Microelectrodes and amperometric assays

• US 5,635,054 A
• Filed: 03/06/1995
• Issued: 06/03/1997
• Est. Priority Date: 12/04/1989
• Status: Expired due to Term

• Current Assignee: Arrowhead Center, Inc.
• Original Assignee: Ecossensors Limited
• Inventors: Girault, Hubert H. J., Seddon, Brian J.
• Primary Examiner(s): Bell, Bruce F.
• Application Number:
  US08/399,176
• Time in Patent Office: 820 Days
• Field of Search: 436/73, 436/74, 436/75, 204/412, 204/413, 204/434, 204/153.1, 205/775, 205/781.5, 205/790
• US Class Current: 205/775
• CPC Class Codes: G01N 27/403 Cells and electrode assemblies
• CPC Class Codes: G01N 27/42 Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte
• CPC Class Codes: G01N 33/1813 Specific cations in water, e.g. heavy metals

Abstract

A photo-ablation technique is used to create apertures (4) in a layer (2) of electrically insulating material and allow electrically conducting material (3) exposed through the apertures to create a microelectrode. The microelectrode can be used for assay methods and in an assay unit.

Claims

1. A method of analyzing trace metals comprising the steps of:

(a) providing a plurality of thick-film printed electrodes on a substrate;

(b) electrolytically depositing a metal film upon at least one of the plurality of thick-film printed electrodes; and

(c) analyzing a sample for heavy metal content by using electrochemical stripping analysis with the plurality of electrodes.

2. A method as defined in claim 1, wherein step (a) further comprises providing a reference electrode.

3. A method as defined in claim 2, wherein said reference electrode is an Ag/AgCl electrode.

4. A method as defined in claim 1, wherein said plurality of electrodes includes at least one thick-film printed carbon electrode.

5. A method as defined in claim 1, wherein said analyzing is voltammetry.

6. A method as defined in claim 5, wherein said voltammetry is anodic stripping voltammetry.

7. A method as defined in claim 1, further comprising preconcentrating a heavy metal on an electrode.

8. A method as defined in claim 1, wherein said sample comprises water.

9. A method as defined in claim 1, wherein said electrolytically deposited metal comprises mercury.

10. A method as defined in claim 1, wherein said thick-film printed electrodes are directly printed on said substrate.

11. An apparatus for heavy metal trace testing comprising:

a plurality of thick-film printed electrodes on a substrate;

a metal film electrodepositor which electrodeposits a metal film on at least one of said electrodes; and

an electrochemical stripping analyzer which analyzes a sample for heavy metal content with said electrodes.

12. An apparatus as defined in claim 11, further comprising at least one reference electrode.

13. An apparatus as defined in claim 12, wherein said reference electrode is an Ag/AgCl electrode.

14. An apparatus as defined in claim 11, wherein said plurality of electrodes includes at least one thick-film printed carbon electrode.

15. An apparatus as defined in claim 11, wherein said analyzer is a voltammetry analyzer.

16. An apparatus as defined in claim 15, wherein said analyzer is an anionic stripping voltammetry analyzer.

17. An apparatus as defined in claim 11, wherein said metal film electrodepositor is adapted to preconcentrate a heavy metal on said electrode.

18. An apparatus as defined in claim 11, wherein said sample comprises water.

19. An apparatus as defined in claim 11, wherein said metal film comprises mercury.

20. An apparatus as defined in claim 11, wherein said thick-film electrodes are printed on said substrate.

21. A method of analyzing trace metals comprising the steps of:

(a) providing a plurality of electrodes upon a plastic substrate;

(b) electrolytically depositing a metal film upon at least one of the plurality of electrodes; and

(c) analyzing a sample for heavy metal content by using electrochemical stripping analysis with the plurality of electrodes.

22. A method as defined in claim 21, wherein step (a) further comprises providing a reference electrode.

23. A method as defined in claim 22, wherein said reference electrode is an Ag/AgCl electrode.

24. A method as defined in claim 21, wherein said plurality of electrodes includes at least one carbon electrode.

25. A method as defined in claim 21, wherein said analyzing is performed by voltammetry.

26. A method as defined in claim 25, wherein said voltammetry is anodic stripping voltammetry.

27. A method as defined in claim 21, further comprising preconcentrating a heavy metal on an electrode.

28. A method as defined in claim 21, wherein said sample comprises water.

29. A method as defined in claim 21, wherein said electrolytically deposited metal comprises mercury.

30. An apparatus for heavy metal testing comprising:

a plurality of electrodes upon a plastic substrate;

a metal film electrodepositor which deposits a metal film on said electrodes; and

an electrochemical stripping analyzer which analyzes a sample for heavy metal content with said electrodes.

31. An apparatus as defined in claim 30, further comprising at least one reference electrode.

32. An apparatus as defined in claim 31, wherein said reference electrode is an Ag/AgCl electrode.

33. An apparatus as defined in claim 30, wherein said plurality of electrodes includes at least one carbon electrode.

34. An apparatus as defined in claim 30, wherein said analyzer is a voltammetry analyzer.

35. An apparatus as defined in claim 34, wherein said analyzer is an anionic stripping voltammetry analyzer.

36. An apparatus as defined in claim 30, wherein said metal film electrodepositor is adapted to preconcentrate a heavy metal on said electrode.

37. An apparatus as defined in claim 30, wherein said sample comprises water.

38. An apparatus as defined in claim 30, wherein said metal film comprises mercury.

39. A method of analyzing trace metals comprising the steps of:

(a) providing a plurality of thick-film printed electrodes on a plastic substrate;

(b) electrolytically depositing a metal film upon at least one of the plurality of thick-film printed electrodes; and

(c) analyzing a sample for heavy metal content by using electrochemical stripping analysis with the plurality of electrodes.

40. A method as defined in claim 39, wherein step (a) further comprises providing a reference electrode.

41. A method as defined in claim 40, wherein said reference electrode is an Ag/AgCl electrode.

42. A method as defined in claim 39, wherein said plurality of electrodes includes at least one thick-film printed carbon electrode.

43. A method as defined in claim 39, wherein said analyzing is voltammetry.

44. A method as defined in claim 43, wherein said voltammetry is anodic stripping voltammetry.

45. A method as defined in claim 39, further comprising preconcentrating a heavy metal on an electrode.

46. A method as defined in claim 39, wherein said sample comprises water.

47. A method as defined in claim 39, wherein said electrolytically deposited metal comprises mercury.

48. A method as defined in claim 39, wherein said thick-film electrodes are directly printed on said substrate.

49. An apparatus for heavy metal testing comprising:

a plurality of thick-film printed electrodes on a plastic substrate;

a metal film electrodepositor which electrodeposits a metal film on at least one of said thick-film electrodes; and

an electrochemical stripping analyzer which analyzes a sample for heavy metal content with said electrodes.

50. An apparatus as defined in claim 49, further comprising at least one reference electrode.

51. An apparatus as defined in claim 50, wherein said reference electrode is an Ag/AgCl electrode.

52. An apparatus as defined in claim 49, wherein said plurality of electrodes includes at least one thick-film printed carbon electrode.

53. An apparatus as defined in claim 49, wherein said analyzer is a voltammetry analyzer.

54. An apparatus as defined in claim 53, wherein said analyzer is an anionic stripping voltammetry analyzer.

55. An apparatus as defined in claim 49, wherein said metal film electrodepositor is adapted to preconcentrate a heavy metal on said electrode.

56. An apparatus as defined in claim 49, wherein said sample comprises water.

57. An apparatus as defined in claim 49, wherein said metal film comprises mercury.

58. An apparatus as defined in claim 49, wherein said thick-film electrodes are directly printed on said substrate.

59. A method of analyzing trace metals comprising the steps of:

(a) providing a plurality of electrodes screen-printed on a substrate;

(c) electrolytically depositing a metal film upon at least one of the plurality of screen-printed electrodes; and

(c) analyzing a sample for heavy metal content by using electrochemical stripping analysis with the plurality of electrodes.

60. The method of claim 59 wherein the step of providing a plurality of screen-printed electrodes further comprises the step of providing at least one reference electrode.

61. The method of claim 60 wherein the step of providing at least one reference electrode further comprises the step of providing a screen-printed Ag/AgCl electrode.

62. The method of claim 59 wherein the step of providing a plurality of screen-printed electrodes further comprises the step of providing at least one screen-printed carbon electrode.

63. The method of claim 59 wherein the step of analyzing a sample for heavy metal content comprises the step of performing anodic stripping voltammetry on the sample.

64. The method of claim 59 further comprising the step of preconcentrating the heavy metal upon an electrode.

65. The method of claim 64 wherein the step of preconcentrating the heavy metal comprises the step of causing adsorptive accumulation of at least one heavy metal upon said metal film.

66. The method of claim 59 wherein the step of electrolytically depositing a metal film comprises the step of electrolytically depositing mercury.

67. The method of claim 59 wherein the step of electrolytically depositing a metal film comprises the step of electrolytically depositing a member selected from the group consisting of platinum, silver, and gold.

68. The method of claim 59 wherein the step of analyzing a sample for heavy metal content further comprises the step of analyzing a sample of liquid food.

69. The method of claim 59 wherein the step of providing a plurality of electrodes further comprises providing a plastic substrate.

70. Apparatus for heavy metal trace testing comprising:

means for providing a plurality of electrodes screen-printed on a substrate;

means for electrolytically depositing a metal film upon at least one of said plurality of screen-printed electrodes; and

means for analyzing a sample for heavy metal content by electrochemical stripping analysis with said plurality of electrodes.

71. The apparatus of claim 70 wherein said means for providing a plurality of screen-printed electrodes further comprises means for providing at least one reference electrode.

72. The apparatus of claim 71 wherein said means for providing at least one reference electrode further comprises means for providing a screen-printed Ag/AgCl electrode.

73. The apparatus of claim 70 wherein said means for providing a plurality of screen-printed electrodes further comprises means for providing at least one screen-printed carbon electrode.

74. The apparatus of claim 70 wherein said means for analyzing a sample for heavy metal content comprises means for performing anodic stripping voltammetry on the sample.

75. The apparatus of claim 70 further comprising means for preconcentrating said heavy metal upon an electrode.

76. The apparatus of claim 75 wherein said means for preconcentrating said heavy metal comprises means for causing adsorptive accumulation of at least one heavy metal upon said metal film.

77. The apparatus of claim 70 wherein said metal film comprises mercury.

78. The apparatus of claim 70 wherein said metal film comprises a member selected from the group consisting of platinum, silver, and gold.

79. The apparatus of claim 70 wherein said means for analyzing a sample for heavy metal content further comprises means for analyzing a sample of liquid food.

80. The apparatus of claim 70 wherein said substrate comprises plastic.

81. A method of analyzing trace metals comprising the steps of:

(a) providing a plurality of printed electrodes on a substrate;

(b) electrolytically depositing a metal film upon at least one of the plurality of printed electrodes; and

(c) analyzing a sample for heavy metal content by using electrochemical stripping analysis with the plurality of electrodes.

82. A method as defined in claim 81, wherein step (a) further comprises providing a reference electrode.

83. A method as defined in claim 82, wherein said reference electrode comprises an Ag/AgCl electrode.

84. A method as defined in claim 81, wherein said plurality of electrodes includes at least one printed carbon electrode.

85. A method as defined in claim 81, wherein said analyzing comprises voltammetry.

86. A method as defined in claim 85, wherein said voltammetry comprises anodic stripping voltammetry.

87. A method as defined in claim 81, further comprising preconcentrating a heavy metal on an electrode.

88. A method as defined in claim 81, wherein said sample comprises water.

89. A method as defined in claim 81, wherein said electrolytically deposited metal comprises mercury.

90. A method as defined in claim 81, wherein said printed electrodes are printed on said substrate.

91. An apparatus for heavy metal trace testing comprising:

a plurality of printed electrodes on a substrate;

a metal film electrodepositor adapted to electrodeposit a metal film on at least one of said electrodes; and

an electrochemical stripping analyzer adapted to analyze a sample for heavy metal content with said electrodes.

92. An apparatus as defined in claim 91, further comprising at least one reference electrode.

93. An apparatus as defined in claim 92, wherein said reference electrode comprises an Ag/AgCl electrode.

94. An apparatus as defined in claim 91, wherein said plurality of electrodes includes at least one printed carbon electrode.

95. An apparatus as defined in claim 91, wherein said analyzer comprises a voltammetry analyzer.

96. An apparatus as defined in claim 95, wherein said analyzer comprises an anionic stripping voltammetry analyzer.

97. An apparatus as defined in claim 91, wherein said metal film electrodepositor is adapted to preconcentrate a heavy metal on said electrode.

98. An apparatus as defined in claim 91, wherein said sample comprises water.

99. An apparatus as defined in claim 91, wherein said metal film comprises mercury.

100. An apparatus as defined in claim 91, wherein said electrodes are printed on said substrate.

101. A method of analyzing trace metals comprising the steps of:

(a) providing a plurality of printed electrodes on a plastic substrate;

(b) electrolytically depositing a metal film upon at least one of the plurality of printed electrodes; and

(c) analyzing a sample for heavy metal content by using electrochemical stripping analysis with the plurality of electrodes.

102. A method as defined in claim 101, wherein step (a) further comprises providing a reference electrode.

103. A method as defined in claim 102, wherein said reference electrode comprises an Ag/AgCl electrode.

104. A method as defined in claim 101, wherein said plurality of electrodes includes at least one printed carbon electrode.

105. A method as defined in claim 101, wherein said analyzing comprises voltammetry.

106. A method as defined in claim 105, wherein said voltammetry comprises anodic stripping voltammetry.

107. A method as defined in claim 101, further comprising preconcentrating a heavy metal on an electrode.

108. A method as defined in claim 101, wherein said sample comprises water.

109. A method as defined in claim 101, wherein said electrolytically deposited metal comprises mercury.

110. A method as defined in claim 101, wherein said electrodes are printed on said substrate.

111. An apparatus for heavy metal testing comprising:

a plurality of printed electrodes on a plastic substrate;

a metal film electrodepositor adapted to electrodeposit a metal film on at least one of said electrodes; and

an electrochemical stripping analyzer adapted to analyze a sample for heavy metal content with said electrodes.

112. An apparatus as defined in claim 111, further comprising at least one reference electrode.

113. An apparatus as defined in claim 112, wherein said reference electrode comprises an Ag/AgCl electrode.

114. An apparatus as defined in claim 111, wherein said plurality of electrodes includes at least one printed carbon electrode.

115. An apparatus as defined in claim 111, wherein said analyzer comprises a voltammetry analyzer.

116. An apparatus as defined in claim 115, wherein said analyzer comprises an anionic stripping voltammetry analyzer.

117. An apparatus as defined in claim 111, wherein said metal film electrodepositor is adapted to preconcentrate a heavy metal on said electrode.

118. An apparatus as defined in claim 111, wherein said sample comprises water.

119. An apparatus as defined in claim 111, wherein said metal film comprises mercury.

120. An apparatus as defined in claim 111, wherein said electrodes are printed on said substrate.

121. A method of analyzing trace metals comprising the steps of:

a) providing a plurality of flat printed electrodes;

b) coating at least one of the plurality of flat printed electrodes with a metal film; and

c) analyzing a sample for heavy metal content with the plurality of electrodes;

wherein said step of providing a plurality of flat printed electrodes further comprises the step of providing at least one flat screen-printed Ag/AgCl reference electrode, and at least one flat screen-printed carbon electrode.

122. The method of claim 121 wherein the step of analyzing a sample for heavy metal content further comprises the step of voltammetrically analyzing the sample.

123. The method of claim 121 wherein the coating step comprises coating with mercury.

124. The method of claim 123 wherein the coating step is performed electrolytically.

125. An apparatus for heavy metal trace testing comprising:

means for providing a plurality of flat printed electrodes;

means for coating at least one of said plurality of flat printed electrodes with a metal film; and

means for analyzing a sample for heavy metal content with said plurality of electrodes;

wherein said means for providing at least one of said plurality of flat printed electrodes comprises means for providing at least one flat screen-printed Ag/AgCl reference electrode, and at least one flat screen-printed carbon electrode.

126. The apparatus of claim 125 wherein said means for analyzing a sample for heavy metal content further comprises means for voltammetrically analyzing said sample.

127. The apparatus of claim 125 wherein said means for coating comprises means for coating with mercury.

128. The apparatus of claim 127 wherein said means for coating comprises means for coating electrolytically.