Luminescent 1-hydroxy-2-pyridinone chelates of lanthanides

1. A compound having the structure:

wherein

R 2 , R 3 , and R 4 are members independently selected from H, an aryl group substituent, a linker to a scaffold moiety, and a linker to a functional moiety;

R 7 , R 8 , and R 9 are members independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocycloalkyl, halogen, CN, CF 3 , —C(O)R 17 , —SO 2 NR 17 R 18 , —NR 17 R 18 , —OR 17 , —S(O) 2 R 17 , —COOR 17 , —S(O) 2 OR 17 , —OC(O)R 17 , —C(O)NR 17 R 18 , —NR 17 C(O)R 18 , —NR 17 SO 2 R 18 , —NO 2 , a linker to a functional moiety, and a linker to a scaffold moiety,

wherein

at least two of R 7 , R 8 , and R 9 are optionally joined to form a ring system which is a member selected from substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;

R 17 and R 18 are each members independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocycloalkyl, a linker to a functional moiety, and a linker to a scaffold moiety; and R 17 and R 18 , together with the atoms to which they are attached, are optionally joined to form a 5- to 7-membered ring;

A and B are members independently selected from carbon, nitrogen, sulfur, and oxygen;

D is a member selected from carbon and nitrogen;

wherein if A is oxygen or sulfur, R 9 is not present;

wherein if B is oxygen or sulfur, R 7 is not present;

Z is a member selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocycloalkyl, N, NR 30 , O, S, and CR 31 R 32 ,

wherein R 30 , R 31 , and R 32 are members independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted heterocycloalkyl;

Y 1 and Y 2 are linker moieties, which are members independently selected from —C(O), —C(O)NR 5 —, —C(O)O—, —C(O)S—, and —C(O)CR 20 R 21 ,

wherein R 5 , R 20 , and R 21 are members independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocycloalkyl, and a functional moiety; and

L 1 and L 2 are linker groups, which are members independently selected from a bond, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted heterocycloalkyl;

wherein at least one of Z, L 1 , and L 2 is substituted with a moiety having the structure:

wherein

L 3 is a linker group, which is a member selected from a bond, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted heterocycloalkyl;

O has the structure:

wherein

Z 2 is a member selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocycloalkyl, N, NR 30 , O, S, and CR 31 R 32 ,

Y 3 and Y 4 are linker moieties, which are members independently selected from —C(O), —C(O)NR 5 —, —C(O)O—, —C(O)S—, and —C(O)CR 20 R 21 ,

L 4 and L 5 are linker groups, which are members independently selected from a bond, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted heterocycloalkyl; and

one of Z 2 , L 4 , and L 5 is linked to L 3 ;

wherein said compound is substituted with at least one functional moiety having the structure:

wherein

L 6 is a linker group, which is a member selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl; and

X 1 is a member selected from a reactive functional group and a targeting moiety.

2. The compound according to claim 1 , wherein the scaffold moiety is a member selected from substituted or unsubstituted alkyl and substituted or unsubstituted heteroalkyl.

3. The compound according to claim 1 , wherein at least one of Z, Y 1 , Y 2 , L 1 , and L 2 is substituted with a functional moiety.

4. The compound according to claim 1 , wherein Z is O, and L and L 2 are each ethyl.

5. The compound according to claim 1 , wherein said targeting moiety comprises a member selected from a small-molecule ligand, a peptide, a protein, a fusion protein, an enzyme, an antibody, an antibody fragment, an antigen, a nucleic acid, a carbohydrate, a lipid, and a pharmacologically active molecule.

6. The compound according to claim 1 , wherein said reactive functional group is a member selected from —OH, —SH, —NH 2 , —C(O)NHNH 2 (hydrazide), maleimide, activated ester, aldehyde, ketone, hydroxylamine, imidoester, isocyanate, isothiocyanate, sulfonylchloride, acylhalide, and —COOY, wherein Y is a member selected from H, a negative charge and a salt counter-ion.

7. The compound according to claim 1 , wherein the functional moiety is a member selected from:

wherein X 2 is a member selected from OH, alkoxy,

wherein R 22 is a member selected from H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl;

v is an integer from 1 to 20; and

w is an integer from 1 to 1,000.

8. The compound according to claim 1 , wherein said functional moiety has the structure:

wherein,

Z 5 is a member selected from H, OR 23 , SR 23 , NHR 23 , OCOR 24 , OC(O)NHR 24 , NHC(O)OR 23 , OS(O) 2 OR 23 , and C(O)R 24 ;

wherein

R 23 is a member selected from H, substituted or unsubstituted alkyl, and substituted or unsubstituted heteroalkyl;

R 24 is a member selected from H, OR 25 , NR 25 NH 2 , SH, C(O)R 25 , NR 25 H, substituted or unsubstituted alkyl, and substituted or unsubstituted heteroalkyl;

wherein

R 25 is a member selected from H, substituted or unsubstituted alkyl, and substituted or unsubstituted alkyl;

X 3 is a member selected from O, S, and NR 26

wherein

R 26 is a member selected from H, substituted or unsubstituted alkyl, and substituted or unsubstituted heteroalkyl; and

j and k are members independently selected from the group consisting of integers from 1 to 20.

9. The compound according to claim 1 , wherein said functional moiety comprises a polyether.

10. The compound according to claim 9 , wherein said polyether is a member selected from polyethylene glycol (PEG) and derivatives thereof.

11. The compound according to claim 10 , wherein said polyether has a molecular weight of about 50 to about 10,000 daltons.

12. The compound according to claim 1 , having a structure selected from:

13. A complex comprising a compound according to claim 1 and a metal ion.

14. The complex according to claim 13 , wherein said metal ion is selected from a lanthanide ion, an actinide ion, and a transition metal ion.

15. The complex according to claim 14 , wherein said lanthanide ion is selected from La 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Er 3+ , Tm 3+ , Yb 3+ , and Lu 3+ .

16. The complex according to claim 14 , wherein said actinide ion is selected from U 6+ , Np 4+ , Np 5+ , Pu 4+ , and Am 3+ .

17. The complex according to claim 14 , wherein said transition metal ion is Fe 3+ .

18. The complex according to claim 13 , wherein the metal is a radioactive isotope.