Tetracationic Bis‐Triarylborane 1,3‐Butadiyne as a Combined Fluorimetric and Raman Probe for Simultaneous and Selective Sensing of Various DNA, RNA, and Proteins

Abstract

A bis-triarylborane tetracation (4-Ar₂ B-3,5-Me₂ C₆ H₂ )-C≡C-C≡C-(3,5-Me₂ C₆ H₂ -4-BAr₂ [Ar=(2,6-Me₂ -4-NMe₃ -C₆ H₂ )⁺ ] (2⁴⁺ ) shows distinctly different behaviour in its fluorimetric response than that of our recently published bis-triarylborane 5-(4-Ar₂ B-3,5-Me₂ C₆ H₂ )-2,2'-(C₄ H₂ S)₂ -5'-(3,5-Me₂ C₆ H₂ -4-BAr₂ ) (3⁴⁺ ). Single-crystal X-ray diffraction data on the neutral bis-triarylborane precursor 2 N confirm its rod-like dumbbell structure, which is shown to be important for DNA/RNA targeting and also for BSA protein binding. Fluorimetric titrations with DNA/RNA/BSA revealed the very strong affinity of 2⁴⁺ and indicated the importance of the properties of the linker connecting the two triarylboranes. Using the butadiyne rather than a bithiophene linker resulted in an opposite emission effect (quenching vs. enhancement), and 2⁴⁺ bound to BSA 100 times stronger than 3⁴⁺ . Moreover, 2⁴⁺ interacted strongly with ss-RNA, and circular dichroism (CD) results suggest ss-RNA chain-wrapping around the rod-like bis-triarylborane dumbbell structure like a thread around a spindle, a very unusual mode of binding of ss-RNA with small molecules. Furthermore, 2⁴⁺ yielded strong Raman/SERS signals, allowing DNA or protein detection at ca. 10 nm concentrations. The above observations, combined with low cytotoxicity, efficient human cell uptake and organelle-selective accumulation make such compounds intriguing novel lead structures for bio-oriented, dual fluorescence/Raman-based applications.