Abstract
Geometric immobilization of polyamine ligands is expected to change their binding properties toward practical ion discrimination. Chemosensor 5 senses only two transition metal ions in water- Hg(II) (K d ≤1 μM) and Cu(II) (K d 56 μM)- which can be compared with bindings of a non-immobilized reference compound (9-(trpnmethyl)-anthracene; 3) with Hg(II) (K d 14 μM) and Cu(II) (K d 39 μM). A related bridged cyclen derivative (7) showed no effect on fluorescence by any metal ion examined. These results suggest that the rigid immobilization of polyamine ligands onto a fluorophore framework may be employed successfully in the creation of selective chemosensors.
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References and Notes
For an overview of work by many laboratories, see: (a) Czarnik, A. W. (1993) Fluorescent Chemosensors for Ion and Molecule Recognition, American Chemical Society, Washington, DC; (b) Czarnik, A. W. (1994) Chemical communication in water using fluorescent chemosensors, Accts. Chem. Res., 27, 302-308.
(a) Saarl, L. A. and Seltz, W. R. (1983) Immobilized morin as fluorescence sensor for determination of aluminum(III), Anyl. Chem. 55, 667–670; (b) Zhujun, Z. and Seitz, W. R. (1986) Optical sensor for oxygen based on immobilized hemoglobin, ibid 58, 220-222; (c) Peterson, J. I., Fitzgerald, R. V., and Buckhold, D. K. (1984) Fiber-optic probe for in vivo measurement of oxygen partial pressure, ibid 56, 62-67.
Additional work aimed at the creation of a fluorescent chemosensor for Hg(II) has been reported; Vaidya, B., Zak, Y., Bastiaans, G. J., Porter, M. D., Hallman, J. L., Nabulsi, N. A. R., Utterback, M. D., Strzelbricka, B., and Bartsch, R. A. (1995) Chromogenic and fluorogenic crown ether compounds for the selective extraction and determination of Hg(II), Anyl. Chem. 67, 4101–4111.
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There was also a fluorescence intensity decrease with Fe(III). However, we conclude that this decrease comes not from the CHEQ, but instead from the absorbance of Fe(III). Indeed, Fe(III) solution has a significant absorbance at 368 nm, which we used as the excitation wavelength. Furthermore, adding EDTA did not change the fluorescent intensity. We confirmed this does not come from Fe(III)-catalyzed decomposition of compound 5 as follows. First, the NMR spectra of compound 5 and 7 taken after extraction with CHC13 showed no sign of decomposion. Second, after the solution was basified with NaOH, Fe(OH)3 was filtered and the pH of the resulting solution was readjusted to pH 7; the emission intensity was the same (±5%) as that of the solution that does not contain any Fe(III). Another piece of supporting evidence is that 1,8-(dihydroxymethyl)anthracene (not shown) and 9-(trpnmethyl)anthracene (3) showed almost same fluorescence effects upon Fe(III) addition as did compounds 5 and 7.
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Yoon, J., Ohler, N.E., Vance, D.H., Aumiller, W.D., Czarnik, A.W. (1997). A Fluorescent Chemosensor with Selectivity for Hg(II). In: Desvergne, J.P., Czarnik, A.W. (eds) Chemosensors of Ion and Molecule Recognition. NATO ASI Series, vol 492. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-3973-1_14
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