TRANSITION METAL COMPLEXES WITH (PYRIDYL)IMIDAZOLE LIGANDS

• US 20100038242A1
• Filed: 09/10/2009
• Published: 02/18/2010
• Est. Priority Date: 05/11/2001
• Status: Active Grant

• Current Assignee: Abbott Diabetes Care Incorporated (Abbott Laboratories Incorporated)
• Original Assignee: Abbott Diabetes Care Incorporated (Abbott Laboratories Incorporated)
• Inventors: Heller, Adam, Mao, Fei
• Granted Patent: US 8,298,388 B2
• Time in Patent Office: Days
• US Class Current: 204/403.140
• CPC Class Codes: C07F 15/0026 without a metal-carbon linkage

Abstract

Novel transition metal complexes of iron, cobalt, ruthenium, osmium, and vanadium are described. The transition metal complexes can be used as redox mediators in enzyme-based electrochemical sensors. The transition metal complexes include substituted or unsubstituted (pyridyl)imidazole ligands. Transition metal complexes attached to polymeric backbones are also described.

Claims

1-48. -48. (canceled)

49. A test strip comprising:

a working electrode;

a counter electrode;

wherein the working electrode comprises an analyte-responsive enzyme and a mediator complex, the mediator complex having the formula;

wherein c is a negative, neutral, or positive charge represented by −

1 to −

5, 0, or +1 to +5, inclusive, respectively;

d is a number of counter ions, X, from 1 to 5, inclusive;

M is osmium or ruthenium;

L₁ is a substituted or an unsubstituted heterocyclic nitrogen-containing ligand;

L₂ is a negatively charged ligand; and

L and L′

are independently;

wherein R′

₁ is a substituted or an unsubstituted alkyl, alkenyl or aryl;

each of R_a and R_b is independently —

H, —

F, —

Cl, —

Br, —

I, —

NO₂, —

CN, —

CO₂H, —

SO₃H, —

NHNH₂, —

SH, —

OH, —

NH₂, or substituted or unsubstituted alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxy, alkylamino, dialkylamino, alkanoylamino, arylcarboxamido, hydrazino, alkylhydrazino, hydroxylamino, alkoxylamino, alkylthio, alkenyl, aryl, or alkyl;

each of R_e and R_d is independently —

H, —

F, —

Cl, —

Br, —

I, —

NO₂, —

CN, —

CO₂H, —

SO₃H, —

NHNH₂, —

SH, —

OH, —

NH₂, or substituted or unsubstituted alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxy, alkylamino, dialkylamino, alkanoylamino, arylcarboxamido, hydrazino, alkylhydrazino, hydroxylamino, alkoxylamino, alkylthio, alkenyl, aryl, or alkyl, or a combination of R_e and R_d forms a saturated or an unsaturated 5- or 6-membered ring; and

each of R′

₃ and R′

₄ is independently —

H, —

F, —

Cl, —

Br, —

I, —

NO₂, —

CN, —

CO₂H, —

SO₃H, —

NHNH₂, —

SH, —

OH, —

NH₂, or substituted or unsubstituted alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxy, alkylamino, dialkylamino, alkanoylamino, arylcarboxamido, hydrazino, alkylhydrazino, hydroxylamino, alkoxylamino, alkylthio, alkenyl, aryl, or alkyl, or a combination of R′

₃ and R′

₄ forms a saturated or an unsaturated 5- or 6-membered ring.

50. The test strip of claim 49, wherein

M is osmium;

L₂ is a halide; and

L and L′

are independently;

wherein R′

₁ is a substituted or an unsubstituted C1-C6 alkyl;

R′

₃ and R′

₄ are independently —

H;

R_a, R_b, R_c, and R_d are independently —

H or C1 alkyl;

c is a negative, neutral, or positive charge represented by −

1 to −

5, 0, or +1 to +5, inclusive, respectively.

51. The test strip of claim 50, wherein L₁ is a substituted or unsubstituted pyridine.

52. The test strip of claim 50, wherein L₁ has the formula:

wherein R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ are independently —

H, —

F, —

Cl, —

Br, —

I, —

NO₂, —

CN, —

CO₂H, —

OH, —

NH₂, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxy, alkylamino, dialkylamino, alkanoylamino, arylcarboxamido, hydrazino, alkylhydrazino, hydroxylamino, alkoxyamino, alkylthio, alkenyl, aryl, or alkyl.

53. The test strip of claim 52, wherein R₁₁ and R₁₅ are independently —

H;

R₁₂ and R₁₄ are the same and —

H or methyl; and

R₁₃ is —

H, C1 to C12 alkoxy, —

NH₂, C1 to C12 alkylamino, C2 to C24 dialkylamino, hydrazino, C1 to C12 alkylhydrazino, hydroxylamino, C1 to C12 alkoxyamino, C1 to C12 alkylthio, or C1 to C12 alkyl.

54. The test strip complex of claim 50, wherein L₁ has the formula:

wherein R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ are independently —

H, methyl, C1-C2 alkoxy, C1-C2 alkylamino, C2-C4 dialkylamino, or a C1-C6 lower alkyl substituted with a reactive group.

55. The test strip of claim 50, wherein L₂ is —

F, —

Cl, or —

Br.

56. The test strip of claim 50, wherein L₂ is —

Cl.

57. The test strip of claim 50, wherein R′

₁ is a C1-C2 alkyl.

58. The test strip of claim 50, wherein R′

₁ is a C1 alkyl.

59. The test strip of claim 50, wherein each of R_a and R_c is —

H.

60. The test strip of claim 50, wherein each of R_a, R_b, and R_c is —

H.

61. The test strip of claim 50, wherein each of R_a, R_b, R_c, and R_d is —

H.

62. The test strip of claim 50, wherein X is a halide.

63. The test strip of claim 50, wherein X is chloride.

64. The test strip of claim 49, wherein the analyte-responsive enzyme is glucose dehydrogenase (GDH).

65. The test strip of claim 49, wherein the analyte-responsive enzyme further comprises an enzyme cofactor.

66. The test strip of claim 64, wherein the enzyme cofactor is flavin adenine dinucleotide (FAD).

67. A test strip comprising:

a working electrode;

a counter electrode;

wherein the working electrode comprises an analyte-responsive enzyme and a mediator complex, the mediator complex having the formula;

wherein

M is cobalt, iron, osmium, ruthenium, or vanadium;

L₁ has the formula;

wherein R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ are independently —

H, —

F, —

Cl, —

Br, —

I, —

NO₂, —

CN, —

CO₂H, —

OH, —

NH₂, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxy, alkylamino, dialkylamino, alkanoylamino, arylcarboxamido, hydrazino, alkylhydrazino, hydroxylamino, alkoxyamino, alkylthio, alkenyl, aryl, or alkyl;

L₂ is chloride;

L and L′

are independently;

wherein R′

₁ is methyl; and

R′

₃, R′

₄, R_a, R_b, R_c, and R_d are independently —

H;

c is a negative, neutral, or positive charge represented by −

1 to −

5, 0, or +1 to +5, inclusive, respectively;

d is a number of X sufficient to balance the charge c; and

X is an anion.

68. The test strip of claim 67, wherein R₁₃ is C1-C2 alkylamino.

69. The test strip of claim 67, wherein R₁₁, R₁₅, R₁₂, and R₁₄ are independently —

H.

70. The test strip of claim 67, wherein the analyte-responsive enzyme is glucose dehydrogenase (GDH).

71. The test strip of claim 67, wherein the analyte-responsive enzyme further comprises an enzyme cofactor.

72. The test strip of claim 71, wherein the enzyme cofactor is flavin adenine dinucleotide (FAD).

74. The test strip of claim 67, wherein the analyte-responsive enzyme is glucose dehydrogenase (GDH).

75. The test strip of claim 67, wherein the analyte-responsive enzyme further comprises an enzyme cofactor.

76. The test strip of claim 71, wherein the enzyme cofactor is flavin adenine dinucleotide (FAD).

73. A test strip comprising:

a working electrode;

a counter electrode;

wherein the working electrode comprises an analyte-responsive enzyme and a mediator complex, the mediator complex having the formula;

wherein

M is osmium;

L₁ has the formula;

wherein R₁₁, R₁₂, R₁₄ and R₁₅ are —

H;

R₁₃ is C1-C2 alkylamino;

L₂ is chloride;

L and L′

are independently;

wherein R′

₁ is methyl; and

R′

₃, R′

₄, R_a, R_b, R_c, and R_d are independently —

H;

c is +2;

d is 2; and

X is chloride.