Abstract
This mini review highlights the synthesis and photophysical evaluation of anion sensors, for nonaqueous solutions, that have been developed in our laboratories over the last few years. We have focused our research mainly on developing fluorescent photoinduced electron transfer (PET) sensors based on the fluorophore-spacer-anion receptor principle using several anthracene (emitting in the blue) and 1,8-naphthalimide (emitting in the green) fluorophores, with the aim of targeting biologically and industrially relevant anions such as acetates, phosphate and amino acids, as well as halides such as fluoride. The receptors and the fluorophore are separated by a short methyl or ethyl spacer, where the charge neutral anion receptors are either aliphatic or aromatic urea (or thiourea) moieties. For these, the anion recognition is through hydrogen bonding, yielding anion:receptor complexes. Such bonding gives rise to enhanced reduction potential in the receptor moieties which causes enhancement in the rate of PET quenching of the fluorophore excited state from the anion:receptor moiety. This design can be further elaborated on by incorporating either two fluorophores, or urea/thiourea receptors into the sensor structures, using anthracene as a fluorophore. For the latter design, the sensors were designed to achieve sensing of bis-anions, such as di-carboxylates or pyrophosphate, where the anion bridged the anthracene moiety. In the case of the naphthalimide based mono-receptor based PET sensors, it was discovered that in DMSO the sensors were also susceptible to deprotonation by anions such as F− at high concentrations. This led to substantial changes in the absorption spectra of these sensors, where the solution changed colour from yellow/green to deep blue, which was clearly visible to the naked eye. Hence, some of the examples presented can act as dual fluorescent-colorimetric sensors for anions. Further investigations into this phenomenon led to the development of simple colorimetric sensors for fluorides, which upon exposure to air, were shown to fix carbon dioxide as bicarbonate.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
A. Bianchi, K. Bowman-James, and E. Gracía-España (1997). Supramolecular Chemistry of Anions, Wiley-VCH, New York.
C. F. Mason (1991). Biology of Freshwater Pollution, 2nd. ed., Longman, New York.
P. A. Gale (2003). Anion and ion-pair receptor chemistry: Highlights from 2000 and 2001. Coord. Chem. Rev. 240, 191–221.
(a) P. A. Gale (2001). Anion receptor chemistry: Highlights from 1999. Coord. Chem. Rev. 213, 79–128; (b) P. A. Gale (2000). Anion coordination and anion-directed assembly: Highlights from 1997 and 1998. Coord. Chem. Rev. 199, 181–233; (c) P. D. Beer, and P. A. Gale (2001). Anion recognition and sensing: The state of the art and future perspectives. Angew. Chem. Int. Ed. 40, 486– 516.
E. Fan, S. A. van Arman, S. Kincaid, and A. D. Hamilton (1993). Molecular recognition—hydrogen-bonding receptors that function in highly competitive solvents. J. Am. Chem. Soc 115, 369– 370.
(a) R. Martínez-Máñez and F. Sancenón (2003). Fluorogenic and chromogenic chemosensors and reagents for anions. Chem. Rev. 103, 4419–4476; (b) C. Suksai, and T. Tuntulani (2003). Chromogenic anion sensors. Chem. Soc. Rev. 32, 192–202.
(a) F. P. Schmidtchen and M. Berger (1997). Artificial organic host molecules for anions. Chem. Rev. 97, 1609–1646; (b) J. Scheerder, J. F. J. Engbersen, and D. N. Reinhoudt (1996). Synthetic receptors for anion complexation. Recl. Trav. Chim. Pays-Bas 115, 307–320.
J. J. R. Frausto da Silva, and R. J. P. Williams (2001). The Biological Chemistry of Elements—The Inorganic Chemistry of Life, 2nd. ed., Oxford University Press, Oxford.
L. Stryer (1988). Biochemistry, 3rd. ed., Freeman & Co., New York.
(a) T. Gunnlaugsson, A. J. Harte, J. P. Leonard, and M. Nieuwenhuyzen (2003). The formation of luminescent supramolecular ternary complexes in water: delayed luminescence sensing of aromatic carboxylates using coordinated unsaturated cationic heptadentate lanthanide ion complexes. Supramol. Chem. 15, 505–519; (b) T. Gunnlaugsson, A. J. Harte, J. P. Leonard, and M. Nieuwenhuyzen (2002). Delayed lanthanide luminescence sensing of aromatic carboxylates using heptadentate triamide Tb(III) Cyclen complexes: The recognition of salicylic acid in water. Chem. Commun., 2134–2135.
P. E. Kruger, P. R. Mackie, and M. Nieuwenhuysen (2001). Optical-structural correlation in a novel quinoxaline-based anion sensor. J. Chem. Soc., Perkin Trans. 2, 1079–1083.
(a) A. P. de Silva, H. Q. N. Gunaratne, T. Gunnlaugsson, A. J. M. Huxley, C. P. McCoy, J. T. Rademacher, and T. E. Rice (1997). Signalling recognition events with fluorescent sensors and switches. Chem. Rev. 97, 1515–1566; (b) D. H. Vance, and A. W. Czarnik (1994). Real-time assay of inorganic pyrophosphatase using a high-affinity chelation-enhanced fluorescence chemosensor. J. Am. Chem. Soc. 116, 9397–9398; (c) M. E. Huston, E. U. Akkaya, and A. W. Czarnik (1989). Chelation enhanced fluorescence detection of non-metal ions. J. Am. Chem. Soc. 111, 8735–8737.
L. Fabbrizzi, M. Licchelli, G. Rabaioli G, and A. Taglietti (2000). The design of luminescent sensors for anions and ionisable analytes. Coord. Chem. Rev. 205, 85–108.
P. D. Beer (1996). Anion selective recognition and optical/electrochemical sensing by novel transition-metal receptor systems. Chem. Commun. 689–696.
B. R. Linton, M. S. Goodman, E. Fan, S. A. van Arman, and A. D. Hamilton (2001). Thermodynamic aspects of dicarboxylate recognition by simple artificial receptors. J. Org. Chem. 66, 7313– 7319.
P. B¨hlmann, S. Nishizawa, K. P. Xiao, and Y. Umezawa (1997). Strong hydrogen bond-mediated complexation of H2PO4− by neutral bis-thiourea hosts. Tetrahedron 53, 1647–1654.
T. R. Kelly and M. H. Kim (1994). Relative binding affinity of carboxylate and its isosteres: nitro, phosphate, phosphonate, sulfonate and δ-lactones. J. Am. Chem. Soc. 116, 7072–7080.
R. A. Bissell, A. P. de Silva., H. Q. N. Gunaratne, P. L. M. Lynch, G. E. M. Maguire, C. P. McCoy, and K. R. A. S. Sandanayake (1993). Fluorescent photoinduced electron-transfer (PET) sensors. Top. Curr. Chem. 168, 223–264.
T. Gunnlaugsson, A. P. Davis, G. M. Hussey, J. Tierney, and M. Glynn (2004). Design, synthesis and photophysical studies of simple fluorescent anion PET sensors using charge neutral thiourea receptors. Org. Biomol. Chem. 2, 1856–1863.
T. Gunnlaugsson, A. P. Davis, and M. Glynn (2001). Fluorescent PET sensing of anions using charge neutral chemosensors. Chem. Commun. 2556–2557.
T. Gunnlaugsson, A. P. Davis, J. E. O’Brien, and M. Glynn (2005). Synthesis and photophysical evaluation of charge neutral thiourea or urea-based fluorescent PET sensors for bis-carboxylates and pyrophosphate. Org. Biomol. Chem. 3, 48–56.
T. Gunnlaugsson, A. P. Davis, J. E. O’Brien, and M. Glynn (2002). Fluorescent sensing of pyrophosphate and bis-carboxylates with charge neutral PET chemosensors. Org. Lett. 4, 2449–2452.
M. Mei and S. Wu (2001). Fluorescent sensor for α,ω-dicarboxylates with charge neutral PET chemosensors. New. J. Chem. 25, 471–475.
S. Nishizawa, H. Kaneda, T. Uchida, and N. Teramae (1998). Anion sensing by a donor spacer-acceptor system: an intramolecular exciplex emission enhanced by hydrogen bond-mediated complexation. J. Chem. Soc., Perkin Trans. 2, 2325–2327.
K. Kim and J. T. Yoon (2002). A new fluorescent PET chemosensor for fluoride ions. Chem. Commun., 770–771.
(a) T. Gunnlaugsson, T. C. Lee, and R. Parkesh (2003). A higjly selective and sensitive fluorescent PET chemosensor for Zn (II). Org. Biomol. Chem. 1, 3265–3267; (b) T. Gunnlaugsson, B. Bichell, and C. Nolan (2002). A novel fluorescent photoinduced electron-transfer (PET) sensor for lithium. Tetrahedron Lett. 43, 4989–4992; (c) T. Gunnlaugsson, M. Nieuwenhuyzen, L. Richard, and V. Thoss (2002). Novel sodium-selective fluorescent PET and optically based chemosensors towards Na+ determination in serum. J. Chem. Soc., Perkin Trans. 2, 141–150.
T. Gunnlaugsson, P. E. Kruger, T. C. Lee, R. Parkesh, F. M. Pfeffer, and G. M. Hussey (2003). Dual responsive chemosensors for anions: the combination of fluorescent PET (photoinduced electron-transfer) and colorimetric chemosensors in a single molecule. Tetrahedron Lett. 35, 6575–6578.
T. Gunnlaugsson, P. E. Kruger, P. Jensen, F. M. Pfeffer, and G. M. Hussey (2003). Simple naphthalimide based anion sensors: deprotonation induced colour changes and CO2 fixation. Tetrahedron Lett. 44, 8909–8913.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Gunnlaugsson, T., Ali, H.D.P., Glynn, M. et al. Fluorescent Photoinduced Electron Transfer (PET) Sensors for Anions; From Design to Potential Application. J Fluoresc 15, 287–299 (2005). https://doi.org/10.1007/s10895-005-2627-y
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/s10895-005-2627-y