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-Ar2B-3,5-Me2C6H2)-C equivalent to C-C equivalent to C-(3,5-Me2C6H2-4-BAr2 [Ar=(2,6-Me-2-4-NMe3-C6H2)(+)] (2(4+)) shows distinctly different behaviour in its fluorimetric response than that of our recently published bis-triarylborane 5-(4-Ar2B-3,5-Me2C6H2)-2,2 '-(C4H2S)(2)-5 '-(3,5-Me2C6H2-4-BAr2) (3(4+)). 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 2(4+) 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 2(4+) bound to BSA 100 times stronger than 3(4+). Moreover, 2(4+) 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, 2(4+) 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.