Chromophoric polymer dots with narrow-band emission

Patent metadata

Field	Value
Publication number	US-10150841-B2
Application number	US-201214366863-A
Country	US
Kind code	B2
Filing date	Dec 27, 2012
Priority date	Dec 30, 2011
Publication date	Dec 11, 2018
Grant date	Dec 11, 2018

Abstract

Polymers, monomers, chromophoric polymer dots and related methods are provided. Highly fluorescent chromophoric polymer dots with narrow-band emissions are provided. Methods for synthesizing the chromophoric polymers, preparation methods for forming the chromophoric polymer dots, and biological applications using the unique properties of narrow-band emissions are also provided.

First claim

What is claimed is:

1. A polymer dot comprising:
a condensed chromophoric polymer comprising a semiconducting polymer, wherein the semiconducting polymer comprises a narrow-band emissive monomer, the condensed chromophoric polymer having an emission spectrum with a full width half maximum (FWHM) of less than about 70 nm, and wherein the ratio of the number of narrow-band emissive monomers to the number of other monomers is about 1:20 or less.

2. The polymer dot of claim 1 , wherein the chromophoric polymer is a homopolymer or a heteropolymer.

3. The polymer dot of claim 1 , wherein the chromophoric polymer further comprises a first general monomer, a second general monomer, or a combination thereof, and wherein the first and second general monomer have an emission spectrum with a full width half maximum of greater than 70 nm.

4. The polymer dot of claim 1 , wherein the narrow-band emissive monomer, the first general monomer, the second general monomer, or a combination thereof are integrated into the backbone of the chromophoric polymer.

5. The polymer dot of claim 1 , wherein the narrow-band emissive monomer is a BODIPY derivative.

6. The polymer dot of claim 5 , wherein the BODIPY derivative has the formula:

wherein each of R 1 , R 2A , R 2B , R 3A , R 3B , R 4A and R 4B is independently selected from the group consisting of hydrogen, alkyl, aralkyl, aryl, and alkoxy-aryl, and wherein the BODIPY derivative is integrated into the chromophoric polymer by attachment to R 1 , R 2A , R 2B , R 3A , R 3B , R 4A , R 4B or a combination thereof.

7. The polymer dot of claim 1 , wherein the narrow-band emissive monomer is a squaraine derivative.

8. The polymer dot of claim 7 , wherein the squaraine derivative has the formula:

each of X 1 and X 2 is independently selected from the group consisting of oxygen, sulfur and nitrogen; each of R 1A and R 1B is independently selected from the group consisting of, but not limited to, alkylene, alkenylene, arylene, heteroarylene, phenylene, azulene, cycloalkylene, and heterocycloalkylene; and each of R 2A and R 2B is a reactive group independently selected from the group consisting of, but not limited to, a halide, hydroxyl, and amino, and wherein the squaraine derivative is integrated into the chromophoric polymer by attachment to R 1A , R 1B , R 2A , R 2B or a combination thereof.

9. The polymer dot of claim 1 , wherein the narrow-band emissive monomer is a metal complex derivative.

10. The polymer dot of claim 1 , wherein the narrow-band emissive monomer is a porphyrin derivative.

11. The polymer dot of claim 1 , wherein the narrow-band emissive monomer is a metalloporphyrin derivative.

12. The polymer dot of claim 1 , wherein the narrow-band emissive monomer is a lanthanide complex derivative.

13. The polymer dot of claim 1 , wherein the narrow-band emissive monomer is a perylene derivative.

14. The polymer dot of claim 1 , wherein the narrow-band emissive monomer is a cyanine derivative.

15. The polymer dot of claim 3 , wherein the first general monomer and the second general monomer are each independently selected from the group consisting of fluorene, a fluorene derivative, phenylene vinylene, a phenylene vinylene derivative, phenylene, a phenylene derivative, benzothiadiazole, a benzothiadiazole derivative, thiophene, a thiophene derivative, carbazole fluorene, and a carbazole fluorene derivative.

16. The polymer dot of claim 1 , wherein the condensed chromophoric polymer further comprises a functional group rendering the surface of the condensed chromophoric polymer available for conjugation or bioconjugation.

17. The polymer dot of claim 16 , wherein the functional group is a hydrophobic functional group.

18. The polymer dot of claim 17 , wherein the hydrophobic functional group is selected from the group consisting of alkyne, strained alkyne, azide, diene, alkene, cyclooctyne, and phosphine.

19. The polymer dot of claim 16 , wherein the functional group is a hydrophilic functional group.

20. The polymer dot of claim 19 , wherein the hydrophilic functional group is selected from the group consisting of carboxylic acid or salts thereof, amino, mercapto, azido, aldehyde, ester, hydroxyl, carbonyl, sulfate, sulfonate, phosphate, cyanate, and succinimidyl ester.

21. The polymer dot of claim 16 , wherein the functional group is conjugated to a biomolecule.

22. The polymer of claim 21 , wherein the biomolecule is selected from the group consisting of a protein, a glycoprotein, a peptide, an amino acid, a metabolite, a drug, a toxin, a nucleic acid, a carbohydrate, a sugar, a lipid, and a fatty acid.

23. The polymer dot of claim 1 , further comprising a polymer physically blended or chemically cross-linked with the chromophoric polymer, wherein the polymer is a conjugated polymer or a non-semiconducting polymer.

24. The polymer dot of claim 1 , wherein the FWHM is less than about 60 nm, less than about 50 nm, less than about 40 nm, less than about 30 nm, or less than about 20 nm.

25. The polymer dot of claim 1 , wherein the condensed chromophoric polymer comprises a quantum yield greater than about 10%, greater than about 20%, greater than about 30%, greater than about 40%, greater than about 50%, greater than about 70%, or greater than about 90%.

26. The polymer dot of claim 1 , wherein the condensed chromophoric polymer is stable over a period of greater than about 1 month, greater than about 3 months, greater than about 6 months, or greater than about 1 year.

27. The polymer dot of claim 1 , wherein the polymer dot is free of secondary structure comprising a beta-phase secondary structure.

28. A polymer dot comprising:
a condensed chromophoric polymer comprising a semiconducting polymer, wherein the semiconducting polymer comprises a narrow-band unit attached to the backbone or a sidechain of the polymer, wherein the narrow-band unit comprises an emission spectrum with a full width half maximum (FWHM) of less than about 70 nm, wherein the backbone comprises a first general monomer, a second general monomer, or a combination thereof, wherein the narrow-band unit comprises a narrow-band emissive monomer, and wherein the ratio of the number of narrow-band emissive monomers to the number of other monomers is about 1:20 or less.

29. The polymer dot of claim 28 , wherein the narrow-band unit is covalently attached to the backbone or the sidechain.

30. The polymer dot of claim 28 , wherein the narrow-band unit comprises a fluorescent nanoparticle embedded in or attached to the polymer dot.

31. The polymer dot of claim 30 , wherein the fluorescent nanoparticle is a quantum dot.

32. The polymer dot of claim 28 , wherein the narrow-band unit comprises a fluorescent molecule.

33. The polymer dot of claim 28 , wherein the fluorescent molecule is a polymer or a dye molecule.

34. The polymer dot of claim 28 , wherein the narrow-band emissive monomer is a BODIPY derivative.

35. The polymer dot of claim 34 , wherein the BODIPY derivative has the formula:

Assignees

• Univ Washington Through Its Center For Commercialization

Inventors

• Chiu Daniel T
• Wu Changfeng
• Rong Yu
• Zhang Yong
• Wu Yi-Che
• Chan Yang-Hsiang
• Zhang Xuanjun
• Yu Jiangbo
• Sun Wei

Classifications

• G01N33/587

  Nanoparticles · CPC title

• A61K49/0019 Primary

  characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules · CPC title

• B82Y30/00

  Nanotechnology for materials or surface science, e.g. nanocomposites · CPC title

• C08G79/00

  Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon {with or without the latter elements in the main chain of the macromolecule} · CPC title

• B82Y40/00

  Manufacture or treatment of nanostructures · CPC title