Transition metal complexes with bidentate ligand having an imidazole ring and sensor constructed therewith
First Claim
1. A transition metal complex having the formula:
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wherein M is osmium;
L is selected from the group consisting of;
R1, R2, and R′
1 are independently substituted or unsubstituted alkyl, alkenyl, or aryl groups;
R3, R4, R5, R6, R′
3, R′
4, Ra, Rb, Rc, and Rd are 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;
c is an integer selected from −
1 to −
5 or +1 to +5 indicating a positive or negative charge;
X represents at least one counter ion;
d is an integer from 1 to 5 representing the number of counter ions, X; and
L1, L2, L3 and L4 are ligands;
wherein L1 comprises a heterocyclic compound coupled to a polymeric backbone, and wherein L1 and L2 in combination form a first bidentate ligand.
4 Assignments
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Accused Products
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. In such instances, transition metal complexes accept electrons from, or transfer electrons to, enzymes at a high rate and also exchange electrons rapidly with the sensor. The transition metal complexes include at least one substituted or unsubstituted biimidazole ligand and may further include a second substituted or unsubstituted biimidazole ligand or a substituted or unsubstituted bipyridine or pyridylimidazole ligand. Transition metal complexes attached to polymeric backbones are also described.
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Citations
18 Claims
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1. A transition metal complex having the formula:
-
wherein M is osmium; L is selected from the group consisting of;
R1, R2, and R′
1 are independently substituted or unsubstituted alkyl, alkenyl, or aryl groups;
R3, R4, R5, R6, R′
3, R′
4, Ra, Rb, Rc, and Rd are 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;
c is an integer selected from −
1 to −
5 or +1 to +5 indicating a positive or negative charge;
X represents at least one counter ion;
d is an integer from 1 to 5 representing the number of counter ions, X; and
L1, L2, L3 and L4 are ligands;
wherein L1 comprises a heterocyclic compound coupled to a polymeric backbone, and wherein L1 and L2 in combination form a first bidentate ligand. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 17)
wherein R16, R17, R18, R19, R20, R21, R22 and R23 are independently —
H,—
F, —
Cl, —
Br, —
I, —
CN, —
CO2H, —
SO3H. —
NHNH2, —
SH, —
OH, —
NHz, or substituted or unsubstituted alkoxylcarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxy, alkylamino, dialkylamino, alkanoylamino, arylcarboxamido, hydrazino, alkylhydrazino, hydroxylamino, alkoxylamino, alkylthio, alkenyl, aryl, or alkyl.
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6. The transition metal complex of claim 1, wherein L3 and L4 in combination form a second bidentate ligand.
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7. The transition metal complex of claim 6, wherein at least one of the first and second bidentate ligands is selected from the group consisting of substituted and unsubstituted 2,2′
- -bipyridines, 2,2′
-biimidazoles, and 2-(2-pyridyl)imidazoles.
- -bipyridines, 2,2′
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8. The transition metal complex of claim 1, wherein the transition complex has the following formula:
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wherein R3, r4, R5, R6, R16, R17, R19, R20, R22 and R23 are —
H;
R1 and R2 are independently substituted or unsubstituted C1 to C12 alkyls; and
R18 and R21 are independent —
H or substituted or unsubstituted C1-C12 alkoxy, C1-12 alkylthio, C1-C12 alkylamino, C2-C24 dialkylamino, or C1-C12 alkyl.
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9. The transition metal complex of claim 8, wherein at least one of R1, R2, R18 and R21 comprises a reactive group selected from the group consisting of carboxy, activated ester, sulfonyl halide, sulfonate ester, isocyanate, isothiocyanate, epoxide, aziridine, halide, aldehyde, ketone, amine, acrylamide, thiol, acyl azide, acyl halide, hydrazine, hydroxylamine, alkyl halide, imidazole, pyridine, phenol, alkyl sulfonate, halotriazine, imido ester, maleimide, hydrazide, hydroxy, and photo-reactive azido aryl groups.
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10. The transition metal complex of claim 8, wherein at least one of R1, R2, R18, and R21 is coupled to a polymeric backbone.
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11. The transition metal complex of claim 1, wherein the transition complex has the following formula:
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wherein R3, R4, R5, R6, R′
3, R′
4, Ra, and Rc are —
H;Rd is —
H or methyl;
Rb is —
H or substituted or unsubstituted C1-C12 alkoxy, C1-12 alkylthio, C1-C12 alkylamino, C2-C24 dialkylamino, or C1-C12 alkyl; and
R1, R′
1 and R2 are independently substituted or unsubstituted C1 to C12 alkyl.
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12. The transition metal complex of claim 11, wherein at least one of R1, R2, and R′
- 1 comprises a reactive group selected from the group consisting of carboxy, activated ester, sulfonyl halide, sulfonate ester, isocyanate, isothiocyanate, epoxide, aziridine, halide, aldehyde, ketone, amine, acrylamide, thiol, acyl azide, acyl halide, hydrazine, hydroxyamine, alkyl halide, imidazole, pyridine, phenol, alkyl sulfonate, halotriazine, imido ester, maleimide, hydrazide, hydroxy, and photo-reactive azido aryl groups.
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13. The transition metal complex of claim 11, wherein at least one of R1, R2, and R′
- 1 is coupled to a polymeric backbone.
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17. The sensor of claim 2 further comprising an enzyme disposed proximate to the working electrode.
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14. A polymer comprising:
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a polymeric backbone; and
a transition metal complex having the following formula;
wherein M is osmium;
L is a bidentate ligand comprising at least one imidazole ring;
c is all integer selected from −
1 to −
5 or +1 to +5 indicating a positive or negative charge;
X represents at least one counter ion;
d is an integer from 1 to 5 representing the number of counter ions, X; and
L1, L2, L3 and L4 are ligands, wherein L1 comprises a heterocyclic ring and is coupled to the polymeric backbone, and wherein L1 and L2 in combination form a bidentate ligand. - View Dependent Claims (15)
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16. A sensor comprising:
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a working electrode;
a counter electrode; and
a redox mediator disposed proximate to the working electrode, the redox mediator having the formula;
wherein M is osmium;
L is a bidentate ligand comprising at least one imidazole ring;
c is an integer selected from −
1 to −
5 or +1 to +5 indicating a positive or negative charge;
X represents at least one counter ion;
d is an integer from 1 to 5 representing the number of counter ions, X; and
L1, L2, L3 and L4 are ligands, and wherein L1 comprises a heterocyclic ring and is coupled to a polymeric backbone, and wherein L1 and L2 in combination form a bidentate ligand. - View Dependent Claims (18)
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Specification