TY  - JOUR
A1  - Ferger, Matthias
A1  - Roger, Chantal
A1  - Köster, Eva
A1  - Rauch, Florian
A1  - Lorenzen, Sabine
A1  - Krummenacher, Ivo
A1  - Friedrich, Alexandra
A1  - Košćak, Marta
A1  - Nestić, Davor
A1  - Braunschweig, Holger
A1  - Lambert, Christoph
A1  - Piantanida, Ivo
A1  - Marder, Todd B.
T1  - Electron‐Rich EDOT Linkers in Tetracationic bis‐Triarylborane Chromophores: Influence on Water Stability, Biomacromolecule Sensing, and Photoinduced Cytotoxicity
JF  - Chemistry – A European Journal
N2  - Three novel tetracationic bis‐triarylboranes with 3,4‐ethylenedioxythiophene (EDOT) linkers, and their neutral precursors, showed significant red‐shifted absorption and emission compared to their thiophene‐containing analogues, with one of the EDOT‐derivatives emitting in the NIR region. Only the EDOT‐linked trixylylborane tetracation was stable in aqueous solution, indicating that direct attachment of a thiophene or even 3‐methylthiophene to the boron atom is insufficient to provide hydrolytic stability in aqueous solution. Further comparative analysis of the EDOT‐linked trixylylborane tetracation and its bis‐thiophene analogue revealed efficient photo‐induced singlet oxygen production, with the consequent biological implications. Thus, both analogues bind strongly to ds‐DNA and BSA, very efficiently enter living human cells, accumulate in several different cytoplasmic organelles with no toxic effect but, under intense visible light irradiation, they exhibit almost instantaneous and very strong cytotoxic effects, presumably attributed to singlet oxygen production. Thus, both compounds are intriguing theranostic agents, whose intracellular and probably intra‐tissue location can be monitored by strong fluorescence, allowing switching on of the strong bioactivity by well‐focused visible light.
KW  - boranes
KW  - DNA/RNA sensors
KW  - fluorescent probes
KW  - singlet oxygen
KW  - theranostics
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-287241
VL  - 28
IS  - 48
ER  - 
TY  - JOUR
A1  - Ferger, Matthias
A1  - Ban, Željka
A1  - Krošl, Ivona
A1  - Tomić, Sanja
A1  - Dietrich, Lena
A1  - Lorenzen, Sabine
A1  - Rauch, Florian
A1  - Sieh, Daniel
A1  - Friedrich, Alexandra
A1  - Griesbeck, Stefanie
A1  - Kenđel, Adriana
A1  - Miljanić, Snežana
A1  - Piantanida, Ivo
A1  - Marder, Todd B.
T1  - Bis(phenylethynyl)arene Linkers in Tetracationic Bis-triarylborane Chromophores Control Fluorimetric and Raman Sensing of Various DNAs and RNAs
JF  - Chemistry-A European Journal
N2  - We report four new luminescent tetracationic bis-triarylborane DNA and RNA sensors that show high binding affinities, in several cases even in the nanomolar range. Three of the compounds contain substituted, highly emissive and structurally flexible bis(2,6-dimethylphenyl-4-ethynyl)arene linkers (3: arene=5,5′-2,2′-bithiophene; 4: arene=1,4-benzene; 5: arene=9,10-anthracene) between the two boryl moieties and serve as efficient dual Raman and fluorescence chromophores. The shorter analogue 6 employs 9,10-anthracene as the linker and demonstrates the importance of an adequate linker length with a certain level of flexibility by exhibiting generally lower binding affinities than 3–5. Pronounced aggregation–deaggregation processes are observed in fluorimetric titration experiments with DNA for compounds 3 and 5. Molecular modelling of complexes of 5 with AT-DNA, suggest the minor groove as the dominant binding site for monomeric 5, but demonstrate that dimers of 5 can also be accommodated. Strong SERS responses for 3–5 versus a very weak response for 6, particularly the strong signals from anthracene itself observed for 5 but not for 6, demonstrate the importance of triple bonds for strong Raman activity in molecules of this compound class. The energy of the characteristic stretching vibration of the C≡C bonds is significantly dependent on the aromatic moiety between the triple bonds. The insertion of aromatic moieties between two C≡C bonds thus offers an alternative design for dual Raman and fluorescence chromophores, applicable in multiplex biological Raman imaging.
KW  - boranes
KW  - Raman probes
KW  - molecular modelling
KW  - fluorescent probes
KW  - DNA/RNA sensors
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256717
VL  - 27
IS  - 16
ER  -