Characterization, modes of interactions with DNA/BSA biomolecules and anti-tumor activity of newly synthesized dinuclear platinum(II) complexes with pyridazine bridging ligand.

Platinum-based drugs are widely recognized efficient anti-tumor agents, but faced with multiple undesirable effects. Here, four dinuclear platinum(II) complexes, [{Pt(1,2-pn)Cl}2(µ-pydz)]Cl2 (C1), [{Pt(ibn)Cl}2(µ-pydz)]Cl2 (C2), [{Pt(1,3-pn)Cl}2(µ-pydz)]Cl2 (C3) and [{Pt(1,3-pnd)Cl}2(µ-pydz)]Cl2 (C4), were designed (pydz is pyridazine, 1,2-pn is ( ±)-1,2-propylenediamine, ibn is 1,2-diamino-2-methylpropane, 1,3-pn is 1,3-propylenediamine, and 1,3-pnd is 1,3-pentanediamine). Interactions and binding ability of C1-C4 complexes with calf thymus DNA (CT-DNA) has been monitored by viscosity measurements, UV-Vis, fluorescence emission spectroscopy and molecular docking. Binding affinities of C1-C4 complexes to the bovine serum albumin (BSA) has been monitored by fluorescence emission spectroscopy. The tested complexes exhibit variable cytotoxicity toward different mouse and human tumor cell lines. C2 shows the most potent cytotoxicity, especially against mouse (4T1) and human (MDA-MD468) breast cancer cells in the dose- and time-dependent manner. C2 induces 4T1 and MDA-MD468 cells apoptosis, further documented by the accumulation of cells at sub-G1 phase of cell cycle and increase of executive caspase 3 and caspase 9 levels in 4T1 cells. C2 exhibits anti-proliferative effect through the reduction of cyclin D3 and cyclin E expression and elevation of inhibitor p27 level. Also, C2 downregulates c-Myc and phosphorylated AKT, oncogenes involved in the control of tumor cell proliferation and death. In order to measure the amount of platinum(II) complexes taken up by the cells, the cellular platinum content were quantified. However, C2 failed to inhibit mouse breast cancer growth in vivo. Chemical modifications of tested platinum(II) complexes might be a valuable approach for the improvement of their anti-tumor activity, especially effects in vivo.

Study on the assessment of humification processes during biodegradation of heavy residual fuel oil.

The aim of this study was to investigate the creation of humic substances during biodegradation of heavy residual fuel oil, because there are indications that substances similar to humic substances are generated during biodegradation of polycyclic aromatic hydrocarbons. In the study, which lasted for 110 days, biodegradation of heavy residual fuel oil was carried out in a layer of artificial soil substrate. The initial concentration of the total petroleum hydrocarbon in the prepared artificial soil substrate (biopile) was 23.1 g kg-1 dry weight (d.w.). At the end of the process, the total petroleum hydrocarbons were reduced to 8.1 g kg-1 d.w. in the inoculated biopile, while the content of humic acids increased during bioremediation from 3.15 g kg-1 d.w. to 4.95 g kg-1 d.w. The humic acids extracted from biopile during the biodegradation process were characterized by various chemical techniques (elemental analysis, spectrofluorimetric analysis, electrochemical measurements, and size exclusion chromatography). The results showed that levels of C, H and the H/C ratio decreased as the biodegradation process progressed. This indicated that humic acids aromatization process took place and this was confirmed by the spectrofluorimetric analysis. The increase of oxygen percentage and the O/C ratio in the humic acids after the biodegradation treatment indicated an increase in functional oxygen groups. Additional analyses of humic acids from the inoculated biopile showed that they were transformed during the bioremediation process. They had greater redox and buffering capacities and a larger portion of the fractions had high molecular mass. Also, the humification parameters (the CHAs/CFAs ratio and CHAs/Corg ratio) increased during the biodegradation. This is one of the few studies that describes the generation of humic substances during the biodegradation of oil compounds.

Investigation of potentially toxic elements in urban sediments in Belgrade, Serbia.

Concentrations of 10 potentially toxic trace elements were measured in soil samples collected from 18 sites in urban areas of Belgrade, the capital and the largest city in Serbia. Samples were analysed in order to assess the extent of soil contamination and to distinguish natural and anthropogenic input. The results demonstrated a general Zn, Pb, and Cd enrichment in surface samples, hence, after comparison with guidelines, it has been determined that there is a potential risk for human health. In the surface and buried samples, traces of cooper were detected. The highest concentrations of Cr (121 ± 12.3 mg/kg) and Ni (94.9 ± 12.6 mg/kg) were found at a sediment depth of 2 m and should be ascribed to geogenic sources. The results of HCA and PCA analysis supported a natural origin of Co, Cu, Mn, Cr, and Ni, while Cd, Zn, and Pb originated from anthropogenic inputs. Based on the pollution indices, Cd made the most dominant contribution, posing a high contamination risk in the studied area. Results of Nemerow pollution index (PIN) and potential ecological risk index (PER) demonstrated that pollution by heavy metals in sediments on several sites is moderately intense.

Combined effects of antimony and sodium diethyldithiocarbamate on soil microbial activity and speciation change of heavy metals. Implications for contaminated lands hazardous material pollution in nonferrous metal mining areas.

The combined effects of antimony (Sb) and sodium diethyldithiocarbamate (DDTC), a common organic flotation reagent, on soil microbial activity and speciation changes of heavy metals were investigated for the first time. The results showed that the exchangeable fraction of Sb was transformed to a stable residual fraction during the incubation period, and the addition of DDTC promoted the transformation compared with single Sb pollution, probably because DDTC can react with heavy metals to form a complex. In addition, the presence of DDTC and Sb inhibited the soil microbial activity to varying degrees. The growth rate constant k of different interaction systems was in the following order on the 28th day: control group ≥ single DDTC pollution > combined pollution > single Sb pollution. A correlation analysis showed that the concentration of exchangeable Sb was the primary factor that affected the toxic reaction under combined pollution conditions, and it significantly affected the characteristics of the soil microorganisms. All the observations provide useful information for a better understanding of the toxic effects and potential risks of combined Sb and DDTC pollution in antimony mining areas.

Treatment of a mud pit by bioremediation.

The mud generated from oil and natural gas drilling, presents a considerable ecological problem. There are still insufficient remedies for the removal and minimization of these very stable emulsions. Existing technologies that are in use, more or less successfully, treat about 20% of generated waste drilling mud, while the rest is temporarily deposited in so-called mud pits. This study investigated in situ bioremediation of a mud pit. The bioremediation technology used in this case was based on the use of naturally occurring microorganisms, isolated from the contaminated site, which were capable of using the contaminating substances as nutrients. The bioremediation was stimulated through repeated inoculation with a zymogenous microbial consortium, along with mixing, watering and biostimulation. Application of these bioremediation techniques reduced the concentration of total petroleum hydrocarbons from 32.2 to 1.5 g kg(-1) (95% degradation) during six months of treatment.

Interactions of the metal tolerant heterotrophic microorganisms and iron oxidizing autotrophic bacteria from sulphidic mine environment during bioleaching experiments.

Iron and sulfur oxidizing chemolithoautotrophic acidophilic bacteria, such as Acidithiobacillus species, hold the dominant role in mine environments characterized by low pH values and high concentrations of reduced sulfur and iron compounds, such as ores, rocks and acid drainage waters from mines. On the other hand, heterotrophic microorganisms, especially their biofilms, from these specific niches are receiving increased attention, but their potential eco-physiological roles have not been fully understood. Biofilms are considered a threat to human health, but biofilms also have beneficial properties as they are deployed in waste recycling and bioremediation systems. We have analyzed interactions of the metal tolerant heterotrophic microorganisms in biofilms with iron oxidizing autotrophic bacteria both from the sulphidic mine environment (copper mine Bor, Serbia). High tolerance to Cu(2+), Cd(2+) and Cr(6+) and the presence of genetic determinants for the respective metal tolerance and biofilm-forming ability was shown for indigenous heterotrophic bacteria that included strains of Staphylococcus and Rhodococcus. Two well characterized bacteria- Pseudomonas aeruginosa PAO1 (known biofilm former) and Cupriavidus metallidurans CH34 (known metal resistant representative) were also included in the study. The interaction and survivability of autotrophic iron oxidizing Acidithiobacillus bacteria and biofilms of heterotrophic bacteria during co-cultivation was revealed. Finally, the effect of heterotrophic biofilms on bioleaching process with indigenous iron oxidizing Acidithiobacillus species was shown not to be inhibitory under in vitro conditions.