F. Berndt et al. / Journal of Photochemistry and Photobiology A: Chemistry 234 (2012) 164–170
169
wavenumbers / cm-1
28000 24000
Acknowledgements
32000
20000
We thank the Moscow State University Supercomputer Cen-
ter (Lomonosov supercomputer) for computational support (to II)
and the Deutsche Forschungsgemeinschaft for financial support (to
NPE, ER-154/9-2).
exp[-t /0.18 ps] exp[-t /0.56 ps]
100
50
0
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
References
[1] E. Bardez, B.T. Goguillon, E. Keh, B. Valeur, Dynamics of excited-state reac-
tions in reversed micelles. 1. Proton transfer involving a hydrophilic fluorescent
probe, J. Phys. Chem. 88 (1984) 1909–1913.
[2] E. Bardez, E. Monnier, B. Valeur, 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 (1985) 5031–5036.
[3] S.K. Pal, D. Mandal, K. Bhattacharyya, Photophysical processes of ethid-
ium bromide in micelles and reverse micelles, J. Phys. Chem. B 102 (1998)
11017–11023.
[4] G. Saroja, B. Ramachandram, S. Saha, A. Samanta, The fluorescence response of
a structurally modified 4-aminophthalimide derivative covalently attached to
a fatty acid in homogeneous and micellar environments, J. Phys. Chem. B 103
(1999) 2906–2911.
[5] N.E. Levinger, L.A. Swafford, Ultrafast dynamics in reverse micelles, Annu. Rev.
Phys. Chem. 60 (2009) 385–406.
at
late
time
-50
300
350
400
450 500 550
wavelength / nm
Fig. 5. Decay-associated spectra, from an analysis of the transient absorption spec-
tra in Fig. 2. Change according to the blue spectrum is assigned to solvation by
acetonitrile. It follows that – in addition to spontaneous fluorescence – also tran-
sient absorption at 449 nm (green vertical line) may be used to monitor solvation
dynamics. (For interpretation of the references to color in this figure legend, the
reader is referred to the web version of the article.)
[6] C. Amitabha, Chemistry and biology of N-(7-nitrobenz-2-oxa-1,3-diazol-4-yl)-
labeled lipids: fluorescent probes of biological and model membranes, Chem.
Phys. Lipids 53 (1990) 1–15.
[7] R. Hutterer, F.W. Schneider, H. Sprinz, M. Hof, Binding and relaxation behaviour
of prodan and patman in phospholipid vesicles: a fluorescence and 1H NMR
study, Biophys. Chem. 61 (1996) 151–160.
[8] J. Sy´kora, P. Kapusta, V. Fidler, M. Hof, On what time scale does solvent relax-
ation in phospholipid bilayers happen? Langmuir 18 (2002) 571–574.
[9] C. De Vequi-Suplicy, C. Benatti, M. Lamy, Laurdan in fluid bilayers: position and
structural sensitivity, J. Fluoresc. 16 (2006) 431–439.
[10] L. Jin, A.C. Millard, J.P. Wuskell, X. Dong, D. Wu, H.A. Clark, L.M. Loew, Charac-
terization and application of a new optical probe for membrane lipid domains,
Biophys. J. 90 (2006) 2563–2575.
[11] W. Zhao, D.E. Moilanen, E.E. Fenn, M.D. Fayer, Water at the surfaces of aligned
phospholipid multibilayer model membranes probed with ultrafast vibrational
spectroscopy, J. Am. Chem. Soc. 130 (2008) 13927–13937.
[12] J. Telser, K.A. Cruickshank, L.E. Morrison, T.L. Netzel, Synthesis and characteriza-
tion of DNA oligomers and duplexes containing covalently attached molecular
labels: comparison of biotin, fluorescein, and pyrene labels by thermody-
namic and optical spectroscopic measurements, J. Am. Chem. Soc. 111 (1989)
6966–6976.
60
40
20
0
-20
at 449 nm
[13] C. Murphy, M. Arkin, Y. Jenkins, N. Ghatlia, S. Bossmann, N. Turro, J. Barton,
Long-range photoinduced electron transfer through a DNA helix, Science 262
(1993) 1025–1029.
-40
[14] T.L. Netzel, K. Nafisi, M. Zhao, J.R. Lenhard, I. Johnson, Base-content
dependence of emission enhancements, quantum yields, and lifetimes for
cyanine dyes bound to double-strand DNA: photophysical properties of
monomeric and bichromomphoric DNA stains, J. Phys. Chem. 99 (1995)
17936–17947.
[15] E.B. Brauns, M.L. Madaras, R.S. Coleman, C.J. Murphy, M.A. Berg, Complex local
dynamics in DNA on the picosecond and nanosecond time scales, Phys Rev Lett
88 (2002) 158101.
0
1
2
time / ps
Fig. 6. Transient absorption time trace ꢂOD( , t) at = 449 nm (black). At this wave-
length the spectral change is dominated by a blue-shift of the Sn ← S1 ESA band. The
measured spectral evolution was globally fitted, and the red line is a cut through
that fit (blue and green: pulse and molecular contributions). (For interpretation of
the references to color in this figure legend, the reader is referred to the web version
of the article.)
[16] L.A. Gearheart, M.M. Somoza, W.E. Rivers, C.J. Murphy, R.S. Coleman, M.A. Berg,
Sodium-ion binding to DNA: detection by ultrafast time-resolved stokes-shift
spectroscopy, J. Am. Chem. Soc. 125 (2003) 11812–11813.
[17] S.K. Pal, L. Zhao, T. Xia, A.H. Zewail, Site- and sequence-selective ultrafast hydra-
tion of DNA, Proc. Natl. Acad. Sci. U. S. A. 100 (2003) 13746–13751.
[18] A. Okamoto, T. Ichiba, I. Saito, Pyrene-labeled oligodeoxynucleotide probe for
detecting base insertion by excimer fluorescence emission, J. Am. Chem. Soc.
126 (2004) 8364–8365.
[19] M.M. Somoza, D. Andreatta, C.J. Murphy, R.S. Coleman, M.A. Berg, Effect of
lesions on the dynamics of DNA on the picosecond and nanosecond timescales
using a polarity sensitive probe, Nucleic Acids Res. 32 (2004) 2494–2507.
[20] J. Gao, H. Liu, E.T. Kool, Assembly of the complete eight-base artificial genetic
helix, xdna, genetic system, Angew. Chem. Int. Ed. 44 (2005) 3118–3122.
[21] A. Trifonov, M. Raytchev, I. Buchvarov, M. Rist, J. Barbaric, H.A. Wagenknecht, T.
Fiebig, Ultrafast energy transfer and structural dynamics in DNA, J. Phys. Chem.
B 109 (2005) 19490–19495.
by acetonitrile, for which solvation times 0.5–0.6 ps have been
reported [26,32] with various probes.
We conclude that ADC can be used to probe dynamic solvation
not only by transient fluorescence but also by transient absorption.
The chromophore can be incorporated into DNA double strands
where it replaces a base pair. There, excitation near 330 nm and
emission around 420 nm make this molecule also suitable for stud-
ies of radiationless energy-transfer to other color centers in the
strand.
[22] L. Bethge, I. Singh, O. Seitz, Designed thiazole orange nucleotides for the
synthesis of single labelled oligonucleotides that fluoresce upon matched
hybridization, Org. Biomol. Chem. 8 (2010) 2439–2448.