Fluorescent Dyes and Quenchers with Rigid Linkers

von Dirk Norbert Hendrik Meineke
Dissertation
Datum der mündl. Prüfung:2017-03-02
Erschienen:2017-03-16
Betreuer:Dr. Vladimir Belov
Gutachter:Prof. Dr. Ulf Diederichsen
Gutachter:Prof. Dr. Stefan Hell
Zum Verlinken/Zitieren: http://dx.doi.org/10.53846/goediss-6190

 

 

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Englisch

Electronic energy transfer (EET) between chromophores is of fundamental importance for many natural processes and technical applications. However, common models fall short in fully describing the process, especially in bichromophoric compounds with a donor and acceptor connected by a linker, at very short distances in near perpendicular geometries. A fundamental problem is the role played by the linker, in particular its size, the angle between chromophores it imposes, and its ability to prevent rotations. This thesis reports a novel strategy to prepare bichromophores containing adamantane or 2-(2-adamantylidene)adamantane as rigid spacers, providing access to bichromophores with fixed chromophore distance, and parallel or perpendicular relative orientation. Novel fluorophores were developed for the linkage to the spacers via spiroatoms, from which bichromophores with identical (blue-blue) and different (blue-red) chromophores were synthesized, each in orthogonal and parallel geometry. These were fully characterized by absorption/fluorescence spectroscopy, time-resolved fluorescence anisotropy and antibunching measurements. Remarkably, efficient energy transfer has been found for all bichromophores, despite of the orthogonal arrangement. The observed EET efficiency was compared to the expected efficiency based on the Förster point-dipole approximation using density functional calculations. The results suggest, that Förster resonance energy transfer (FRET) is not sufficient to explain the EET efficiency of 100 %. This novel strategy allows the synthesis of rigid bichromophores with a well-defined chromophore separation and relative orientation.
Keywords: chemistry; organic synthesis; fluorescence; spectroscopy; dyes; anisotropy; energy transfer; FRET
 
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