Full Access
Use of Styrene Radical Cations as Probes for the Complexation Dynamics of Charged Guests with α- and β-Cyclodextrins
R. S. Murphy,
C. Bohne,
R. S. Murphy
Department of Chemistry, University of Victoria, Victoria, B.C., Canada
Search for more papers by this authorCorresponding Author
C. Bohne
Department of Chemistry, University of Victoria, Victoria, B.C., Canada
*To whom correspondence should be addressed at: Department of Chemistry, University of Victoria, P.O. Box 3065, Victoria, B.C., Canada V8W 3V6. Fax: 250-721-7147; [email protected]Search for more papers by this authorR. S. Murphy,
C. Bohne,
R. S. Murphy
Department of Chemistry, University of Victoria, Victoria, B.C., Canada
Search for more papers by this authorCorresponding Author
C. Bohne
Department of Chemistry, University of Victoria, Victoria, B.C., Canada
*To whom correspondence should be addressed at: Department of Chemistry, University of Victoria, P.O. Box 3065, Victoria, B.C., Canada V8W 3V6. Fax: 250-721-7147; [email protected]Search for more papers by this authorFirst published: 01 May 2007
ABSTRACT
The complexation dynamics of radical cations with cyclodextrins (CD) was studied using photophysical techniques. Radical cations of 4-vinylanisole and trans-anethole were formed within α- and β-CD cavities by two-photon photolysis of the respective styrene precursors. Exit of the radical cations from α-CD complexes with 1:1 and 1:2 (guest : CD) stoichiometries and β-CD complexes with 1:1 stoichiometries occurred with lifetimes shorter than 100 ns. Most of the radical cations formed escape from the CD cavities, but a small portion do react with α-CD when this host is present in high concentrations.
REFERENCES
- 1 Szejtli, J., T. Osa 1996 Cyclodextrins. In Comprehensive Supramolecular Chemistry (Edited by J.L. Atwood, J.E. Davies, D. D. MacNicol, F. Vögtle, J.-M. Lehn), Elsevier Science Ltd., New York
- 2 Jicsinszky, L., E. Fenyvesi, H. Hashimoto, A. Ueno 1996 Cyclodextrin derivatives In Comprehensive Supramolecular Chemistry Vol. 3: Cyclodextrins (Edited by J.L. Atwood, J.E. Davies, D.D. MacNicol, F. Vögtle, J.-M. Lehn), pp. 57–188. Elsevier Science Ltd., New York .
- 3 Uekama, K., F. Hirayama, T. Irie (1998) Cyclodextrin drug carrier systems. Chem. Rev, 98, 2045–2076.
- 4
De Guidi, G.,
G. Condorelli,
S. Giuffrida,
G. Puglisi,
G. Giammona (1993) Effect of β-cyclodextrin complexation on the photohaemolitic activity induced by ketoprofen and naproxen sensitization.
J. Incl. Phenom, 15, 43–58.
10.1007/BF00706473 Google Scholar
- 5 Hoshino, T., K. Ishida, T. Irie, F. Hirayama, K. Uekama, M. Yamasaki (1988) Reduction of photohemolytic activity of benoxaprofen by β-cyclodextrin complexations. J. Incl. Phenom, 6, 415–423.
- 6 Condorelli, G., G. De Guidi, S. Giuffrida, L. L. Costanzo (1993) Photosensitizing action of nonsteroidal antiinflammatory drugs on cell membranes and design of protective systems. Coord. Chem. Rev, 125, 115–128.
- 7 Sortino, S., G. De Guidi, G. Marconi, S. Monti (1998) Triplet photochemistry of suprofen in aqueous environment and in the β-cyclodextrin inclusion complex. Photochem. Photobiol, 67, 603–611.
- 8 Monti, S., S. Sortino, G. De Guidi, G. Marconi 1998 Supramolecular photochemistry of 2-(3-benzoylphenyl)propionic acid (ketoprofen). A study in the β-cyclodextrin cavity New J. Chem. pp 599–604
- 9 Jimenez, M. C., M. A. Miranda, R. Tormos (1995) Photodecarboxylation of 2-phenylpropionic acid in solution and induced within β-cyclodextrin. Tetrahedron, 51, 2953–2958.
- 10 Fenyvesi, E., L. Szente, N. R. Russell, M. McNamara 1996 Specific Guest Types In Comprehensive Supramolecular Chemistry Vol. 3: Cyclodextrins (Edited by J.L. Atwood, J.E. Davies, D.D. MacNicol, F. Vögtle, J.-M. Lehn), pp. 305–366. Elsevier Science Ltd., New York .
- 11 Rohrbach, R. P., L. J. Rodriguez, E. M. Eyring, J. F. Wojcik (1977) An equilibrium and kinetic investigation of salt–cycloamylose complexes. J. Phys. Chem, 81, 944–948.
- 12 Turro, N. J., T. Okubo, C.-J. Chung (1982) Analysis of static and dynamic host–guest associations of detergents with cyclodextrins via photoluminescence methods. J. Am. Chem. Soc, 104, 1789–1794.
- 13 Turro, N. J., J. D. Bolt, Y. Kuroda, I. Tabushi (1982) A study of the kinetics of inclusion of halonaphthalenes with β-cyclodextrin via time correlated phosphorescence. Photochem. Photobiol, 35, 69–72.
- 14 Hashimoto, S., J. K. Thomas (1985) Fluorescence study of pyrene and naphthalene in cyclodextrin–amphiphile complex systems. J. Am. Chem. Soc, 107, 4655–4662.
- 15 Barra, M., C. Bohne, J. C. Scaiano (1990) Effect of cyclodextrin complexation on the photochemistry of xanthone. Absolute measurement of the kinetics for triplet-state exit. J. Am. Chem. Soc, 112, 8075–8079.
- 16 Liao, Y., J. Frank, J. F. Holzwarth, C. Bohne 1995 Effect of excitation on the host–guest equilibrium constants of cyclodextrin complexes J. Chem. Soc. Chem. Commun., pp 199–200
- 17 Liao, Y., C. Bohne (1996) Alcohol effect on equilibrium constants and dissociation dynamics of xanthone–cyclodextrin complexes. J. Phys. Chem, 100, 734–743.
- 18 Liao, Y., J. Frank, J. F. Holzwarth, C. Bohne 1995 Comments on the interpretation of triplet excited-state decay data for the determination of the equilibrium constants in host–guest cyclodextrins complexes J. Chem. Soc. Chem. Commun., pp 2435–2436
- 19 Barra, M. (1997) Deuterium isotope effect on the complexation of β-cyclodextrin and triplet xanthone in aqueous solution. Supramol. Chem, 8, 263–266.
- 20 Barros, T. C., K. Stefaniak, J. F. Holzwarth, C. Bohne (1998) Complexation of naphthylethanols with β-cyclodextrin. J. Phys. Chem. A, 102, 5639–5651.
- 21 Kleinman, M. H., C. Bohne 1997 Use of photophysical probes to study dynamic processes in supramolecular structures In Organic Photochemistry: Molecular and Supramolecular Photochemistry (Edited by V. Ramamurthy and K. Schanze), pp. 391–466. Marcel Dekker, Inc., New York .
- 22 Bortolus, P., S. Monti 1996 Photochemistry in cyclodextrin cavities Adv. Photochem 21 1–133 and references therein
- 23 Martinez, L. J., J. C. Scaiano (1997) Transient intermediates in the laser flash photolysis of ketoprofen in aqueous solutions: unusual photochemistry for the benzophenone chromophore. J. Am. Chem. Soc, 119, 11066–11070.
- 24 Monti, S., S. Sortino, G. De Guidi, G. Marconi (1997) Photochemistry of 2-(3-benzoylphenyl)propionic acid (ketoprofen). Part 1. A picosecond and nanosecond time resolved study in aqueous solution. J. Chem. Soc. Faraday Trans, 93, 2269–2275.
- 25 Johnston, L. J., N. P. Schepp (1993) Reactivities of radical cations: characterization of styrene radical cations and measurements of their reactivity toward nucleophiles. J. Am. Chem. Soc, 115, 6564–6571.
- 26 Johnston, L. J., N. P. Schepp (1995) Laser flash photolysis studies of the reactivity of styrene radical cations. Pure Appl. Chem, 67, 71–78.
- 27 Schepp, N. P., L. J. Johnston (1994) Nanosecond and picosecond dynamics of the radical cation mediated dimerization of 4-methoxystyrene. J. Am. Chem. Soc, 116, 6895–6903.
- 28 Cozens, F. L., R. Bogdanova, M. Regimbald, H. Garcia, V. Marti, J. C. Scaiano (1997) Photochemical and thermal behavior of styrenes within acidic and nonacidic zeolites. radical cation versus carbocation formation. J. Phys. Chem. B, 101, 6921–6928.
- 29 Brancaleon, L., D. Brousmiche, V. Jayathirtha Rao, L. J. Johnston, V. Ramamurthy (1998) Photoinduced electron transfer reactions within zeolites: detection of radical cations and dimerization of arylalkenes. J. Am. Chem. Soc, 120, 4926–4933.
- 30 Connors, K. A. 1987 Binding Constants—The Measurement of Molecular Complex Stability John Wiley & Sons, New York .
- 31 Benesi, H. A., J. H. Hildebrand (1949) A spectrophotometric investigation of the interaction of iodine with aromatic hydrocarbons. J. Am. Chem. Soc, 71, 2703–2707.
- 32 Yang, H., C. Bohne (1995) Chiral discrimination in the fluorescence quenching of pyrene complexed to β-cyclodextrin. J. Photochem. Photobiol. A Chem, 86, 209–217.
- 33 Murov, S. L., I. Carmichael, G. L. Hug 1993 Handbook of Photochemistry Marcel Dekker, Inc., New York .
- 34 Janata, E., R. H. Schuler (1982) Rate constant for scavenging e-(aq) in N2O saturated solutions. J. Phys. Chem, 86, 2078–2084.
- 35 Buxton, G. V., C. L. Greenstock, W. P. Helman, A. B. Ross (1988) Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (·OH/·O−) in aqueous solution. J. Phys. Chem. Ref. Data, 17, 513–886.
- 36 Rekharsky, M. V., Y. Inoue (1998) Complexation thermodynamics of cyclodextrins. Chem. Rev, 98, 1875–1917.
- 37 Connors, K. A. (1997) The stability of cyclodextrin complexes in solution. Chem. Rev, 97, 1325–1357.
- 38 Xu, W., J. N. Demas, B. A. DeGraff, M. Whaley (1993) Interactions of pyrene with cyclodextrins and polymeric cyclodextrins. J. Phys. Chem, 97, 6546–6554.
- 39 Murphy, R. S., T. C. Barros, J. Barnes, B. Mayer, G. Marconi, C. Bohne (1999) Complexation of fluorenone and xanthone to cyclodextrins: comparison of theoretical and experimental studies. J. Phys. Chem. A, 103, 137–146.
- 40 Schepp, N. P., L. J. Johnston (1996) Reactivity of radical cations. Effect of radical cation and alkene structure on the absolute rate constants of radical cation mediated cycloaddition reactions. J. Am. Chem. Soc, 118, 2872–2881.
- 41 Workentin, M. S., N. P. Schepp, L. J. Johnston, D. D. M. Wayner (1994) Solvation control of chemoselectivity in reactions of radical cations. J. Am. Chem. Soc, 116, 1141–1142.
- 42 Wayner, D. D. M. 1989 Redox properties In Handbook of Organic Photochemistry (Edited by J. C. Scaiano), pp. 363–368. CRC Press, Boca Raton , FL .
