NEAR-IR GLUCOSE SENSORS

1 .- 89 . (canceled)

90 . A sensor for detecting an analyte comprising a polymer, wherein the polymer comprises one or more residues of the compound of Formula IA:

or a tautomer or a salt thereof,

R 15 , at each occurrence, is independently H or C 1 -C 6 alkyl;

R 1 at each occurrence, is H, optionally substituted C 1 -C 6 alkyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted C 2 -C 6 alkynyl, optionally substituted C 2 -C 10 heteroalkyl, polymerizable moiety, an NIR dye moiety, an electron-withdrawing group, or an electron-donating group;

X 1 and X 2 are independently H or C 1 -C 6 alkyl;

R 2 is H or C 1 -C 6 alkyl;

Z is a C 6 -C 14 arylene optionally substituted with R 11 , R 12 , R 14 , and L 2 R 13 ;

R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 , and R 14 are independently H, optionally substituted C 1 -C 6 alkyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted C 2 -C 6 alkynyl, optionally substituted C 2 -C 10 heteroalkyl, polymerizable moiety, NIR dye moiety, electron-withdrawing group, or electron-donating group;

R 9 and R 10 are independently H, C 1 -C 6 alkyl, polymerizable moiety, or NIR dye moiety;

L 1 , L 2 , and L 3 are independently a bond or a linker group; and

wherein at least one R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , or R 14 is an NIR dye moiety and at least one R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , or R 14 is a polymerizable moiety.

91 . The sensor of claim 90 , wherein the electron-withdrawing group is selected from the group consisting of halogen, C(O)R′, COOR′, C(O)NH 2 , C(O)NR′R″, CF 3 , CN, SO 3 H, SO 2 CF 3 , SO 2 R′, SO 2 NR′R″, ammonium, alkyl ammonium, and NO 2 , wherein R′ and R″ are independently H or C 1 -C 6 alkyl; and/or

wherein electron-donating group is selected from the group consisting of NR N1 R N2 , OR′, NHC(O)R′, OC(O)R′, phenyl, and vinyl, wherein R N1 , R N2 , and R′ are independently H or C 1 -C 6 alkyl.

92 . The sensor of claim 90 , wherein L 1 , L 2 , or L 3 are, independently, a bond or a linker group selected from optionally substituted amino, optionally substituted amido, —O—, optionally substituted —CH 2 C 6 H 4 O—, C 2 -C 20 PEG linker, optionally substituted C 6 -C 10 arylene, optionally substituted five to ten member heteroarylene, optionally substituted —C 1 -C 6 alkylene-Ar—, optionally substituted —C 2 -C 6 alkenylene-Ar—, optionally substituted —C 2 -C 6 alkynylene-Ar—, optionally substituted —C(O)NH—C 1 -C 6 alkylene-Ar—, optionally substituted —C 1 -C 6 alkylene-C(O)NH—C 1 -C 6 alkylene-Ar—, —(CH 2 CH 2 O) n —, —(CH 2 CH 2 O) p CH 2 CH 2 —, optionally substituted C 1 -C 10 alkyl, optionally substituted C 2 -C 10 alkenyl, optionally substituted C 2 -C 10 alkynyl, and optionally substituted C 2 -C 20 heteroalkyl, wherein n is an integer from 1 to 10 , p is 2, 3, 4, or 5, and Ar is C 6 -C 10 arylene or five to ten member heteroarylene.

93 . The sensor of claim 90 , wherein L 1 , L 2 , or L 3 , independently comprises one or more substituents selected from a carboxylic group, a sulfonic acid group, ammonium, and an amino group.

94 . The sensor of claim 90 , wherein polymerizable moiety is selected from —NH(CO)C(R)CH 2 , —O(CO)C(R)CH 2 , and —CHCH 2 , wherein R is H or C 1 -C 3 alkyl.

95 . The sensor of claim 90 , wherein the NIR dye moiety is cyanine, hemicyanine, fluorone, oxazine, phenanthridine, rhodamine, rosamine, indolium, quinolinium, benzophenoxazine, benzopyrillium, bisindoylmaleimide, boron-dipyrromethene, boron-aza-dipyrromethene, carbopyronins, perylene, porphyrin, ruthenium complex, lanthanide complex, benzoxanthenium, xanthene, fluorescein, squaraine, coumarin, anthracene, tetracene, pentacene, or pyrene dye residue.

96 . The sensor of claim 90 , wherein the NIR dye moiety has the structure selected from:

or a tautomer or a salt thereof, wherein R N1 and R N2 are independently C 1 -C 10 alkyl optionally substituted with one or more groups selected from —SO 3 H, —SO 3 —, —CO 2 H, or —CO 2 —, and

denotes the point of attachment to L 2 ; or

the NIR dye moiety has the structure of:

wherein R′, at each occurrence, is independently H, optionally substituted C 1 -C 10 alkyl, optionally substituted C 2 -C 10 alkenyl, optionally substituted C 2 -C 10 alkynyl, or optionally substituted C 2 -C 20 heteroalkyl.

97 . The sensor of claim 90 , wherein the NIR dye moiety has the structure of:

wherein Y 1 is selected from O, P(O)R′, SiR′R″, and NR′, wherein R′ and R″ are independently H or C 1 -C 6 alkyl;

R 20 and R 21 are independently H, C 1 -C 6 alkyl, or R 21 and R 20 , together with the nitrogen atom to which they are attached, form a form a 6- or 5-memebered ring optionally substituted with a polymerizable moiety;

R 23 and R 24 are independently H, C 1 -C 6 alkyl, or R 23 and R 24 , together with the nitrogen atom to which they are attached, form a form a 6- or 5-membered ring optionally substituted with a polymerizable moiety;

R 22 and R 25 are independently H, C 1 -C 6 alkyl, or R 21 and R 22 , together with the atoms to which they are attached, form a 6- or 5-membered ring, or R 24 and R 25 , together with the atoms to which they are attached, form a 6- or 5-membered ring; and

R 26 and R 27 are independently H, C 1 -C 6 alkyl, or R 26 and R 20 , together with the atoms to which they are attached, form a 6- or 5-membered ring, or R 27 and R 23 , together with the atoms to which they are attached, form a 6- or 5-membered ring.

98 . The sensor of claim 97 , wherein Y 1 is SiMe 2 .

99 . The sensor of claim 90 , wherein the compound has the structure of Formula II:

or a tautomer or a salt thereof,

wherein the dotted lines denote an absence of a bond;

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , L 1 , L 2 and L 3 are as defined in claim 90 , and wherein at least one R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , or R 14 is an NIR dye moiety and at least one R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , or R 14 is a polymerizable moiety.

100 . The sensor of claim 90 , wherein the compound has a structure of Formula III:

or a tautomer or a salt thereof,

wherein the dotted lines denote an absence of a bond;

R 15 , at each occurrence, is independently H or C 1 -C 6 alkyl;

R 1 , at each occurrence, is H, optionally substituted C 1 -C 6 alkyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted C 2 -C 6 alkynyl, optionally substituted C 2 -C 10 heteroalkyl, polymerizable moiety, NIR dye moiety, electron-withdrawing group, or electron-donating group;

X 1 and X 2 are independently H or C 1 -C 6 alkyl;

R 2 is H or C 1 -C 6 alkyl;

R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , and R 14 are independently H, optionally substituted C 1 -C 6 alkyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted C 2 -C 6 alkynyl, optionally substituted C 2 -C 10 heteroalkyl, polymerizable moiety, NIR dye moiety, electron withdrawing group, or electron donating group;

R 9 , R 10 , and R 13 are independently H, optionally substituted C 1 -C 6 alkyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted C 2 -C 6 alkynyl, optionally substituted C 2 -C 10 heteroalkyl, polymerizable moiety, or NIR dye;

L 1 , L 2 , and L 3 are independently linker group or a bond; and

wherein at least one R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , or R 14 is a polymerizable moiety.

101 . The sensor of claim 100 , wherein the electron-withdrawing group is selected from the group consisting of halogen, C(O)R′, COOR′, C(O)NH 2 , C(O)NR′R″, CF 3 , CN, SO 3 H, SO 2 CF 3 , SO 2 R′, SO 2 NR′R″, ammonium, alkyl ammonium, and NO 2 , wherein R′ and R″ are independently H or C 1 -C 6 alkyl; and/or

wherein the electron-donating group is selected from the group consisting of NR N1 R N2 , OR′, NHC(O)R′, OC(O)R′, phenyl, and vinyl, wherein R N1 , R N2 , and R′ are independently H or C 1 -C 6 alkyl.

102 . The sensor of claim 100 , wherein L 1 , L 2 , and L 3 , are, independently, a bond or a linker group selected from optionally substituted amino, optionally substituted amido, —O—, optionally substituted —CH 2 C 6 H 4 O—, C 2 -C 20 PEG linker, optionally substituted C 6 -C 10 arylene, optionally substituted five to ten member heteroarylene, optionally substituted —C 1 -C 6 alkylene-Ar—, optionally substituted C 2 -C 6 alkenylene-Ar—, optionally substituted C 2 -C 6 alkynylene-Ar—, optionally substituted —C(O)NH-C 1 -C 6 alkylene-Ar—, optionally substituted —C 1 -C 6 alkylene-C(O)NH—C 1 -C 6 alkylene-Ar—, —(CH 2 CH 2 O) n —, —(CH 2 CH 2 O) p CH 2 CH 2 —, optionally substituted C 1 -C 10 alkyl, optionally substituted C 2 -C 10 alkenyl, optionally substituted C 2 -C 10 alkynyl, and optionally substituted C 2 -C 20 heteroalkyl, wherein n is an integer from 1 to 10, p is 2, 3, 4, or 5, and Ar is C 6 -C 10 arylene or five to ten member heteroarylene.

103 . The sensor of claim 90 , wherein the polymer is a hydrogel.

104 . The sensor of claim 90 , wherein the compound has excitation and emission spectra in the NIR optical window of mammalian skin.

105 . The sensor of claim 90 , wherein the compound has an absorption maximum between about 500 nm and about 900 nm and an emission maximum between about 600 nm and about 1000 nm.

106 . The sensor of claim 90 , wherein the residue of the compound is present at a concentration from about 0.01 mM to about 20 mM, about 0.1 mM to about 20 mM, about 0.5 mM to about 10 mM, about 1 mM to about 20 mM, about 5 mM to about 20 mM, or about 5 mM to about 10 mM.

107 . The sensor of claim 90 , wherein the polymer further comprises the residues of HEMA, N,N-dimethylacrylamide, poly-ethylene glycol diacrylamide, or mixtures therof.

108 . The sensor of claim 90 , wherein the polymer further comprises the residues of 2-(acryloyloxy)ethyl]trimethylammonium chloride, 2-carboxyethyl acrylate, poly-ethylene glycol diacrylamide, or mixtures thereof.

109 . The sensor of claim 90 , wherein the polymer further comprises the residues N,N-dimethylacrylamide, acrylamide, poly-ethylene glycol diacrylamide, or mixtures thereof.

110 . The sensor of claim 90 , wherein the analyte is glucose.

111 . The sensor of claim 90 , further comprising a catalase.