RESUMEN

A cobalt(III) complex, [Co(L)]Cl (complex 1, where L = 1,8-[N,N-bis{(3-formyl-2-hydroxy-5-methyl)benzyl}]-1,4,8,11-tetraaza-5,5,7,12,12,14-hexamethylcyclotetradecane) with distorted octahedral geometry has been synthesized and characterized using various spectroscopic techniques. The structure of the ligand has remarkably rich hydrogen intermolecular interactions such as H···H, H···C/C···H, and H···O/O···H that vary with the presence of the metal ion, and the structure of complex 1 has Cl···H interactions; this result has been proved by Hirshfeld surface and two-dimensional (2D) fingerprint maps analyses. The complex exhibits a quasi-reversible Co(III)/Co(II) redox couple with E 1/2 = -0.76 V. Calf thymus DNA (CT DNA) binding abilities of the ligand and complex 1 were confirmed by spectroscopic and electrochemical analyses. According to absorption studies, the ligand and complex 1 bind to CT DNA via intercalative binding mode, with intrinsic binding strengths of 1.41 × 103 and 8.64 × 103 M-1, respectively. A gel electrophoresis assay shows that complex 1 promotes the pUC19 DNA cleavage under dark and light irradiation conditions. Complex 1 has superior antimicrobial activity than the ligand. The cytotoxicity of complex 1 was tested against MDA-MB-231 breast cancer cells with values of IC50 of 1.369 µg mL-1 in the dark and 0.9034 µg mL-1 after light irradiation. Besides, cell morphological studies confirmed the morphological changes with AO/EB dual staining, reactive oxygen species (ROS) staining, mitochondria staining, and Hoechst staining on MDA-MB-231 cancer cells by fluorescence microscopy. Complex 1 was found to be a potent antiproliferative agent against MDA-MB-231 cells, and it can induce mitochondrial-mediated and caspase-dependent apoptosis with activation of downregulated caspases. The biotoxicity assay of complex 1 on the development of Artemia nauplii was evaluated at an IC50 value of 200 µg mL-1 and with excellent biocompatibility.

RESUMEN

The microbial fuel cell is a unique advantageous technology for the scientific community with the simultaneous generation of green energy along with bioelectroremediation of persistent hazardous materials. In this work, a novel approach of integrated system with bioelectricity generation from septic tank wastewater by native microflora in the anode chamber, while Psathyrella candolleana with higher ligninolytic enzyme activity was employed at cathode chamber for the biodegradation of polycyclic aromatic hydrocarbons (PAHs). Six MFC systems designated as MFC1, MFC2, MFC3, MFC4, MFC5, and MFC6 were experimented with different conditions. MFC1 system using natural microflora of STWW (100%) at anode chamber and K3[Fe(CN)6] as cathode buffer showed a power density and current density of 110 ± 10 mW/m2 and 90 ± 10 mA/m2 respectively. In the other five MFC systems 100% STWW was used at the anode and basidiomycetes fungi in the presence or absence of individual PAHs (naphthalene, acenaphthene, fluorene, and anthracene) at the cathode. MFC2, MFC3, MFC4, MFC5, and MFC6 had showed power density of 132 ± 17 mW/m2, 138 ± 20 mW/m2, 139 ± 25 mW/m2, and 147 ± 10 mW/m2 respectively. MFC2, MFC3, MFC4, MFC5, and MFC6 had showed current density of 497 ± 17 mA/m2, 519 ± 10 mA/m2, 522 ± 21 mA/m2 and 525 ± 20 mA/m2 respectively. In all the MFC systems, the electrochemical activity of anode biofilm was evaluated by cyclic voltammetry analysis and biofilms on all the MFC systems electrode surface were visualized by confocal laser scanning microscope. Biodegradation of PAHs during MFC experimentations in the cathode chamber was estimated by UV-Vis spectrophotometer. Overall, MFC6 system achieved maximum power density production of 525 ± 20 mA/m2 with 77% of chemical oxygen demand removal and 54% of coulombic efficiency at the anode chamber and higher anthracene biodegradation (62 ± 1.13%) at the cathode chamber by the selected Psathyrella candolleana at 14th day. The present natural microflora - basidiomycetes fungal coupled MFC system offers excellent opening towards the simultaneous generation of green electricity and PAHs bioelectroremediation.

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We report on the synthesis and characterization of trans N, N'-di-substituted macrocyclic "tet a" probe (L) for metal ion sensing. Both the colorimetric and fluorescent titration studies are performed with different metal ions. The results have suggested that the probe L is very selective and sensitive towards Zn2+ ions with significant changes in color. The pendant armed macrocyclic "tet a" probe has exhibited 1.28× 105 M-1 binding constant and virtuous selectivity for Zn2+ ion than other common metal ions. The detection limit of the probe towards Zn2+ ion is 0.027 nM. The selective sensing of Zn2+ ion is efficiently reversible with EDTA, which is demonstrated for five cycles without losing sensitivity. The time-resolved single-photon counting (TCSPC) studies have determined the average lifetime value for the probe L and L+ Zn2+ ion of 1.29 and 2.96 ns, respectively. The theoretical DFT studies have well supported the experimental outcomes. The practical application of the probe in visualizing intracellular Zn2+ ion distribution in live Artemia salina has proved the low cytotoxicity and cell membrane permeability of probe, which makes it capable of sensing Zn2+ ion in HeLa cells. Thus, the probe L can act as a selective recognition of Zn2+ ion in living cell applications.

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RESUMEN

A mono-N-substituted probe L containing a bromosalicylaldehyde pendant arm attached to a tetraazamacrocyclic "tet a" moiety was synthesized via straight forward reaction. The probe L crystallizes in a monoclinic P21/n space group. The probe L displayed quick sensitivity and selectivity towards Hg2+ ions due to its hopeful Chelation Enhancement Quenching (CHEQ) feature. Interestingly, the probe L exhibits turn-off fluorescence response to Hg2+ ion and turn-on fluorescence signals to HSO4- ions. When the probe L was complexed with HSO4- in 1:1 mode (L + HSO4- formation), improved turn-on fluorescence emission was detected due to the chelation enhanced fluorescence effect through sensor complex. The macrocyclic "tet a" probe L exhibited a binding constant value of 3.89 × 106 M-1 and 5.58 × 105 M-1 for Hg2+ and HSO4-, respectively. Probe L exhibited good selectivity to Hg2+ rather than other common metal ions and HSO4- over other common anions. The limit of detection (LOD) of Hg2+ and HSO4- were found to be 1 nM and 7 µM, respectively. The time-resolved fluorescence emission single-photon counting study was used to determine the average lifetime value for the probe L and L + HSO4- ions as 0.47 and 1.02 ns, respectively. The practical application of the probe in visualizing intracellular Hg2+ and HSO4- ions distribution in live Artemia salina was demonstrated. Furthermore, the probe L with Hg2+cations was found to be cytotoxic against breast cancer cells in nature and can be delivered as an anticancer agent. Besides the probe L with HSO4- exhibit strong fluorescence emission with low cytotoxicity, and it can be recommended for live-cell imaging.

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