Biosensors comprising semiconducting electrodes or ruthenium containing mediators and method of using the same

• US 20060113187A1
• Filed: 10/05/2005
• Published: 06/01/2006
• Est. Priority Date: 11/22/2004
• Status: Abandoned Application

• Current Assignee: Nipro Diagnostics, Inc.
• Original Assignee: Nipro Diagnostics, Inc.
• Inventors: Popovich, Natasha D., Bell, Douglas, Slomski, Dennis, Deng, David Z., Hunter, Thomas J.
• Application Number:
  US11/242,925
• Publication Number:
  US 20060113187A1
• Time in Patent Office: Days
• US Class Current: 204/403.10
• CPC Class Codes: C12Q 1/005 involving specific analytes or enzymes including groups of enzymes, e.g. oxydases; C12Q1/004 takes precedence

Abstract

Disclosed herein are biosensors for measuring analyte concentration in a bodily fluid comprising at least one electrode comprising semiconducting, conducting, or thin film carbon material, and an electron mediator comprising a ruthenium containing electron mediator, or a ferricyanide material or ferrocene carboxylic acid. Methods of measuring analyte concentration in a bodily fluid using such biosensors are also disclosed.

Claims

1. A biosensor for measuring analyte in a fluid, said biosensor comprising:

at least one semiconducting electrode; and

a reaction reagent system comprising a ruthenium containing electron mediator and an oxidation-reduction enzyme specific for said analyte.

2. The biosensor of claim 1, wherein said ruthenium containing material comprises ruthenium hexaamine (III) trichloride.

3. The biosensor of claim 1, wherein the at least one semiconducting electrode comprises a material chosen from tin oxide, indium oxide, titanium dioxide, manganese oxide, iron oxide, and zinc oxide.

4. The biosensor of claim 3, wherein the at least one semiconducting electrode comprises zinc oxide doped with indium, tin oxide doped with indium, indium oxide doped with zinc, or indium oxide doped with tin.

5. The biosensor of claim 1, wherein the at least one semiconducting electrode comprises an allotrope of carbon doped with boron, nitrogen, or phosphorous.

6. The biosensor of claim 1, wherein the analyte is chosen from glucose, cholesterol, lactate, acetoacetic acid (ketone bodies), theophylline, and hemoglobin A1c.

7. The biosensor of claim 6, wherein the analyte comprises glucose and the at least one oxidation-reduction enzyme specific for the analyte is chosen from glucose oxidase, PQQ-dependent glucose dehydrogenase and NAD-dependent glucose dehydrogenase.

8. The biosensor of claim 1, wherein the fluid comprises blood and the

reaction reagent system comprises a red blood cell binding agent for capturing red blood cells from the fluid, said red blood cell binding agent comprising lectins.

9. The biosensor of claim 1, wherein the reaction reagent system further comprises at least one buffer material comprising potassium phosphate.

10. The biosensor of claim 1, wherein the reaction reagent system further comprises at least one surfactant chosen from non-ionic, anionic, and zwitterionic surfactants.

11. The biosensor of claim 1, wherein the reaction reagent system further comprises at least one polymeric binder chosen from hydroxypropyl-methyl cellulose, sodium alginate, microcrystalline cellulose, polyethylene oxide, hydroxyethylcellulose, polypyrrolidone, PEG, and polyvinyl alcohol.

12. The biosensor of claim 1, wherein the reaction reagent system comprises 0.01 to 0.3% of a non-ionic surfactant and 0.1 to 3%, of a polymeric binder material.

13. The biosensor of claim 12, wherein the reaction reagent system comprises 0.05 to 0.25% of an alkyl phenoxy polyethoxy ethanol and 0.5 to 2.0% of polyvinyl alcohol.

14. A biosensor for measuring analyte in a fluid, said biosensor comprising:

at least one conducting electrode; and

a reaction reagent system comprising a ruthenium containing electron mediator and an oxidation-reduction enzyme specific for said analyte.

15. The biosensor of claim 14, wherein said ruthenium containing material comprises ruthenium hexaamine (III) trichloride.

16. The biosensor of claim 14, wherein the at least one conducting electrode comprises a metal chosen from or derived from gold, platinum, rhodium, palladium, silver, iridium, carbon, steel, metallorganics, and mixtures thereof.

17. The biosensor of claim 16, wherein the at least one carbon electrode further comprising Cr.

18. The biosensor of claim 14, wherein the analyte is chosen from glucose, cholesterol, lactate, acetoacetic acid (ketone bodies), theophylline, and hemoglobin A1c.

19. The biosensor of claim 18, wherein the analyte comprises glucose and the at least one oxidation-reduction enzyme specific for the analyte is chosen from glucose oxidase, PQQ-dependent glucose dehydrogenase and NAD-dependent glucose dehydrogenase.

20. The biosensor of claim 14, wherein the fluid comprises blood and the reaction reagent system comprises a red blood cell binding agent for capturing red blood cells from the fluid, said red blood cell binding agent comprising lectins.

21. The biosensor of claim 14, wherein the reaction reagent system further comprises at least one buffer material comprising potassium phosphate.

22. The biosensor of claim 14, wherein the reaction reagent system further comprises at least one surfactant chosen from non-ionic, anionic, and zwitterionic surfactants.

23. The biosensor of claim 14, wherein the reaction reagent system further comprises at least one polymeric binder chosen hydroxypropyl-methyl cellulose, sodium alginate, microcystalline cellulose, polyethylene oxide, hydroxyethylcellulose, polypyrrolidone, PEG, and polyvinyl alcohol.

24. The biosensor of claim 14, wherein the reaction reagent system comprises 0.01 to 0.3% of a non-ionic surfactant and 0.1 to 3%, of a polymeric binder material.

25. The biosensor of claim 24, wherein the reaction reagent system comprises 0.05 to 0.25% of an alkyl phenoxy polyethoxy ethanol and 0.5 to 2.0% of polyvinyl alcohol.

26. A biosensor for measuring analyte in a fluid, said biosensor comprising:

at least one semiconducting electrode; and

a reaction reagent system comprising an electron mediator and an oxidation-reduction enzyme specific for said analyte.

27. The biosensor of claim 26, wherein the at least one semiconducting electrode comprises a material chosen from tin oxide, indium oxide, titanium dioxide, manganese oxide, iron oxide, and zinc oxide.

28. The biosensor of claim 26, wherein the at least one semiconducting electrode comprises zinc oxide doped with indium, tin oxide doped with indium, indium oxide doped with zinc, or indium oxide doped with tin.

29. The biosensor of claim 26, wherein the at least one semiconducting electrode comprises an allotrope of carbon doped with boron, nitrogen, or phosphorous.

30. The biosensor of claim 26, wherein the analyte is chosen from glucose, cholesterol, lactate, acetoacetic acid (ketone bodies), theophylline, and hemoglobin A1c.

31. The biosensor of claim 30, wherein the analyte comprises glucose and the at least one oxidation-reduction enzyme specific for the analyte is chosen from glucose oxidase, PQQ-dependent glucose dehydrogenase and NAD-dependent glucose dehydrogenase.

32. The biosensor of claim 26, wherein the fluid comprises blood and the reaction reagent system comprises a red blood cell binding agent for capturing red blood cells from the fluid, said red blood cell binding agent comprising lectins.

33. The biosensor of claim 26, wherein the reaction reagent system further comprises at least one buffer material comprising potassium phosphate.

34. The biosensor of claim 26, wherein the reaction reagent system further comprises at least one surfactant chosen from non-ionic, anionic, and zwitterionic surfactants.

35. The biosensor of claim 26, wherein the reaction reagent system further comprises at least one polymeric binder chosen from hydroxypropyl-methyl cellulose, sodium alginate, microcrystalline cellulose, polyethylene oxide, hydroxyethylcellulose, polypyrrolidone, PEG, and polyvinyl alcohol.

36. The biosensor of claim 26, wherein the reaction reagent system comprises 0.01 to 0.3% of a non-ionic surfactant and 0.1 to 3%, of a polymeric binder material.

37. The biosensor of claim 36, wherein the reaction reagent system comprises 0.05 to 0.25% of an alkyl phenoxy polyethoxy ethanol and 0.5 to 2.0% of polyvinyl alcohol.

38. The biosensor of claim 26, wherein the electron mediator comprises a ferricyanide material, ferrocene carboxylic acid or a ruthenium containing material.

39. The biosensor of claim 38, wherein the ferricyanide material comprises potassium ferricyanide and the ruthenium containing material comprises ruthenium hexaamine (III) trichloride.

40. A biosensor for measuring analyte in a fluid, said biosensor comprising:

at least one thin film carbon electrode; and

a reaction reagent system comprising an electron mediator and an oxidation-reduction enzyme specific for said analyte.

41. The biosensor of claim 40, wherein the electron mediator comprises a ferricyanide material, ferrocene carboxylic acid, or a ruthenium containing material.

42. The biosensor of claim 41, wherein the ferricyanide material comprises potassium ferricyanide and the ruthenium containing material comprises ruthenium hexaamine (III) trichloride.

43. The biosensor of claim 40, wherein the at least one thin film carbon electrode comprises sputtered carbon or screen printed carbon.

44. The biosensor of claim 43, wherein said sputtered carbon further comprises Cr.

45. The biosensor of claim 40, wherein the analyte is chosen from glucose, cholesterol, lactate, acetoacetic acid (ketone bodies), theophylline, and hemoglobin A1c.

46. The biosensor of claim 45, wherein the analyte comprises glucose and the at least one oxidation-reduction enzyme specific for the analyte is chosen from glucose oxidase, PQQ-dependent glucose dehydrogenase and NAD-dependent glucose dehydrogenase.

47. The biosensor of claim 40, wherein the fluid comprises blood and the reaction reagent system comprises a red blood cell binding agent for capturing red blood cells from the fluid, said red blood cell binding agent comprising lectins.

48. The biosensor of claim 40, wherein the reaction reagent system further comprises at least one buffer material comprising potassium phosphate.

49. The biosensor of claim 40, wherein the reaction reagent system further comprises at least one surfactant chosen from non-ionic, anionic, and zwitterionic surfactants.

50. The biosensor of claim 40, wherein the reaction reagent system further comprises at least one polymeric binder chosen from hydroxypropyl-methyl cellulose, sodium alginate, microcystalline cellulose, polyethylene oxide, hydroxyethylcellulose, polypyrrolidone, PEG, and polyvinyl alcohol.

51. The biosensor of claim 40, wherein the reaction reagent system comprises 0.01 to 0.3% of a non-ionic surfactant and 0.1 to 3%, of a polymeric binder material.

52. The biosensor of claim 51, wherein the reaction reagent system comprises 0.05 to 0.25% of an alkyl phenoxy polyethoxy ethanol and 0.5 to 2.0% of polyvinyl alcohol.

53. A method of measuring the concentration of analyte in a fluid, said method comprising:

contacting said fluid with a biosensor comprising;

at least one semiconducting electrode; and

a reaction reagent system comprising a ruthenium containing electron mediator and an oxidation-reduction enzyme specific for said analyte;

detecting an electrical signal from said biosensor; and

measuring the electrical signal to thereby determine the concentration of the analyte in the liquid.

54. The method of claim 53, wherein said ruthenium containing material comprises ruthenium hexaamine (III) trichloride.

55. The method of claim 53, wherein the at least one semiconducting electrode comprises a material chosen from tin oxide, indium oxide, titanium dioxide, manganese oxide, iron oxide, and zinc oxide.

56. The method of claim 55, wherein the at least one semiconducting electrode comprises zinc oxide doped with indium, tin oxide doped with indium, indium oxide doped with zinc, or indium oxide doped with tin.

57. The method of claim 53, wherein the at least one semiconducting electrode comprises an allotrope of carbon doped with boron, nitrogen, or phosphorous.

58. The method of claim 53, wherein the analyte is chosen from glucose, cholesterol, lactate, acetoacetic acid (ketone bodies), theophylline, and hemoglobin A1c.

59. The method of claim 58, wherein the analyte comprises glucose and the at least one oxidation-reduction enzyme specific for the analyte is chosen from glucose oxidase, PQQ-dependent glucose dehydrogenase and NAD-dependent glucose dehydrogenase.

60. The method of claim 53, wherein the fluid comprises blood and the reaction reagent system comprises a red blood cell binding agent for capturing red blood cells from the fluid, said red blood cell binding agent comprising lectins.

61. The method of claim 53, wherein the reaction reagent system further comprises at least one buffer material comprising potassium phosphate.

62. The method of claim 53, wherein the reaction reagent system further comprises at least one surfactant chosen from non-ionic, anionic, and zwitterionic surfactants.

63. The method of claim 53, wherein the reaction reagent system further comprises at least one polymeric binder chosen from hydroxypropyl-methyl cellulose, sodium alginate, microcystalline cellulose, polyethylene oxide, hydroxyethylcellulose, polypyrrolidone, PEG, and polyvinyl alcohol.

64. The method of claim 53, wherein the reaction reagent system comprises 0.01 to 0.3% of a non-ionic surfactant and 0.1 to 3%, of a polymeric binder material.

65. The method of claim 64, wherein the reaction reagent system comprises 0.05 to 0.25% of an alkyl phenoxy polyethoxy ethanol and 0.5 to 2.0% of polyvinyl alcohol.

66. A method of measuring the concentration of analyte in a fluid, said method comprising:

contacting said fluid with a biosensor comprising;

at least one conducting electrode; and

a reaction reagent system comprising a ruthenium containing electron mediator and an oxidation-reduction enzyme specific for said analyte;

detecting an electrical signal from said biosensor; and

measuring the electrical signal to thereby determine the concentration of the analyte in the liquid.

67. The method of claim 66, wherein said ruthenium containing material comprises ruthenium hexaamine (III) trichloride.

68. The method of claim 66, wherein the at least one conducting electrode comprises a metal chosen from or derived from gold, platinum, rhodium, palladium, silver, iridium, carbon, steel, metallorganics, and mixtures thereof.

69. The method of claim 68, wherein the at least one carbon electrode comprises sputtered carbon or screen printed carbon.

70. The method of claim 69, wherein said sputtered carbon further comprises Cr.

71. The method of claim 69, wherein the analyte comprises is chosen from glucose, cholesterol, lactate, acetoacetic acid (ketone bodies), theophylline, and hemoglobin A1c.

72. The method of claim 71, wherein the analyte comprises glucose and the at least one oxidation-reduction enzyme specific for the analyte is chosen from glucose oxidase, PQQ-dependent glucose dehydrogenase and NAD-dependent glucose dehydrogenase.

73. The method of claim 66, wherein the fluid comprises blood and the reaction reagent system comprises a red blood cell binding agent for capturing red blood cells from the fluid, said red blood cell binding agent comprising lectins.

74. The method of claim 66, wherein the reaction reagent system further comprises at least one buffer material comprising potassium phosphate.

75. The method of claim 66, wherein the reaction reagent system further comprises at least one surfactant chosen from non-ionic, anionic, and zwitterionic surfactants.

76. The method of claim 66, wherein the reaction reagent system further comprises at least one polymeric binder chosen from hydroxypropyl-methyl cellulose, sodium alginate, microcystalline cellulose, polyethylene oxide, hydroxyethylcellulose, polypyrrolidone, PEG, and polyvinyl alcohol.

77. The method of claim 66, wherein the reaction reagent system comprises 0.01 to 0.3% of a non-ionic surfactant and 0.1 to 3%, of a polymeric binder material.

78. The method of claim 77, wherein the reaction reagent system comprises 0.05 to 0.25% of an alkyl phenoxy polyethoxy ethanol and 0.5 to 2.0% of polyvinyl alcohol.

79. A method of measuring the concentration of analyte in a fluid, said method comprising:

contacting said fluid with a biosensor comprising;

at least one semiconducting electrode; and

a reaction reagent system comprising an electron mediator and an oxidation-reduction enzyme specific for said analyte;

detecting an electrical signal from said biosensor; and

measuring the electrical signal to thereby determine the concentration of the analyte in the liquid.

80. The method of claim 79, wherein the at least one semiconducting electrode comprises a material chosen from tin oxide, indium oxide, titanium dioxide, manganese oxide, iron oxide, and zinc oxide.

81. The method of claim 80, wherein the at least one semiconducting electrode comprises zinc oxide doped with indium, tin oxide doped with indium, indium oxide doped with zinc, or indium oxide doped with tin.

82. The method of claim 79, wherein the at least one semiconducting electrode comprises an allotrope of carbon doped with boron, nitrogen, or phosphorous.

83. The method of claim 79, wherein the analyte is chosen from glucose, cholesterol, lactate, acetoacetic acid (ketone bodies), theophylline, and hemoglobin A1c.

84. The method of claim 83, wherein the analyte comprises glucose and the at least one oxidation-reduction enzyme specific for the analyte is chosen from glucose oxidase, PQQ-dependent glucose dehydrogenase and NAD-dependent glucose dehydrogenase.

85. The method of claim 79, wherein the fluid comprises blood and the reaction reagent system comprises a red blood cell binding agent for capturing red blood cells from the fluid, said red blood cell binding agent comprising lectins.

86. The method of claim 79, wherein the reaction reagent system further comprises at least one buffer material comprising potassium phosphate.

87. The method of claim 79, wherein the reaction reagent system further comprises at least one surfactant chosen from non-ionic, anionic, and zwitterionic surfactants.

88. The method of claim 79, wherein the reaction reagent system further comprises at least one polymeric binder chosen from hydroxypropyl-methyl cellulose, sodium alginate, microcystalline cellulose, polyethylene oxide, hydroxyethylcellulose, polypyrrolidone, PEG, and polyvinyl alcohol.

89. The method of claim 79, wherein the electron mediator comprises a ferricyanide material, ferrocene carboxylic acid, or a ruthenium containing material.

90. The method of claim 89, wherein the ferricyanide material comprises potassium ferricyanide and the ruthenium containing material comprises ruthenium hexaamine (III) trichloride.

91. The method of claim 79, wherein the reaction reagent system comprises 0.01 to 0.3% of a non-ionic surfactant and 0.1 to 3%, of a polymeric binder material.

92. The method of claim 91, wherein the reaction reagent system comprises 0.05 to 0.25% of an alkyl phenoxy polyethoxy ethanol and 0.5 to 2.0% of polyvinyl alcohol.

93. A method of measuring the concentration of analyte in a fluid, said method comprising:

contacting said fluid with a biosensor comprising;

at least one thin film carbon electrode; and

a reaction reagent system comprising an electron mediator and an oxidation-reduction enzyme specific for said analyte;

detecting an electrical signal from said biosensor; and

measuring the electrical signal to thereby determine the concentration of the analyte in the liquid.

94. The method of claim 93, wherein the electron mediator comprises a ferricyanide material, ferrocene carboxylic acid, or a ruthenium containing material.

95. The method of claim 94, wherein the ferricyanide material comprises potassium ferricyanide and the ruthenium containing material comprises ruthenium hexaamine (III) trichloride.

96. The method of claim 93, wherein the at least one thin film carbon electrode comprises sputtered carbon or screen printed carbon.

97. The method of claim 96, wherein said sputtered carbon further comprises Cr.

98. The method of claim 93, wherein the analyte is chosen from glucose, cholesterol, lactate, acetoacetic acid (ketone bodies), theophylline, and hemoglobin A1c.

99. The method of claim 98, wherein the analyte comprises glucose and the at least one oxidation-reduction enzyme specific for the analyte is chosen from glucose oxidase, PQQ-dependent glucose dehydrogenase and NAD-dependent glucose dehydrogenase.

100. The method of claim 93, wherein the fluid comprises blood and the reaction reagent system comprises a red blood cell binding agent for capturing red blood cells from the fluid, said red blood cell binding agent comprising lectins

101. The method of claim 93, wherein the reaction reagent system further comprises at least one buffer material comprising potassium phosphate.

102. The method of claim 93, wherein the reaction reagent system further comprises at least one surfactant chosen from non-ionic, anionic, and zwitterionic surfactants.

103. The method of claim 93, wherein the reaction reagent system further comprises at least one polymeric binder chosen from hydroxypropyl-methyl cellulose, sodium alginate, microcystalline cellulose, polyethylene oxide, hydroxyethylcellulose, polypyrrolidone, PEG, and polyvinyl alcohol.

104. The method of claim 93, wherein the reaction reagent system comprises 0.01 to 0.3% of a non-ionic surfactant and 0.1 to 3%, of a polymeric binder material.

105. The method of claim 104, wherein the reaction reagent system comprises 0.05 to 0.25% of an alkyl phenoxy polyethoxy ethanol and 0.5 to 2.0% of polyvinyl alcohol.