Electrochemical detection system and method of analysis

• US 4,404,065 A
• Filed: 01/14/1980
• Issued: 09/13/1983
• Est. Priority Date: 01/14/1980
• Status: Expired due to Term

• Current Assignee: Esa S.R.O. (Logisteed Limited)
• Original Assignee: Environmental Sciences Associates Incorporated
• Inventors: Matson, Wayne R.
• Primary Examiner(s): Kaplan, G. L.
• Application Number:
  US06/111,917
• Time in Patent Office: 1,338 Days
• Field of Search: 204/195 R, 204/1 T, 204/195 B, 204/411, 73/61.1 C, 23/230 R, 422/70, 436/161
• US Class Current: 205/780.5
• CPC Class Codes: B01D 15/36 involving ionic interaction
• CPC Class Codes: G01N 27/403 Cells and electrode assemblies
• CPC Class Codes: G01N 30/02 Column chromatography
• CPC Class Codes: G01N 30/34 of fluid composition, e.g. gradient G01N30/36 takes precedence
• CPC Class Codes: G01N 30/64 Electrical detectors
• CPC Class Codes: G01N 33/6803 General methods of protein analysis not limited to specific proteins or families of proteins

Abstract

An electrochemical detection apparatus is provided. The apparatus comprises a flow-cell having at least one active testing electrode, at least one reference electrode, and at least one counter electrode. Each electrode comprises a liquid impervious solid body having a bore extending therethrough with the electrode active surface located in the bore. The electrodes are arranged in a stack, electrically insulated from one another with their respective bores aligned so as to define a flow channel through which liquid to be detected can be passed. In a preferred embodiment of the invention at least one of the reference electrodes is actively driven to supply a stable reference potential against which other electrochemical responses can be measured. Various electrochemical responses are achieved by varying the construction, number and arrangement of electrodes in the stack, and the potentials applied to the electrodes. The detection apparatus has particular utility for use in monitoring chromatographic eluant.

Claims

1. A flow cell for electrochemical testing a sample in solution, said cell comprising:

a holder assembly having an inlet for directing a stream of said sample to be tested into said cell, and an outlet for directing tested sample from said cell;

a plurality of electrode elements arranged in a stack in said holder assembly and including at least one active testing electrode, at least one reference electrode, and at least one counter electrode, at least one of said active testing electrodes comprising a solid phase electrode in the form of a solid disk of electrically conductive material having at least one bore extending therethrough and having an active electrode surface located in said at least one bore, said plurality of electrodes being arranged in said stack so that said electrodes are electrically insulated from one another with their respective bores aligned so as to define at least one flow channel connecting said inlet and said outlet; and

,

a flow restrictor formed of electrically conductive material located in the bore of at least one of said disks and electrically connected to said disk.

2. A flow cell according to claim 1, wherein at least two of said plurality of electrodes comprise solid phase electrodes in the form of substantially flat generally round disks, and said bores are formed through the approximate centers of each of said disks.

3. A flow cell according to claim 1, comprising at least three electrode elements, at least one of said elecrode elements being an active testing electrode, and including means for connecting said active testing electrodes to controlled testing potentials;

at least one other of said electrode elements being a reference electrode, and including means connecting said reference electrodes to a reference potential; and

at least yet one other of said electrode elements being a counter electrode, and including means connecting said counter electrodes to yet another potential.

4. A flow cell according to claim 3, wherein at least one of said active testing electrodes comprises a disk of electrically conductive material in which the active surface area comprises wall areas of said disks subtending said bore.

5. A flow cell according to claim 4, wherein at least one of said disks comprises a metal disk.

6. A flow cell according to claim 4, wherein at least one of said disks comprises a graphite disk.

7. A flow cell according to claim 6, wherein said wall areas of said at least one graphite disk are coated at least in part with solid phase active electrode material.

8. A flow cell according to claim 7, wherein said solid phase active electrode material is selected from the group consisting of mercury, gold, silver, bismuth, PbO₂ and MnO₂.

9. A flow cell according to claim 3, and including a plurality of solid phase active testing electrode elements, and means connecting at least some of said plurality to different testing potentials.

10. A flow cell according to claim 3, wherein said reference electrode element comprises a salt-bridge medium located in said bore.

11. A flow cell according to claim 3, wherein said reference electrode element comprises an inert metal terminal.

12. A flow cell according to claim 3, wherein said reference electrode element comprises a metal or metal oxide terminal selected from the group consisting of palladium, palladium oxide and platinum.

13. A flow cell according to claim 12, wherein said reference electrode element comprises a disk of electrically insulating material in which surface areas on said disk subtending said bore are coated at least in part with said metal or metal oxide.

14. A flow cell according to claim 3, wherein said reference electrode element comprises at least one wire terminal formed of a metal oxide, and extending into said bore.

15. A flow cell according to claim 3, wherein at least one of said electrodes selected from the group consisting of said active testing electrodes and said counter electrodes comprises a disk of electrically insulating material in which the surface areas of said disk subtending said bore are coated at least in part with solid phase active electrode material.

16. A flow cell according to claim 15 wherein said solid phase active electrode material is selected from the group consisting of mercury, gold, silver, bismuth, PbO₂ and MnO₂.

17. A flow cell according to claim 3 wherein said reference electrode comprises an inert metal or metal oxide terminal.

18. A flow cell according to claim 17 wherein said inert metal or metal oxide terminal is selected from the group consisting of palladium, palladium oxide and platinum.

19. A flow cell according to claim 1, wherein said flow restrictor is located in the bore of at least one of said active testing electrodes.

20. A flow cell according to claim 1, wherein said flow restrictor comprises a solid body shaped in the form of a truncated tetrahedron, with a sharp point thereof facing said inlet.

21. A flow cell according to claim 1, including spacers formed of electrically insulating material located between at least some of said electrode elements, said spacers each having at least one bore extending therethrough and aligned with said flow channel.

22. A flow cell according to claim 1, wherein at least some of said electrode elements are coated at least in part with an electrically insulated material, and said bore extends through said coating.

23. In a chromatography apparatus having a chromatographic column through which a sample can be passed whereby species in said sample are separated to produce an eluant fluid stream, an electrochemical detector for analyzing said eluant stream, the improvement wherein said detector comprises a flow cell as defined by claim 1.

24. In a chromatography apparatus having a chromatography column through which a sample can be passed whereby species in said sample are separated to produce an eluant fluid stream, an electrochemical detector for analyzing said eluant stream, the improvement wherein said detector comprises a flow cell as defined by claim 23.

25. In a chromotography apparatus according to claim 23 or claim 24 wherein said fluid comprises a liquid carrier stream.

26. In a chromatography apparatus according to claim 23 or claim 24 wherein said fluid comprises a gas carrier stream.

27. A flow cell for electrochemically testing a sample stream, said cell comprising in combination:

a holder assembly having an inlet for directing said stress to be tested into said cell, and an outlet for directing tested sample from said cell;

at least one reference electrode comprising a flat solid body mounted in said holder assembly, said body having (a) a pair of generally planar surfaces, (b) a bore extending therethrough between said planar surfaces, and (c) an active electrode surface located within said bore;

at least one counter electrode comprising a flat solid body mounted in said holder assembly, said body having (a) a pair of generally planar surfaces, (b) a bore extending therethrough between said planar surfaces and (c) an active electrode surface located within said bore;

at least one active testing electrode comprising a solid phase electrode in the form of a flat solid body mounted in said holder assembly, each of said bodies having (a) a pair of generally planar surfaces (b) a bore extending therethrough between said planar surfaces, (c) solid phase active electrode surface located within said bore; and

, (d) a plug of porous, electrically conductive material located in the bore of at least one of said bodies and electrically connected to said body;

said at least one reference electrode, said at least one counter electrode, and said at least one active testing electrode being mounted in said holder assembly electrically insulated from one another with their respective bores aligned with one another so as to define a flow channel between said inlet and said outlet.

28. An electrochemical testing apparatus for measuring a sample material in solution comprising:

a flow cell having at least one flow path therethrough, an inlet for directing a stream containing said sample material to be tested into said cell, and an outlet for directing tested sample material from said cell;

a plurality of electrodes including at least one solid phase testing electrode located in said at least one flow path, each of said electrodes having at least one bore extending therethrough and forming a boundary or boundaries for said at least one flow path, said electrodes being positioned in serial arrangement along said at least one flow path;

a plug of porous, electrically conductive material located in the bore of at least one of said solid phase testing electrodes and electrically connected to said electrodes; and

,

means connecting at least said at least one solid phase electrode to an active testing potential source;

means connecting at least one other of said electrodes to a reference potential source;

means connecting at least yet another of said electrodes to yet another potential source; and

, means coupled to said means for connecting for producing an electrical signal readout representative of current flow between selected of said electrodes.

29. An electrochemical testing apparatus according to claim 28 wherein said reference electrode comprises an electrically non-conductive solid body with said bore extending therethrough and having a salt-bridge reference located in the bore in said body, and wherein said reference potential source comprises a constant current potential.

30. An electrochemical testing apparatus according to claim 28 wherein said reference electrode comprises an electrically non-conductive solid body with said bore extending therethrough and having an inert metal or metal oxide terminal located in the bore in said body, and wherein said reference potential source comprises a constant current potential source.

31. An electrochemical testing apparatus according to claim 30 wherein said inert metal or metal oxide terminal is selected from the group consisting of palladium, palladium oxide and platinum.

32. An electrochemical testing apparatus according to claim 28 wherein said reference electrode comprises an electrically non-conductive solid body with said at least one bore extending therethrough and having an inert metal or metal oxide terminal located within said at least one bore, and wherein said reference potential source comprises a feed back network and follower amplifier for applying a variable potential which is responsive to changes in said stream.

33. An electrochemical testing apparatus according to claim 32 wherein said inert metal or metal oxide terminal is selected from the group consisting of palladium, palladium oxide and platinum.

34. In a method of electrochemically analyzing a sample material to identify selected substances therein, the steps of:

dissolving said sample material in a carrier therefor to form a test fluid, and passing a stream of said test fluid through an electrolytic flow cell in contact with a detection electrode,

the improvement wherein said flow cell comprises a plurality of electrode elements including at least one solid phase testing electrode arranged in a stack in a holder, each of said electrode elements in said stack comprising a solid body having at least one bore extending therethrough and an active electrode surface located in said at least one bore, said plurality of electrodes being arranged in said stack so that said electrodes are electrically insulated from one another with their respective bores aligned so as to define at least one flow channel for said stream, said flow cell having a plug of electrically conductive material located in the bore of at least one of said solid phase testing electrodes and electrically connected to said electrode, passing said stream through said at least one flow channel in contact with said active electrode surfaces, applying electrical potentials across said stream between selected of said electrodes in said stack, deriving electrical signals resulting on selected of said electrodes in said stack, and sorting said signals to obtain signals which identify said selected substances.

35. In a method according to claim 34, including the step of deriving an electrical signal corresponding to charge transfer reactions of materials in said stream.

36. In a method according to claim 34, including the step of deriving an electrical signal corresponding to the electrical double layer of said stream.

37. In a method according to any one of claims 34, 35, or 36, wherein said carrier comprises a gas.

38. In a method according to any one of claims 34, 35 or 36, wherein said carrier comprises a liquid.

39. In a method according to claim 34 and including the steps of applying to at least one of said electrodes a controlled testing potential;

applying to at least one other of said electrodes a reference potential; and

applying to at least yet one other of said electrodes yet another potential.

40. In a method according to claim 39, and including the steps of sensing changes in said stream and varying said reference potential responsive to said changes in said stream.

41. In a method according to claim 34, including the step of passing said test fluid through a chromatography column whereby to separate species of said sample material to produce, an eluant fluid stream, and passing said eluant fluid stream through said flow cell.

42. A flow cell for electrochemically testing a sample in solution, said cell comprising:

a holder having an inlet for directing a stream of said sample to be tested into said cell, an outlet for directing tested sample from said cell, and a flow channel connecting said inlet and said outlet;

a plurality of electrode elements including at least one solid phase testing electrode, at least one reference electrode and at least one counter electrode, arranged in a stack in said holder, at least one of said electrode elements in said stack comprising a solid, porous body having active electrode surfaces located in the pores of said body, at least one other of said electrode elements in said stack comprising a solid body having at least one bore extending therethrough and having a plug of porous, electrically conductive material having active electrode surfaces located in said bores, said bores and said pores being aligned so as to define said flow channel in part.

43. A flow cell according to claim 42, comprising at least three electrode elements, at least one of said solid phase electrode elements being an active testing electrode, and including means for connecting said at least one active testing electrode to a controlled testing potential;

at least one other of said electrode elements being a reference electrode, and including means connecting said at least one reference electrode to a reference potential; and

at least yet one other of said electrode elements being a counter electrode, and including means connecting said at least one counter electrode to yet another potential.

44. A flow cell according to claim 43, and including a plurality of active testing electrode elements, and means connecting at least some of said plurality to different testing potentials.

45. A flow cell according to claim 44, wherein said reference electrode element comprises a metal or metal oxide terminal selected from the group consisting of palladium, palladium oxide and platinum.

46. A flow cell according to claim 45, wherein said reference electrode element comprises at least one wire terminal formed for said metal or metal oxide, and extending into said channel, and at least one other of said electrode elements in said stack comprises a solid body having at least one bore extending therethrough and having a plug of porous, electrically conductive material located in said bore and electrically connected to said body.

47. A flow cell according to claim 43, wherein said reference electrode element comprises an inert metal or metal oxide terminal.

48. A flow cell according to claim 42, wherein said plug is located in the bore of at least one of said active testing electrodes.

49. A flow cell according to claim 42, wherein said material comprises graphite.

50. A flow cell according to claim 42, and including solid phase active electrode material deposited in at least some of the pores of said plug.

51. A flow cell according to claim 50, wherein said solid phase active electrode material is selected from the group consisting of mercury, gold, silver, bismuth, PbO₂ and MnO₂.

52. A flow cell according to claim 42, including spacers formed of electrically insulating material located between at least some of said electrode elements, said spacers each having at least one bore extending therethrough and aligned with said channel.

53. A flow cell according to claim 42, wherein said holder comprises a solid body of polytetrafluoroethylene.

54. In a chromatography apparatus having a chromatographic column through which a sample can be passed whereby species in said sample are separated to produce an eluant fluid stream, and an electrochemical detector for analyzing said eluant stream, the improvement wherein said detector comprises a flow cell as defined by claim 42.

55. In a chromatography apparatus according to claim 54 wherein said fluid comprises a liquid carrier stream.

56. In a chromatography apparatus according to claim 54 wherein said fluid comprises a gas carrier stream.

58. In a method according to claim 53, including the step of deriving an electrical signal corresponding to charge transfer reactions of materials in said stream.

57. In a method of electrochemically analyzing a sample material to identify selected substances therein, the steps of:

dissolving said sample material in a carrier therefor to form a test fluid and passing a stream of said test fluid through an electrolytic flow cell in contact with said detection electrode,

the improvement wherein said flow cell comprises a plurality of electrode elements including at least one solid phase testing electrode arranged in a stack in a holder, at least one of said electrode elements in said stack comprising a solid, porous having active electrode surfaces located in the pores of said, at least one other of said electrode elements in said stack comprising a solid body having at least one bore extending therethrough and having a plug of porous, electrically conductive material having an active electrode surface located in said at least one bore, said plurality of electrodes being arranged in said stack and electrically insulated from one another in said holder with said at least one bore and said pores being aligned so as to define at least one flow channel for said stream, applying electrical potentials across said stream between selected of said electrodes in said stack, deriving electrical signals resulting on selected of said electrodes in said stack, and sorting said signals to obtain signals which identify said selected substances.

59. In a method according to claim 57, including the step of deriving an electrical signal corresponding to the electrical double layer of said stream.

60. In a method according to any one of claims 57, 58, or 59, wherein said carrier comprises a gas.

61. In a method according to any one of claims 57, 58 or 59, wherein said carrier comprises a liquid.

62. In a method according to claim 57, and including the steps of applying to said at least one solid phase testing electrode a controlled testing potential;

applying to at least one other of said electrodes a reference potential; and

applying to at least yet one other of said electrodes yet another potential.

63. In a method according to claim 62, and including the steps of sensing changes in said stream and varying said reference potential responsive to said changes in said stream.

64. In a method according to claim 57, including the step of passing said test fluid through a chromatography column whereby to separate species of said sample material to produce an eluant fluid stream, and passing said eluant fluid stream through said flow cell.

65. An electrochemical apparatus for testing a sample material in solution, said apparatus comprising, in combination:

an electrolytic cell for holding said sample to be tested, said electroyltic cell having a plurality of electrically discrete electrodes located therein, at least one of said plurality comprising a solid phase active testing electrode, at least one other of said plurality comprising a counter electrode, and at least one other of said electrodes comprising a reference electrode, wherein at least one of said electrodes selected from the group consisting of said active testing electrode and said counter electrode comprises a plug of porous, electrically conductive material, and said reference electrode comprises an inert metal or metal oxide terminal, and including means connecting said solid phase active testing electrode to an active testing potential source;

means connecting said at least one counter electrode to yet another potential source, and means connecting said at least one reference electrode to a feed back network and follower amplifier for applying a variable potential which is responsive to electrochemical changes in said sample.

66. An electrochemical apparatus according to claim 65 wherein said reference electrode comprises an inert metal or metal oxide terminal selected from the group consisting of palladium, palladium oxide and platinum.

67. An electrochemical flow cell for testing a sample material in solution, said apparatus comprising, in combination:

a holder assembly having an inlet for directing a stream of said sample to be tested into said cell, and an outlet for directing tested sample from said cell;

a plurality of electrically discrete electrodes located in a stack in said holder assembly, said plurality including at least one solid phase active testing electrode, at least one counter electrode, and at least one reference electrode, at least one of said solid phase active testing electrodes in said stack comprising a solid body having at least one bore extending therethrough and defining in part a flow channel connecting said inlet and said outlet, a plug of porous, electrically conductive material located in said flow channel in said at least one bore, and including means connecting said at least one solid phase active testing electrode to an active testing potential source, means connecting said at least one counter electrode to yet another potential source, and means connecting said at least one reference electrode to a feed back network and follower amplifier for applying a variable potential which is responsive to electrochemical changes in said sample.

68. An electrochemical flow cell according to claim 67 wherein said reference electrode comprises an inert metal or metal oxide terminal selected from the group consisting of palladium, palladium oxide and platinum.