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G.M. Roberts and V.G. Stavros
this work to a plethora of more complex systems. One can envisage that future studies will entail working towards understanding the general role that this seemingly
ubiquitous mechanism plays in the UV photochemistry of larger biomolecules. In
particular, the tantalizing prospects of expanding this field to: (i) probe dynamics
in species such as nucleosides and nucleotides in the gas phase; and (ii) investigate
the dynamics of these bio-molecular building-blocks in solution, will invariably assist in cultivating such knowledge. Progress towards achieving both of these goals
is currently underway. Techniques such as electrospray ionization [95–97], laser
desorption [98–101] and laser-induced acoustic desorption [102], can provide the
means to entrain large biomolecules into the gas phase and by-pass issues such as
thermal decomposition. Likewise, experiments in solution are beginning to showcase the transference of knowledge attained from gas phase measurements; recent
ultrafast studies on phenol [74] and para-methylthiophenol [74, 103] in the condensed phase reveal some distinct parallels with findings from the gas phase, even
though the solvent can, in principle, manipulate 1 πσ ∗ mediated behavior. Furthermore, liquid microjets [104–106] offer significant potential for applying highly differential gas phase techniques (such as time-resolved photoelectron spectroscopy)
to biomolecules in the condensed phase. These are fertile grounds for new and more
expansive experiments, which will undoubtedly aid in constructing a more global
picture of 1 πσ ∗ driven photochemistry in the molecular building-blocks of life.
References
1. V. Sundstrom, Annu. Rev. Phys. Chem. 59, 53–77 (2008)
2. P. Kukura, D.W. McCamant, S. Yoon, D.B. Wandschneider, R.A. Mathies, Science 310,
1006–1009 (2005)
3. M. Garavelli, D. Polli, P. Altoe, O. Weingart, K.M. Spillane, C. Manzoni, D. Brida, G.
Tomasello, G. Orlandi, P. Kukura, R.A. Mathies, G. Cerullo, Nature 467, 440–443 (2010)
4. G.D. Scholes, G.R. Fleming, A. Olaya-Castro, R. van Grondelle, Nat. Chem. 3, 763–774
(2011)
5. S.R. Meech, Chem. Soc. Rev. 38, 2922–2934 (2009)
6. I.R. Lee, W. Lee, A.H. Zewail, Proc. Natl. Acad. Sci. USA 103, 258–262 (2006)
7. W.J. Schreier, T.E. Schrader, F.O. Koller, P. Gilch, C.E. Crespo-Hernandez, V.N. Swaminathan, T. Carell, W. Zinth, B. Kohler, Science 315, 625–629 (2007)
8. G.P. Pfeifer, Y.H. You, A. Besaratinia, Mutat. Res. 571, 19–31 (2005)
9. J. Li, Z.Y. Liu, C. Tan, X.M. Guo, L.J. Wang, A. Sancar, D.P. Zhong, Nature 466, 887–890
(2010)
10. C.T. Middleton, K. de La Harpe, C. Su, Y.K. Law, C.E. Crespo-Hernandez, B. Kohler, Annu.
Rev. Phys. Chem. 60, 217–239 (2009)
11. C.E. Crespo-Hernandez, B. Cohen, P.M. Hare, B. Kohler, Chem. Rev. 104, 1977–2019
(2004)
12. S. Ullrich, T. Schultz, M.Z. Zgierski, A. Stolow, Phys. Chem. Chem. Phys. 6, 2796–2801
(2004)
13. M. Barbatti, A.J.A. Aquino, J.J. Szymczak, D. Nachtigallova, P. Hobza, H. Lischka, Proc.
Natl. Acad. Sci. USA 107, 21453–21458 (2010)
14. A.L. Sobolewski, W. Domcke, C. Dedonder-Lardeux, C. Jouvet, Phys. Chem. Chem. Phys.
4, 1093–1100 (2002)
15. D.R. Yarkony, Rev. Mod. Phys. 68, 985–1013 (1996)
G.M. Roberts and V.G. Stavros
this work to a plethora of more complex systems. One can envisage that future studies will entail working towards understanding the general role that this seemingly
ubiquitous mechanism plays in the UV photochemistry of larger biomolecules. In
particular, the tantalizing prospects of expanding this field to: (i) probe dynamics
in species such as nucleosides and nucleotides in the gas phase; and (ii) investigate
the dynamics of these bio-molecular building-blocks in solution, will invariably assist in cultivating such knowledge. Progress towards achieving both of these goals
is currently underway. Techniques such as electrospray ionization [95–97], laser
desorption [98–101] and laser-induced acoustic desorption [102], can provide the
means to entrain large biomolecules into the gas phase and by-pass issues such as
thermal decomposition. Likewise, experiments in solution are beginning to showcase the transference of knowledge attained from gas phase measurements; recent
ultrafast studies on phenol [74] and para-methylthiophenol [74, 103] in the condensed phase reveal some distinct parallels with findings from the gas phase, even
though the solvent can, in principle, manipulate 1 πσ ∗ mediated behavior. Furthermore, liquid microjets [104–106] offer significant potential for applying highly differential gas phase techniques (such as time-resolved photoelectron spectroscopy)
to biomolecules in the condensed phase. These are fertile grounds for new and more
expansive experiments, which will undoubtedly aid in constructing a more global
picture of 1 πσ ∗ driven photochemistry in the molecular building-blocks of life.
References
1. V. Sundstrom, Annu. Rev. Phys. Chem. 59, 53–77 (2008)
2. P. Kukura, D.W. McCamant, S. Yoon, D.B. Wandschneider, R.A. Mathies, Science 310,
1006–1009 (2005)
3. M. Garavelli, D. Polli, P. Altoe, O. Weingart, K.M. Spillane, C. Manzoni, D. Brida, G.
Tomasello, G. Orlandi, P. Kukura, R.A. Mathies, G. Cerullo, Nature 467, 440–443 (2010)
4. G.D. Scholes, G.R. Fleming, A. Olaya-Castro, R. van Grondelle, Nat. Chem. 3, 763–774
(2011)
5. S.R. Meech, Chem. Soc. Rev. 38, 2922–2934 (2009)
6. I.R. Lee, W. Lee, A.H. Zewail, Proc. Natl. Acad. Sci. USA 103, 258–262 (2006)
7. W.J. Schreier, T.E. Schrader, F.O. Koller, P. Gilch, C.E. Crespo-Hernandez, V.N. Swaminathan, T. Carell, W. Zinth, B. Kohler, Science 315, 625–629 (2007)
8. G.P. Pfeifer, Y.H. You, A. Besaratinia, Mutat. Res. 571, 19–31 (2005)
9. J. Li, Z.Y. Liu, C. Tan, X.M. Guo, L.J. Wang, A. Sancar, D.P. Zhong, Nature 466, 887–890
(2010)
10. C.T. Middleton, K. de La Harpe, C. Su, Y.K. Law, C.E. Crespo-Hernandez, B. Kohler, Annu.
Rev. Phys. Chem. 60, 217–239 (2009)
11. C.E. Crespo-Hernandez, B. Cohen, P.M. Hare, B. Kohler, Chem. Rev. 104, 1977–2019
(2004)
12. S. Ullrich, T. Schultz, M.Z. Zgierski, A. Stolow, Phys. Chem. Chem. Phys. 6, 2796–2801
(2004)
13. M. Barbatti, A.J.A. Aquino, J.J. Szymczak, D. Nachtigallova, P. Hobza, H. Lischka, Proc.
Natl. Acad. Sci. USA 107, 21453–21458 (2010)
14. A.L. Sobolewski, W. Domcke, C. Dedonder-Lardeux, C. Jouvet, Phys. Chem. Chem. Phys.
4, 1093–1100 (2002)
15. D.R. Yarkony, Rev. Mod. Phys. 68, 985–1013 (1996)