Spatial distribution of major and trace elements in artificial lakes in Serbia: health risk indices and suitability of water for drinking and irrigation purposes.

Lakes and reservoirs are the main water resources for household, irrigation, and industrial use. Hence, it is necessary to control water pollution and have reliable information on water quality, which refers to its suitability for a particular purpose. The main objective of this study was to evaluate the suitability of water for drinking and irrigation purposes from ten artificial lakes on the territory of the Republic of Serbia. The physicochemical parameters were determined using standard analytical methods, whereas the optical emission spectrometry with inductively coupled plasma, ICP-OES, was used to determine the concentrations of 23 macro-, micro-, and trace elements in water. Health risk indices of drinking water and its suitability for irrigation purposes were evaluated. The results of physicochemical parameters, except for total organic matter, indicated that most samples were within the recommended values. Among analyzed elements, the concentration of Mg was elevated in the water of the lakes Srebrno and Prvonek. The results of health risk assessment clearly showed that there was no acute health risk (HQA < 1), whereas long-term risk (HQL) in the studied lakes was observed with respect to As (lakes Grliste and Srebrno), Mn (lakes Srebrno and Prvonek), Ni (Lake Vrutci), and Sr (Lake Grliste). The irrigation criteria indicated that the water from the examined lakes had satisfactory quality for this purpose, except for residual sodium carbonates (RSC). This criterion indicated low quality or unsuitability of the water in 7 lakes. The main outcomes provided valuable information on the suitability of water from the artificial lakes for intended uses.

Synthesis, Crystal Structure, Theoretical Calculations, Antibacterial Activity, Electrochemical Behavior, and Molecular Docking of Ni(II) and Cu(II) Complexes with Pyridoxal-Semicarbazone.

New Ni (II) and Cu (II) complexes with pyridoxal-semicarbazone were synthesized and their structures were solved by X-ray crystallography. This analysis showed the bis-ligand octahedral structure of [Ni(PLSC-H)2]·H2O and the dimer octahedral structure of [Cu(PLSC)(SO4)(H2O)]2·2H2O. Hirshfeld surface analysis was employed to determine the most important intermolecular interactions in the crystallographic structures. The structures of both complexes were further examined using density functional theory and natural bond orbital analysis. The photocatalytic decomposition of methylene blue in the presence of both compounds was investigated. Both compounds were active toward E. coli and S. aureus, with a minimum inhibition concentration similar to that of chloramphenicol. The obtained complexes led to the formation of free radical species, as was demonstrated in an experiment with dichlorofluorescein-diacetate. It is postulated that this is the mechanistic pathway of the antibacterial and photocatalytic activities. Cyclic voltammograms of the compounds showed the peaks of the reduction of metal ions. A molecular docking study showed that the Ni(II) complex exhibited promising activity towards Janus kinase (JAK), as a potential therapy for inflammatory diseases, cancers, and immunologic disorders.

In Vitro Evaluation of Antiproliferative Properties of Novel Organotin(IV) Carboxylate Compounds with Propanoic Acid Derivatives on a Panel of Human Cancer Cell Lines.

The synthesis of novel triphenyltin(IV) compounds, Ph3SnLn (n = 1-3), with oxaprozin (3-(4,5-diphenyloxazol-2-yl)propanoic acid), HL1, and the new propanoic acid derivatives 3-(4,5-bis(4-methoxylphenyl)oxazol-2-yl)propanoic acid, HL2, and 3-(2,5-dioxo-4,4-diphenylimidazolidin-1-yl)propanoic acid, HL3, has been performed. The ligands represent commercial drugs or their derivatives and the tin complexes have been characterized by standard analytical methods. The in vitro antiproliferative activity of both ligands and organotin(IV) compounds has been evaluated on the following tumour cell lines: human prostate cancer (PC-3), human colorectal adenocarcinoma (HT-29), breast cancer (MCF-7), and hepatocellular cancer (HepG2), as well as on normal mouse embryonic fibroblast cells (NIH3T3) with the aid of MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-12 diphenyltetrazolium bromide) and CV (crystal violet) assays. Contrary to the inactive ligand precursors, all organotin(IV) carboxylates showed very good activity with IC50 values ranging from 0.100 to 0.758 µM. According to the CV assay (IC50 = 0.218 ± 0.025 µM), complex Ph3SnL1 demonstrated the highest cytotoxicity against the caspase 3 deficient MCF-7 cell line. Inductively coupled plasma mass spectrometry (ICP-MS) analysis indicated a two-fold lower concentration of tin in MCF-7 cells in comparison to platinum. To investigate the mechanism of action of the compound Ph3SnL1 on MCF-7 cells, morphological, autophagy and cell cycle analysis, as well as the activation of caspase and ROS/RNS and NO production, has been performed. Results suggest that Ph3SnL1 induces caspase-independent apoptosis in MCF-7 cells.

Assessment of spa mineral water quality from Vrnjacka Banja, Serbia: geochemical, bacteriological, and health risk aspects.

The goal of this study is to evaluate the quality of seven natural mineral water sources in the Vrnjacka Banja area used in the treatment of various diseases. The 24 macro- and microelements were determined by inductively coupled plasma optical emission spectrometry (ICP-OES). The results show that element content was within allowed limits of concentration, except for B, As, and Se. The evaluated content of these elements can be associated with geological and anthropogenic factors. The sample S6 contains more than twice the concentration of As, meaning that the use of water from this source should be limited due to the negative impact of this element on human health. The calculated values of weekly (EWI) and oral (OI) intakes as well as the acute hazard quotient (HQA) of selected toxic and potentially toxic elements indicate no health risks to the consumers. The highest hazard quotient (HQL) observed for As in sample S6 (2.0·10-1) demonstrated a significant risk of carcinogenic diseases in long-term consumption from this source. The estimated non-carcinogenic (DIA) and carcinogenic (DIL) dermal intakes with acute (HQA) and long-term (HQL) hazard quotient values for sample S3 show that there is no health risk to those who use the water from this thermal source for bathing. The presence of aerobic mesophilic bacteria at 22 °C and 37 °C in samples S3, S6, and S7 as well as sulphite-reducing Clostridia species in sample S5 were detected, potentially indicating some non-faecal or faecal contamination.

Novel diphenyltin(IV) complexes with carboxylato N-functionalized 2-quinolone ligands: Synthesis, characterization and in vitro anticancer studies.

Three new diphenyltin(IV) complexes, bis(3-(4-methyl-2-oxoquinolinyl-1(2H)-yl)propanoato)diphenyltin(IV) (1), bis(2-(4-methyl-2-oxoquinolin-1(2H)-yl)ethanoato)diphenyltin(IV) (2), and bis(2-(4-hydroxy-2-oxoquinolin-1(2H)-yl)ethanoato)diphenyltin(IV) (3), were synthesized and characterized by elemental microanalysis, FT-IR spectroscopy, and multinuclear (1H, 13C and 119Sn) NMR spectroscopy. Crystal structure of ligand precursor, 2-(4-methyl-2-oxoquinolinyl-1-(2H)-yl)acetic acid (HL2), has been determined by X-ray diffraction studies. Asymmetric bidentate coordination of the carboxylato ligands and skew trapezoidal structures are assumed for the synthesized complexes. In vitro anticancer activity of the synthesized diphenyltin(IV) complexes was evaluated against three human: MCF-7 (breast adenocarcinoma), A375 (melanoma), HCT116 (colorectal carcinoma), and three mouse tumor cell lines: 4T1 (breast carcinoma), B16 (melanoma), CT26 (colon carcinoma) using MTT and CV assays. The IC50 values fall in the range from 0.1 to 3.7 µM. Flow cytometric analysis and fluorescent microscopy suggest that complex 1 induces caspase-dependent apoptosis followed with strong blockade of cell division in HCT116 cells. Since complex 1 showed ROS/RNS scavenging potential mentioned cytotoxicity was not connected with oxidative stress.

Novel triphenyltin(IV) compounds with carboxylato N-functionalized 2-quinolones as promising potential anticancer drug candidates: in vitro and in vivo evaluation.

Three newly synthesized triphenyltin(IV) compounds, Ph3SnL1 (L1- = 3-(4-methyl-2-oxoquinolin-1(2H)-yl)propanoato), Ph3SnL2 (L2- = 2-(4-methyl-2-oxoquinolin-1(2H)-yl)ethanoato), and Ph3SnL3 (L3- = 2-(4-hydroxy-2-oxoquinolin-1(2H)-yl)ethanoato), were characterized by elemental microanalysis, FT-IR spectroscopy and multinuclear (1H, 13C and 119Sn) NMR spectroscopy. A single X-ray diffraction study indicates that compounds Ph3SnL1 and Ph3SnL2 exhibit a 1D zig-zag chain polymeric structure, which in the case of Ph3SnL2 is additionally stabilized by π-interactions. In addition, the synthesized compounds were further examined using density functional theory and natural bond orbital analysis. The compounds have been evaluated for their in vitro anticancer activity against three human cell lines: MCF-7 (breast adenocarcinoma), A375 (melanoma), HCT116 (colorectal carcinoma), and three murine cell lines: 4T1 (breast carcinoma), B16 (melanoma), CT26 (colon carcinoma) using MTT and CV assays. The IC50 values fall in the nanomolar range, indicating that these compounds possess better anticancer activity than cisplatin. The study of the effect of the newly developed drug Ph3SnL1 showed its plasticity in achieving an antitumor effect in vitro, which depends on the specificity of the phenotype and the redox status of the malignant cell line and ranges from the initiation of apoptotic cell death to the induction of differentiation to a more mature cell form. In the syngeneic model of murine melanoma, Ph3SnL1 showed the potential to reduce the tumor volume similar to cisplatin, but in a well-tolerated form and with low systemic toxicity, representing a significant advantage over the conventional drug.

Trimethyltin(IV) Bearing 3-(4-Methyl-2-oxoquinolin-1(2H)-yl)propanoate Causes Lipid Peroxidation-Mediated Autophagic Cell Death in Human Melanoma A375 Cells.

A novel trimethyltin(IV) complex (Me3SnL), derived from 3-(4-methyl-2-oxoquinolin-1(2H)-yl)propanoate ligand, has been synthesized and characterized by elemental microanalysis, UV/Vis spectrophotometry, FT-IR and multinuclear (1H, 13C and 119Sn) NMR spectroscopies. Furthermore, the structure of the ligand precursor HL was solved using SC-XRD (single-crystal X-ray diffraction). The prediction of UV/Vis and NMR spectra by quantum-chemical methods was performed and compared to experimental findings. The protein binding affinity of Me3SnL towards BSA was determined by spectrofluorometric titration and subsequent molecular docking simulations. Me3SnL has been evaluated for its in vitro anticancer activity against three human cell lines, MCF-7 (breast adenocarcinoma), A375 (melanoma) and HCT116 (colorectal carcinoma), and three mouse tumor cell lines, 4T1 (breast carcinoma), B16 (melanoma) and CT26 (colon carcinoma), using MTT and CV assays. The strong inhibition of A375 cell proliferation, ROS/RNS upregulation and robust lipid peroxidation lead to autophagic cell death upon treatment with Me3SnL.

Advanced Nanomaterials in Biomedical Application.

Over the last few decades, great efforts have been dedicated to the discovery of various nanomaterials [...].

Chemical Composition, Antioxidant Potential, and Nutritional Evaluation of Cultivated Sorghum Grains: A Combined Experimental, Theoretical, and Multivariate Analysis.

Sorghum grain (Sorghum bicolor L. Moench) is a gluten-free cereal with excellent nutritional value and is a good source of antioxidants, including polyphenols, as well as minerals with proven health benefits. Herein, the phenolic composition, elemental profile, and antioxidant activity of sixteen food-grade sorghum grains (S1-S16) grown under agroecological conditions in Serbia were determined. Nine phenolic compounds characteristic of sorghum grains, such as luteolinidin, 5-methoxyluteolinidin, luteolidin derivative, luteolidin glucoside, apigeninidin, 7-methoxyapigeninidin, apigeninidin glucoside, and cyanidin derivative, were quantified. The antioxidant potential of the analyzed sorghum grains was evaluated by UV/Vis (DPPH, ABTS, and FRAP) and Electron Paramagnetic Resonance spectroscopy (hydroxyl and ascorbyl radical scavenging assays). The content of macro- and microelements was determined by Inductively Coupled Plasma Optical Emission spectroscopy. Theoretical daily intakes of selected major and trace elements were assessed and compared with the Recommended Daily Allowance or Adequate Intake. Sample S8 had the highest amount of phenolic compounds, while S4, S6, and S8 exhibited the strongest antioxidative potential. The sorghum studied could completely satisfy the daily needs of macro- (K, Mg, and P) and microelements (Se, Zn, Fe). Pattern recognition techniques confirmed the discrimination of samples based on phenolic profile and elemental analysis and recognized the main markers responsible for differences between the investigated samples. The reaction between hydroxyl radicals and luteolinidin/apigeninidin was investigated by Density Functional Theory and thermodynamically preferred mechanism was determined.

Effect of Beetroot Powder Incorporation on Functional Properties and Shelf Life of Biscuits.

The demand for ready-to-use functional foods is high, which encourages manufacturers to develop new, nutritionally valuable products. As an excellent source of biologically active compounds, beetroot (Beta vulgaris L.) is considered to have highly beneficial effects on health. This research aimed to evaluate the impact of replacing spelt flour (SF) with 15%, 20% and 25% beetroot powder (BP). The physicochemical and functional properties of biscuits baked at different temperatures (150 and 170 °C) were followed at the beginning, and after 3 and 6 months of storage as standard conditions. Moisture content and water activity (aw) gave insight into the biscuits' shelf life. The value of aw from 0.35 to 0.56 indicated appropriate storability. Dietary fiber content in fresh biscuits ranged from 6.1% to 7.6%, protein from 9.2% to 8.9% and sugar from 30.6% to 35.9%. The content of betalain, total polyphenols and flavonoids, and antioxidant activity (DPPH, FRAP) increased with beetroot powder content incorporated. A slight decrease of all the mentioned parameters during the storage indicated satisfied retention of bioactive molecules. The content of prevalent phenolic compounds gallic and protocatechuic acid, identified by HPLC, decreased from 22.2-32.0 and 21.1-24.9 in fresh biscuits to 18.3-23.4 and 17.3-20.3 mg/100 g upon six months of storage, respectively. An increase of the L* and a* and a decrease of the b* coordinate values, compared with the control sample without beetroot values, was noticed as well as the expected level of their change during the storage. The obtained results indicated that biscuits enriched with beetroot powder showed a significantly improved functional, nutritional and antioxidant potential during storage.

Antioxidant Activity and Multi-Elemental Analysis of Dark Chocolate.

Cocoa beans are part of the cocoa plant fruit (Theobroma cacao L.) used to prepare various products such as chocolate, cocoa butter, jelly, liqueurs, cosmetics, etc. Dark chocolate is consumed worldwide by different populations and is known for its good taste, making it one of the most favoured food products. This work aimed to determine the content of total polyphenols (TPC), total flavonoids (TFC), and the antioxidant potential measured through the ability to scavenge DPPH free radicals (DPPH), ferric reducing power (FRAP), and total antioxidant capacity (TAC), as well as major and trace elements contained in twelve commercially available dark chocolate samples, with cocoa content ranging from 40% to 99%. The total polyphenols content ranged between 10.55 and 39.82 mg/g GAE, while the total flavonoid content was from 10.04 to 37.85 mg/g CE. All applied antioxidant assays indicate that the sample with the highest cocoa percentage shows the greatest antioxidant activity (DPPH: 48.34% of inhibition; FRAP: 89.00 mg/g GAE; TAC: 83.86 mg/g AAE). Statistical methods were applied to establish the differences between the samples concerning TPC, TFC, DPPH, FRAP and TAC, as well as to differentiate the samples according to the mineral content. The results indicated that the differences in TPC and TFC between different samples depended on the cocoa content and the addition of dried fruit pieces. A good correlation between antioxidant potency composite index (ACI) and declared cocoa content was noticed (R2 = 0.8034), indicating that the declared percentage of cocoa is a reliable indicator for antioxidant activity of analysed dark chocolate samples. The nutritional evaluation proved that the studied chocolate samples were an excellent source of Mg, Fe, Mn and Cu.

Anticancer Potential of Xanthohumol and Isoxanthohumol Loaded into SBA-15 Mesoporous Silica Particles against B16F10 Melanoma Cells.

Xanthohumol (XN) and isoxanthohumol (IXN), prenylated flavonoids from Humulus lupulus, have been shown to possess antitumor/cancerprotective, antioxidant, antiinflammatory, and antiangiogenic properties. In this study, mesoporous silica (SBA-15) was loaded with different amounts of xanthohumol and isoxanthohumol and characterized by standard analytical methods. The anticancer potential of XN and IXN loaded into SBA-15 has been evaluated against malignant mouse melanoma B16F10 cells. When these cells were treated with SBA-15 containing xanthohumol, an increase of the activity correlated with a higher immobilization rate of XN was observed. Considering the amount of XN loaded into SBA-15 (calculated from TGA), an improved antitumor potential of XN was observed (IC50 = 10.8 ± 0.4 and 11.8 ± 0.5 µM for SBA-15|XN2 and SBA-15|XN3, respectively; vs. IC50 = 18.5 ± 1.5 µM for free XN). The main mechanism against tumor cells of immobilized XN includes inhibition of proliferation and autophagic cell death. The MC50 values for SBA-15 loaded with isoxanthohumol were over 300 µg/mL in all cases investigated.

Synthesis, characterization and in vitro biological evaluation of novel organotin(IV) compounds with derivatives of 2-(5-arylidene-2,4-dioxothiazolidin-3-yl)propanoic acid.

Two novel triphenyltin(IV) compounds, [Ph3SnL1] (L1 = 2-(5-(4-fluorobenzylidene)-2,4-dioxotetrahydrothiazole-3-yl)propanoate (1)) and [Ph3SnL2] (L2 = 2-(5-(5-methyl-2-furfurylidene)-2,4-dioxotetrahydrothiazole-3-yl)propanoate (2)) were synthesized and characterized by FT-IR, (1H and 13C) NMR spectroscopy, mass spectrometry, and elemental microanalysis. The in vitro anticancer activity of the synthesized organotin(IV) compounds was determined against four tumor cell lines: PC-3 (prostate), HT-29 (colon), MCF-7 (breast), and HepG2 (hepatic) using MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-12 diphenyltetrazolium bromide) and CV (crystal violet) assays. The IC50 values are found to be in the range from 0.11 to 0.50 µM. Compound 1 exhibits the highest activity toward PC-3 cells (IC50 = 0.115 ±â€¯0.009 µM; CV assay). The tin and platinum uptake in PC-3 cells showed a threefold lower uptake of tin in comparison to platinum (as cisplatin). Together with its higher activity this indicates a much higher cell inhibition potential of the tin compounds (calculated to ca. 50 to 100 times). Morphological analysis suggested that the compounds induce apoptosis in PC-3 cells, and flow cytometry analysis revealed that 1 and 2 induce autophagy as well as NO (nitric oxide) production.