A dual-emissive-materials design concept enables tumour hypoxia imaging
Source abstract
Abstract
Luminescent materials are widely used for imaging and sensing owing to their high sensitivity, rapid response and facile detection by many optical technologies. Typically materials must be chemically tailored to achieve intense, photostable fluorescence, oxygen-sensitive phosphorescence or dual emission for ratiometric sensing, often by blending two dyes in a matrix. Dual-emissive materials combining all of these features in one easily tunable molecular platform are desirable, but when fluorescence and phosphorescence originate from the same dye, it can be challenging to vary relative fluorescence/phosphorescence intensities for practical sensing applications. Heavy-atom substitution alone increases phosphorescence by a given, not variable amount. Here, we report a strategy for modulating fluorescence/phosphorescence for a single-component, dual-emissive, iodide-substituted difluoroboron dibenzoylmethane-poly(lactic acid) (BF(2)dbm(I)PLA) solid-state sensor material. This is accomplished through systematic variation of the PLA chain length in controlled solvent-free lactide polymerization combined with heavy-atom substitution. We demonstrate the versatility of this approach by showing that films made from low-molecular-weight BF(2)dbm(I)PLA with weak fluorescence and strong phosphorescence are promising as 'turn on' sensors for aerodynamics applications, and that nanoparticles fabricated from a higher-molecular-weight polymer with balanced fluorescence and phosphorescence intensities serve as ratiometric tumour hypoxia imaging agents.
Source: europepmc · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Luminescence and Fluorescent Materials · Nanoplatforms for cancer theranostics · Lanthanide and Transition Metal Complexes
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (26)
Show source-provided references
1. Yuste, R. Fluorescence microscopy today. Nature Methods 2, 902–904 (2005).10.1038/nmeth1205-902 ↗
2. Lower, S. K. & El-Sayed, M. A. The triplet state and molecular electronic processes in organic molecules. Chem. Rev. 66, 199–241 (1966).10.1021/cr60240a004 ↗
3. Zhang, G., Kooi, S. E., Demas, J. N. & Fraser, C. L. Emission colour tuning with polymer molecular weight for boron dibenzoylmethane-polylactide. Adv. Mater. 20, 2099–2104 (2008).10.1002/adma.200702681 ↗
4. Köse, M. E., Omar, A., Virgin, C. A., Carroll, B. F. & Schanze, K. S. Principal component analysis calibration method for dual-luminophore oxygen and temperature sensor films: Application to luminescence imaging. Langmuir 21, 9110–9120 (2005).10.1021/la050999+ ↗
5. Koo, Y. E. L. et al. Real-time measurements of dissolved oxygen inside live cells by organically modified silicate fluorescent nanosensors. Anal. Chem. 76, 2498–2505 (2004).10.1021/ac035493f ↗
6. Zhang, G. et al. Multi-emissive difluoroboron dibenzoylmethane polylactide exhibiting intense fluorescence and oxygen sensitive room temperature phosphorescence. J. Am. Chem. Soc. 129, 8942–8943 (2007).10.1021/ja0720255 ↗
7. Scypinski, S. & Love, L. J. C. Room-temperature phosphorescence of polynuclear aromatic hydrocarbons in cyclodextrins. Anal. Chem. 56, 322–327 (1984).10.1021/ac00267a005 ↗
8. Mitchell, C. A., Gurney, R. W., Jang, S.-H. & Kahr, B. On the mechanism of matrix-assisted room temperature phosphorescence. J. Am. Chem. Soc. 120, 9726–9727 (1998).10.1021/ja981963p ↗
9. Carretero, A. S., Castillo, A. S. & Gutiérrez, A. F. A review of heavy-atom-induced room-temperature phosphorescence: A straightforward phosphorimetric method. Crit. Rev. Anal. Chem. 35, 3–14 (2005).10.1080/10408340590947871 ↗
10. Chow, Y. L., Cheng, X. C. & Johansson, C. I. Molecular interactions of dibenzoylmethanatoboron difluoride (DBMBF2) in the excited and ground states in solution. J. Photochem. Photobiol. A 57, 247–255 (1991).10.1016/1010-6030(91)85020-H ↗
11. Cogné-Laage, E. et al. Diaroyl(methanato)boron difluoride compounds as medium sensitive two-photon fluorescent probes. Chem. Eur. J. 10, 1445–1455 (2004).10.1002/chem.200305321 ↗
12. Nagai, A., Kokado, K., Nagata, Y. & Chujo, Y. 1,3-Diketone-based organoboron polymers: Emission by extending π-conjugation along a polymeric ligand. Macromolecules 41, 8295–8298 (2008).10.1021/ma801690d ↗
13. Qin, Y., Kiburu, I., Shah, S. & Jäkle, F. Synthesis and characterization of organoboron quinolate polymers with tunable luminescence properties. Macromolecules 39, 9041–9048 (2006).10.1021/ma061805f ↗
14. Pfister, A., Zhang, G., Zareno, J., Horwitz, A. F. & Fraser, C. L. Boron polylactide nanoparticles exhibiting fluorescence and phosphorescence in aqueous medium. ACS Nano 2, 1252–1258 (2008).10.1021/nn7003525 ↗
15. McClure, D. S. Triplet–singlet transitions in organic molecules. Lifetime measurements of the triplet state. J. Chem. Phys. 17, 905–913 (1949).10.1063/1.1747085 ↗
16. Adachi, C., Baldo, M. A., Thompson, M. E. & Forrest, S. R. Nearly 100% internal phosphorescence efficiency in an organic light-emitting device. J. Appl. Phys. 90, 5048–5051 (2001).10.1063/1.1409582 ↗
17. Baldo, M. A., O’Brien, D. F., Thompson, M. E. & Forrest, S. R. Excitonic singlet–triplet ratio in a semiconducting organic thin film. Phys. Rev. B 60, 14422–14428 (1999).10.1103/PhysRevB.60.14422 ↗
18. Twarowski, A. J. & Good, L. Phosphorescence quenching by molecular oxygen: Zinc tetraphenylporphin on solid supports. J. Phys. Chem. 91, 5252–5257 (1987).10.1021/j100304a024 ↗
19. Höckel, M. & Vaupel, P. Tumor hypoxia: Definitions and current clinical, biologic, and molecular aspects. J. Natl Cancer Inst. 93, 266–276 (2001).10.1093/jnci/93.4.266 ↗
20. Harris, A. L. Hypoxia—a key regulatory factor in tumour growth. Nature Rev. Cancer 2, 38–47 (2002).
21. Dewhirst, M. W. et al. Review of methods used to study oxygen transport at the microcirculatory level. Int. J. Cancer 90, 237–255 (2000).10.1002/1097-0215(20001020)90:5<237::AID-IJC1>3.0.CO;2-T ↗
22. Sorg, B. S., Moeller, B. J., Donovan, O., Cao, Y. & Dewhirst, M. W. Hyperspectral imaging of hemoglobin saturation in tumor microvasculature and tumor hypoxia development. J. Biomed. Opt. 10, 44004 (2005).10.1117/1.2003369 ↗
23. Baran, J., Duda, A., Kowalski, A., Szymanski, R. & Penczek, S. Intermolecular chain transfer to polymer with chain scission: General treatment and determination of kp/ktr in L, L-lactide polymerization. Macromol. Rapid Commun. 18, 325–333 (1997).
24. Save, M., Schappacher, M. & Soum, A. Controlled ring-opening polymerization of lactones and lactides initiated by lanthanum isopropoxide, 1. General aspects and kinetics. Macromol. Chem. Phys. 203, 889–899 (2002).10.1002/1521-3935(20020401)203:5/6<889::AID-MACP889>3.0.CO;2-O ↗
25. Crosby, G. A. & Demas, J. N. Measurement of photoluminescence quantum yields. J. Phys. Chem. 75, 991–1024 (1971).10.1021/j100678a001 ↗
26. Melhuish, W. H. Quantum efficiencies of fluorescence of organic substances: Effect of solvent and concentration of the fluorescent solute. J. Phys. Chem. 65, 229–235 (1961).10.1021/j100820a009 ↗