Synthesis, Surface Modification and Magnetic Properties Analysis of Heat-Generating Cobalt-Substituted Magnetite Nanoparticles.

Here, we present the results of the synthesis, surface modification, and properties analysis of magnetite-based nanoparticles, specifically Co0.047Fe2.953O4 (S1) and Co0.086Fe2.914O4 (S2). These nanoparticles were synthesized using the co-precipitation method at 80 °C for 2 h. They exhibit a single-phase nature and crystallize in a spinel-type structure (space group Fd3¯m). Transmission electron microscopy analysis reveals that the particles are quasi-spherical in shape and approximately 11 nm in size. An observed increase in saturation magnetization, coercivity, remanence, and blocking temperature in S2 compared to S1 can be attributed to an increase in magnetocrystalline anisotropy due to the incorporation of Co ions in the crystal lattice of the parent compound (Fe3O4). The heating efficiency of the samples was determined by fitting the Box-Lucas equation to the acquired temperature curves. The calculated Specific Loss Power (SLP) values were 46 W/g and 23 W/g (under HAC = 200 Oe and f = 252 kHz) for S1 and S2, respectively. Additionally, sample S1 was coated with citric acid (Co0.047Fe2.953O4@CA) and poly(acrylic acid) (Co0.047Fe2.953O4@PAA) to obtain stable colloids for further tests for magnetic hyperthermia applications in cancer therapy. Fits of the Box-Lucas equation provided SLP values of 21 W/g and 34 W/g for CA- and PAA-coated samples, respectively. On the other hand, X-ray photoelectron spectroscopy analysis points to the catalytically active centers Fe2+/Fe3+ and Co2+/Co3+ on the particle surface, suggesting possible applications of the samples as heterogeneous self-heating catalysts in advanced oxidation processes under an AC magnetic field.

FETPY: a Diiron(I) Thio-Carbyne Complex with Prominent Anticancer Activity In Vitro and In Vivo.

FETPY, an organo-diiron(I) complex, showed strong cytotoxicity across a panel of human and mouse cancer cell lines, combined with an outstanding selectivity compared to nonmalignant cells. Enhanced iron uptake in aggressive, low-differentiated cell lines, caused membrane lipid peroxidation, which resulted in ferroptosis in human ovarian cancer cells. FETPY induced significant morphological changes in murine B16-F1 and B16-F10 melanoma cells, leading to senescence and/or trans-differentiation into Schwann-like cells, thus significantly reducing their tumorigenic potential. Additionally, FETPY substantially suppressed tumor growth in low- and high-grade syngeneic melanoma models when administered in a therapeutic regimen. FETPY is featured by satisfactory water solubility (millimolar range), an amphiphilic character (Log Pow = -0.17), and excellent stability in a biological medium (DMEM). These important requisites for drug development are rarely met in iron complexes investigated so far as possible anticancer agents. Overall, FETPY holds promise as a safe and potent targeted antitumor agent.

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.

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.

Okara-Enriched Gluten-Free Bread: Nutritional, Antioxidant and Sensory Properties.

The aim of this study was to produce an eco-innovative gluten-free bread with a pleasant taste and a unique formulation that includes the highest quality grains and pseudocereals (buckwheat; rice; and millet); and okara; a by-product of soy milk production. The mixture of pseudocereal and cereal flour contained buckwheat flour 45%, rice flour 33%, and millet flour 22%. Three gluten-free breads; each containing different contents of gluten-free flour (90%, 80%, and 70%, respectively); okara (10%, 20%, and 30%, respectively); and a control sample (without okara); were prepared and subjected to sensory evaluation. The okara-enriched gluten-free bread with the highest sensory score was selected for further analysis of physico-chemical (total proteins; total carbohydrates; insoluble fiber; soluble fiber; sugars; total lipids; saturated fatty acids; and salt) and functional properties (total phenolic content and antioxidant properties). The highest sensory scores were obtained for 30% okara-enriched gluten-free bread including taste; shape; odor; chewiness; and cross-section properties; classifying this bread in the category of very good quality and excellent quality (mean score 4.30 by trained evaluators and 4.59 by consumers). This bread was characterized by a high content of dietary fiber (14%), the absence of sugar; low content of saturated fatty acids (0.8%), rich source of proteins (8.8%) and certain minerals (e.g.,; iron; zinc); and low energy value (136.37 kcal/100g DW). Total phenolic content was 133.75 mgGAE/100g FW; whereas ferric reducing power; ABTS radical cation; and DPPH radical scavenging activity were 119.25 mgAA/100g FW; 86.80 mgTrolox/100g FW; and 49.92 mgTrolox/100g FW; respectively. Okara addition in gluten-free bread production enables the formulation of high-nutritive; good antioxidative; low-energy bread; and better soy milk waste management.

Self-Heating Flower-like Nanoconstructs with Limited Incorporation of Yttrium in Maghemite: Effect of Chemical Composition on Heating Efficiency, Cytotoxicity and Genotoxicity.

Partial cation substitution can significantly change the physical properties of parent compounds. By controlling the chemical composition and knowing the mutual relationship between composition and physical properties, it is possible to tailor the properties of materials to those that are superior for desired technological application. Using the polyol synthesis procedure, a series of yttrium-substituted iron oxide nanoconstructs, γ-Fe2-xYxO3 (YIONs), was prepared. It was found that Y3+ could substitute Fe3+ in the crystal structures of maghemite (γ-Fe2O3) up to a limited concentration of ~1.5% (γ-Fe1.969Y0.031O3). Analysis of TEM micrographs showed that crystallites or particles were aggregated in flower-like structures with diameters from 53.7 ± 6.2 nm to 97.3 ± 37.0 nm, depending on yttrium concentration. To be investigated for potential applications as magnetic hyperthermia agents, YIONs were tested twice: their heating efficiency was tested and their toxicity was investigated. The Specific Absorption Rate (SAR) values were in the range of 32.6 W/g to 513 W/g and significantly decreased with increased yttrium concentration in the samples. Intrinsic loss power (ILP) for γ-Fe2O3 and γ-Fe1.995Y0.005O3 were ~8-9 nH·m2/Kg, which pointed to their excellent heating efficiency. IC50 values of investigated samples against cancer (HeLa) and normal (MRC-5) cells decreased with increased yttrium concentration and were higher than ~300 µg/mL. The samples of γ-Fe2-xYxO3 did not show a genotoxic effect. The results of toxicity studies show that YIONs are suitable for further in vitro/in vivo studies toward to their potential medical applications, while results of heat generation point to their potential use in magnetic hyperthermia cancer treatment or use as self-heating systems for other technological applications such as catalysis.

Elemental Profile, General Phytochemical Composition and Bioaccumulation Abilities of Selected Allium Species Biofortified with Selenium under Open Field Conditions.

Allium species are known as a rich source of many compounds with potential healing effects. Biofortification is recognized as an effective agrotechnical measure for raising the level of biogenic elements-especially microelements in the edible parts of these species, so Allium can be considered as a 'natural dietary supplement'. The aim of this research was to test the effects of foliar application of Se fertilizer (Na2SeO4) in different doses (control-0, 10, 20 and 30 g per ha) on the content of macro, microelements and secondary metabolites (SMs)-free phenolics, flavonoids and hydroxycinnamic acid derivatives in the edible parts, i.e., leaves of two selected Allium species in Serbia (A. odorum and A. schoenoprasum), which grew in open field conditions over the course of two growing seasons. The bioaccumulation factor (BAF), as an indicator of the ability of plants to accumulate biogenic elements, was also determined. Although with no full regularity, the dose of 10 g of Se per ha yielded the highest content for the most biogenic elements for both alliums in the first growing season, i.e., a dose of 20 g of Se per ha for A. schoenoprasum, and a dose of 30 g of Se per ha for A. odorum in the second growing season. The obtained results justified the Se-biofortification of different alliums. The BAF values indicated the ability of both Allium species to accumulate S, K and P in their leaves during both growing seasons. The accumulation of potentially toxic elements was not recorded for either species, emphasizing the safety of the produced plant material for human consumption. Additionally, Se-treated plants had higher SM contents compared to control plants. The growing season also showed an impact on SM content; i.e., in the second season, characterized as drought-stressed, the synthesis of SMs was significantly higher compared to that in the first season. Further research should be directed towards finding the appropriate dose of Se, expanded in the sense of conducting research in controlled conditions, as well as different ways of applying Se fertilizer. The idea of this study was also to popularize the examined Allium species, which are rarely grown in the territory of Serbia.

Obtaining Medical Textiles Based on Viscose and Chitosan/Zinc Nanoparticles with Improved Antibacterial Properties by Using a Dielectric Barrier Discharge.

This study aimed to obtain functional viscose textiles based on chitosan coatings with improved antibacterial properties and washing durability. For that reason, before functionalization with chitosan/zinc nanoparticles (NCH+Zn), the viscose fabric was modified by nonthermal gas plasma of dielectric barrier discharge (DBD) to introduce into its structure functional groups suitable for attachment of NCH+Zn. NCH+Zn were characterized by measurements of hydrodynamic diameter and zeta potential and AFM. DBD-plasma-modified and NCH+Zn-functionalized fabrics were characterized by zeta potential measurements, ATR-FTIR spectroscopy, the calcium acetate method (determination of content of carboxyl and aldehyde groups), SEM, breaking-strength measurements, elemental analysis, and ICP-OES. Their antibacterial activity was determined under dynamic contact conditions. In addition to SEM, the NCH+Zn distributions on viscose fabrics were also indirectly characterized by measuring their absorbent capacities before and after functionalization with NCH+Zn. Washing durability was monitored through changes in the zeta potential, chitosan and zinc content, and antibacterial activity after 1, 3, and 5 washing cycles. The obtained results showed that DBD plasma modification contributed to the simultaneous improvement of NCH+Zn sorption and antibacterial properties of the viscose fabric functionalized with NCH+Zn, and its washing durability, making it suitable for the production of high-value-added medical textiles.

Polyphenolics and Chemical Profiles of Domestic Norwegian Apple (Malus × domestica Borkh.) Cultivars.

Using modern analytical techniques, a comprehensive study of the chemical composition of fruits from apple cultivars grown in Western Norway during 2019 and 2020 was done. Metals, sugars, organic acids, antioxidant tests, and polyphenol content have been observed. In all investigated samples, the most dominant sugars were glucose, fructose, and sucrose. Among 11 tested organic acids, the dominant was malic acid, followed by citric and maleic acid. The most common metal was potassium, followed by magnesium and zinc. The quantification of polyphenols showed that among the 11 quantified polyphenols, chlorogenic acid, quercetin 3-O-rhamnoside, quercetin 3-O-glucoside, quercetin, and phlorizin were the most abundant. A detailed study of the polyphenolic profile of nine investigated apple samples provided 30 identified polyphenolic compounds from the class of hydroxybenzoic and hydroxycinnamic acids, flavonoids, and dihydrochalcones. In addition to the identified 3-O-caffeoylquinic acid, its two isomers of 5-O-caffeoylquinic acid and three esters were also found. Present polyphenols of the tested apples provided significant data on the quality of Norwegian apples, and they contribute to the distinguishing of these apple samples.

Micro/trace/toxic elements and insecticide residues level in monofloral bee-collected sunflower pollen- health risk assessment.

The aim of the current research was to determine the content of (potentially) toxic elements and insecticide residues in monofloral sunflower bee-collected pollen. For micro- and trace elements determination Inductively Coupled Plasma Optical Emission (ICP-OES) analytical method was used while insecticide residue content was monitored by applying Liquid Chromatography-Mass Spectrometry (LC-MS/MS) technique. In total, seventeen micro/trace elements were quantified. None of the twenty four examined insecticides were detected above the limit of detection (LOD) which makes studied sunflower bee-collected pollen eco-friendly both to bees and humans. Based on presence of several toxic as well as potentially toxic elements calculations for estimated weekly intakes (EWI), and oral intakes (OI) were made and used for health risk assessment based on the computation of two different health risk quotients (HQ)- acute (HQA) and long-term (HQL). The obtained results proved that all HQ values for adults were negligible or low except in case of HQL value for arsenic (0.32) which can be characterized as medium. However, in case of children much more precaution is needed due to significant HQL risk for arsenic (1.511). The attained data can help to make additional linkage between bee-collected pollen as food ingredients and potential benefits/risks for human health.

Rosemary Essential Oils as a Promising Source of Bioactive Compounds: Chemical Composition, Thermal Properties, Biological Activity, and Gastronomical Perspectives.

Rosemary (Rosmarinus officinalis L.) is a plant worldwide cultivated mainly for essential oils, extracts, and as a spice. Up-to-date results showed diversity in composition of the essential oils, which may influence their quality, biological activity, and thermal properties. Therefore, the aim of this study was to investigate the chemical composition, antimicrobial activity, and thermal properties of the rosemary essential oils originating from Serbia and Russia. Additionally, oils were added to the sunflower oils in order to investigate possible antioxidant activity during the frying. Investigation of the chemical profile marked α-pinene, eucalyptol, and camphor as the most abundant compounds in both oils. However, overall composition influenced in such manner that Russian oil showed significantly higher antimicrobial activity, while Serbian oil proved to be better antioxidant agent in case of frying of sunflower oil. This would significantly influence possible application of the oils, which could be used as an antioxidant agent for extension of the food shelf life, or antimicrobial agent for protection against different microbial strains.

Chitosan Nanoparticles Functionalized Viscose Fabrics as Potentially Durable Antibacterial Medical Textiles.

This research proposed two pretreatments of viscose fabrics: oxidation with 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO) and coating with TEMPO-oxidized cellulose nanofibrils (TOCN), to introduce functional groups (COOH and CHO) suitable for irreversible binding of chitosan nanoparticles without and with embedded zinc (NCS and NCS + Zn, respectively) and consequently achieving washing durable antibacterial properties of the chitosan nanoparticles functionalized fabrics. The characterizations of pretreated and chitosan nanoparticles functionalized fabrics were performed by FTIR and XPS spectroscopy, elemental analysis, inductively coupled plasma optical emission spectrometry, zeta potential measurements, scanning electron microscopy, determination of COOH and CHO groups content, and antimicrobial activity under dynamic contact conditions. Influence of pretreatments on NCS and NCS + Zn adsorption, chemical, electrokinetic, and antibacterial properties as well as morphology, and washing durability of NCS and NCS + Zn functionalized fabrics were studied and compared. Washing durability was evaluated through changes in the chitosan and zinc content, zeta potential, and antibacterial activity after 1, 3, and 5 washing cycles. Pretreatments improved washing durability of antibacterial properties of chitosan nanoparticles functionalized fabrics. The NCS and NCS + Zn functionalized pretreated fabrics preserved antibacterial activity against S. aureus after five washing cycles, while antibacterial activity against E. coli was preserved only after one washing cycle in the case NCS + Zn functionalized pretreated viscose fabrics.

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.

Antitumor potential of cisplatin loaded into SBA-15 mesoporous silica nanoparticles against B16F1 melanoma cells: in vitro and in vivo studies.

CP (cisplatin) and mesoporous silica SBA-15 (Santa Barbara amorphous 15) loaded with CP (→SBA-15|CP) were tested in vitro and in vivo against low metastatic mouse melanoma B16F1 cell line. SBA-15 only, as drug carrier, is found to be not active, while CP and SBA-15|CP revealed high cytotoxicity in lower µM range. The activity of SBA-15|CP was found similar to the activity of CP alone. Both CP and SBA-15|CP induced inhibition of cell proliferation (carboxyfluorescein succinimidyl ester - CFSE assay) along with G2/M arrest (4',6-diamidino-2-phenylindole - DAPI assay). Apoptosis (Annexin V/ propidium iodide - PI assay), through caspase activation (apostat assay) and nitric oxide (NO) production (diacetate(4-amino-5-methylamino-2',7'-difluorofluorescein-diacetat) - DAF FM assay), was identified as main mode of cell death. However, slight elevated autophagy (acridine orange - AO assay) was detected in treated B16F1 cells. CP and SBA-15|CP did not affect production of ROS (reactive oxygen species) in B16F1 cells. Both SBA-15|CP and CP induced in B16F1 G2 arrest and subsequent senescence. SBA-15|CP, but not CP, blocked the growth of melanoma in C57BL/6 mice. Moreover, hepato- and nephrotoxicity in SBA-15|CP treated animals were diminished in comparison to CP confirming multiply improved antitumor potential of immobilized CP. Outstandingly, SBA-15 boosted in vivo activity and diminished side effects of CP.

Synthesis, chemical characterization, PARP inhibition, DNA binding and cellular uptake of novel ruthenium(II)-arene complexes bearing benzamide derivatives in human breast cancer cells.

Inhibitors of poly(ADP-ribose) polymerase-1 (PARP-1) showed remarkable clinical efficacy in BRCA-mutated tumors. Based on the rational drug design, derivatives of PARP inhibitor 3-aminobenzamide (3-AB), 2-amino-4-methylbenzamide (L1) and 3-amino-N-methylbenzamide (L2), were coordinated to the ruthenium(II) ion, to form potential drugs affecting DNA and inhibiting PARP enzyme. The four conjugated complexes of formula: C1 [(ƞ6-toluene)Ru(L1)Cl]PF6, C2 [(ƞ6-p-cymene)Ru(L1)Cl]PF6, C3 [(ƞ6-toluene)Ru(L2)Cl2] and C4 [(ƞ6-p-cymene)Ru(L2)Cl2], have been synthesized and characterized. Colorimetric 3-(4.5-dimethylthiazol-2-yl)-2.5-diphenyltetrazolium bromide (MTT) assay showed the highest antiproliferative activity of C1 in HCC1937, MDA-MB-231, and MCF-7 breast cancer cells. Efficiency of inhibition of PARP-1 enzymatic activity in vitro decreased in order: C2 > C4 > 3-AB>C1 > C3. ICP-MS study of intracellular accumulation and distribution in BRCA1-mutated HCC1937 revealed that C1-C4 entered cells within 24 h. The complex C1 showed the highest intracellular accumulation, nuclear-targeting properties, and exhibited the highest DNA binding (39.2 ±â€¯0.6 pg of Ru per µg of DNA) that resulted in the cell cycle arrest in the S phase.

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.

Evaluation of azamethiphos and dimethoate degradation using chlorine dioxide during water treatment.

Chlorine dioxide (ClO2) degradation of the organophosphorus pesticides azamethiphos (AZA) and dimethoate (DM) (10 mg/L) in deionized water and in Sava River water was investigated for the first time. Pesticide degradation was studied in terms of ClO2 level (5 and 10 mg/L), degradation duration (0.5, 1, 2, 3, 6, and 24 h), pH (3.00, 7.00, and 9.00), and under light/dark conditions in deionized water. Degradation was monitored using high-performance liquid chromatography. Gas chromatography coupled with triple quadrupole mass detector was used to identify degradation products of pesticides. Total organic carbon was measured to determine the extent of mineralization after pesticide degradation. Real river water was used under recommended conditions to study the influence of organic matter on pesticide degradation. High degradation efficiency (88-100% for AZA and 85-98% for DM) was achieved in deionized water under various conditions, proving the flexibility of ClO2 degradation for the examined organophosphorus pesticides. In Sava River water, however, extended treatment duration achieved lower degradation efficiency, so ClO2 oxidized both the pesticides and dissolved organic matter in parallel. After degradation, AZA produced four identified products (6-chlorooxazolo[4,5-b]pyridin-2(3H)-one; O,O,S-trimethyl phosphorothioate; 6-chloro-3-(hydroxymethyl)oxazolo[4,5-b]pyridin-2(3H)-one; O,O-dimethyl S-hydrogen phosphorothioate) and DM produced three (O,O-dimethyl S-(2-(methylamino)-2-oxoethyl) phosphorothioate; e.g., omethoate; S-(2-(methylamino)-2-oxoethyl) O,O-dihydrogen phosphorothioate; O,O,S-trimethyl phosphorodithioate). Simple pesticide degradation mechanisms were deduced. Daphnia magna toxicity tests showed degradation products were less toxic than parent compounds. These results contribute to our understanding of the multiple influences that organophosphorus pesticides and their degradation products have on environmental ecosystems and to improving pesticide removal processes from water.

Chemical Composition, Total Phenols and Flavonoids Contents and Antioxidant Activity as Nutritive Potential of Roasted Hazelnut Skins (Corylus avellana L.).

The present study evaluates natural composition of Serbian roasted hazelnut skins (HS) with potential role in application as functional nutrient of various food products. Total phenols (TPC) and flavonoids contents (TFC) in HS extracts obtained with different ethanol concentrations (10%-I, 50%-II and 96%-III) and their antioxidant activities were investigated. The highest total phenols content (706.0 ± 9.7 mgGAE/gextract) was observed in 96% ethanol HS extract. Ethanol HS extracts showed very high antioxidant activity with effective concentrations (EC50) ranged between 0.052 and 0.066 mg/mL. The phenol and flavonoid content of roasted HS extracts I-III was determined by HPLC-ESI-MS/MS analyses. Contents of lipids, proteins, carbohydrates, metals, and C, H, N, S elements in roasted HS were also determined. Relatively high C/N, C/P and C/N/P ratios, rich metal contents and fatty acids composition indicated that hazelnut skin might be a good candidate for use as either human or fungal functional nutrient. In addition, possible application of phenolic HS extracts as UV booster was studied by recording UV spectra (220-440 nm) of 10 mg/L of HS extracts I-III combined with 10 mg/L of chemical sunscreen agent benzophenone-3 and in vitro sun protection factor (SPF) was calculated.

Antitumor activity of organoruthenium complexes with chelate aromatic ligands, derived from 1,10-phenantroline: Synthesis and biological activity.

The monocationic chloro complexes containing chelating N∩N ligands: [(η6-p-cymene)Ru(L1-4)Cl]+ (1-4), where L1 = 4-methyl-1,10-phenantroline, L2 = dipyrido[3,2-a:2',3'-c]phenazine, L3 = 11-chloro-dipyrido[3,2-a:2',3'-c]phenazine, L4 = 11-nitro-dipyrido[3,2-a:2',3'-c]phenazine; p-cymene = 1-methyl-4-isopropylbenzene) have been prepared and characterized as the hexafluorophosphate salts. The biological activity of 1-4 has been investigated in selected 2D monolayer cell cultures (A549, PANC-1, MDA-MB-231, MRC-5). All investigated ruthenium complexes showed similar or even better cytotoxicity to cisplatin. However, there was no significant reduction in growth of PANC-1 cells in a 3D cell culture of multicellular tumor spheroids (MCTS) after treatment with 2-4, while the cisplatin treatment induced retardation in MCTS growth. Flow cytometry analysis of the cell cycle of PANC-1 cells shows that 3 caused changes of cell cycle phase distribution characterized by slight accumulation of cells in the G2-M phase. Absence of the Sub-G1 phase in the cell cycle of the treated cells indicated that there was no fragmentation of DNA for the analyzed time intervals (48 and 72 h treatment). Fluorescent microscopy, after acridine orange/ethidium bromide staining, revealed that the investigated ruthenium complexes induced some characteristics of apoptotic morphology (shrinking and condensation of chromatin) with notably preserved integrity of the plasma membrane. Investigation of cellular uptake and DNA - fraction accumulation performed by inductively coupled plasma mass spectrometry in PANC-1 cells with equimolar concentrations (5 µM) of 2-4 and cisplatin showed more efficient cellular uptake and DNA - fraction accumulation of complex 3 compared to complexes 2 and 4.

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.