Tetracationic Bis‐Triarylborane 1,3‐Butadiyne as a Combined Fluorimetric and Raman Probe for Simultaneous and Selective Sensing of Various DNA, RNA, and Proteins
Open Access
- 27 February 2020
- journal article
- research article
- Published by Wiley in Chemistry – A European Journal
- Vol. 26 (27), 6017-6028
- https://doi.org/10.1002/chem.201905328
Abstract
A new bis‐triarylborane tetracation (4‐Ar2B‐3,5‐Me2C6H2)‐C≡C‐C≡C‐(3,5‐Me2C6H2‐4‐BAr2 [Ar = (2,6‐Me2‐4‐NMe3‐C6H2)+] (24+) 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) (34+). Single‐crystal X‐ray diffraction data on the neutral bis‐triarylborane precursor 2N 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.Funding Information
- Hrvatska Zaklada za Znanost (IP-2018-01-5475)
- Deutscher Akademischer Austauschdienst
- Julius-Maximilians-Universität Würzburg
- Alexander von Humboldt-Stiftung
This publication has 89 references indexed in Scilit:
- Exploiting the Nanoparticle Plasmon Effect: Observing Drug Delivery Dynamics in Single Cells via Raman/Fluorescence Imaging SpectroscopyACS Nano, 2013
- Synthesis of 2‐ and 2,7‐Functionalized Pyrene Derivatives: An Application of Selective C-H BorylationChemistry – A European Journal, 2012
- Multimodal spectroscopy detects features of vulnerable atherosclerotic plaqueJournal of Biomedical Optics, 2011
- A multimodal spectroscopy system for real-time disease diagnosisReview of Scientific Instruments, 2009
- Infrared and Raman spectra of ethyl trifluoromethanesulfonate, CF3SO2OCH2CH3. An experimental and theoretical studyJournal of Raman Spectroscopy, 2005
- The Conversion of Phenols to the Corresponding Aryl Halides Under Mild ConditionsSynthesis, 2005
- Preparation and Properties of Phosphaethynes Bearing Bulky Aryl Groups with Electron-Donating Substituents at the Para PositionThe Journal of Organic Chemistry, 2004
- Analysis of Thermal Melting CurvesOligonucleotides, 2003
- Theoretical aspects of DNA-protein interactions: Co-operative and non-co-operative binding of large ligands to a one-dimensional homogeneous latticeJournal of Molecular Biology, 1974
- THE ATTRACTIONS OF PROTEINS FOR SMALL MOLECULES AND IONSAnnals of the New York Academy of Sciences, 1949