Amino-Terephthalonitrile-Based Single Benzene Fluorophores with Large Stokes Shifts and Solvatochromic Behavior.

We have synthesized a small library of blue-to-green emissive single benzene-based fluorophores (SBFs) in a short synthetic sequence. The molecules exhibit good Stokes shift in the range of 60-110 nm and select examples also possess very high fluorescence quantum yields of up to 87%. Theoretical investigations into the ground state and excited state geometries of many of these compounds reveal that good degree of planarization between the electron donor secondary amines and electron accepting benzodinitrile units can be achieved under certain solvatochromic conditions, giving rise to the strongly fluorescent behavior. On the other hand, the excited state geometry which lacks co-planarity of the donor amine and the single benzene moiety can open up a non-fluorescent channel. Additionally, in molecules with a dinitrobenzene acceptor, the perpendicular nitro moieties render the molecules completely non-emissive.

Groove binding mediated structural modulation and DNA cleavage by quinoline appended chalcone derivative.

The present study embodies the detail DNA binding interaction of a potential bioactive quinoline appended chalcone derivative (E)-3-(anthracen-10-yl)-1-(6,8-dibromo-2-methylquinolin-3-yl)prop-2-en-1-one (ADMQ) with calf thymus DNA (ctDNA) and its consequences by UV-Vis absorption, steady state fluorescence spectroscopy, fluorescence anisotropy, circular dichromism, helix melting, agarose gel electrophoresis, molecular docking, Induced Fit Docking (IFD) and molecular dynamics (MD) simulation. The UV-Vis absorption and fluorescence study reveal that the molecule undergoes considerable interaction with the nucleic acid. The control KI quenching experiment shows the lesser accessibility of ADMQ molecule to the ionic quencher (I(-)) in presence of ctDNA as compared to the bulk aqueous phase. Insignificant change in helix melting temperature as well as in circular dichromism (CD) spectra points toward non-covalent groove binding interaction. The moderate rotational confinement of this chalcone derivative (anisotropy=0.106) trapped in the nucleic acid environment, the comparative displacement assay with well-known minor groove binder Hoechst 33258 and intercalator Ethidium Bromide establishes the minor groove binding interactions of the probe molecule. Molecular docking, IFD and MD simulation reveal that the DNA undergoes prominent morphological changes in terms of helix unwinding and bending to accommodate ADMQ in a crescent shape at an angle of 110° in a sequence specific manner. During interaction, ADMQ rigidifies and bends the sugar phosphate backbone of the nucleic acid and thereby shortens its overall length by 3.02Å. Agarose gel electrophoresis experiment with plasmid pBR 322 reveals that the groove binded ADMQ result in a concentration dependent cleavage of plasmid DNA into its supercoiled and nicked circular form. The consolidated spectroscopic research described herein provides quantitative insight into the interaction of a heterocyclic chalcone derivative with relevant target nucleic acid, which may be useful for the future research on chalcone based therapeutic agents.