Five new anionic aqueous dioxidovanadium­(V) complexes, [{VO2L1,2}­A­(H2O) n ]α (1–5), with the aroylhydrazone ligands pyridine-4-carboxylic acid (3-ethoxy-2-hydroxybenzylidene)­hydrazide (H2L1) and furan-2-carboxylic acid (3-ethoxy-2-hydroxybenzylidene)­hydrazide (H2L2) incorporating different alkali metals (A = Na+, K+, Cs+) as countercation were synthesized and characterized by various physicochemical techniques. The solution-phase stabilities of 1–5 were determined by time-dependent NMR and UV–vis, and also the octanol/water partition coefficients were obtained by spectroscopic techniques. X-ray crystallography of 2–4 confirmed the presence of vanadium­(V) centers coordinated by two cis-oxido-O atoms and the O, N, and O atoms of a dianionic tridentate ligand. To evaluate the biological behavior, all complexes were screened for their DNA/protein binding propensity through spectroscopic experiments. Finally, a cytotoxicity study of 1–5 was performed against colon (HT-29), breast (MCF-7), and cervical (HeLa) cancer cell lines and a noncancerous NIH-3T3 cell line. The cytotoxicity was cell-selective, being more active against HT-29 than against other cells. In addition, the role of hydrophobicity in the cytotoxicity was explained in that an optimal hydrophobicity is essential for high cytotoxicity. Moreover, the results of wound-healing assays indicated antimigration in case of HT-29 cells. Remarkably, 1 with an IC50 value of 5.42 ± 0.15 μM showed greater activity in comparison to cisplatin against the HT-29 cell line.

The synthesis and characterization of one oxidoethoxidovanadium­(V) [VVO­(L1)­(OEt)] (1) and two nonoxidovanadium­(IV) complexes, [VIV(L2–3)2] (2 and 3), with aroylhydrazone ligands incorporating naphthalene moieties, are reported. The synthesized oxido and nonoxido vanadium complexes are characterized by various physicochemical techniques, and their molecular structures are solved by single crystal X-ray diffraction (SC-XRD). This revealed that in 1 the geometry around the vanadium atom corresponds to a distorted square pyramid, with a O4N coordination sphere, whereas that of the two nonoxido VIV complexes 2 and 3 corresponds to a distorted trigonal prismatic arrangement with a O4N2 coordination sphere around each “bare” vanadium center. In aqueous solution, the VVO moiety of 1 undergoes a change to VVO2 species, yielding [VVO2(L1)]− (1′), while the nonoxido VIV-compounds 2 and 3 are partly converted into their corresponding VIVO complexes, [VIVO­(L2–3)­(H2O)] (2′ and 3′). Interaction of these VVO2, VIVO, and VIV systems with two model proteins, ubiquitin (Ub) and lysozyme (Lyz), is investigated through docking approaches, which suggest the potential binding sites: the interaction is covalent for species 2′ and 3′, with the binding to Glu16, Glu18, and Asp21 for Ub, and His15 for Lyz, and it is noncovalent for species 1′, 2, and 3, with the surface residues of the proteins. The ligand precursors and complexes are also evaluated for their in vitro antiproliferative activity against ovarian (A2780) and prostate (PC3) human cancer cells and in normal fibroblasts (V79) to check the selectivity of the compounds for cancer cells.

Chromium is an important toxic environmental pollutant. Chromium pollution results largely from industrial activities, but other natural and anthropogenic sources also contribute to the problem. Plants that are exposed to environmental contamination by chromium are affected in diverse ways, including a tendency to suffer metabolic stress. The stress imposed by Cr exposure also extends to oxidative metabolic stress in plants that leads to the generation of active toxic oxygen free radicals. Such active free radicals degrade essential biomolecules and distort plant biological membranes. In this chapter, we describe sources of environmental chromium contamination, and provide information about the toxic impact of chromium on plant growth and metabolism. In addition, we address different phytoremediation processes that are being studied for use worldwide, in contaminated regions, to address and mitigate Cr pollution. There has been a long history of attempts to successfully mitigate the toxic effects of chromium-contaminated soil on plants and other organisms. One common approach, the shifting of polluted soil to landfills, is expensive and imposes environmental risks and health hazards of its own. Therefore, alternative eco-friendly bioremediation approaches are much in demand for cleaning chromium-polluted areas. To achieve its cleaning effects, bioremediation utilizes living organisms (bacteria, algae, fungi, and plants) that are capable of absorbing and processing chromium residues in ways which amend or eliminate it. Phytoremediation (bioremediation with plants) techniques are increasingly being used to reduce heavy metal contamination and to minimize the hazards of heavy metal toxicity. To achieve this, several processes, viz., rhizofiltration, phytoextraction, phytodetoxification, phytostabilization, and phytovolatilization, have been developed and are showing utility in practice, or promise. Sources of new native hyperaccumulator plants for use at contaminated sites are needed and constitute a key goal of ongoing phytoremediation research programs. Such new plants are needed to enhance the attractiveness of phytoremediation as an effective, affordable, and eco-friendly technique to achieve successful clean-up of metal-contaminated sites worldwide.

The synthesis, structure and characterization of mixed ligand oxidovanadium(iv) complexes [V^IVOL^1–2(L^N–N)] (1–3) are reported. With a view to evaluating their biological activity, their DNA/HSA interaction and cytotoxicity activity have been explored.

The synthesis of ethoxido-bridged dinuclear oxidovanadium(IV) complexes of the general formula (HNEt)[(VOL)(μ-OEt)] (1-3) with the azo dyes 2-(2'-carboxy-5'-X-phenylazo)-4-methylphenol (HL, X = H; HL, X = NO) and 2-(2'-carboxy-5'-Br-phenylazo)-2-naphthol (HL) as ligands is reported. The ligands differ in the substituents at the phenyl ring to probe their influence on the redox behavior, biological activity, and magnetochemistry of the complexes, for which the results are presented and discussed. All synthesized ligands and vanadium(IV) complexes have been characterized by various physicochemical techniques, namely, elemental analysis, electrospray ionization mass spectrometry, spectroscopic methods (UV/vis and IR), and cyclic voltammetry. X-ray crystallography of 1 and 3 revealed the presence of a twisted arrangement of the edged-shared bridging core unit. In agreement with the distorted nature of the twisted core, antiferromagnetic exchange interactions were observed between the vanadium(IV) centers of the dinuclear complexes with a superexchange mechanism operative. These results have been verified by DFT calculations. The complexes were also screened for their in vitro cytotoxicity against HeLa and HT-29 cancer cell lines. The results indicated that all the synthesized vanadium(IV) complexes (1-3) were cytotoxic in nature and were specific to a particular cell type. Complex 1 was found to be the most potent against HeLa cells (IC value 1.92 μM).