Photoactivatable Derivatives for Chemical and Biological
Applications – Design, Synthesis and Mechanistic Investigations
Tomáš Slanina, Burkhard König, Petr Klán
The presentation will be divided into three parts.
The first part deals with design, synthesis and mechanistic investigations of photoremovable
protecting groups (PPGs)1
, which are suitable for specific visible light assisted release of substrates (e.
g. drugs, hormones, inhibitors) in tissue with a high temporal and spatial resolution. The key
properties of photoremovable protecting groups are summarized and current limitations and issues
of PPGs are introduced. The progress in this field developed by us will be discussed. New
chromophores based on xanthene and BODIPY structural motif are capable of cargo release by visible
to NIR light. The release of fluoride as a poor nucleofuge will be introduced. Finally, a new strategy of
photochemical biorthogonal “catch and release” strategy will be shown.
The second part of the presentation will focus on molecules capable of in vivo releasing carbon
monoxide upon absorption of visible light (photoCORM). Biogenic carbon monoxide has in
physiological concentrations anti-inflammatory and anti-proliferative effects2
and acts as an
important signaling molecule.3
The third part summarizes mechanistic studies on photoinduced electron transfer and heavy atom
effect. The mechanism of several photocatalytic systems was elucidated by means of steady-state
and transient absorption and emission spectroscopy. The mechanistic studies were accomplished
with sophisticated physico-chemical methods out of which some were especially developed for
studying of photocatalytic mechanisms.
The thesis was published in 5 impacted journals4-8
, 2 were submitted and 3 further publications are
currently in preparation.
(1) Pelliccioli, A. P.; Wirz, J. Photoch. Photobio. Sci. 2002, 1, 441.
(2) Motterlini, R.; Otterbein, L. E. Nat. Rev. Drug Discov. 2010, 9, 728.
(3) Kim, H. P.; Ryter, S. W.; Choi, A. M. K. Annu. Rev. Pharmacool. Toxicol. 2006, 46, 411.
(4) Antony, L. A. P.; Slanina, T.; Šebej, P.; Šolomek, T.; Klán, P. Org. Lett. 2013, 15, 4552.
(5) Šebej, P.; Wintner, J.; Müller, P.; Slanina, T.; Al Anshori, J.; Antony, L. A. P.; Klán, P.; Wirz, J. J.
Org. Chem. 2013, 78, 1833.
(6) Ghosh, T.; Slanina, T.; König, B. Chem. Sci. 2015, 6, 2027.
(7) Hering, T.; Slanina, T.; Hancock, A.; Wille, U.; König, B. Chem. Commun. 2015, 51, 6568.
(8) Slanina T.; Šebej P.; Heckel A.; Givens R. S.; Klán P. Org. Lett. 2015, in print, doi:
10.1021/acs.orglett.5b02374