Magnesium electrode

• US 5,350,518 A
• Filed: 08/11/1993
• Issued: 09/27/1994
• Est. Priority Date: 03/18/1991
• Status: Expired due to Term

• Current Assignee: Nova Biomedical Corporation (Nova Chemicals)
• Original Assignee: Nova Biomedical Corporation (Nova Chemicals)
• Inventors: Hiti, John, Young, Chung C.
• Primary Examiner(s): SPEAR JR, FRANK
• Application Number:
  US08/105,340
• Time in Patent Office: 412 Days
• Field of Search: 204/418, 210/638, 210/645, 210/490, 210/500.25, 210/500.27
• US Class Current: 210/638
• CPC Class Codes: G01N 27/3335 the membrane containing at least one organic component G01N27/3271 takes precedence; aspects concerning the enzyme reagent in enzyme electrodes C12Q1/001

Abstract

The magnesium ion content of a sample is determined by contacting the sample with a magnesium ion selective membrane including a 1,10-phenanthroline having an H group at positions 2 and 9. Examples of preferred 1,10-phenanthrolines include 4,7-diphenyl-1,10-phenanthroline, N-dodecyl-N-methyl-1,10-phenanthroline-4-carboxamide, 4-undecyl-1,10-phenanthroline, 4,7-diundecyl-1,10-phenanthroline and 5-nonyl-1,10-phenanthroline-4-carboxylate.

Claims

1. A method of determining the magnesium ion content of a sample comprising contacting said sample with an electrode comprising a magnesium ion selective membrane comprising, as a magnesium selective compound, a 1,10-phenanthroline having an H group at positions 2 and 9, and reading the output of said electrode.

2. The method of claim 1, wherein said sample is biological fluid.

3. The method of claim 2, wherein said sample is undiluted plasma.

4. The method of claim 1, wherein said sample is whole blood.

5. The method of claim 1, wherein said sample is serum.

6. The method of claim 5, wherein said sample is undiluted serum.

7. The method of claim 4, wherein said sample is contacted with said selective membrane, and said output corresponds to a change in potential.

8. The method of claim 1, wherein each of the C atoms at positions 3-8 of said 1,10-phenanthroline is bonded, by the bond which does not participate in the fused ring structure, to an H.

9. The method of claim 1, wherein each of the C atoms at positions 3-8 of said 1,10-phenanthroline is substituted at the bond which does not participate in the fused ring structure.

10. The method of claim 1, wherein said 1,10-phenanthroline has the formula ##STR5## wherein each R¹ -R⁶ is any of:

H;

any of F, Cl, Br, I, NO₂, CN, or CF₃ ;

C_1-18 alkyl;

C_1-18 aryl;

C_1-18 alkenyl;

or

(CH₂)_m Y, wherein m is 0 or an integer between 1 and 4 inclusive Y is any of --OR⁷, --NR⁷ R⁸, --OCOR⁷, --NR⁷ COR⁸, --COR⁷, --COOR⁷, SO₃ R⁷, OSiR⁷ R⁸ R⁹, wherein each R⁷, R⁸, and R⁹ are any of H, alkyl, branched alkyl, aryl, or substituted aryl;

or

C_n --R¹⁰ --R¹¹, wherein n is 0 or an integer between 1 and 17 inclusive, R¹⁰ is C, N, NCO, or CH₂ --Z--CH₂ wherein Z is any of O, NH, S, OCO, or CO, R¹¹ is ##STR6## and R¹¹ is linked to R¹⁰ at any of positions 3, 4, 5, 6, 7, or 8 of R¹¹, R¹² -R¹⁷ are any of H, C_1-18 alkyl, C_1-18 aryl, or deleted, provided that if R¹¹ is linked to R¹⁰ at position 3 of R¹¹ then R¹² is deleted, if R¹¹ is linked to R¹⁰ at position 4 of R¹¹ then R¹³ is deleted, if R¹¹ is linked to R¹⁰ at position 5 of R¹¹ then R¹⁴ is deleted, if R¹¹ is linked to R¹⁰ at position 6 of R¹¹ then R¹⁵ is deleted, if R¹¹ is linked to R¹⁰ at position 7 of R¹¹ then R¹⁶ is deleted, if R¹¹ is linked to R¹⁰ at position 8 of R¹¹ then R¹⁷ is deleted, provided that one of R¹ -R⁶ is other than H and that each of the C atoms at positions 2 and 9 of the 1,10-phenanthroline is bonded, by the bond which does not participate in the fused ring structure, to an H.

11. The method of claim 1, wherein said 1,10-phenanthroline has the formula ##STR7## wherein each R¹ -R⁶ is any of:

H;

any of F, Cl, Br, I, NO₂, CN, or CF₃ ;

C_1-18 alkyl;

C_1-18 aryl;

C_1-18 alkenyl;

or

(CH₂)_m Y, wherein m is 0 or an integer between 1 and 4 inclusive, Y is any of --OR⁷, --NR⁷ R⁸, --OCOR⁷, --NR⁷ COR⁸, --COR⁷, --COOR⁷, SO₃ R⁷, OSiR⁷ R⁸ R⁹, wherein each R⁷, R⁸, and R⁹ are any of H, alkyl, branched alkyl, aryl, or substituted aryl;

provided that one of R¹ -R⁶ is other than H and that each of the C atoms at positions 2 and 9 of said 1,10-phenanthroline is bonded, by the bond which does not participate in the fused ring structure, to an H.

12. The method of claim 11, wherein R¹ -R⁶ include a total of at least 6 carbon atoms.

13. The method of claim 11, wherein R¹ -R⁶ include a total of at least eleven carbon atoms.

14. The method of claim 11, wherein R¹ is an alkyl or aryl group having between 1 and 18 carbon atoms.

15. The method of claim 11, wherein R² is an alkyl or aryl group having between 1 and 18 carbon atoms.

16. The method of claim 11, wherein R³ is an alkyl or aryl group having between 1 and 18 carbon atoms.

17. The method of claim 11, wherein R⁴ is an alkyl or aryl group having between 1 and 18 carbon atoms.

18. The method of claim 11, wherein R⁵ is an alkyl or aryl group having between 1 and 18 carbon atoms.

19. The method of claim 11, wherein R⁶ is an alkyl or aryl group having between 1 and 18 carbon atoms.

20. The method of claim 11, wherein said membrane further comprises a plasticizer.

21. The method of claim 11, wherein said membrane further comprises a matrix.

22. The method of claim 21, wherein said matrix comprises PVC.

23. The method of claim 11, wherein said membrane further comprises an ion excluder.

24. The method of claim 1 wherein said compound is 4,7-diphenyl-1,10-phenanthroline.

25. The method of claim 1, wherein said compound is N-dodecyl-N-methyl-1,10-phenanthroline-4-carboxamide.

26. The method of claim 1, wherein said compound is 4-undecyl-1,10-phenanthroline.

27. The method of claim 1, wherein said compound is 4,7-diundecyl-1,10-phenanthroline.

28. The method of claim 1, wherein said compound is 5-nonyl 1,10-phenanthroline-4-carboxylate.

29. A method of making a magnesium ion selective membrane comprising adding, as a magnesium selective compound, a 1,10-phenanthroline having an H group at positions 2 and 9, to a membrane.

30. The method of claim 29, wherein each of the C atoms at positions 3-8 of said 1,10 phenanthrolines is bonded, by the bond which does not participate in the fused ring structure, to an H.

31. The method of claim 29, wherein each of the C atoms at positions 3-8 of said 1,10-phenanthroline is substituted at the bond which does not participate in the fused ring structure.

32. The method of claim 29, wherein said 1,10-phenanthroline has the formula ##STR8## wherein each R¹ -R⁶ is any of:

H;

any of F, Cl, Br, I, NO₂, CN, or CF₃ ;

C_1-18 alkyl;

C_1-18 aryl;

C_1-18 alkenyl;

or

(CH₂)_m Y, wherein m is 0 or an integer between 1 and 4 inclusive, Y is any of --OR⁷, --NR⁷ R⁸, --OCOR⁷, --NR⁷ COR⁸, --COR⁷, --COOR⁷, SO₃ R⁷, OSiR⁷ R⁸ R⁹, wherein each R⁷, R⁸, and R⁹ are any of H, alkyl, branched alkyl, aryl, or substituted aryl;

or

C_n --R¹⁰ --R¹¹, wherein n is 0 or an integer between 1 and 17 inclusive, R¹⁰ is C, N, NCO, or CH₂ --Z--CH₂ wherein Z is any of O, NH, S, OCO, or CO, R¹¹ is ##STR9## and R¹¹ is linked to R¹⁰ at any of positions 3, 4, 5, 6, 7, or 8 of R¹¹, R¹² -R¹⁷ are any of H, C_1-18 alkyl, C_1-18 aryl, or deleted, provided that if R¹¹ is linked to R¹⁰ at position 3 of R¹¹ then R¹² is deleted, if R¹¹ is linked to R¹⁰ at position 4 of R¹¹ then R¹³ is deleted, if R¹¹ is linked to R¹⁰ at position 5 of R¹¹ then R¹⁴ is deleted, if R¹¹ is linked to R¹⁰ at position 6 of R¹¹ then R¹⁵ is deleted, if R¹¹ is linked to R¹⁰ at position 7 of R¹¹ then R¹⁶ is deleted, if R¹¹ is linked to R¹⁰ at position 8 of R¹¹ then R¹⁷ is deleted, provided that one of R¹ -R⁶ is other than H and that each of the C atoms at positions 2 and 9 of the 1,10-phenanthroline is bonded, by the bond which does not participate in the fused ring structure, to an H.

33. The method of claim 29, wherein said 1,10-phenanthroline has the formula ##STR10## wherein each R¹ -R⁶ is any of:

H;

any of F, Cl, Br, I, NO₂, CN, or CF₃ ;

C_1-18 alkyl;

C_1-18 aryl;

C_1-18 alkenyl;

or

(CH₂)_m Y, wherein m is 0 or an integer between 1 and 4 inclusive, Y is any of --OR⁷, --NR⁷ R⁸, --OCOR⁷, --NR⁷ COR⁸, --COR⁷, --COOR⁷, SO₃ R⁷, OSiR⁷ R⁸ R⁹, wherein each R⁷, R⁸, and R⁹ are any of H, alkyl, branched alkyl, aryl, or substituted aryl;

provided that one of R¹ -R⁶ is other than H and that each of the C atoms at positions 2 and 9 of said 1,10-phenanthroline is bonded, by the bond which does not participate in the fused ring structure, to an H.

34. The method of claim 33, wherein R¹ -R⁶ include a total of at least 6 carbon atoms.

35. The method of claim 33, wherein R¹ -R⁶ include a total of at least eleven carbon atoms.

36. The method of claim 33, wherein R¹ is an alkyl or aryl group having between 1 and 18 carbon atoms.

37. The method of claim 33, wherein R² is an alkyl or aryl group having between 1 and 18 carbon atoms.

38. The method of claim 33, wherein R³ is an alkyl or aryl group having between 1 and 18 carbon atoms.

39. The method of claim 33, wherein R⁴ is an alkyl or aryl group having between 1 and 18 carbon atoms.

40. The method of claim 33, wherein R⁵ is an alkyl or aryl group having between 1 and 18 carbon atoms.

41. The method of claim 33, wherein R⁶ is an alkyl or aryl group having between 1 and 18 carbon atoms.

42. The method of claim 33, wherein said membrane further comprises a plasticizer.

43. The method of claim 33, wherein said membrane further comprises a matrix.

44. The method of claim 43, wherein said matrix comprises PVC.

45. The method of claim 33, wherein said membrane further comprises an ion excluder.

46. The method of claim 29, wherein said compound is 4,7-diphenyl-1,10-phenanthroline.

47. The method of claim 29, wherein said compound is N-dodecyl-N-methyl-1,10-phenanthroline-4-carboxamide.

48. The method of claim 29, wherein said compound is 4-undecyl-1,10-phenanthroline.

49. The method of claim 29, wherein said compound is 4,7-diundecyl-1,10-phenanthroline.

50. The method of claim 29, wherein said compound is 5-nonyl 1,10-phenanthroline-4-carboxylate.

51. A preparation of N-methyl-N-dodecyl-1,10-phenanthroline-4-carboxamide.

52. A preparation of 5-nonyl 1,10-phenanthroline-4-carboxylate.

53. A method of sequestering the Mg⁺⁺ ions in a sample comprising, contacting said sample with a 1,10-phenanthroline having an H group at positions 2 and 9, said 1,10-phenanthroline being linked to a substrate.

54. The method of claim 53, wherein each of the C atoms at positions 3-8 of said 1,10-phenanthroline is bonded, by the bond which does not participate in the fused ring structure, to an H.

55. The method of claim 53, wherein each of the C atoms at positions 3-8 of said 1,10-phenanthroline is substituted at the bond which does not participate in the fused ring structure.

56. The method of claim 53, wherein said 1,10-phenanthroline has the formula ##STR11## wherein each R¹ -R⁶ is any of:

H;

any of F, Cl, Br, I, NO₂, CN, or CF₃ ;

C_1-18 alkyl;

C_1-18 aryl;

C_1-18 alkenyl;

or

(CH₂)_m Y, wherein m is 0 or an integer between 1 and 4 inclusive, Y is any of --OR⁷, --NR⁷ R⁸, --OCOR⁷, --NR⁷ COR⁸, --COR⁷, --COOR⁷, SO₃ R⁷, OSiR⁷ R⁸ R⁹, wherein each R⁷, R⁸, and R⁹ are any of H, alkyl, branched alkyl, aryl, or substituted aryl;

or

C_n --R¹⁰ --R¹¹, wherein n is 0 or an integer between 1 and 17 inclusive, R¹⁰ is C, N, NCO, or CH₂ --Z--CH₂ wherein Z is any of O, NH, S, OCO, or CO, R¹¹ is ##STR12## and R¹¹ is linked to R¹⁰ at any of positions 3, 4, 5, 6, 7, or 8 of R¹¹, R¹² -R¹⁷ are any of H, C_1-18 alkyl, C_1-18 aryl, or deleted, provided that if R¹¹ is linked to R¹⁰ at position 3 of R¹¹ then R¹² is deleted, if R¹¹ is linked to R¹⁰ at position 4 of R¹¹ then R¹³ is deleted, if R¹¹ is linked to R¹⁰ at position 5 of R¹¹ then R¹⁴ is deleted, if R¹¹ is linked to R¹⁰ at position 6 of R¹¹ then R¹⁵ is deleted, if R¹¹ is linked to R¹⁰ at position 7 of R¹¹ then R¹⁶ is deleted, if R¹¹ is linked to R¹⁰ at position 8 of R¹¹ then R¹⁷ is deleted, provided that one of R¹ -R⁶ is other than H and that each of the C atoms at positions 2 and 9 of the 1,10-phenanthroline is bonded, by the bond which does not participate in the fused ring structure, to an H.

57. The method of claim 53, wherein said 1,10-phenanthroline has the formula ##STR13## wherein each R¹ -R⁶ is any of:

H;

any of F, Cl, Br, I , NO₂, CN, or CF₃ ;

C_1-18 alkyl;

C_1-18 aryl;

C_1-18 alkenyl;

or

(CH₂)_m Y, wherein m is 0 or an integer between 1 and 4 inclusive, Y is any of --OR⁷, --NR⁷ R⁸, --OCOR⁷, --NR⁷ COR⁸, --COR⁷, --COOR⁷, SO₃ R⁷, OSiR⁷ R⁸ R⁹, wherein each R⁷, R⁸, and R⁹ are any of H, alkyl, branched alkyl, aryl, or substituted aryl;

provided that one of R¹ -R⁶ is other than H and that each of the C atoms at positions 2 and 9 of said 1,10-phenanthroline is bonded, by the bond which does not participate in the fused ring structure, to an H.

58. The method of claim 57, wherein R¹ -R⁶ include a total of at least 6 carbon atoms.

59. The method of claim 57, wherein R¹ -R⁶ include a total of at least eleven carbon atoms.

60. The method of claim 57, wherein R¹ is an alkyl or aryl group having between 1 and 18 carbon atoms.

61. The method of claim 57, wherein R² is an alkyl or aryl group having between 1 and 18 carbon atoms.

62. The method of claim 57, wherein R³ is an alkyl or aryl group having between 1 and 18 carbon atoms.

63. The method of claim 57, wherein R⁴ is an alkyl or aryl group having between 1 and 18 carbon atoms.

64. The method of claim 57, wherein R⁵ is an alkyl or aryl group having between 1 and 18 carbon atoms.

65. The method of claim 57, wherein R⁶ is an alkyl or aryl group having between 1 and 18 carbon atoms.

66. The method of claim 57, wherein said membrane further comprises a plasticizer.

67. The method of claim 57, wherein said membrane further comprises a matrix.

68. The method of claim 67, wherein said matrix comprises PVC.

69. The method of claim 57, wherein said membrane further comprises an ion excluder.

70. The method of claim 53, wherein said compound is 4,7-diphenyl-1,10-phenanthroline.

71. The method of claim 53, wherein said compound is N-dodecyl-N-methyl-1,10-phenanthroline-4-carboxamide.

72. The method of claim 53, wherein said compound is 4-undecyl-1,10-phenanthroline.

73. The method of claim 53, wherein said compound is 4,7-diundecyl-1,10-phenanthroline.

74. The method of claim 53, wherein said compound is 5-nonyl 1,10-phenanthroline-4-carboxylate.

75. A magnesium ion selective membrane comprising, as a magnesium selective compound, N-dodecyl-N-methyl-1,10-phenanthroline-4-carboxamide.

76. An electrode for determining the magnesium ion concentration of a liquid sample comprising the selective membrane of claim 75.

77. A magnesium ion selective membrane comprising, as a magnesium selective compound, 4-undecyl-1,10-phenanthroline.

78. An electrode for determining the magnesium ion concentration of a liquid sample comprising the selective membrane of claim 77.

79. A magnesium ion selective membrane comprising, as a magnesium selective compound, 4,7-diundecyl-1,10-phenanthroline.

80. An electrode for determining the magnesium ion concentration of a liquid sample comprising the selective membrane of claim 79.

81. A magnesium ion selective membrane comprising, as a magnesium selective compound, 5-nonyl 1,10-phenanthroline-4-carboxylate.

82. An electrode for determining the magnesium ion concentration of a liquid sample comprising the selective membrane of claim 81.