Emissive polymers and devices incorporating these polymers

• US 8,465,678 B2
• Filed: 04/01/2011
• Issued: 06/18/2013
• Est. Priority Date: 05/05/1998
• Status: Expired due to Fees

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Swager, Timothy M., Yang, Jye-Shane, Williams, Vance, Miao, Yijun, Lugmair, Claus G., Levitsky, Igor A., Kim, Jinsang, Deans, Robert
• Primary Examiner(s): Mui, Christine T
• Application Number:
  US13/078,658
• Publication Number:
  US 20110175035A1
• Time in Patent Office: 809 Days
• Field of Search: 252/500, 252/301.35, 252/301.16
• US Class Current: 252/500
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: C08F 232/00 Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
• CPC Class Codes: C08F 257/02 on to polymers of styrene or alkyl-substituted styrenes
• CPC Class Codes: C08G 61/00 Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule C08G2/00 - C08G16/00 take precedence
• CPC Class Codes: C08G 61/10 only aromatic carbon atoms, e.g. polyphenylenes
• CPC Class Codes: C08L 101/12 characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity liquid crystal materials or compositions C09K19/00
• CPC Class Codes: C08L 65/00 Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain C08L7/00 - C08L57/00, C08L61/00 take precedence; Compositions of derivatives of such polymers
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G01N 2021/7786 Fluorescence
• CPC Class Codes: G01N 21/6428 Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" in vivo A61B5/00; immunoassay G01N33/53
• CPC Class Codes: G01N 21/643 non-biological material
• CPC Class Codes: G01N 21/7703 using reagent-clad optical fibres or optical waveguides using measurement of total internal reflection or attenuated total reflection G01N21/552; optical fibres or waveguides per se G02B
• CPC Class Codes: H10K 10/466 Lateral bottom-gate IGFETs comprising only a single gate
• CPC Class Codes: H10K 10/701 Organic molecular electronic devices
• CPC Class Codes: H10K 30/65 Light-sensitive field-effect devices, e.g. phototransistors
• CPC Class Codes: H10K 50/11 characterised by the electroluminescent [EL] layers
• CPC Class Codes: H10K 85/111 comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
• CPC Class Codes: H10K 85/151 Copolymers
• CPC Class Codes: H10K 85/154 Ladder-type polymers
• CPC Class Codes: H10K 85/30 : Coordination compounds
• CPC Class Codes: H10K 85/615 : Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
• CPC Class Codes: Y02E 10/549 : Organic PV cells

Abstract

The present invention relates to a class of luminescent and conductive polymer compositions having chromophores, and particularly solid films of these compositions exhibiting increased luminescent lifetimes, quantum yields and amplified emissions. These desirable properties can be provided through polymers having rigid groups designed to prevent polymer reorganization, aggregation or π-stacking upon solidification. These polymers can also display an unusually high stability with respect to solvent and heat exposures. The invention also relates to a sensor and a method for sensing an analyte through the luminescent and conductive properties of these polymers. Analytes can be sensed by activation of a chromophore at a polymer surface. Analytes include aromatics, phosphate ester groups and in particular explosives and chemical warfare agents in a gaseous state. The present invention also relates to devices and methods for amplifying emissions by incorporating a polymer having an energy migration pathway and/or providing the polymer as a block co-polymer or as a multi-layer.

Claims

1. An amplification device, comprising:

a pi-conjugated polymer having an energy migration pathway that transports an excitation energy of the polymer upon exposure of the polymer to electromagnetic radiation, and a chromophore covalently attached to the polymer and in electronic communication with the energy migration pathway, wherein the chromophore emits an emission of radiation greater than that emitted from an essentially identical chromophore associated with a polymer that is free of an energy migration pathway, under essentially identical conditions;

a source of energy applicable to the polymer to cause the emission of radiation; and

a detector positioned to detect the emission of radiation,

wherein a luminescence characteristic of the chromophore is changed upon interaction of the polymer and/or chromophore with an analyte molecule.

2. An amplification device of claim 1, wherein the excitation energy is transferred from the energy migration pathway to the chromophore to cause the emission of radiation.

3. An amplification device of claim 1, wherein the energy migration pathway has a length of about 30 angstroms or greater.

4. An amplification device of claim 1, wherein the luminescence characteristic is a fluorescence emission.

5. An amplification device of claim 4, wherein the fluorescence emission is increased in the presence of the analyte molecule.

6. An amplification device of claim 4, wherein the fluorescence emission is decreased in the presence of the analyte molecule.

7. An amplification device as in claim 1, wherein the source of energy is electromagnetic radiation, electrical energy, or chemical energy.

8. An amplification device as in claim 1, wherein the polymer is a polyarylene, polyarylene vinylene, polyarylene ethynylene, or ladder polymer.

9. An amplification device, comprising:

a polymer having an energy migration pathway that transports an excitation energy of the polymer upon exposure of the polymer to electromagnetic radiation, wherein the energy migration pathway has a length of about 30 angstroms or greater, and a chromophore in electronic communication with the energy migration pathway, wherein the chromophore emits an emission of radiation greater than that emitted from an essentially identical chromophore associated with a polymer that is free of an energy migration pathway, under essentially identical conditions;

a source of energy applicable to the polymer to cause the emission of radiation; and

a detector positioned to detect the emission of radiation,

wherein a luminescence characteristic of the chromophore is changed upon interaction of the polymer and/or chromophore with an analyte molecule.

10. An amplification device of claim 9, wherein the excitation energy is transferred from the energy migration pathway to the chromophore to cause the emission of radiation.

11. An amplification device of claim 9, wherein the energy migration pathway has a length of about 30 angstroms or greater.

12. An amplification device of claim 9, wherein the chromophore is covalently attached to the polymer.

13. An amplification device of claim 9, wherein the chromophore is non-covalently associated with the polymer.

14. An amplification device of claim 9, wherein the luminescence characteristic is a fluorescence emission.

15. An amplification device of claim 14, wherein the fluorescence emission is increased in the presence of the analyte molecule.

16. An amplification device of claim 14, wherein the fluorescence emission is decreased in the presence of the analyte molecule.

17. An amplification device as in claim 9, wherein the source of energy is electromagnetic radiation, electrical energy, or chemical energy.

18. An amplification device as in claim 9, wherein the polymer is a polyarylene, polyarylene vinylene, polyarylene ethynylene, or ladder polymer.

19. An amplification device, comprising:

a polymer having an energy migration pathway that transports an excitation energy of the polymer upon exposure of the polymer to electromagnetic radiation, and a chromophore in electronic communication with the energy migration pathway, wherein the chromophore emits a fluorescence emission greater than that emitted from an essentially identical chromophore associated with a polymer that is free of an energy migration pathway, under essentially identical conditions;

a source of energy applicable to the polymer to cause the fluorescence emission; and

a detector positioned to detect the fluorescence emission,

wherein the fluorescence emission is decreased upon interaction of the polymer and/or chromophore with an analyte molecule.

20. An amplification device of claim 19, wherein the excitation energy is transferred from the energy migration pathway to the chromophore to cause the emission of radiation.

21. An amplification device of claim 19, wherein the energy migration pathway has a length of about 30 angstroms or greater.

22. An amplification device of claim 19, wherein the chromophore is covalently attached to the polymer.

23. An amplification device of claim 19, wherein the chromophore is non-covalently associated with the polymer.

24. An amplification device as in claim 19, wherein the source of energy is electromagnetic radiation, electrical energy, or chemical energy.

25. An amplification device as in claim 19, wherein the polymer is a polyarylene, polyarylene vinylene, polyarylene ethynylene, or ladder polymer.