| Sonstiges: |
- Nachgewiesen in: USPTO Patent Grants
- Sprachen: English
- Patent Number: 10533,092
- Publication Date: January 14, 2020
- Appl. No: 15/837959
- Application Filed: December 11, 2017
- Assignees: BECTON, DICKINSON AND COMPANY (Franklin Lakes, NJ, US)
- Claim: 1. A water soluble light harvesting multichromophore comprising a conjugated segment having the structure of formula (I): [chemical expression included] wherein: F 1 is a fused tricyclic co-monomer substituted with a water soluble group (WSG); M 1 is an aryl or heteroaryl co-monomer; n is an integer from 1 to 100,000; and * denotes a site for covalent attachment to the unsaturated backbone of a conjugated polymer or an end group; wherein at least one of F 1 and M 1 is substituted with a branched non-ionic water soluble group (WSG) comprising two or more water soluble polymers each having 6-50 monomeric units; wherein the branched non-ionic water soluble group is capable of imparting solubility in water in excess of 50 mg/mL to the multichromophore, and has one of the following formulae: [chemical expression included] wherein: each B 1 and B 2 are independently a branching group selected from the group consisting of CH, N, C(═O)N, SO 2 N, a tri-substituted aryl group, a tetra-substituted aryl group, and a tri-substituted heteroaryl group; each W 1 is independently a water soluble polymer comprising 6-24 monomeric units; T 3 is an optional linker to the fused 6-5-6 tricyclic co-monomer; and each p and q are independently 0 or 1, wherein if present, each T 1 and each T 2 are independently a linker, wherein each T 1 is independently selected from the group consisting of (CH 2) n —O—, —O—(CH 2) n —, —(CH 2) n —, and —O—.
- Claim: 2. The water soluble light harvesting multichromophore according to claim 1 , wherein the fused tricyclic co-monomer is described by the following structure: [chemical expression included] wherein: Y is C(R 3) 2 , —C(R 3) 2 C(R 3) 2 —, —C(R 3) 2 Si(R 3) 2 —, NR 3 , Si(R 3) 2 or Se; each Z is independently CH, CR or N, wherein at least two of Z in each ring is CH or CR; each R 3 is independently selected from H, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, substituted acyl, alkoxy, substituted alkoxy, amido, substituted amido, an aralkyl, a substituted aralkyl, a PEG moiety, -L 1 -Z 1 , where L 1 is a linker and Z 1 is a chemoselective tag and a WSG; and each R is independently H, WSG, halogen, alkoxy, substituted alkoxy, alkyl or substituted alkyl, and wherein any two convenient R groups are optionally cyclically linked.
- Claim: 3. The water soluble light harvesting multichromophore according to claim 2 , wherein the fused tricyclic co-monomer is described by one of the following structures: [chemical expression included] [chemical expression included] wherein: each R 3 is independently selected from H, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, substituted acyl, alkoxy, substituted alkoxy, amido, substituted amido, an aralkyl, a substituted aralkyl, a PEG moiety, -L 1 -Z 1 , where L 1 is a linker and Z 1 is a chemoselective tag and a WSG.
- Claim: 4. The water soluble light harvesting multichromophore according to claim 1 , wherein the branched non-ionic WSG is selected from one of the following structures: [chemical expression included] [chemical expression included] wherein: T 5 is an optional linker to the fused 6-5-6 tricyclic co-monomer; T 6 is a linker; each s is an integer from 6 to 24; and each R 11 is independently hydrogen, an alkyl or a substituted alkyl.
- Claim: 5. The water soluble light harvesting multichromophore according to claim 1 , wherein F 1 is selected from one of the following co-monomers: [chemical expression included] [chemical expression included]
- Claim: 6. The water soluble light harvesting multichromophore according to claim 1 , wherein the aryl or heteroaryl co-monomers are independently selected from one of formulae (XXIII)-(XXVI): [chemical expression included] wherein Cy 2-7 is an aryl or heteroaryl group comprising 2 to 7 fused and/or unfused rings; Y 2 , Y 3 and Y 4 are independently selected from —CR 3 —, NR 3 , N, O, S and —C(═O)— and together form a 5 or 6 membered fused aryl or heteroaryl ring; each R 3 is one or more ring substituents independently selected from H, halogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, substituted acyl, sulfonic acid, cyano, alkoxy substituted alkoxy and -T 1 -Z 1 ; R 1 and R 2 are independently selected from H, halogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, substituted acyl, sulfonic acid, cyano, alkoxy, substituted alkoxy and -T 1 -Z 1 , or R 1 and R 2 together form a 5- or 6-membered fused aryl, heteroaryl ring, cycloalkyl or heterocycle which can be optionally substituted; Y 5 is N or CR 5 and Y 7 is N or CR 7 ; R 4 -R 7 are independently selected from H, halogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, substituted acyl, sulfonic acid, cyano, alkoxy, substituted alkoxy and -T 1 -Z 1 ; Z 1 is a chemoselective functional group or a linked signaling chromophore; and T 1 is a linker.
- Claim: 7. The water soluble light harvesting multichromophore according to claim 6 , wherein the aryl or heteroaryl co-monomers are independently selected from one of the following structures (a) to (x): [chemical expression included] [chemical expression included] [chemical expression included] [chemical expression included] wherein: Y 8 is C(R 3) 2 , —C(R 3) 2 C(R 3) 2 —, —C(R 3) 2 Si(R 3) 2 —, NR 3 or Si(R 3) 2 ; X is S or O; each R 3 is independently H, a water solubilizing group, amino, substituted amino, halogen, cyano, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, substituted acyl, sulfonic acid, cyano, alkoxy, substituted alkoxy and -T 1 -Z 1 ; R 1 and R 2 are independently selected from H, halogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, substituted acyl, sulfonic acid, cyano, alkoxy, substituted alkoxy and -T 1 -Z 1 , or R 1 and R 2 together form a 5- or 6-membered fused aryl, heteroaryl, cycloalkyl or heterocycle ring which can be optionally substituted; Z 1 is a chemoselective functional group or a linked signaling chromophore; and T 1 is a linker.
- Claim: 8. The water soluble light harvesting multichromophore according to claim 6 , wherein the aryl or heteroaryl co-monomers are independently selected from one of the following structures (ba) to (cd): [chemical expression included] [chemical expression included] [chemical expression included] [chemical expression included] wherein: X is S or O; Y 9 is C(R 4) 2 , —C(R 4) 2 C(R 4) 2 — or Si(R 4) 2 ; each R 4 is independently H, a water solubilizing group, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, substituted acyl, sulfonic acid, cyano, alkoxy, substituted alkoxy and -T 1 -Z 1 ; and R 1 and R 2 are independently selected from H, halogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, substituted acyl, sulfonic acid, cyano, alkoxy, substituted alkoxy and -T 1 -Z 1 , or R 1 and R 2 together form a 5- or 6-membered fused aryl or heteroaryl ring which can be optionally substituted.
- Claim: 9. The water soluble light harvesting multichromophore according to claim 6 , wherein the aryl or heteroaryl co-monomers are independently selected from a substituted or unsubstituted 1,4-phenyl, a substituted or unsubstituted 1,3-phenyl, a substituted or unsubstituted 4,4′-biphenyl, a substituted or unsubstituted 2,5-pyridyl, and a substituted or unsubstituted 2,6-pyridyl.
- Claim: 10. The water soluble light harvesting multichromophore according to claim 9 , wherein the aryl or heteroaryl co-monomer is selected from one of the following structures: [chemical expression included] wherein Z 2 -Z 5 are each independently CR or N, where at least one Z 2 -Z 5 is N; and each R and each R 11 -R 16 are independently selected from the group consisting of hydrogen, water solubilizing group, halogen, cyano, alkoxy, substituted alkoxy, alkyl and substituted alkyl.
- Claim: 11. The water soluble light harvesting multichromophore according to claim 6 , wherein each co-monomer is substituted with a WSG independently selected from one of the following structures: [chemical expression included] [chemical expression included] [chemical expression included] wherein: T 5 is an optional linker; each T 6 is an linker; R 11 and R are independently H, alkyl or substituted alkyl; and each s is an integer from 1 to 50.
- Claim: 12. The water soluble light harvesting multichromophore according to claim 6 , wherein the aryl or heteroaryl co-monomers are independently selected from one of the following structures: [chemical expression included] [chemical expression included] [chemical expression included] [chemical expression included] [chemical expression included] [chemical expression included] [chemical expression included] [chemical expression included]
- Claim: 13. The water soluble light harvesting multichromophore according to claim 1 , wherein the branched non-ionic water soluble group (WSG) has the formula: [chemical expression included]
- Claim: 14. The water soluble light harvesting multichromophore according to claim 1 , wherein the branched non-ionic water soluble group (WSG) has the formula: [chemical expression included]
- Claim: 15. The water soluble light harvesting multichromophore according to claim 1 , wherein the branched non-ionic water soluble group (WSG) has the formula: [chemical expression included]
- Patent References Cited: 7144950 December 2006 Bazan et al. ; 7153358 December 2006 Weber et al. ; 7214489 May 2007 Bazan et al. ; 7241513 July 2007 Suzuki et al. ; 7270956 September 2007 Bazan et al. ; 7318964 January 2008 Cho et al. ; 7629448 December 2009 Bazan et al. ; 7666594 February 2010 Bazan et al. ; 7691491 April 2010 Saitoh et al. ; 7811755 October 2010 Bazan et al. ; 7897684 March 2011 Bazan et al. ; 7914984 March 2011 Bazan et al. ; 8101416 January 2012 Bazan et al. ; 8110673 February 2012 Bazan et al. ; 8158444 April 2012 Gaylord et al. ; 8227187 July 2012 Bazan et al. ; 8309672 November 2012 Bazan et al. ; 8338532 December 2012 Bazan et al. ; 8354239 January 2013 Gaylord et al. ; 8362193 January 2013 Gaylord et al. ; 8383762 February 2013 Beaujuge et al. ; 8455613 June 2013 Gaylord et al. ; 8546081 October 2013 Bazan et al. ; 8575303 November 2013 Gaylord et al. ; 8617814 December 2013 Bazan et al. ; 8669055 March 2014 Bazan et al. ; 8759444 June 2014 Bazan et al. ; 8802450 August 2014 Gaylord et al. ; 8822633 September 2014 Marrocco et al. ; 8835113 September 2014 Bazan et al. ; 8841072 September 2014 Bazan et al. ; 8969509 March 2015 Liu et al. ; 8993335 March 2015 Bazan et al. ; 9085799 July 2015 Bazan et al. ; 9139869 September 2015 Gaylord et al. ; 9159465 October 2015 Bazan et al. ; 9371559 June 2016 Bazan et al. ; 9383353 July 2016 Gaylord et al. ; 9547008 January 2017 Gaylord et al. ; 9691990 June 2017 Mun et al. ; 9722252 August 2017 Liu et al. ; 2004/0142344 July 2004 Bazan et al. ; 2005/0031801 February 2005 Shundo et al. ; 2005/0191229 September 2005 Chiang et al. ; 2008/0064042 March 2008 Bazan et al. ; 2008/0293164 November 2008 Gaylord et al. ; 2009/0214969 August 2009 Coggan et al. ; 2009/0230362 September 2009 Bazan et al. ; 2010/0136702 June 2010 Bazan et al. ; 2011/0256549 October 2011 Gaylord et al. ; 2012/0028828 February 2012 Gaylord et al. ; 2012/0252986 October 2012 Liu et al. ; 2013/0190193 July 2013 Bazan et al. ; 2014/0011010 January 2014 Devadoss ; 2015/0226746 August 2015 Bazan et al. ; 2016/0266131 September 2016 Liang et al. ; 2016/0266132 September 2016 Gaylord et al. ; 2016/0341720 November 2016 Bazan et al. ; 2016/0349267 December 2016 Gaylord et al. ; 2017/0115298 April 2017 Gaylord et al. ; WO 2004/001379 December 2003 ; WO 2004/077014 September 2004 ; WO 2004/092324 October 2004 ; WO 2005/086617 September 2005 ; WO 2006/074471 July 2006 ; WO 2006/074482 July 2006 ; WO 2006/083932 August 2006 ; WO 2008/100344 August 2008 ; WO 2010/151807 December 2010 ; WO 2011/091086 July 2011 ; WO 2016/073052 May 2016 ; WO 2016/144653 September 2016 ; WO2016144652 September 2016 ; WO2017105928 June 2017 ; WO 2017/180998 October 2017
- Other References: Bu et al. “Photochemically colour-tuneable white fluorescence illuminants consisting of conjugated polymer nanospheres”, Nat Commun., 2014, vol. 5, No. 3799, pp. 1-8. cited by applicant ; Feng et al. “Water-soluble fluorescent conjugated polymers and their interactions with biomacromolecules for sensitive biosensors,” Chem. Soc. Rev., vol. 39, 2010, pp. 2411-2419. cited by applicant ; Liu et al. “Blue-Light-Emitting Fluorene-Based Polymers with Tunable Electronic Properties,” Chem. Mater. 2001, vol. 13, pp. 1984-1991. cited by applicant ; Liu et al. “Optimization of the Molecular Orbital Energies of Conjugated Polymers for Optical Amplification of Fluorescent Sensors,” J. Am. Chem. Soc. 2006, vol. 128, pp. 1188-1196. cited by applicant ; Marsitzky et al. “Self-Encapsulation of Poly-2,7-fluorenes in a Dendrimer Matrix,” Journal of the American Chemical Society (2001), vol. 123, No. 29, pp. 6965-6972. cited by applicant ; Pan et al. “Synthesis and properties of fluorenyl-pyridinyl alternatingcopolymers for light-emitting diodes,” Polym. Int. 2014, pp. 1105-1111. cited by applicant ; Ritchie et al. “Effect of meta-linkages on the photoluminescence and electroluminescence properties of light-emitting polyfluorene alternating copolymers,” J. Mater. Chem. 2006, vol. 16, pp. 1651-1656. cited by applicant ; Traina et al. “Design and Synthesis of Monofunctionalized, Water-Soluble Conjugated Polymers for Biosensing and Imaging Applications,” J. Am. Chem. Soc. 2011, vol. 133, No. 32, pp. 12600-12607. cited by applicant ; Wang et al. “Effect of Transannular π-π Interaction on Emission Spectral Shift and Fluorescence Quenching in Dithia[3.3]paracyclophane—Fluorene Copolymers,” Macromolecules 2006, vol. 39, pp. 7277-7285. cited by applicant ; Wu et al. “Synthesis and Characterization of Poly(fluorene)-Based Copolymers Containing Various 1,3,4-Oxadiazole Dendritic Pendants,” Macromolecules 2006, vol. 39, No. 13, pp. 4298-4305. cited by applicant ; Yang et al. “Enhancement of color purity in blue-emitting fluorene—pyridine-based copolymers by controlling the chain rigidity and effective conjugation length,” Polymer, 2004, pp. 865-872. cited by applicant ; Zalipsky et al. “Functionalized poly(ethylene glycol) for preparation of biologically relevant conjugates,” Bioconjugate Chemistry 1995, vol. 6, No. 2, pp. 150-165. cited by applicant ; Zhang et al. “Novel fluorene/trifluoromethylphenylene copolymers: Synthesis, spectra stability and electroluminescence,” Dyes and Pigments, 2012, pp. 380-385. cited by applicant ; Zhu et al. “Water-Soluble Conjugated Polymers for Imaging, Diagnosis, and Therapy”, Chem. Rev., 2012, vol. 112, No. 8, pp. 4687-4735. cited by applicant ; Liu, J. et al. “PEGylated conjugated polyelectrolytes containing 2,1,3-benzoxadiazole units for targeted cell imaging”, Polymer Chemistry, 2012, vol. 3, pp. 1567-1575. cited by applicant
- Primary Examiner: Fang, Shane
- Attorney, Agent or Firm: Blessent, Michael J. ; Field, Bret E. ; Bozicevic, Field & Francis LLP
|
