a) support means; (b) a cell block positioned on said support means and including an electrolytic cell to contain a quantity of a sample serum; (c) an electrode body in said cell having a plurality of electrically discrete active testing electrode segments and at least one reference electrode segment, at least a first said active testing electrode segment being adapted to detect and measure a first quantity corresponding to both iron and copper, and at least a second active testing electrode segment being adapted to detect and measure a different quantity selected from iron and copper, whereby the quantity of iron can be determined by comparing the electrochemical measures of said electrode segments; (d) means to apply to said first active testing electrode segment a potential for measuring both iron and copper from serum; (e) means to apply to said second active testing electrode segment a potential for measuring a different quantity selected from iron and copper; (f) means to compare signals corresponding to electric currents to said first and second active testing electrode segments to determine, by said comparison, the quantity of iron in said sample.
Claim 10
Dependent Claim
195 words
Apparatus for electrochemical testing of serum iron comprising: (a) support means; (b) a cell block positioned on said support means and including an electrolytic cell to contain a quantity of a sample serum; (c) an electrode body in said cell having a plurality of electrically discrete active testing electrode segments and at least one reference electrode segment, at least a first said active testing electrode segment being adapted to detect and measure a first quantity corresponding to both iron and copper, and at least a second active testing electrode segment being adapted to detect and measure a different quantity selected from iron and copper, whereby the quantity of iron can be determined by comparing the electrochemical measures of said electrode segments; (d) means to apply to said first active testing electrode segment a potential for measuring both iron and copper from serum; (e) means to apply to said second active testing electrode segment a potential for measuring a different quantity selected from iron and copper; (f) means to compare signals corresponding to electric currents to said first and second active testing electrode segments to determine, by said comparison, the quantity of iron in said sample.
Claim 11
Dependent Claim
60 words
The apparatus of claim 7, wherein said means to apply a potential to said first active testing electrode segment is operative over a range from zero to 1 volt, and wherein said means to apply a potential to said second active testing electrode segment is operative with respect to said first electrode over a range between zero and 300 millivolts.
Claim 12
Dependent Claim
50 words
The apparatus of claim 7, wherein said means to apply a potential to said first active testing electrode segment is operative between about 0.4 and about 0.5 volts, and said means to apply a potential to said second active testing electrode is operative between about 0.2 and about 0.3 volts.
Claim 13
Dependent Claim
43 words
The apparatus of claim 9, wherein said means to apply a potential to said first active testing electrode is operative at about 460 millivolts, and said means to apply a potential to said second active testing electrode is operative at about 250 millivolts.
Claim 14
Dependent Claim
252 words
Apparatus for electrochemical testing of serum iron comprising: (a) support means; (b) a cell block positioned on said support means and including an electrolytic cell to contain a quantity of a sample of serum; (c) an electrode body in said cell having a plurality of electrically discrete active electrode segments and at least one reference electrode segment, at least a first of said active testing electrode segments being adapted to detect and measure both iron and copper, and at least a second of said active testing electrode segments being adapted to detect and measure a different quantity selected from iron and copper, whereby the quantity of iron can be determined by comparing the electrochemical measures of said active testing electrode segments; (d) stirring means in said cell; (e) sample input means to receive a measured quantity of a serum sample for testing; (f) input means to introduce electrolyte liquid to said cell; (g) outlet means to discharge electrolyte from said cell; (h) means to supply electrolyte liquid to said cell and to discharge electrolyte through said outlet means; (i) means to apply to said first active testing electrode segment a potential for measuring both iron and copper from serum; (j) means to apply to said second active testing electrode segment a potential for measuring a different quantity selected from iron and copper; and (k) means to compare signals corresponding to electric currents to said first and second active testing electrodes to determine, by said comparison, the quantity of iron in said sample.
Claim 15
Dependent Claim
252 words
Apparatus for electrochemical testing of serum iron comprising: (a) support means; (b) a cell block positioned on said support means and including an electrolytic cell to contain a quantity of a sample of serum; (c) an electrode body in said cell having a plurality of electrically discrete active electrode segments and at least one reference electrode segment, at least a first of said active testing electrode segments being adapted to detect and measure both iron and copper, and at least a second of said active testing electrode segments being adapted to detect and measure a different quantity selected from iron and copper, whereby the quantity of iron can be determined by comparing the electrochemical measures of said active testing electrode segments; (d) stirring means in said cell; (e) sample input means to receive a measured quantity of a serum sample for testing; (f) input means to introduce electrolyte liquid to said cell; (g) outlet means to discharge electrolyte from said cell; (h) means to supply electrolyte liquid to said cell and to discharge electrolyte through said outlet means; (i) means to apply to said first active testing electrode segment a potential for measuring both iron and copper from serum; (j) means to apply to said second active testing electrode segment a potential for measuring a different quantity selected from iron and copper; and (k) means to compare signals corresponding to electric currents to said first and second active testing electrodes to determine, by said comparison, the quantity of iron in said sample.
Claim 16
Dependent Claim
91 words
In apparatus according to claim 11, means to flush electrolyte through said cell to remove electrolyte therefrom and to replace it with fresh electrolyte, said means comprising conduit means to supply electrolyte to said input, conduit means to receive electrolyte from said outlet, an optical emitter and an optical detector on opposite sides of one of said conduit means, and curved transparent walls in said conduit between said emitter and said detector, whereby radiation from said emitter is more fully focussed on said detector while electrolyte liquid is in said conduit.
Claim 17
Dependent Claim
200 words
Apparatus for electrochemical testing of serum iron comprising; (a) support means; (b) a cell block positioned on said support means and including an electrolytic cell to contain a quantity of a sample of serum; (c) an electrode body in said cell having a plurality of electrically discrete active electrode segments and at least one reference electrode segment, at least a first of said active testing electrode segments being adapted to measure a first charge transfer for both iron and copper, and at least a second of said active testing electrode segments being adapted to measure a second charge transfer for a different quantity selected from iron and copper, whereby the quantity of iron can be determined by comparing the measures of said charge transfers; (d) means to apply to said first active testing electrode segment a first potential for measuring the charge transfer of both iron and copper; (e) means to apply to said second active testing electrode segment a second potential for measuring the charge transfer of a different quantity selected from iron and copper; (f) means to compare signals corresponding to first and second charge transfers to determine, by said comparison, the quantity of iron in said sample.
Claim 18
Dependent Claim
200 words
Apparatus for electrochemical testing of serum iron comprising; (a) support means; (b) a cell block positioned on said support means and including an electrolytic cell to contain a quantity of a sample of serum; (c) an electrode body in said cell having a plurality of electrically discrete active electrode segments and at least one reference electrode segment, at least a first of said active testing electrode segments being adapted to measure a first charge transfer for both iron and copper, and at least a second of said active testing electrode segments being adapted to measure a second charge transfer for a different quantity selected from iron and copper, whereby the quantity of iron can be determined by comparing the measures of said charge transfers; (d) means to apply to said first active testing electrode segment a first potential for measuring the charge transfer of both iron and copper; (e) means to apply to said second active testing electrode segment a second potential for measuring the charge transfer of a different quantity selected from iron and copper; (f) means to compare signals corresponding to first and second charge transfers to determine, by said comparison, the quantity of iron in said sample.
Claim 19
Dependent Claim
27 words
The apparatus according to claim 13, including means for subtracting a signal corresponding to said second charge transfer from a signal corresponding to said first charge transfer.
Claim 20
Dependent Claim
33 words
The apparatus of claim 13, wherein said means to apply said first potential is operative at about 460 millivolts, and said means to apply said second potential is operative at about 250 millivolts.
Claim 21
Dependent Claim
23 words
Apparatus according to claim 7, including means to flush from said cell electrolyte containing a sample and to replace it with new electrolyte.
Claim 22
Dependent Claim
23 words
Apparatus according to claim 15, including digital display means for displaying the result obtained by subtracting said second signal from a first signal.
Claim 23
Dependent Claim
25 words
Apparatus according to claim 17 including calibration means for converting said display to a digital readout of micrograms of iron per 100 milliliters of serum.
Claim 24
Dependent Claim
21 words
The method of claim 3, and including the step of converting the result of said signal subtraction to a digital display.
Claim 25
Dependent Claim
130 words
An electrode for electrochemical testing adapted to measure simultaneously at least two electrolytic potentials with reference to a reference potential comprising: a hollow cylindrical electrode body of an insulating material, open at least at one end; a smooth cylindrical inner surface on said electrode body; at least one reference electrode segment and at least two active testing electrode segments mounted at the inner surface of said electrode body and having their respective surfaces flush with the inner surface of said body, each of said segments being electrically insulated from each other electrode segment and separated therefrom by said insulating material; said reference electrode segment having at least its surface formed of a reference metal; and means to connect each of said active testing electrode segments to a different electrical potential.
Claim 26
Dependent Claim
130 words
An electrode for electrochemical testing adapted to measure simultaneously at least two electrolytic potentials with reference to a reference potential comprising: a hollow cylindrical electrode body of an insulating material, open at least at one end; a smooth cylindrical inner surface on said electrode body; at least one reference electrode segment and at least two active testing electrode segments mounted at the inner surface of said electrode body and having their respective surfaces flush with the inner surface of said body, each of said segments being electrically insulated from each other electrode segment and separated therefrom by said insulating material; said reference electrode segment having at least its surface formed of a reference metal; and means to connect each of said active testing electrode segments to a different electrical potential.
Claim 27
Dependent Claim
63 words
An electrode according to claim 20, having first, second, third and fourth electrode segments; said first and second segments being active testing electrode segments adapted to measure simultaneously two electrolytic potentials; said third segment being a reference electrode segment; and said fourth segment being adapted to provide an electrolytic current source different from the potentials on said first, second and third electrode segments.
Claim 28
Dependent Claim
23 words
The electrode of claim 21, wherein said reference electrode segment comprises silver and said first, second and fourth electrode segments each comprise carbon.
Claim 29
Dependent Claim
74 words
In serum iron testing by electrochemical methods, the steps of: preparing a substantially iron free matrix comprising between 51/2 and 81/2 Formal HCl in isopropanol; adding to said matrix a measured quantity of a serum sample to be tested, thereby releasing serum iron from binding to serum components and separating the charge transfer potentials of iron and copper; and thereafter measuring the quantity of electrolytic current corresponding to iron charge transfer in said sample.
Claim 30
Dependent Claim
74 words
In serum iron testing by electrochemical methods, the steps of: preparing a substantially iron free matrix comprising between 51/2 and 81/2 Formal HCl in isopropanol; adding to said matrix a measured quantity of a serum sample to be tested, thereby releasing serum iron from binding to serum components and separating the charge transfer potentials of iron and copper; and thereafter measuring the quantity of electrolytic current corresponding to iron charge transfer in said sample.
Claim 31
Dependent Claim
152 words
An electrolytic cell for electrochemically testing a sample in solution, said cell comprising: a sensing electrode in the form of a hollow cylindrical body defining an enclosure for holding said solution for testing, said body (a) being formed of an electrically insulating material, and (b) having a substantially smooth cylindrical inner surface; at least two active testing electrode segments mounted at the inner surface of said body, said electrode segments having electrically active surfaces which are (a) substantially flush with said smooth inner surface, and (b) electrically insulated from one another by said insulating material; a counter electrode having an electrically active surface mounted in said enclosure; a reference electrode having an electrically active surface mounted in said enclosure; and, means for connecting (a) said at least two active testing segments to different electrical potentials, (b) said reference electrode to a reference potential, and (c) said counter electrode to yet another potential.
Claim 32
Dependent Claim
152 words
An electrolytic cell for electrochemically testing a sample in solution, said cell comprising: a sensing electrode in the form of a hollow cylindrical body defining an enclosure for holding said solution for testing, said body (a) being formed of an electrically insulating material, and (b) having a substantially smooth cylindrical inner surface; at least two active testing electrode segments mounted at the inner surface of said body, said electrode segments having electrically active surfaces which are (a) substantially flush with said smooth inner surface, and (b) electrically insulated from one another by said insulating material; a counter electrode having an electrically active surface mounted in said enclosure; a reference electrode having an electrically active surface mounted in said enclosure; and, means for connecting (a) said at least two active testing segments to different electrical potentials, (b) said reference electrode to a reference potential, and (c) said counter electrode to yet another potential.
Claim 33
Dependent Claim
60 words
An electrolytic cell according to claim 24 wherein said reference electrode comprises one or more electrode segments mounted at the inner surface of said body, each of said reference electrode segments having an electrically active surface which is (a) substantially flush with the inner surface of said body, and (b) electrically insulated from all other electrode segments on said body.
Claim 34
Dependent Claim
61 words
An electrolytic cell according to claim 24 wherein said counter electrode comprises one or more electrode segments mounted at the inner surface of said body, each of said counter electrode segments having an electrically active surface which is (a) substantially flush with the inner surface of said body, and (b) being electrically insulated from all other electrode segments on said body.
Claim 35
Dependent Claim
12 words
An electrode according to claim 24 wherein said reference electrode comprises silver.
Claim 36
Dependent Claim
28 words
An electrode according to any one of claims 24 to 26 wherein said reference electrode comprises silver, and said active testing electrodes and said counter electrode comprise carbon.
Claim 37
Dependent Claim
97 words
An electrolytic cell assembly comprising first and second electrolytic cells as defined by claim 24, said first electrolytic cell being adapted to hold a sample in a reagent and to measure charge transfer reactions of said sample and said reagent, said second electrolytic cell being adapted to hold said reagent alone and to measure charge transfer reactions of said reagent alone, said first and said second electrolytic cells having corresponding active electrode segments, and means for pairing electrode segments in said first electrolytic cell with corresponding electrode segments in said second electrolytic cell at the same potential.
Claim 38
Dependent Claim
94 words
In a method of electrochemically analyzing a sample material to identify selected substances therein, the steps of: dissolving said sample in a reagent to form a test solution, charging a quantity of said test solution to an electrolytic cell in contact with a plurality of active testing electrodes, simultaneously providing a plurality of electrical potentials across said solution from said plurality of active testing electrodes, deriving signals from said active testing electrodes corresponding to charge transfer reactions of materials in said solution, and sorting said signals to obtain signals which identify said selected substances.
Claim 39
Dependent Claim
94 words
In a method of electrochemically analyzing a sample material to identify selected substances therein, the steps of: dissolving said sample in a reagent to form a test solution, charging a quantity of said test solution to an electrolytic cell in contact with a plurality of active testing electrodes, simultaneously providing a plurality of electrical potentials across said solution from said plurality of active testing electrodes, deriving signals from said active testing electrodes corresponding to charge transfer reactions of materials in said solution, and sorting said signals to obtain signals which identify said selected substances.
Claim 40
Dependent Claim
59 words
Apparatus for electrochemical testing a sample in solution to identify selected substances therein, said apparatus comprising at least one electrolytic cell as defined by claim 24, and further comprising means for comparing signals corresponding to electric current flow at at least two active testing segments to determine, by said comparison, the quantity of said selected substances in said sample.
Claim 41
Dependent Claim
60 words
Apparatus according to claim 31, including (a) stirring means mounted in said sensing electrode; (b) sample input means for introducing a measured quantity of sample into said sensing electrode; (c) input means for introducing electrolyte liquid to said sensing electrode; (d) outlet means for discharging electrolyte from said sensing electrode; and (e) means for supplying electrolyte to said input means.
Claim 42
Dependent Claim
144 words
Apparatus according to claims 31 or 32 for electrochemical testing a sample selected from the group consisting of blood and serum, containing both iron and copper, wherein one of said active electrode segments is adapted to measure a first charge transfer for both iron and copper, and another of said active electrode segments is adapted to measure a second charge transfer for a different quantity selected from iron and copper, and including means for applying to said one active electrode segment a first potential for measuring the charge transfer of both iron and copper; means for applying to said another active electrode segment a second potential for measuring the charge transfer of said different quantity selected from iron and copper; and means for comparing signals corresponding to first and second charge transfers to determine, by said comparison, the quantity of iron in said sample.
Claim 43
Dependent Claim
95 words
Apparatus according to claims 31 or 32, and including means for flushing electrolyte through said cell to remove electrolyte therefrom and to replace it with fresh electrolyte, said means for flushing comprising a first conduit for receiving spent electrolyte from said cell, an optical emitter and an optical detector on opposite sides of one of said first and second conduits, and curved transparent walls in said one of said conduits between said emitter and said detector, whereby radiation from said emitter is more fully focussed on said detector while electrolyte liquid is in said conduit.
Claim 44
Dependent Claim
44 words
In a method according to claim 30, the step of applying a potential of between about zero and 1 volt to one of said active testing electrodes, and a potential of between about zero and 300 millivolts to another of said active testing electrodes.
Claim 45
Dependent Claim
38 words
In a method according to claim 30, wherein said sample is suspected of containing a metal selected from the group consisting of molybdenum, tungsten, titanium, vanadium, and uranium, the improvement wherein said reagent comprises an alcoholic HCl solution.
Claim 46
Dependent Claim
25 words
In a method according to claim 30, wherein said sample is suspected of containing chromium, the improvement wherein said reagent comprises an alcoholic hydroxide solution.
Claim 47
Dependent Claim
50 words
In a method according to claim 30, wherein said sample is selected from the group consisting of blood and serum and contains both iron and copper, the improvement wherein said reagent comprises a substantially iron-free misture of a lower aliphatic alcohol, and HCl between about 51/2 Formal and 81/2 Formal.
Claim 48
Dependent Claim
110 words
In a method according to claim 38, including the steps of introducing a predetermined quantity of said sample into said mixture to form said test solution, and adding a measured quantity of said test solution to an electrolytic cell; applying to a first active testing electrode in said cell a potential to measure the quantity of copper and iron in said cell; applying to a second active testing electrode in said cell a potential to measure a different quantity selected from copper and iron; obtaining signals corresponding to current flow at each of said first and second active testing electrodes; and comparing said signals to measure the quantity of iron.
Claim 49
Dependent Claim
63 words
In a method according to claim 39, wherein a potential of between about 0.4 and about 0.5 volts is applied to said first active testing electrode, a potential of between about 0.2 and 0.3 volts is applied to said second active testing electrode, and the signal from said second active testing electrode is subtracted from the signal from said first active testing electrode.
Claim 50
Dependent Claim
35 words
In a method according to claim 40, wherein said potential applied to said first active testing electrode is about 460 millivolts and the potential applied to said second active testing electrode is about 250 millivolts.
Claim 51
Dependent Claim
12 words
In a method according to claim 38, wherein said alcohol comprises isopropanol.
Claim 52
Dependent Claim
15 words
In a method according to claim 38, wherein said HCl concentration is about 7 Formal.
Claim 53
Dependent Claim
14 words
A composition according to claim 4, and including a minute quantity of silver iron.
References Cited (Backward Citations)
US3298934A
Cited
US3556950A
Cited
GB1372245A
Cited
GB1460892A
Cited
US3918910A
Cited
GB1465417A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1983-11-11 | 1984-05-12 | 1984-11-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-11-11 | 1988-05-12 | 1988-11-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-11-11 | 1992-05-12 | 1992-11-11 | $7700.00 | Window Closed / Lapsed |