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joint IAP and DCB seminar on Physical Chemistry From Computational Photobiology to the Development of Biomimetic Molecular Devices

Date Do, 15.03.2012 - Do, 15.03.2012
Time 11.15
Speaker Prof. Massimo Olivucci, Laboratory for Computational Photochemistry & Photobiology, Bowling Green State University, OH, USA
Location Universität Bern, Institut für Angewandte Physik, Gebäude exakte Wissenschaften, Hörsaal B116, Sidlerstrasse 5, 3012 Bern
Program During the last few years QM/MM computations based on the CASPT2//CASSCF approach have been employed to investigate spectroscopic and photochemical properties of light-sensitive proteins. In this lecture we will show how the same technology could be used to design light-driven molecular devices. In our lab we are exploring the possibility of designing and synthesizing molecules that could mimic the photoisomerization of the visual pigment Rhodopsin and, in particular its low-temperature photochromism [1]. When embedded in the opsin cavity the Rhodopsin chromophore displays an ultrafast and stereoselective photoisomerization with high quantum yield. In order to design a chromophore displaying a similar efficiency in common solvents we have been looking at diverse alkylated Schiff bases featuring a single isomerizable double bond. In this lecture we show that the indanylidene-pyrroline (NAIP) framework [2-4] provides a computationally and synthetically viable prototype for the development of systems that reproduce the excited state electronic structure and photoisomerization dynamics of Rhodopsin in methanol. We will also show that, on the basis of these studies we have been able to achieve systems that, in perspective, can be used as mechanical or electrostatic switches capable of inverting, reversibly, a ca. 15 D dipole moment upon double bond photoisomerization [5]. [1] Shapiro I., Ryazantsev M. N., Frutos L.-M., Ferré N., Lindh R. & Olivucci M. (2011) J Am Chem Soc 133:3354-3364. [2] Lumento F., Zanirato, V., Fusi, S., Busi, E., Latterini, L., Elisei, F., Sinicropi, A., Andruniów, T., Ferré, N., Basosi, R. & Olivucci, M. (2007) Angew Chem Int Ed Engl 46:414-420. [3] Sinicropi A., Martin, E., Ryasantsev, M., Helbing, J., Briand, J., Sharma, D., Léonard, J., Haacke, S., Cannizzo, A., Chergui, M., Zanirato, V., Fusi, S., Santoro, F., Basosi, R., Ferré, N. & Olivucci, M. (2008) Proc. Nat. Acad. Sci. USA 105:17642-17647. [4] Briand J., Bräm, O., Réhault, J., Léonard, J., Cannizzo, A., Chergui, M., Zanirato, V., Olivucci, M., Helbing, J. & Haacke, S. (2010) Phys Chem Chem Phys 12:3178 - 3187. [5] Melloni A., Rossi Paccani, R., Donati, D., Zanirato, V., Sinicropi, A., Parisi, M. L., Martin, E., Ryazantsev, M., Ding, W. J., Frutos, L. M., Basosi, R., Fusi, S., Latterini, L., Ferré, N. & Olivucci, M. (2010) J Am Chem Soc 132:9310-9319.
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Link www.iap.unibe.ch
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