Abstract
In the preceding chapters we saw many examples of excited-state reactions. By an excited-state reaction we mean a molecular process which changes the structure of the excited-state fluorophore, and which occurs subsequent to excitation. Such reactions occur because light absorption frequently changes the electron distribution within a fluorophore, which in turn changes its chemical or physical properties. The best-known example of an excited-state reaction is that of phenol, which in neutral solution can lose the phenolic proton in the excited state. Deprotonation occurs more readily in the excited state because the electrons on the phenolic hydroxyl groups are shifted into the phenol ring, making this hydroxyl group more acidic.
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References
Ireland, J. F., and Wyatt, P. A. H., 1976, Acid-base properties of electronically excited states of organic molecules, in Advances in Physical Organic Chemistry, V. Gold and D. Bethell (eds.), Academic Press, New York, pp. 132–215.
Wan, P., and Shukla, D., 1993, Utility of acid-base behavior of excited states of organic molecules, Chenu Rev. 93: 571–584.
Martynov, I. Y., Demyashkevich, A. B., Uzhinov, B. M., and Kuz’min, M. G., 1977, Proton transfer reactions in the excited electronic states of aromatic molecules, Usp. Khim. (Russian Chemical Physics) 46: 3–31.
Shizuka, H., 1985, Excited state proton-transfer reactions and proton-induced quenching of aromatic compounds, Acc. Chem. Res. 18: 141–147.
Schulman, S. G., 1976, Acid-base chemistry of excited singlet states, in Modern Fluorescence Spectroscopy, E. L. Wehry (ed.), Plenum Press, New York, pp. 239–275.
Gafni, A., and Brand, L., 1978, Excited state proton transfer reactions of acridine studied by nanosecond fluorometry, Chem Phys. Lett. 58: 346–350.
Ofran, M., and Feitelson, J., 1978, Time dependence of dissociation in the excited state of ß-naphthol, Chem. Phys. Lett. 19:427–431.
Tsutsumi, K., and Shizuka, H., 1980, Proton transfer and acidity constant in the excited state of naphthols by dynamic analyses, Z Phys. Chem. N. F. 122: 129–142.
Harris, C. M., and Seiinger, B. K., 1980, Proton-induced fluorescence quenching of 2-naphthol, J. Phys. Chem. 84: 891–898.
Harris, C. M., and Sellinger, B. K., 1980, Acid-base properties of 1-naphthol. Proton-induced fluorescence quenching, J. Phys. Chem. 84: 1366–1371.
Webb, S. P., Yeh, S.W., Philips, L. A., Tolbert, M. A., and Clark, J. H., 1984, Ultrafast excited-state proton transfer in 1-naphthol, J. Am. Chem Soc. 106: 7286–7288.
Boyer, R., Deckey, G., Marzzacco, C., Mulvaney, M., Schwab, C., and Halpern, A. M., 1985, The photophysical properties of 2- naphthol, J. Chem. Educ. 62: 630–632.
Bardez, E., Monnier, E., and Valeur, B., 1985, Dynamics of excited-state reactions in reversed micelles. 2. Proton transfer involving various fluorescent probes according to their sites of solubilization, J. Phys. Chem. 89: 5031–5036.
Loken, M. R., Hayes, J. W., Gohlke, J. R., and Brand, L., 1972, Excited-state proton transfer as a biological probe. Determination of rate constants by means of nanosecond fluorometry, Biochemistry 11: 4779–4786.
Laws, W. R., and Brand, L., 1979, Analysis of two-state excited-state reactions. The fluorescence decay of 2-naphthol, J. Phys. Chem. 83: 795–802.
Htun, M. T., Suwaiyan, A., and Klein, U. K. A., 1995, Time-resolved spectroscopy of 4-hydroxy-l-naphthalenesulphonate in alcohol-water mixtures, Chem. Phys. Lett. 243: 506–511.
Laws, W. R., Posner, G. H., and Brand, L., 1979, A covalent fluorescence probe based on excited state proton transfer, Arch. Biochem. Biophys. 193: 88–100.
Marciniak, B., Kozubek, H., and Paszyc, S., 1992, Estimation of pKa in the first excited single state, J. Chem. Educ. 69: 247–249.
Davenport, L., Knutson, J. R., and Brand, L., 1986, Excited-state proton transfer of equilenin and dihydroequilenin: Interaction with bilayer vesicles, Biochemistry 25: 1186–1195.
Lin, H., and Gryczynski, I., unpublished observations.
Förster, Th., 1950, Die pH-abhangigkeit der fluoreszenz von naphthalinderivaten, Z Electrocherru 54: 531–553.
Grabowski, Z. R., and Grabowska, A., 1976, The Förster cycle reconsidered, Z Phys. Chem. N. F. 104: 197–208.
Grabowski, Z. R., 1981, Generalized Förster cycle applied to coordination compounds, J. Lumin. 24/25: 559–562.
Grabowski, Z. R., and Rubaszewska, W., 1977, Generalised Förster cycle, J. Chem. Soc., Faraday Trans. 173:11–28.
Birks, J. B., 1970, Photophysics of Aromatic Molecules, Wiley- Interscience, New York.
Brand, L., and Laws, W. R., 1983, Excited-state proton transfer, in Time-Resolved Fluorescence Spectroscopy in Biochemistry and Biology, R. D. Cundall and F. E. Dale (eds.), Plenum Press, New York, pp. 319–340.
Lakowicz, J. R., and Baiter, A., 1982, Differential wavelength de-convolution of time-resolved fluorescence intensities: A new method for the analysis of excited state processes, Biophys. Chem. 16: 223–240.
Rumbles, G., Smith, T. A., Brown, A. J., Carey, M., and Soutar, I., 1997, Autoreconvolution—an extension to the “reference convolution” procedure for the simultaneous analysis of two fluorescence decays from one sample, J. Fluoresc. 7 (3): 217–229.
Lakowicz, J. R., and Baiter, A., 1982, Theory of phase-modulation fluorescence spectroscopy for excited state processes, Biophys. Chem. 16: 99–115.
Lakowicz, J. R., and Baiter, A., 1982, Analysis of excited state processes by phase-modulation fluorescence spectroscopy, Biophys. Chem. 16: 117–132.
Lakowicz, J. R., and Baiter, A., 1982, Detection of the reversibility of an excited state reaction by phase modulation fluorometry, Chem. Phys. Lett. 92: 117–121.
Spencer, R. D., and Weber, G., 1969, Measurement of subnanosec-ond fluorescence lifetimes with a cross-correlation phase fluorome-ter, Ann. N.Y. Acad. Sci. 158: 361–376.
Veselova, T. V., Limareva, L. A., Cherkasov, A. S., and Shirokov, V. I., 1965, Fluorometric study of the effect of solvent on the fluorescence spectrum of 3-amino-N-methylphthalimide, Opt. Spectwsc. 19: 39–43.
Bakhshiev, N. G., Mazurenko, Yu. T., and Piterskaya, I. V., 1966, Luminescence decay in different portions of the luminescence spectrum of molecules in viscous solutions, Opt. Spectrosc. 21: 307–309.
Gryczynski, I., unpublished observations.
Lofroth, J-E., 1985, Recent developments in the analysis of fluorescence intensity and anisotropy data, in Analytical Instrumentation, A. J. W. G. Visser (ed.), Marcel Dekker, New York, pp. 403–431.
Itoh, M., Tokumura, K., Tanimoto, Y., Okada, Y., Takeuchi, H., Obi, K., and Tanaka, I., 1982, Time-resolved and steady-state fluorescence studies of the excited state proton transfer in 3-hydroxyflavone and 3-hydroxychromone, J. Am. Chem. Soc. 104: 4146–4150.
McMorrow, D., and Kasha, M., 1984, Intramolecular excited-state proton transfer in 3-hydroxyflavone. Hydrogen-bonding solvent perturbations, J. Phys. Chem. 88: 2235–2243.
Bulska, H., 1983, Intramolecular cooperative double proton transfer in [2,2/bipyridyl]-3,3-diol, Chem. Phys. Lett. 98: 398–402.
Borowicz, P., Grabowska, A., Wortmann, R., and Liptay, W., 1992, Tautomerization in fluorescent states of bipyridyl-diols: A direct confirmation of the intramolecular double proton transfer by electro-optical emission measurements, J. Lumin. 52: 265–273.
Klopffer, W., 1977, Intramolecular proton transfer in electronically excited molecules, in Advances in Photochemistry, J. N. Pitts, G. S. Hammond, and K. Gollnick (eds.), John Wiley and Sons, New York, pp. 311–358.
Waluk, J., Bulska, H., Pakula, B., and Sepiol, J., 1981, Red edge excitation study of cooperative double proton transfer in 7-azain-dole, J; Lumin. 24/25:519–522.
Kim, Y. T., Yardley, J. T., and Hochstrasser, R. M., 1989, Solvent effects on intramolecular proton transfer, Chem. Phys. 136: 311–319.
Sytnik, A., Gormin, D., and Kasha, M., 1994, Interplay between excited state intramolecular proton transfer and charge transfer in flavonols and their use as protein-binding site fluorescence probes, Proc. Natl. Acad. Sci. U.S.A. 91: 11968–11972.
Sekikawa, T., Kobayashi, T., and Inabe, T., 1997, Femtosecond fluorescence study of proton-transfer process in thermochromic crystalline salicylideneanilines, J. Phys. Chem. B 101: 10645–10652.
Chapman, C. F., and Maroncelli, M., 1992, Excited state tautomerization of 7-azaindole in water, J. Phys. Chem. 96: 8430–8441.
Szabo, A. G., Krajcarski, D. T., Cavatorta, P., Masotti, L., and Barcellona, M. L., 1986, Excited state pKa behaviour of DAPI. A rationalization of the fluorescence enhancement of DAPI in DAPI- nucleic acid complexes, Photochem. Photobiol. 44: 143–150.
Gutman, M., Huppert, D., and Nachliel, E., 1982, Kinetic studies of proton transfer in the microenvironment of a binding site, Eur. J. Biochem. 121: 637–642.
Gutman, M., Nachliel, E., and Huppert, D., 1982, Direct measurement of proton transfer as a probing reaction for the microenvironment of the apomyoglobin heme-binding site, Eur. J. Biochem. 125: 175–181.
Hresko, R. C., Sugar, I. P., Barenholz, Y., and Thompson, T. E., 1986, Lateral distribution of a pyrene-labeled phosphatidylcholine in phosphatidylcholine bilayers: Fluorescence phase and modulation study, Biochemistry 25: 3813–3823.
Bauer, R. K., Kowalczyk, A., and Baiter, A., 1977, Phase fluorometer study of the excited state reactions of 4-methylumbelliferone, Z Naturforsch. A 32: 560–564.
Nemkovich, N. A., Matseiko, V. I., Rubinov, A. N., and Tomin, V. I., 1979, Kinetics of the spontaneous luminescence of p-methylumbel-liferone solutions in the nanosecond region, Opt. Spectrosc. 47: 490–493.
Baiter, A., and Rolinski, O., 1984, Excited state reactions of 4- methylumbelliferone studied by nanosecond fluorometry, Z Naturforsch. A 39:1035–1040.
de Melo, J. S., and Macanita, A. L., 1993, Three interconverting excited species: Experimental study and solution of the general photokinetic triangle by time-resolved fluorescence, Chem Phys. Lett. 204: 556–562.
Beechem, J. M., Ameloot, M., and Brand, L., 1985, Global analysis of fluorescence decay surfaces: Excited-state reactions, Chem Phys. Lett. 120: 466–472.
Ameloot, M., Boens, N., Andriessen, R., Van den Bergh, V., and De Schryver, F. C., 1991, Non a priori analysis of fluorescence decay surfaces of excited state processes. 1. Theory, J. Phys. Chem 95: 2041–2047.
Andriessen, R., Boens, N., Ameloot, M., and De Schryver, F. C., 1991, Non a priori analysis of fluorescence decay surfaces of ex-cited-state processes. 2. Intermolecular excimer formation of py-rene, J. Phys. Chem. 95: 2047–2058.
Boens, N., Andriessen, R., Ameloot, M., Van Dommelen, L., and De Schryver, F. C., 1992, Kinetics and identifiability of intramolecular two-state excited state processes. Global compartmental analysis of the fluorescence decay surface, J. Phys. Chem. 96: 6331–6342.
Van Dommelen, L., Boens, N., Ameloot, M., De Schryver, F. C., and Kowalczyk, A., 1993, Species-associated spectra and upper and lower bounds on the rate constants of reversible intramolecular two-state excited state processes with added quencher. Global compartmental analysis of the fluorescence decay surface, J. Phys. Chem 97: 11738–11753.
Van Dommelen, L., Boens, N., De Schryver, F. C., and Ameloot, M., 1995, Distinction between different competing kinetic models of irreversible intramolecular two-state excited-state processes with added quencher. Global compartmental analysis of the fluorescence decay surface, J. Phys. Chem. 99: 8959–8971.
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Lakowicz, J.R. (1999). Excited-State Reactions. In: Principles of Fluorescence Spectroscopy. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-3061-6_18
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DOI: https://doi.org/10.1007/978-1-4757-3061-6_18
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