Modes of Interactions with DNA/HSA Biomolecules and Comparative Cytotoxic Studies of Newly Synthesized Mononuclear Zinc(II) and Heteronuclear Platinum(II)/Zinc(II) Complexes toward Colorectal Cancer Cells.

A series of mono- and heteronuclear platinum(II) and zinc(II) complexes with 4,4',4″-tri-tert-butyl-2,2':6',2″-terpyridine ligand were synthesized and characterized. The DNA and protein binding properties of [ZnCl2(terpytBu)] (C1), [{cis-PtCl(NH3)2(µ-pyrazine)ZnCl(terpytBu)}](ClO4)2 (C2), [{trans-PtCl(NH3)2(µ-pyrazine)ZnCl(terpytBu)}](ClO4)2 (C3), [{cis-PtCl(NH3)2(µ-4,4'-bipyridyl)ZnCl(terpytBu)}](CIO4)2 (C4) and [{trans-PtCl(NH3)2(µ-4,4'-bipyridyl)ZnCl(terpytBu)}](CIO4)2 (C5) (where terpytBu = 4,4',4″-tri-tert-butyl-2,2':6',2″-terpyridine), were investigated by electronic absorption, fluorescence spectroscopic, and molecular docking methods. Complexes featuring transplatin exhibited lower Kb and Ksv constant values compared to cisplatin analogs. The lowest Ksv value belonged to complex C1, while C4 exhibited the highest. Molecular docking studies reveal that the binding of complex C1 to DNA is due to van der Waals forces, while that of C2-C5 is due to conventional hydrogen bonds and van der Waals forces. The tested complexes exhibited variable cytotoxicity toward mouse colorectal carcinoma (CT26), human colorectal carcinoma (HCT116 and SW480), and non-cancerous mouse mesenchymal stem cells (mMSC). Particularly, the mononuclear C1 complex showed pronounced selectivity toward cancer cells over non-cancerous mMSC. The C1 complex notably induced apoptosis in CT26 cells, effectively arrested the cell cycle in the G0/G1 phase, and selectively down-regulated Cyclin D.

Metal complexes with valuable biomolecules produced by Pseudomonas aeruginosa: a review of the coordination properties of pyocyanin, pyochelin and pyoverdines.

Pseudomonas aeruginosa is an opportunistic, Gram-negative bacterium, involved in severe infections associated with cystic fibrosis, pneumonia, burn wounds, ocular diseases, and immunosuppressive illnesses, and is a major cause of intrahospital infections. This bacterium is also one of the most commercially and biotechnologically significant microorganisms, since it can produce valuable biomolecules which represent a rich source of potential drug candidates. On the other hand, metal complexes have been used in medicine for both therapeutic and diagnostic purposes since ancient times. This class of compounds can adopt different geometries and generally have a three-dimensional shape, contributing to their higher clinical success compared to flat purely organic compounds. In the present review article, attention has been devoted to the three natural products derived from P. aeruginosa, namely pyocyanin, pyochelin, and pyoverdine(s) and their ability to form complexes with different metal ions, including iron(II/III), manganese(II/III), gallium(III), chromium(III), nickel(II), copper(II), zinc(II) and cadmium(II). Investigation of the coordination properties of pyocyanin, pyochelin, and pyoverdine(s) towards these metal ions is important because the resulting bacterially derived natural product-metal complex can serve as a model for the study of metal ion metabolism (transport and storage) in living systems and might also be considered as a novel therapeutic agent for potential use in medicine.

Structural Characterization, Antimicrobial Activity and BSA/DNA Binding Affinity of New Silver(I) Complexes with Thianthrene and 1,8-Naphthyridine.

Three new silver(I) complexes [Ag(NO3)(tia)(H2O)]n (Ag1), [Ag(CF3SO3)(1,8-naph)]n (Ag2) and [Ag2(1,8-naph)2(H2O)1.2](PF6)2 (Ag3), where tia is thianthrene and 1,8-naph is 1,8-naphthyridine, were synthesized and structurally characterized by different spectroscopic and electrochemical methods and their crystal structures were determined by single-crystal X-ray diffraction analysis. Their antimicrobial potential was evaluated against four bacterial and three Candida species, and the obtained results revealed that these complexes showed significant activity toward the Gram-positive Staphylococcus aureus, Gram-negative Pseudomonas aeruginosa and the investigated Candida species with minimal inhibitory concentration (MIC) values in the range 1.56-7.81 µg/mL. On the other hand, tia and 1,8-naph ligands were not active against the investigated strains, suggesting that their complexation with Ag(I) ion results in the formation of antimicrobial compounds. Moreover, low toxicity of the complexes was detected by in vivo model Caenorhabditis elegans. The interaction of the complexes with calf thymus DNA (ct-DNA) and bovine serum albumin (BSA) was studied to evaluate their binding affinity towards these biomolecules for possible insights into the mode of antimicrobial activity. The binding affinity of Ag1-3 to BSA was higher than that for DNA, indicating that proteins could be more favorable binding sites for these complexes in comparison to the nucleic acids.

Examination of the influence of phenyltrimethylammonium chloride (PTMA) concentration on acetochlor adsorption by modified montmorillonite.

The results presented in this paper show an impact of the concentration of the aromatic organic cation on the adsorption of acetochlor on the surface of the organic-modified montmorillonite. Natural montmorillonite from Bogovina (Boljevac municipality, Serbia) was used for organic modification in this experiment. Cation exchange capacity of this montmorillonite (86 mmol 100 g-1 of clay) was determined using the methylene blue method. In pretreatment, montmorillonite was modified with NaCl. For the purpose of organic modification, three different concentrations of phenyltrimethylammonium chloride (PTMA) have been selected, based on calculated CEC value: 43 mmol 100 g-1 of clay (0.5 CEC), 86 mmol 100 g-1 of clay (1 CEC) and 129 mmol 100 g-1 of clay (1.5 CEC). The changes in the properties of the inorganic and organic modified montmorillonite were examined using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and batch equilibrium method. Freundlich coefficients show higher uptake of the herbicide by montmorillonite modified with PTMA, compared to inorganic-modified montmorillonite. The results also indicate the influence of the organic cation concentration on the adsorption of the selected herbicide.

Influence of the organic complex concentration on adsorption of herbicide in organic modified montmorillonite.

This study was undertaken to determine the impact of the organic complex concentration on the adsorption of herbicide (acetochlor) at the surface of the organic modified montmorillonite. In this work, natural montmorillonite from Bogovina (Boljevac municipality, Serbia) was used for organic modification. Cation-exchange capacity of this montmorillonite was determined using a methylene blue method (86 mmol/100 g of clay). Montmorillonite has been modified first with NaCl and then with hexadecyltrimethylammonium bromide (HDTMA-bromide) organic complex. Saturation of cation exchange capacity (CEC) was 50%, 100%, and 150%. Changes in the properties of the inorganic and organic montmorillonite have been examined using the X-ray diffraction, Fourier transform infrared spectroscopy, and batch equilibrium method. Montmorillonite modified with HDTMA-bromide demonstrated higher uptake of the herbicide, compared to the inorganic montmorillonite. Comparing the values Freundlich coefficients in batch equilibrium method, it can be seen that the adsorption of acetochlor decreased in the series: 0.5 CEC HM > 1 CEC HM > 1.5 CEC HM > NaM.

Near-infrared spectroscopy study for determination of adsorbed acetochlor in the organic and inorganic bentonites.

NIR spectroscopy is used to determine acetochlor herbicide adsorption on Na-montmorillonite (NaP) and organically modified montmorillonite (NaOM). Both montmorillonites NIR spectra shows bands at 7061 and 6791 cm(-1). Organo-montmorillonite is characterised by two emphasized bands at 5871 and 5667 cm(-1) that are attributed to the fundamental overtones of the mid-IR bands at 2916 and 2850 cm(-1). Bands at 6017 and 6013 cm(-1) are attributed to acetochlor adsorbed to organo-montmorillonite and Na-montmorillonite, which is confirmed by X-ray powder diffraction (XRPD). Greater quantity of acetochlor is adsorbed to organo-clays compared to non-modified montmorillonite. Acetochlor poses high risk to environmental contamination. Organo-clays are the most useful for removing acetochlor from water and soil.