RESUMO
Hydrazone-hydrazide-based linkers perform a crucial role in environmental as well as biological fields. Such linkers are employed to detect exact metal ions at a minute level; hence, numerous probes are available. Even though thiophene-based molecules have a unique position in the medicinal arena, only very few chemosensors are reported based on such a moiety. In this current work, a novel hydrazide-hydrazone-based fluorogenic molecule 5-bromo-2-hydroxy-N'-[(1E)-1-(thiophen-2-yl)ethylidene]benzohydrazide (L) has been successfully designed and synthesized. The sensing studies of L demonstrated a ratio metric as well as turn-on-enhanced fluorescence and colorimetric response toward Fe3+ and Cu2+ ions, respectively and it was observed to be insensitive toward various metal ions. The Job plots revealed that the binding stoichiometry of L and metal ions is 2 : 1. In addition, density functional theory (DFT) results strongly suggested that L can be used as a powerful colorimetric sensor for the detection of Cu2+ ions. In vitro antimicrobial activities of L were evaluated by disk diffusion and results revealed good antibacterial activities against E. coli. Further, molecular docking was executed with DNA gyrase (PDB ID: 1KZN) of E. coli and the calculated interaction energy value was found to be -7.7 kcal mol-1. Finally, molecular docking, fluorescence, colorimetry and the HOMO-LUMO energy gap of the compound can provide new insights into developing drugs and detecting metals in biomolecules.
RESUMO
Bidentate enantiopure Schiff base ligands, (R or S)-N-1-(Ar)ethyl-2-oxo-1-naphthaldiminato-κ(2)N,O, diastereoselectively yield Δ/Λ-chiral four-coordinated, non-planar Cu(N^O)2 complexes [Ar = C6H5 R/S-L1, m-C6H4OMe R-L2, p-C6H4OMe R/S-L3, and p-C6H4Br R/S-L4]. Two N,O-chelate ligands coordinate to the copper(II) atom in distorted square-planar mode, and induce metal-centered Δ/Λ-chirality at the copper atom in the C2-symmetric complexes. In the solid state, the R-L1 (or R-L4) ligand chirality diastereoselectively induces a Λ-Cu configuration in Λ-Cu-R-L1 (or Λ-Cu-R-L4), the S-L1 ligand a Δ-Cu configuration in Δ-Cu-S-L1, forming enantiopure crystals upon crystallization. Conversely, the R-L2 ligand combines both Λ/Δ-Cu-R-L2 as a diastereomeric pair in the crystals. In solution, electronic circular dichroism (CD) spectra show full or partial diastereoselectivity towards Λ-Cu for R ligands and towards Δ-Cu for S ligands. The electronic CD spectra measured on all complexes obtained from R ligands (or S ligands), e.g. Cu-R-L1, Cu-R-L2, Cu-R-L3, and Cu-R-L4 (or Cu-S-L1, Cu-S-L3, and Cu-S-L4), show consistent spectral features. TDDFT calculations of the electronic CD spectra for the diastereomers Λ-Cu-R-L1 and Δ-Cu-R-L1 suggest that the CD spectra are largely dominated by the configuration at the metal center (Λ vs. Δ). The experimental CD spectrum of Cu-R-L1 agrees well with the one calculated for the Λ-Cu-R-L1 configuration. Cyclic voltammetry of Cu-R-L1 reveals a quasi-reversible redox wave corresponding to one-electron transfer for the [Cu(II)L2](0)/[Cu(I)L2](-1) couple in acetonitrile. DSC analyses for the complexes show an exothermic peak between 377 and 478 K (ΔH = -12 to -43 kJ mol(-1)), corresponding to a phase transformation from distorted square-planar/tetrahedral to regular tetrahedral geometry on heating.