Redox Polymers

Patent metadata

Field	Value
Publication number	US-2016296147-A1
Application number	US-201615134116-A
Country	US
Kind code	A1
Filing date	Apr 20, 2016
Priority date	Nov 15, 1999
Publication date	Oct 13, 2016
Grant date	—

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.

First claim

1 - 15 . (canceled)

16 . An analyte sensor comprising:
a substrate comprising a non-conductive base material, wherein the substrate comprises a first surface and a second surface that is opposite the first surface; a counter electrode disposed on the first surface of the substrate; a working electrode comprising a conductive layer disposed on the second surface of the substrate; and a reagent positioned on the working electrode, the reagent comprising:
an analyte responsive enzyme; and
a mediator comprising a polymeric transition metal complex comprising:
a polymer backbone; and
at least one spacer attached to the polymer backbone, the at least one spacer comprising at least one non-cyclic functional group selected from the group consisting of —(CR r R s )—, —O—, —S—, —C(O)O—, —S(O) 2 NR k , —OC(O)NR m —, —OC(S)NR n , —C(O)NR t —, —NR u —, —CR v ═N—O—, —CR w ═NNR x —, and —(SiR y R z )—, and wherein R r and R s are independently hydrogen, chlorine, fluorine, or substituted or unsubstituted alkyl, alkoxy, alkenyl, or alkynyl, and R k , R m , R n , R t , R u , R v , R w , R x , R y , and R z are independently hydrogen or substituted or unsubstituted alkyl.

17 . The analyte sensor of claim 16 , wherein the analyte-responsive enzyme is an enzyme selected from the group consisting of glucose oxidase and glucose dehydrogenase.

18 . The analyte sensor of claim 16 , wherein the polymer backbone comprises a nitrogen containing heterocyclic ring.

19 . The analyte sensor unit of claim 16 , wherein the mediator further comprises a plurality of transition metal complexes, each transition metal complex having the formula:

wherein M is osmium;
L 1 is a ligand comprising a heterocycle and is coordinatively bound to M via a heteroatom of the heterocycle;
L 2 , L 3 , L 4 , L 5 , and L 6 are ligands comprising a nitrogen-containing heterocycle, wherein each of L 1 , L 2 , L 3 , L 4 , L 5 , and L 6 ligands is independently a monodentate ligand or is combined with at least one other ligand to form a multidentate ligand; and
wherein at least one of L 1 , L 2 , L 3 , L 4 , L 5 , and L 6 is covalently coupled to the at least one spacer arm.

20 . The analyte sensor of claim 19 , wherein the nitrogen-containing heterocycle comprises a substituted or unsubstituted pyridine, imidazole, 2,2′-bipyridine, 2-(2-pyridyl)imidazole, or 2,2′-biimidazole.

21 . The analyte sensor of claim 19 , wherein at least two of L 1 , L 2 , L 3 , L 4 , L 5 , and L 6 are combined to form at least one multidentate ligand.

22 . The analyte sensor of claim 19 , wherein at least four of L 1 , L 2 , L 3 , L 4 , L 5 , and L 6 are combined to form at least two multidentate ligand.

23 . The analyte sensor of claim 19 , wherein at least four of L 1 , L 2 , L 3 , L 4 , L 5 , and L 6 are combined to form at least two multidentate ligands selected from the group consisting of substituted and unsubstituted 2,2′-bipyridines, 2-(2-pyridyl)imidazoles, and 2,2′-biimidazoles.

24 . The analyte sensor of claim 23 , wherein the mediator comprises at least one substituted or unsubstituted 2,2′-biimidazole or 2-(2-pyridyl)imidazole.

25 . The analyte sensor of claim 19 , wherein the mediator has the formula:

wherein M is osmium;
R 1 and R 2 are independently substituted or unsubstituted alkyl;
R 3 , R 4 , R 5 , and R 6 are independently —H, —F, —Cl, —Br, or substituted or unsubstituted C1 to C12 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; and
d is an integer from 1 to 5 representing the number of counter ions, X.

26 . The analyte sensor of claim 19 , wherein the mediator has the formula:

wherein M is osmium;
R′ 1 are substituted or unsubstituted alkyl;
R′ 3 and R′ 4 and independently —H, —F, —Cl, —Br, or substituted or unsubstituted C1 to C12 alkyl;
R a , R b , R c and R d are independently —H, —F, —Cl, —Br, —CN, —CO 2 H, —SO 3 H, —NO 2 , —NH 2 , —NHNH 2 , —SH, or substituted or unsubstituted C1 to C12 alkylamino, C2 to C24 dialkylamino, C1 to C12 alkoxy, or C1 to C12 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; and
d is an integer from 1 to 5 representing the number of counter ions, X.

27 . The analyte sensor of claim 19 , wherein the mediator has the formula:

wherein M is osmium;
R 18 and R 21 are independently —H, —F, —Cl, —Br, —CN, —CO 2 H, —SO 3 H, —NO 2 , —NH 2 , —NHNH 2 , —SH, or substituted or unsubstituted C1 to C12 alkylamino, C2 to C24 dialkylamino, C1 to C12 alkoxy, or C1 to C12 alkyl;
R 16 , R 17 , R 19 , R 20 , R 22 and R 23 —H or substituted or unsubstituted C1 to C12 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; and
d is an integer from 1 to 5 representing the number of counter ions, X.

28 . The analyte sensor of claim 16 , wherein the analyte-responsive enzyme further comprises an enzyme cofactor.

29 . The analyte sensor unit of claim 28 , wherein the enzyme cofactor is flavin adenine dinucleotide.

30 . The analyte sensor of claim 16 , wherein the polymer is crosslinked.

31 . The analyte sensor of claim 16 , wherein the spacer comprises —C(O)O— or —S(O) 2 NR k —, wherein R k , is hydrogen or substituted or unsubstituted alkyl.

32 . The analyte sensor of claim 16 , wherein the spacer comprises —C(O)NR t —.

33 . The analyte sensor of claim 16 , wherein the spacer comprises —(CR r R s )—, wherein R r and R s are independently hydrogen, chlorine, fluorine, or substituted or unsubstituted alkyl, alkoxy, alkenyl, or alkynyl.

34 . The analyte sensor of claim 16 , wherein the spacer comprises —O— or —S—.

35 . The analyte sensor of claim 16 , wherein the spacer comprises —CR v ═N—O— or —CR w ═NNR x —, wherein R v , is hydrogen or substituted or unsubstituted alkyl and wherein R w and R x are independently hydrogen or substituted or unsubstituted alkyl.

36 . The analyte sensor of claim 16 , wherein the spacer comprises —(SiR y R z )—, wherein R y and R z are independently hydrogen or substituted or unsubstituted alkyl.

Assignees

• Abbott Diabetes Care Inc

Inventors

• Mao Fei
• Heller Adam

Classifications

• C07F9/005 Primary

  Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages · CPC title

• C08F8/42

  Introducing metal atoms or metal-containing groups · CPC title

• A61B5/14532

  for measuring glucose, e.g. by tissue impedance measurement · CPC title

• A61B5/1486 Primary

  using enzyme electrodes, e.g. with immobilised oxidase · CPC title

• A61B5/1477

  non-invasive · CPC title