Nutritional Value, Phytochemical Composition and Biological Activities of Lycium barbarum L. fruits from Serbia.

Cultivation of goji berries (GB), fruits of Lycium barbarum L. (Solanaceae), is expanding worldwide, including in Europe. In this study, a comparative analysis of the nutritional value, chemical composition and in vitro biological activities of GB from different locations in Serbia was performed. Proximate compositions were evaluated according to standard methods. Minerals were assessed by inductively coupled plasma techniques, while fatty acids, sterols, and phenolic profiles were analyzed by gas- and liquid chromatography-based techniques coupled with flame-ionization, mass spectrometry, or diode array detection. The total content of phenolics, flavonoids, carotenoids, and polysaccharides was assessed using spectrophotometric methods. Methanol extracts from GB were examined for their antioxidant, enzyme inhibitory (α-amylase, α-glucosidase, acetylcholinesterase and tyrosinase) and antibacterial activities. Despite significant variations among samples from different locations, the results confirmed that GB are a valuable source of dietary fiber and protein and are characterized by favorable fatty acid profiles. Phytochemical analysis revealed that ß-sitosterol, Δ5-avenasterol, and 24-methyldesmosterol are the predominant sterols and caffeic acid, gallic acid, quercetin and rutin are the main phenols. All GB samples showed both antioxidant and mild antimicrobial activity. A dose-dependent anti-enzymatic activity (IC50 ranging 1.68-6.88 mg/mL) was demonstrated. The results support further promotion of GB cultivation in Serbia and further investigations on their potential applications in various industries.

Potentially toxic elements in sediments near mines-a comprehensive approach for the assessment of pollution status and associated risk for the surface water environment.

This research is focused on the assessment of the pollution status of river and lake sediments near Pb, Zn, and Cu mines and tailings in the southeastern part of Serbia-Krajiste area. The study is based on hypothesis that investigated rivers and lakes in the Krajiste area could be polluted by potentially toxic elements (PTEs) and that these elements could pose considerable ecological risk to the studied surface water environment. High PTE contents are detected in studied river sediments (up to 7892 mg kg-1 for Zn, 3224 mg kg-1 for Cu, 36,790 mg kg-1 for Pb, 64.2 mg kg-1 for Cd, and 1444 mg kg-1 for As). Given that the contents of the studied elements in most of the river sediments exceeded the background values, values prescribed by regulations of the Republic of Serbia, as well as probable effect concentration (PEL), it is possible to conclude that sediments were heavily polluted and that detrimental effects can be expected. Contamination indices including the enrichment factor (EF), contamination factor (CF), index of geoaccumulation (Igeo), potential ecological risk index (Eri), ecological risk index (RI), pollution load index (PLI), and aggregative toxicity index (ATI) were used to assess the degree of pollution by PTEs. The ecological risk assessment revealed that there is a significant risk observed for toxic elements (primarily Pb, Cu, Cd, and As) at this moment. The highest contamination indices (EF, Igeo, CF, PLI, and ATI) are mainly associated with historical and current mining activities. The Monte Carlo analysis based on the risk assessment indices was used to evaluate the uncertainty. The most pronounced toxic risk is found for the Pb, Cu, Cd, and As which assessment was in the range of high and extremely high-risk probabilities. The obtained results suggest that levels of toxic elements pose a significant ecological risk to the surface water environment near Pb, Zn, and Cu mines in the Krajiste area. The methodology applied in this paper could be very useful for other researchers dealing with the problem of environmental pollution by toxic elements.

Common millet and soybean intercropping with bio-fertilizer as sustainable practice for managing grain yield and quality.

Climate changes are one of the biggest threats to food security. Sustainable agriculture, focused on eco-friendly practices for highly efficient food production, enables greater resilience and safety. This study experimented on intercropping and bio-fertilizer application as convenient ecological solutions for crop yield stability and quality. The experiment was conducted during 2018 and 2020 with soybean and common millet sown in three sowing patterns: alternating rows, alternating strips 1 (2 rows of soybean + 2 rows of millet), and alternating strips 2 (2 rows of soybean + 4 rows of millet), as well as sole crops (control), with or without a bio-fertilizer Coveron. Grain yield and nutrient grain yield response were calculated through land equivalent ratio (LER) and element-LER (E-LER), while quality was estimated based on the concentration of antioxidants (phytate phosphorus, total phenolic compounds, and yellow pigment) and elements in grains, including potential bio-availability of essential elements. Results revealed LER values to be >1 for all sowing patterns, with the highest one achieved in alternating strips 1 (1.38) together with a greater level of all antioxidants in millet grain. Intercropping significantly enhanced Fe and Mn accumulation in both crops and simultaneously decreased the concentration of potentially toxic elements (Al, Cr) in millet grain. Potential bio-availability of essential elements, expressed through the ratio between phytic acid and Ca, Mg, Fe, and Zn revealed smaller values in intercropped soybean and millet with the bio-fertilizer. The bio-fertilizer also increased the concentration of some micro-elements in millet grain, classifying it as a highly dependent plant to microbial inoculation. Interaction of intercropping and bio-fertilizer was most pronounced for LER, E-LER, and accumulation of Fe and Mn in grains. These results highlighted the benefits of soybean-common millet intercropping, especially in combination with the bio-fertilizer, in light of enhanced land utilization and nutrient absorption, thus increasing the resilience of soybean and millet under dry land conditions and low-input systems toward stability and food security.

The effect of Artemisia annua L. extract on microbiologically influenced corrosion of A36 steel caused by Pseudomonas aeruginosa.

The protective effect of A. annua against microbiologically influenced corrosion (MIC) of A36 steel caused by P. aeruginosa (PA) in a simulated marine environment was investigated using electrochemical, spectroscopic, and surface techniques. PA was found to accelerate the local dissolution of A36 which led to the formation of a porous α-FeOOH and γ-FeOOH surface layer. 2D and 3D profiles of treated coupons, obtained by optical profilometer, revealed the formation of crevices in the presence of PA. On the contrary, adding A. annua to the biotic medium led to the formation of a thinner, more uniform surface without significant damage. Electrochemical data showed that the addition of A. annua prevented the MIC of A36 steel with an inhibition efficiency of 60%. The protective effect was attributed to the formation of a more compact Fe3O4 surface layer, as well as the adsorption of phenolics, such as caffeic acid and its derivatives on the A36 steel surfaces, as detected by FTIR and SEM-EDS analysis. ICP-OES confirmed that Fe and Cr species more readily diffuse from A36 steel surfaces incubated in biotic media (Fe; 1516.35 ± 7.94 µg L-1 cm-2, Cr; 11.77 ± 0.40 µg L-1 cm-2) compared to the inhibited media (Fe; 35.01 ± 0.28 µg L-1 cm-2, Cr; 1.58 ± 0.01 µg L-1 cm-2).

The influence of bismuth participation on the morphological and electrochemical characteristics of gallium oxide for the detection of adrenaline.

In this work, we investigated the morphological and electrochemical properties of gallium/bismuth mixed oxide. The bismuth concentration was varied from 0 to 100%. The correct ratio was determined with inductively coupled plasma-optical emission spectroscopy (ICP-OES), while surface characteristics were determined using scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurement. Electrochemical characteristics were studied using electrochemical impedance spectroscopy (EIS) in the Fe2+/3+ couple. The obtained materials were tested for adrenaline detection. After square wave voltammetry (SWV) optimization, the best electrode showed a wide linear working range from 7 to 100 µM at pH 6 of the Britton-Robinson buffer solution (BRBS) supporting electrolyte. The limit of detection (LOD) for the proposed method was calculated as 1.9 µM, with a limit of quantification (LOQ) of 5.8 µM. The excellent selectivity of the proposed method, with good repeatability and reproducibility, strongly suggests the possible application of the procedure for the determination of adrenaline in artificially prepared real samples. The practical applicability with good recovery values indicates that the morphology of the materials is closely connected with other parameters, which further suggests that the developed approach can offer a low-cost, rapid, selective, and sensitive method for adrenaline monitoring.

Microbial fuel cells as an electrical energy source for degradation followed by decolorization of Reactive Black 5 azo dye.

The problem of wastewater has long been ubiquitous and has great consequences for the environment and its inhabitants. Microbial fuel cells (MFCs) have enormous potential for the treatment of wastewaters polluted with azo dyes. The amount of energy that can be produced from a single-chamber MFC is sufficient to perform decolorization and degradation of such dyes, which are widely used in the textile industry. This study on the azo dye, reactive black 5 (RB5), provides an alternative method through three parallel-connected MFCs to obtain electricity that directly serves for the dye's electrochemical degradation. We examined degradation followed by decolorization of RB5 using Fe and Pt electrodes, together with H2O2, to achieve the electro-Fenton process. The amount of voltage produced (295 mV), the current density (276 mA m-3) and the power density (50 mW m-3) were sufficient to degrade 25 mg L-1 RB5 dye with 0.5 mM H2O2 in just 2 h. The dye degradation mechanism was investigated using UV-VIS, FT-IR and HPLC-MS/MS. The ecotoxicity of the degradation products was assessed using a bacterial model, Aliivibrio fischeri. These tests showed that there was successful degradation of the dye to products whose toxicity is less than that of RB5.

Hepatoprotective Effect of Mixture of Dipropyl Polysulfides in Concanavalin A-Induced Hepatitis.

The main biologically active components of plants belonging to the genus Allium, responsible for their biological activities, including anti-inflammatory, antioxidant and immunomodulatory, are organosulfur compounds. The aim of this study was to synthetize the mixture of dipropyl polysulfides (DPPS) and to test their biological activity in acute hepatitis. C57BL/6 mice were administered orally with DPPS 6 h before intravenous injection of Concanavalin A (ConA). Liver inflammation, necrosis and hepatocytes apoptosis were determined by histological analyses. Cytokines in liver tissue were determined by ELISA, expression of adhesive molecules and enzymes by RT PCR, while liver mononuclear cells were analyzed by flow cytometry. DPPS pretreatment significantly attenuated liver inflammation and injury, as evidenced by biochemical and histopathological observations. In DPPS-pretreated mice, messenger RNA levels of adhesion molecules and NADPH oxidase complex were significantly reduced, while the expression of SOD enzymes was enhanced. DPPS pretreatment decreased protein level of inflammatory cytokines and increased percentage of T regulatory cells in the livers of ConA mice. DPPS showed hepatoprotective effects in ConA-induced hepatitis, characterized by attenuation of inflammation and affection of Th17/Treg balance in favor of T regulatory cells and implicating potential therapeutic usage of DPPS mixture in inflammatory liver diseases.

Chemical Characterization, Antioxidant and Antimicrobial Properties of Goji Berries Cultivated in Serbia.

Since the fruits of Lycium L. species (Fructus Lycii, goji berries) are promoted as a "superfood" with plenty of health benefits, there is extensive research interest in their nutritional and phytochemical composition. In the present study, the nutritional value, minerals, fatty acid composition, and bioactive compounds of L. barbarum L., red, yellow, and black goji berry (L. ruthenicum Murray.) cultivated in Serbia were investigated. Antioxidant and antimicrobial properties of their methanol extracts were assessed. Red goji berry had the highest content of fats, dietary fiber, iron, total carotenoids, and 2-O-ß-d-glucopyranosyl-l-ascorbic acid (AA-2ßG). The yellow goji berry extract showed the highest level of flavonoids and the most prominent antimicrobial (especially against Gram-negative bacteria) properties. The highest total phenolic content and the most potent antioxidant activity were observed for the extract of black goji berry. Therefore, all goji berries could be a valuable source of bioactive compounds in the food and pharmaceutical industry.

Oxidative degradation and mineralization of bentazone from water.

Bentazone degradation efficiency and mineralization in water solutions using chlorine dioxide treatment were evaluated. Double distilled water and a river water sample spiked with bentazone were studied and compared after chlorine dioxide treatment. Degradation efficiency was determined using high-performance liquid chromatography (HPLC). Daphnia magna toxicity testing and total organic carbon (TOC) analysis were used to ascertain the toxicity of the degraded solutions and mineralization degree. Bentazone degradation products were identified using gas chromatography with a triple quadrupole mass detector (GC-MS-MS). A simple mechanistic scheme for oxidative degradation of bentazone was proposed based on the degradation products that were identified. Decrease in D. magna mortality, high degradation efficiency and partial bentazone mineralization were achieved by waters containing bentazone degradation products, which indicate the formation of less toxic compounds than the parent bentazone and effective removal of bentazone from the waters. Bentazone degraded into four main degradation products. Humic acid from Sava River water influenced bentazone degradation, resulting in a lower degradation efficiency in this matrix (about 10% lower than in distilled water). Chlorine dioxide treatment of water to degrade bentazone is efficient and offers a novel approach in the development of new technology for removal of this herbicide from contaminated water.

Examination of degradation and ecotoxicology of pethoxamid and metazachlor after chlorine dioxide treatment.

Chlorine dioxide has been reported as very efficiently removing pesticides and other organic compounds from water matrixes. Due to pesticide toxicity and potential toxicity of their degradation products, it is important to monitor these compounds as environmental pollutants in ground and surface waters. Evaluating the effects of chlorine dioxide treatment is necessary, and toxicity studies are used to ascertain the severity of effects of intermediates due to incomplete degradation of the parent compounds. In this paper, for the first time, chlorine dioxide is applied and evaluated for the removal of chloroacetamide herbicides (pethoxamid and metazachlor) from waters (deionized water and Sava River water). The degradation degree of herbicides was measured by high-performance liquid chromatography, the main degradation products were identified using gas chromatography with a triple quadrupole mass detector, and the degree of mineralization was monitored by total organic carbon analysis. Four and two degradation products were identified after pethoxamid and metazachlor degradation, respectively. Total organic carbon analysis showed mineralization occurred, but it was incomplete. The mineralization and the characteristics of the degradation products obtained were tested using Daphnia magna and showed lower toxicity than the parent herbicides. The advantage of the applied treatment was a very high degradation percentage for pethoxamid removal from deionized water and Sava River water (100% and 97%, respectively), with higher mineralization efficiency (65%) than metazachlor. Slightly lower degradation efficiency in the Sava River water was due to chlorine dioxide oxidizing the herbicides and dissolved organic matter simultaneously.

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.

Evaluation of trace metals in thyroid tissues: Comparative analysis with benign and malignant thyroid diseases.

Evaluation of trace metals at level of solid tissue can provide better information than blood or urine and, therefore, could highlight the role of metals in the etiology of organ-specific disease. The current study aimed to establish the baseline content of four essential (Mn, Cu, Zn, Se) and four toxic metals (As, Cd, Pb, U) in the healthy thyroid tissues (HTTs) by considering sex, age and smoking habits. A further aim was to examine whether differences in the content of metals exist in regard to the thyroid diseases, such as benign tumor (BT), Hashimoto's thyroiditis (HT), multinodular goiter (MNG) and thyroid cancer (TC). A total number of investigated tissue samples were 423. All metals were quantified by inductively coupled plasma-mass spectrometry (ICP-MS). It was found that the content of Cu and U was higher in HTTs of women, while the content of Zn was higher in HTTs of men. Increased content of Zn and decreased content of U was found in the group of HTTs above 50 years compared to a younger group (<50 years). Increased content of Cd, Pb and U distinguish smokers from the non-smokers. In comparison with other population groups worldwide, investigated Serbian population had up to 15 times reduced content of Se. Despite the difference in metal's profile according to biological variables, this study also demonstrated, for the first time, that each thyroid disease has its unique metal's profile. The most altered metal's content was found in tissues with HT. Contrarily, the greatest similarity in metal's content with HTTs was found in BT tissues. Based on the increased content, metal's that dominantly discriminated HTTs from the HT, MNG and TC was As, Pb and Cd, respectively. Reported results could highlight the role of toxic and essential trace metals in the not very well clarified etiology of thyroid diseases and, moreover, could provide a molecular basis for pathophysiological changes of metal's hazardous effects on thyroid health at the tissue level.