Abstract
The experimental procedures of time-resolved laser photolysis studies of pyrene excimer formation in solution have been scrutinized and the appropriate modifications have been implemented. Contrary to the experimental methods applied in all related previous work, the selection of a suitable excitation wavelength (such that the corresponding pyrene absorbance is less than 0.5 absorbance units) utilized in our study results in simple homogeneous kinetics. Consequently, the rate parameters obtained and the mechanism proposed differ significantly from those published previously. The rate constant values of the unimolecular decay of the pyrene monomer, the unimolecular decay of the pyrene excimer, and the excimer formation in decane solution (η = 0.860 mPa s) at 25 °C are (2.38 ± 0.01) × 106 s−1, (2.78 ± 0.02) × 107 s−1, and (3.11 ± 0.06) × 109 M−1 s−1, respectively. The dissociation of the excimer to form a singlet excited state pyrene and a ground state pyrene was shown to be negligible. The energies of activation corresponding to the monomer and excimer unimolecular decays were found to be 2.51 ± 0.07 and 25.7 ± 0.7 kJ mol−1, respectively. Also, our temperature resolved laser photolysis data revealed that the excimer formation has a negative energy of activation equal to −11.2 ± 0.5 kJ mol−1. This unique phenomenon may be attributed to steric effects in the collision of the reactants. The current findings are important for the correct data analysis and interpretation in many applications of the pyrene excimer.
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T. Förster, K. Kasper, Ein Konzentrationsumsehlag der fluoreszenz des pyrenes, Z. Electrochem., 1955, 59, 976–980.
B. Stevens, E. Hutton, Radiative life-time of the pyrene dimer and the possible role of excited dimers in energy transfer processes, Nature, 1960, 186, 1045–1046.
J. B. Birks, L. G. Christophorou, Excimer fluorescence spectra of pyrene derivatives, Spectrochim. Acta, 1963, 19, 401–410.
J. B. Birks, L. G. Christophorou, Excimer formation in polycyclic hydrocarbons and their derivatives, Nature, 1963, 197, 1064–1065.
J. B. Birks, L. G. Christophorou, Resonance interactions of fluorescent organic molecules in solution, Nature, 1962, 196, 33–35.
J. B. Birks, L. G. Christophorou, Excimer fluorescence of aromatic hydrocarbons in solution, Nature, 1962, 194, 442–443.
J. B. Birks, L. G. Christophorou, ‘Excimer’ fluorescence I. Solution spectra of 1:2-benzanthracene and derivatives, Proc. R. Soc. London, Ser. A, 1963, 274, 552–564.
J. B. Birks, D. J. Dyson, I. H. Munro, ‘Excimer’ fluorescence II. Lifetime studies of pyrene solutions, Proc. R. Soc. London, Ser. A, 1963, 275, 575–588.
J. B. Birks, M. D. Lumb, I. H. Munro, ‘Excimer’ fluorescence V. Influence of solvent viscosity and temperature, Proc. R. Soc. London, Ser. A, 1964, 280, 289–297.
A. Szabo, Theoretical approaches to reversible diffusion-influenced reactions: monomer-excimer kinetics, J. Chem. Phys., 1991, 95, 2481–2490.
K. Sienicki, M. A. Winnik, Transient effects in monomer-excimer kinetics, J. Chem. Phys., 1987, 87, 2766–2772.
J. M. G. Martinho, M. N. Berberan-Santos, Diffusion-influenced excimer formation kinetics, J. Chem. Phys., 1991, 95, 1817–1824.
M. N. Berberan-Santos, J. M. G. Martinho, Reversibility in monomer-excimer kinetics, Chem. Phys. Lett., 1991, 178, 1–8.
J. Andre, F. Baros, M. A. Winnik, Kinetics of partly diffusion controlled reactions. 22. Diffusion effects on the kinetics of excimer formation, J. Phys. Chem., 1990, 94, 2942–2948.
J. M. Vanderkooi, J. B. Callis, Pyrene. A probe of lateral diffusion in the hydrophobic region of membranes, Biochemistry, 1974, 13, 4000–4006.
M. A. Winnik, J. M. G. Martinho, Transient effects in pyrene monomer-excimer kinetics, J. Phys. Chem., 1987, 91, 3640–3644.
J. M. G. Martinho, J. P. Farinha, M. N. Berberan-Santos, J. Duhamel, M. A. Winnik, Test of a model for reversible excimer kinetics: pyrene in cyclohexanol, J. Chem. Phys., 1992, 96, 8143–8149.
J. Duhamel, M. A. Winnik, F. Baros, J. C. Andre, J. M. G. Martinho, Diffusion effects on pyrene excimer kinetics: determination of the excimer formation rate coefficient time dependence, J. Phys. Chem., 1992, 96, 9805–9810.
M. Y. Berezin, S. Achilefu, Fluorescence lifetime measurements and biological imaging, Chem. Rev., 2010, 110, 2641–2684.
T. M. Figueira-Duarte, K. Müllen, Pyrene-based materials for organic electronics, Chem. Rev., 2011, 111, 7260–7314.
J. B. Birks, Photophysics of Aromatic Molecules, Wiley-Interscience, London, 1970.
O. Valdes-Aguilera, C. Pathak, D. Neckers, Pyrene as a fluorescent probe for monitoring polymerization rates, Macromolecules, 1990, 23, 689–692.
A. Stroeks, M. Shmorhun, A. M. Jamieson, R. Simha, Cure monitoring of epoxy resins by excimer fluorescence, Polymer, 1988, 29, 467–470.
F. W. Wang, R. E. Lowry, B. M. Fanconi, Novel fluorescence method for cure monitoring of epoxy resins, Polymer, 1986, 27, 1529–1532.
F. W. Wang, R. E. Lowry, W. H. Grant, Novel excimer fluorescence method for monitoring polymerization: 1. Polymerization of methyl methacrylate, Polymer, 1984, 25, 690–692.
P. Somerharju, Pyrene-labeled lipids as tools in membrane biophysics and cell biology, Chem. Phys. Lipids, 2002, 116, 57–74.
M. Ollmann, G. Schwarzmann, K. Sandhoff, H.-J. Galla, Pyrene-labeled gangliosides: Micelle formation in aqueous solution, lateral diffusion, and thermotropic behavior in phosphatidylcholine bilayers, Biochemistry, 1987, 26, 5943–5952.
H.-J. Galla, W. Hartmann, U. Theilen, E. Sackmann, On two-dimensional passive random walk in lipid bilayers and fluid pathways in biomembranes, J. Membr. Biol., 1979, 48, 215–236.
H.-J. Müller, M. Luxnat, H. J. Galla, Lateral diffusion of small solutes and partition of amphipaths in defect structures of lipid bilayers, Biochim. Biophys. Acta, 1986, 856, 283–289.
P. Hammarström, B. Kalman, B. H. Jonsson, U. Carlsson, Pyrene excimer fluorescence as a proximity probe for investigation of residual structure in the unfolded state of human carbonic anhydrase II, FEBS Lett., 1997, 420, 63–68.
X. Song, B. I. Swanson, Rational design of an optical sensing system for multivalent proteins, Langmuir, 1999, 15, 4710–4712.
D. Sahoo, V. Narayanaswami, C. M. Kay, R. O. Ryan, Pyrene excimer fluorescence: a spatially sensitive probe to monitor lipid-induced helical rearrangement of apolipophorin III, Biochemistry, 2000, 39, 6594–6601.
D. Sahoo, P. M. M. Weers, R. O. Ryan, V. Narayanaswami, Lipid-triggered conformational switch of apolipophorin III helix bundle to an extended helix organization, J. Mol. Biol., 2002, 321, 201–214.
A. Irurzun, J. Nieva, Entry of Semliki forest virus into cells: effects of concanamycin A and nigericin on viral membrane fusion and infection, Virology, 1997, 227, 488–492.
J. Smit, R. Bittman, Low-pH-dependent fusion of Sindbis virus with receptor-free cholesterol- and sphingolipid-containing liposomes, J. Virol., 1999, 73, 8476–8484.
S. Nishizawa, Y. Kato, N. Teramae, Fluorescence sensing of anions via intramolecular excimer formation in a pyrophosphate-induced self-assembly of a pyrene-functionalized Guanidium receptor, J. Am. Chem. Soc., 1999, 121, 9463–9464.
R.-H. Yang, W.-H. Chan, A. W. M. Lee, P.-F. Xia, H.-K. Zhang, K. Li, A ratiometric fluorescent sensor for Ag with high selectivity and sensitivity, J. Am. Chem. Soc., 2003, 125, 2884–2885.
Y. Suzuki, T. Morozumi, H. Nakamura, New fluorimetric alkali and alkaline earth metal cation sensors based on noncyclic crown ethers by means of intramolecular excimer formation of pyrene, J. Phys. Chem. B, 1998, 102, 7910–7917.
S. K. Kim, J. H. Bok, R. A. Bartsch, J. Y. Lee, J. S. Kim, A fluoride-selective PCT chemosensor based of formation of a static pyrene excimer, Org. Lett., 2005, 7, 4839–4842.
E. J. Jun, H. N. Won, J. S. Kim, K.-H. Lee, J. Yoon, Unique blue shift due to the formation of static pyrene excimer: highly selective fluorescent chemosensor for Cu2+, Tetrahedron Lett., 2006, 47, 4577–4580.
Q. Dai, W. Liu, X. Zhuang, J. Wu, H. Zhang, P. Wang, Ratiometric fluorescence sensor based on a pyrene derivative and quantification detection of heparin in aqueous solution in serum, Anal. Chem., 2011, 83, 6559–6564.
A. Ueno, I. Suzuki, Host–guest sensory systems for detecting organic compounds by pyrene excimer fluorescence, Anal. Chem., 1990, 62, 2461–2466.
R. Häner, S. M. Biner, S. M. Langenegger, T. Meng, V. L. Malinovskii, A highly sensitive, excimer-controlled molecular beacon, Angew. Chem., Int. Ed., 2010, 49, 1227–1230.
K. Yamana, T. Iwai, Y. Ohtani, S. Sato, M. Nakamura, H. Nakano, Bis-pyrene-labeled oligonucleotides: sequence specificity of excimer and monomer fluorescence changes upon hybridization with DNA, Bioconjugate Chem., 2002, 13, 1266–1273.
G. Tong, J. Lawor, G. Tregear, J. Haralambidis, Oligonucleotide-polyamide hybrid molecules containing multiple pyrene residues exhibit significant excimer fluorescence, J. Am. Chem. Soc., 1995, 117, 12151–12158.
F. D. Lewis, Y. Zhang, R. L. Letsinger, Bispyrenyl excimer fluorescence: a sensitive oligonucleotide probe, J. Am. Chem. Soc., 1997, 119, 5451–5452.
P. L. Paris, J. M. Langenhan, E. T. Kool, Probing DNA sequences in solution with a monomer-excimer fluorescence color change, Nucleic Acids Res., 1998, 26, 3789–3793.
D. Tang, P. Lu, D. Liao, X. Yang, Y. Zhang, C. Yu, Label-free detection of polynucleotide single-base mismatch via pyrene probe excimer emission, Spectrochim. Acta, 2011, 78, 747–752.
K. Yamana, M. Takei, H. Nakano, Synthesis of oligonucleotide derivatives containing pyrene labeled glycerol linkers: enhanced excimer fluorescence on binding to a complementary DNA sequence, Tetrahedron Lett., 1997, 38, 6051–6054.
H.-J. Galla, E. Sackmann, Lateral diffusion in the hydrophobic region of membranes: use of pyrene excimers as optical probes, Biochim. Biophys. Acta, 1974, 339, 103–115.
H.-J. Galla, W. Hartmann, Excimer-forming lipids in membrane research, Chem. Phys. Lipids, 1980, 27, 199–219.
E. H. W. Pap, A. Hanicak, A. Hoek, K. W. A. Wirtz, J. W. G. Visser, Quantitative analysis of lipid–lipid and lipid–protein interactions in membranes by use of pyrene-labeled phosphoinositides, Biochemistry, 1995, 34, 9118–9125.
M. F. Blackwell, K. Gounaris, J. Barber, Evidence the pyrene excimer formation in membranes is not diffusion-controlled, Biochim. Biophys. Acta, 1986, 858, 221–234.
M. A. Winnik, T. Redpath, D. H. Richards, The dynamics of end-to-end cyclization in polystyrene probed by pyrene excimer formation, Macromolecules, 1980, 13, 328–335.
F. W. Wang, R. E. Lowry, R. R. Cavanagh, Picosecond excimer fluorescence spectroscopy: applications to local motions of polymers and polymerization monitoring, Polymer, 1985, 26, 1657–1661.
F. M. Winnik, Photophysics of preassociated pyrenes in aqueous polymer solutions and in other organized media, Chem. Rev., 1993, 93, 587–614.
M. Danko, J. Libiszowski, T. Biela, M. Wolszczak, A. Duda, Molecular dynamics of star-shaped poly(L-lactide)s in tetrahydrofuran as solvent monitored by fluorescence spectroscopy, J. Polym. Sci., Part A: Polym. Chem., 2005, 43, 4586–4599.
M. Danko, J. Libiszowski, M. Wolszczak, D. Racko, A. Duda, Fluorescence study of the dynamics of a star-shaped poly(ε-caprolactone)s in THF: a comparison with star-shaped poly(L-lactide)s, Polymer, 2009, 50, 2209–2219.
J. Yip, J. Duhamel, X. P. Qiu, F. M. Winnik, Fluorescence studies of a series of monodisperse telechelic α,ω-dipyrenyl poly(N-isopropylacrylamide)s in ethanol and in water, Can. J. Chem., 2011, 89, 163–172.
H. Siu, J. Duhamel, Global analysis of the fluorescence decays of a pyrene-labeled polymer using a blob model, Macromolecules, 2004, 37, 9287–9289.
A. K. Mathew, H. Siu, J. Duhamel, A blob model to study chain folding by fluorescence, Macromolecules, 1999, 32, 7100–7108.
J. Duhamel, New insights in the study of pyrene excimer fluorescence to characterize macromolecules and their supramolecular assemblies in solution, Langmuir, 2012, 28, 6527–6538.
M. Ingratta, J. Hollinger, J. Duhamel, A case for using randomly labeled polymers to study long-range polymer chain dynamics by fluorescence, J. Am. Chem. Soc., 2008, 130, 9420–9428.
M. Ingratta, J. Duhamel, Correlating pyrene excimer formation with polymer chain dynamics in solution. Possibilities and limitations, Macromolecules, 2007, 40, 6647–6657.
S. Teertstra, W. Lin, M. Gauthier, M. Ingratta, J. Duhamel, Comparison of the long range polymer chain dynamics of polystyrene and cis-polyisoprene using polymers randomly labeled with pyrene, Polymer, 2009, 50, 5456–5466.
M. Ingratta, J. Duhamel, Effect of time on the rate of long range polymer segmental intramolecular encounters, J. Phys. Chem. B, 2009, 113, 2284–2292.
K. S. Focsaneanu, J. Scaiano, Potential analytical applications of differential fluorescence quenching: pyrene monomer and excimer emissions as sensors for electron deficient molecules, Photochem. Photobiol. Sci., 2005, 4, 817–821.
J. Huang, Z. Zhu, S. Bamrungsap, G. Zhu, M. You, X. He, K. Wang, W. Tan, Competition-mediated pyrene-switching aptasensor: probing lysozyme in Human Serum with a Monomer-Excimer Fluorescence Switch, Anal. Chem., 2010, 82, 10158–10163.
P. Conlon, C. J. Yang, Y. Wu, Y. Chen, K. Martinez, Y. Kim, N. Stevens, A. A. Marti, S. Jockusch, N. J. Turro, W. Tan, Pyrene excimer signaling molecular beacons for probing nucleic acids, J. Am. Chem. Soc., 2008, 130, 336–342.
M. Goedeweeck, M. Auweraer, F. Schryver, Molecular dynamics of a peptide chain, studied by intramolecular excimer formation, J. Am. Chem. Soc., 1985, 107, 2334–2341.
S. Chen, J. Duhamel, G. J. Bahun, A. Adronov, Quantifying the presence of unwanted fluorescent species in the study of pyrene-labeled macromolecules, J. Phys. Chem. B, 2011, 115, 9921–9929.
A. Nautiyal, P. B. Bisht, Steady state and time-resolved studies of pyrene in solution and in single microcrystals, J. Lumin., 2010, 130, 1829–1833.
J. R. Platt, Classification of spectra of cata-condensed hydrocarbons, J. Chem. Phys., 1949, 17, 484–495.
P. R. Salvi, P. Foggi, E. Castelucci, The two-photon excitation spectrum of pyrene, Chem. Phys. Lett., 1983, 98, 206–211.
B.-C. Wang, J.-C. Chang, H.-C. Tso, H.-F. Hsu, C.-Y. Cheng, Theoretical investigation the electroluminescence characteristics of pyrene and its derivatives, J. Mol. Struct. (THEOCHEM), 2003, 629, 11–20.
V. Lukeš, M. Ilčin, J. Kollár, P. Hrdlovič, Š. Chmela, On the geometrical structure and spectral properties of pyrene monomer and sterically constrained intramolecular pyrene dimers, Chem. Phys., 2010, 377, 123–131.
R. Huenerbein, S. Grimme, Time-dependent density functional study of excimers and exciplexes of organic molecules, Chem. Phys., 2008, 343, 362–371.
S. Shirai, S. Iwata, T. Tani, S. Inagaki, Ab initio studies of aromatic excimers using multiconfiguration quasi-degenerate perturbation theory, J. Phys. Chem. A, 2011, 115, 7687–7699.
H. Fujiwara, H. Fukumura, Laser ablation of a pyrene-doped poly(methyl methacrylate) film: dynamics of pyrene transient species by spectroscopic measurements, J. Phys. Chem., 1995, 99, 11844–11853.
N. Nakashima, Y. Kume, N. Mataga, Electronic excitation transfer between the same kind of excited molecules in rigid solvents under high-density excitation with lasers, J. Phys. Chem., 1975, 79, 1788–1793.
D. Gomez-Diaz, J. C. Mejuto, J. M. Navaza, Physicochemical properties of liquid mixtures. 1. Viscosity, density, surface tension and refractive index of cyclohexane + 2,2,4-trimethylpentane binary liquid systems from 25 °C to 50 °C, J. Chem. Eng. Data, 2001, 46, 720–724.
D. C. Landaverde-Cortes, G. A. Iglesias-Silva, M. Ramos-Estrada, K. R. Hall, Densities and viscosities of MTBE + nonane or decane at p = 0.1 MPa from (273.15 to 363.15) K, J. Chem. Eng. Data, 2008, 53, 288–292.
R. Williams, Delayed fluorescence of complex molecules in the vapor phase, J. Chem. Phys., 1958, 28, 577–581.
T. Förster, Excimers, Angew. Chem., Int. Ed. Engl., 1969, 8, 333–343.
P. Foggi, L. Pettini, I. Shnta, R. Righini, S. Califano, Transient absorption and vibrational relaxation dynamics of the lowest excited singlet state of pyrene in solution, J. Phys. Chem., 1995, 99, 7439–7445.
A. C. Benniston, A. Harriman, S. L. Howell, C. A. Sams, Y.-G. Zhi, Intramolecular excimer formation and delayed fluorescence in sterically constrained pyrene dimers, Chem.–Eur. J., 2007, 13, 4665–4674.
E. J. Bowen, Fluorescence quenching in solution and in the vapour state, Trans. Faraday Soc., 1954, 50, 97–102.
H. Siu, J. Duhamel, The importance of considering nonfluorescent pyrene aggregates for the study of pyrene-labeled associative thickeners by fluorescence, Macromolecules, 2005, 38, 7184–7186.
D. F. Anghel, J. L. Toca-Herrera, F. M. Winnik, W. Rettig, R. V. Klitzing, Steady-state fluorescence investigation of pyrene-labeled poly(acrylic acid)s in aqueous solution and in the presence of sodium dodecyl sulfate, Langmuir, 2002, 18, 5600–5606.
J. Kollár, P. Hrdlovič, Š. Chmela, Spectral properties of bichromophoric pyrene derivatives: monomer vs. excimer fluorescence, J. Photochem. Photobiol., A, 2010, 214, 33–39.
B. Stevens, Some effects of molecular orientation on fluorescence emission and energy transfer in crystalline aromatic hydrocarbons, Spectrochim. Acta, 1962, 18, 439–448.
J. M. Roberston, J. G. White, The crystal structure of pyrene. A quantitative X-ray investigation, J. Chem. Soc., 1947, 358–368.
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Hanlon, A.D., Milosavljevic, B.H. Appropriate excitation wavelength removes obfuscations from pyrene excimer kinetics and mechanism studies. Photochem Photobiol Sci 12, 787–797 (2013). https://doi.org/10.1039/c2pp25307k
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DOI: https://doi.org/10.1039/c2pp25307k