Orally Administrated Lactiplantibacillus plantarum BGAN8-Derived EPS-AN8 Ameliorates Cd Hazards in Rats.

Cadmium (Cd) is a highly toxic metal that is distributed worldwide. Exposure to it is correlated with a vast number of diseases and organism malfunctions. Exopolysaccharides (EPS) derived from Lactiplantibacillus plantarum BGAN8, EPS-AN8, previously showed great potential for the in vitro protection of intestinal cells from this metal. Here, we investigated the potential of food supplemented with EPS-AN8 to protect rats from the hazardous effects of Cd exposure. After thirty days of exposure to lower (5 ppm) and higher (50 ppm)-Cd doses, the administration of EPS-AN8 led to decreased Cd content in the kidneys, liver, and blood compared to only Cd-treated groups, whereas the fecal Cd content was strongly enriched. In addition, EPS-AN8 reversed Cd-provoked effects on the most significant parameters of oxidative stress (MDA, CAT, GST, and GSH) and inflammation (IL-1ß, TNF-α, and IFN-γ) in the duodenum. Moreover, micrographs of the duodenum were in line with these findings. As the gut microbiota has an important role in maintaining homeostasis, we used 16S rRNA amplicon sequencing and investigated the effects of Cd and EPS-AN8 on one part of the microbiota presented in the duodenum. Although Cd decreased the growth of lactobacilli and mostly favored the blooming of opportunistic pathogen bacteria, parallel intake of EPS-AN8 reversed those changes. Therefore, our results imply that EPS-AN8 might be extremely noteworthy in combatting this toxic environmental pollutant.

Voltammetric immunoassay based on MWCNTs@Nd(OH)3-BSA-antibody platform for sensitive BSA detection.

An electrochemical approach is presented based on multiwall carbon nanotubes (MWCNTs) and neodymium(III) hydroxide (Nd(OH)3) nanoflakes for detection of bovine serum albumin (BSA). The materials were characterized morphologically (XRPD, SEM, and HR-TEM) and electrochemically (DPV, EIS). The MWCNTs@Nd(OH)3 composite was used as support for bovine serum albumin polyclonal antibody (anti-BSA). After the antibody immobilization on the electrochemical platform and antigen/antibody binding time (optimum 60 min), the proposed approach shows a linear voltammetric response toward BSA concentration in the range 0.066 to 6.010 ng mL-1 at maximum peak potential of 0.13 V (vs. Ag/AgCl). Limit of detection (LOD) and limit of quantification (LOQ) were 18 pg mL-1 and 61 pg mL-1, respectively. The precision of the method calculated as relative standard deviation (RSD) of five independent measurements was better 3%. The selectivity of the optimized method regarding structurally similar proteins (human serum albumin and human hemoglobin), ions (Na+, K+, Ca2+, and NO2-), or compounds (glucose, ascorbic acid, dopamine, uric acid, paracetamol, and glycine) was found to be satisfactory, with the current changes of less than 5% in the presence of up to 1 × 105 times higher concentrations (depending on the compound) of the listed potential interfering compounds. Practical applicability of immunosensor for BSA determination in cow whey sample, with recovery values in the range 97 to 103%, shows that the developed method has high potential for precise and accurate detection of BSA, as well as exceptional miniaturization possibilities for on-site and equipment-free sensing.

First Report about Mineral Content, Fatty Acids Composition and Biological Activities of Four Wild Edible Mushrooms.

The goal of this research was a comprehensive analysis of four wild edible mushroom species, Cantharellus cinereus, Clavariadelphus pistillaris, Clitocybe nebularis and Hygrocybe punicea, which have not been analyzed so far. Extracts of different polarities have been prepared and evaluated for their antioxidant activities by DPPH, ABTS, FRAP, TRP and CUPRAC methods. For all extracts, total phenolic content was determined. Based on the analysis, it was shown that solvent type had a significant effect on the antioxidant capacities of mushroom extracts, so water extracts showed the highest activity. Furthermore, the analysis includes determination of mineral composition, fatty acid profiles and antimicrobial activity. Unsaturated fatty acids, which are very important for human health, are dominant in the studied mushroom species. Linoleic and oleic acid consist of over 50 % of the total fatty acid composition. Seventeen biologically important and toxic elements have been analyzed by ICP-OES and ICP-MS and results showed that the element concentrations were species-dependent. Also, it has been found that analyzed mushrooms did not show any antimicrobial activity. Chemometric analysis was used to understand the connection between the extracts of different polarities.

Distribution of elements in seeds of some wild and cultivated fruits. Nutrition and authenticity aspects.

BACKGROUND: The compositional, functional, and nutritional properties of fruits are important for defining their quality. Fruit seeds should be better exploited as they are also considered to be a good source of bioactive components. Twenty macro, micro, and trace elements were identified and quantified in the seeds of 70 genuine wild and cultivated fruit species/cultivars by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry. Sophisticated chemometric techniques were also used to establish criteria for the classification of the analyzed samples. RESULTS: Calcium and P were the most abundant elements, followed by K and Na. The content of microelements and trace elements differed among the different cultivars/genotypes. The content of Ba, Pb, and Sr was significantly higher in wild fruits, whereas Fe, Mg, Mn, Ni and Zn content was higher in cultivated fruits. CONCLUSION: All of the statistical procedures that were used - Kruskal-Wallis, Mann-Whitney U-test, and principal component analysis (PCA) - confirm a unique set of parameters that could be used as phytochemical biomarkers to differentiate fruit-seed samples belonging to different cultivars/genotypes according to their botanical origin. This kind of investigation may contribute to intercultivar/genetic discrimination and may enhance the possibilities of acquiring a valuable authenticity factor. © 2018 Society of Chemical Industry.

Oral cadmium exposure affects skin immune reactivity in rats.

Skin can acquire cadmium (Cd) by oral route, but there is paucity of data concerning cutaneous effects of this metal. Cd acquired by oral route can affect skin wound healing, but the effect of Cd on other activities involved in skin homeostasis, including skin immunity, are not explored. Using the rat model of 30-day oral administration of Cd (5 ppm and 50 ppm) in drinking water, basic aspects of immune-relevant activity of epidermal cells were examined. Dose-dependent Cd deposition in the the skin was observed (0.035 ±â€¯0.02 µg/g and 0.127 ±â€¯0.04 µg/g at 5 ppm and 50 ppm, respectively, compared to 0.012 ±â€¯0.009 µg/g at 0 ppm of Cd). This resulted in skin inflammation (oxidative stress at both Cd doses and dose-dependent structural changes in the skin and the presence/activation of innate immunity cells). At low Cd dose inflammatory response (nitric oxide and IL-1ß) was observed. Other inflammatory cytokines (IL-6 and TNF) response occurred at 50 ppm, which was increased further following skin sensitization with contact allergen dinitro-chlorobenzene (DNCB). Epidermal cells exposed to both Cd doses enhanced concanavalin A (ConA)-stimulated lymphocyte production of IL-17. This study showed for the first time the effect of the metal which gained access to the skin via gut on immune reactivity of epidermal cells. Presented data might be relevant for the link between dietary Cd and the risk of skin pathologies.

Wild Bilberry (Vaccinium myrtillus L., Ericaceae) from Montenegro as a Source of Antioxidants for Use in the Production of Nutraceuticals.

The aim of this study was to establish correlation of chemical composition and antioxidant activity of bilberry plants from Montenegro. Total phenolic, tannin, flavonoid, procyanidin and anthocyanin contents were determined in fruits and leaves extracts using spectrophotometric methods, while the measurements of metal content was carried out in an Inductively Coupled Atomic Emission Spectrometer. Qualitative and quantitative analyses of major phenolics were achieved by HPLC. In the investigated extracts, the most abundant phenolic was chlorogenic acid, followed by protocatechuic acid, while resveratrol, isoquercetin, quecetin and hyperoside were also present in significant quantities. Antioxidant potential was evaluated using two in vitro assays-FRAP and DPPH-being in the accordance with the cyclic voltammetry tests, performed as well. The results revealed that all the investigated extracts were rich in phenolic and essential mineral constituents, with significant antioxidant activity, depending on the polyphenolic and mineral contents, which was confirmed by principal component analysis.

Antioxidative responses of the tissues of two wild populations of Pelophylax kl. esculentus frogs to heavy metal pollution.

Heavy metal pollution of the aquatic environment is of great concern worldwide. Heavy metals are capable of inducing oxidative stress by increasing the formation of reactive oxygen species (ROS), and directly affecting the antioxidant defense system (AOS) in living organisms. The frog Pelophylax kl. esculentus is a semiaquatic species with semipermeable skin and a complex lifecycle, and represents a potentially useful bioindicator organism. The aim of this study was to investigate the accumulation of several heavy metals (Cd, Co, Cr, Cu, Fe, Hg, Ni, Pb and Zn), and their effects on selected parameters of the AOS, including the activities of superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GSH-Px), glutathione reductase (GR), phase II biotransformation enzyme glutathione-S-transferase (GST), the total glutathione (GSH) contents and sulfhydryl (SH) group concentrations, as well as cholinesterases (ChEs) activities in the liver, skin and muscle of P. kl. esculentus. Frog samples were collected at two sites (the Danube-Tisza-Danube canal (DTDC) and the river Ponjavica) in Serbia, which are characterized by different levels of metal pollution. Differences between the metal contents in different tissues showed that the skin of frogs from the DTDC accumulated statistically higher concentrations of Cd, Cu, Pb and Zn, while only the Fe concentration was lower. No significant differences between metal concentrations in muscle tissues of frogs from the DTDC and Ponjavica were observed. Examination of the parameters of the AOS revealed that frogs from the DTDC had higher concentrations of GSH in the liver and of SH groups in the skin and muscle, whereas the activities of the antioxidative enzymes SOD, GHS-Px and GR in the liver and of GR in the skin were lower than in frogs from the Ponjavica. The relationship between metal concentrations and AOS parameters showed the highest number of correlations with GSH, GR and CAT, and with Ni, Zn, Hg, Cr and Cd. Based on the results in this study, we concluded that increased concentrations of heavy metals in frog tissues can alter the AOS, which leads to higher concentrations of GSH and SH groups and lower activities of antioxidative enzymes. The response of the AOS to metal pollutants allowed us to make a distinction between different frog tissues, and to conclude that the liver and skin are more suitable for assessing metal-induced oxidative stress in frogs than muscle.

Bioaccumulation and effects of metals on oxidative stress and neurotoxicity parameters in the frogs from the Pelophylax esculentus complex.

Metals are involved in the formation of reactive oxygen species and can induce oxidative stress. The aim of this study was to assess the effects of several metals on oxidative stress in the skin and muscle of the Pelophylax esculentus "complex" frogs (parental species Pelophylax ridibundus, Pelophylax lessonae, and their hybrid Pelophylax esculentus) that inhabit the wetland Obedska Bara in Serbia, and the potential use of these species as bioindicator organisms in biomonitoring studies. The biomarkers of oxidative stress (SOD, CAT, GSH-Px, GR, GST activities and GSH, SH concentrations) and cholinesterase activity were investigated. The concentrations of nine metals (Fe, Cu, Zn, As, Cd, Cr, Hg, Ni, and Pb) were measured in the water and tissues. Correlations were established between metals and biomarkers in the tissues. The results of metal accumulation distinguished the skin of P. lessonae and muscle of P. ridibundus from other P. esculentus complex species. The oxidative stress biomarkers observed in P. ridibundus and P. esculentus had greater similarity than in P. lessonae. The P. lessonae displayed the highest number of correlations between biomarkers and metals. The results of tissue responses revealed that skin was more susceptible to metal-induced oxidative stress, with only exception of As. In the light of these findings, we can suggest the use of P. esculentus complex species as a biomonitoring species in studies of metal accumulation and metal-induced oxidative stress, but with special emphasis on P. lessonae.

Leaching of major and minor elements during the transport and storage of coal ash obtained in power plant.

In power plant, coal ash obtained by combustion is mixed with river water and transported to the dump. Sequential extraction was used in order to assess pollution caused by leaching of elements during ash transport through the pipeline and in the storage (cassettes). A total of 80 samples of filter ash as well as the ash from active (currently filled) and passive (previously filled) cassettes were studied. Samples were extracted with distilled water, ammonium acetate, ammonium oxalate/oxalic acid, acidic solution of hydrogen-peroxide, and a hydrochloric acid. Concentrations of the several elements (Al, As, Cd, Co, Cu, Cr, Fe, Ba, Ca, Mg, Ni, Pb, and Zn) in all extracts were determined by inductively coupled plasma atomic emission spectrometry. Pattern recognition method was carried out in order to provide better understanding of the nature of distribution of elements according to their origins. Results indicate possible leaching of As, Ca, Cd, Cu, Zn, and Pb. Among these elements As, Cd, and Pb are toxicologically the most important but they were not present in the first two phases with the exception of As. The leaching could be destructive and cause negative effects on plants, water pollution, and damage to some life forms.

Concentration and mobility of trace elements (Li, Ba, Sr, Ag, Hg, B) and macronutrients (Ca, Mg, K) in soil-orchid system on different bedrock types.

The mobility of chemical elements in the soil-orchid system has been poorly studied. The aim of this study is to evaluate the uptake and mobility of several trace (Li, Ba, Sr, Ag, Hg, and B) and macronutrients (Ca, Mg, and K) in the orchid Anacamptis morio (L.) R.M.Bateman, Pridgeon & M.W.Chase from soils in western Serbia. The sampling sites are characterized by three different bedrock types-cherts, limestones, and serpentines, which are the source of the significant chemical differences in the elemental status of the soil and plant tissues. The four-step Community Bureau of Reference sequential extraction procedure was used to determine the distribution of fractions and predict their potential phytoavailability. The orchid and soil samples were analyzed for total elemental content analysis using ICP-OES. The greatest potential for plant availability was determined for Ba and Sr, representing about 80% of the total soil content. More than 40% of Li in the soils was found to be potentially phytoavailable. Significant correlations were found between the total content of Li, B, and Sr in soils. Between 38 and 60% of Li content and more than 80% of Ba and Sr content were determined to be potentially phytoavailable by sequential analysis. The highest bioconcentration factor (> 1) was determined in the case of B and Sr for all orchid organs, while translocation factor for Li was highest in tubers and leaves. The studied elements were mainly stored in tubers and roots, indicating the exclusion strategy of A. morio as a metal tolerance mechanism. The data obtained showed significant differences in metal content in soils and plants originating from sites with different parent materials, suggesting that bedrock type and associated soil properties are important factors that determine chemical element mobility and uptake.

Antioxidative enzymes, alkaline phosphatases and Hsp70 expression in larvae of Lymantria dispar (Lepidoptera: Erebidae) from unpolluted and polluted forests after chronic cadmium treatment.

Long-term exposure of populations to pollution may result in enhanced ability to cope with environmental stress. To compare the responses of two Lymantria dispar populations living in unpolluted and polluted forests (UP and PP, respectively), we chronically exposed larvae to cadmium at concentrations of 50 and 100 µg Cd/g dry food (Cd1 and Cd2, respectively). We examined cadmium accumulation in the midgut and hemolymph, activities of superoxide dismutase (SOD), catalase (CAT), and alkaline phosphatases (ALP) in the midgut, as well as Hsp70 protein expression in the midgut, hemolymph, and brain and evaluated these parameters as biomarkers of cadmium contamination. Larvae from PP, fed a control diet, showed higher activity of SOD and increased Hsp70 expression compared with larvae from UP. Excessive amounts of Cd were accumulated in the midgut of all Cd-fed larvae, whereas Cd content in the hemolymph was elevated only in larvae from PP after Cd2 treatment. In larvae from UP, Cd2 treatment decreased the activity of CAT and induced the expression of Hsp70 in the midgut and hemolymph. In larvae from PP, exposure to both Cd concentrations strongly attenuated SOD and CAT activities, while Hsp70 expression was not induced in any organ/tissue. Cd did not affect ALP activity in either population. Midgut Cd content proved to be a suitable indicator of Cd contamination for both polluted and unpolluted habitats.

Is a Lead Isotope Ratios in Wine Good Marker for Origin Assessment?

Lead isotope ratio pattern (206Pb/207Pb, 208Pb/206Pb, 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb) was analyzed in 59 samples of Serbian wine, from four geographical regions. By utilization of powerful inductively coupled plasma mass spectrometry (ICP-QMS), lead isotope ratios were used as unique "fingerprint", when combined with multivariate methods of analysis (Principal Component Analysis), provided information on the geographical origin of wine. In validation of ICP- QMS method and quantitative analysis, the certified reference material NIST SRM 981 was employed to test the mass-bias correction and thallium isotopes 203Tl and 205Tl (NIST SRM 997) as an internal standard. The obtained results were discussed in correlation with the corresponding values of LIRs of different European and Australian wines. In addition, the impact of anthropogenic Pb from different sources on the total Pb isotopic composition in Serbian wines was analyzed too. On the other side, the obtained values of Pb content were compared with the applicable health safety standards, according to the International Code of Oenological Practices.

Lead isotope ratios as tool for elucidation of chemical environment in a system of Macrolepiota procera (Scop.) Singer - soil.

The analysis of isotope ratios of lead in the mushrooms and soil, where they were grown, assisted with a principal component analysis, offered a new perspective for understanding possible chemical environment in a real setup of those compartments. The content of lead and its isotope compositions were determined in soil samples and mushroom Macrolepiota procera from unpolluted area of Mountain Goc, Serbia. Sequential extraction procedure based on the Commission of the European Community Bureau of Reference (BCR) was applied on soil samples in order to determine the distribution of lead in the labile and un-labile fractions of the soil. Caps and stipes of mushrooms were subjected to microwave acid-assisted digestion prior to measurements by inductively coupled plasma quadrupole mass spectrometer for determination of lead content and lead isotope ratios. Information about the chemical fractionation of Pb in soil, Pb isotopic data from soil fractions and fruiting bodies allowed a more detailed insight on the uptake mechanisms. Lead was predominantly associated with reducible fraction (~ 60%). Only its small portion (∼ 1%) was present in the exchangeable and acid-extractable fractions suggesting the low mobility of Pb. Lead isotope analysis revealed the presence of anthropogenic lead in the surface soil. Significant lower 206Pb/207Pb compared with other fractions was found in exchangeable and acid-soluble fraction (1.331 ± 0.010), which corresponds to the isotope ratio of European gasoline. The highest 206Pb/207Pb ratio was observed in reducible fraction (1.162 ± 0.007), while in oxidizable and residual fraction, those values were similar (1.159 ± 0.006 and 1.159 ± 0.004, respectively). Distinction of exchangeable and acid-extractable fractions from others was also confirmed, for the first time, by principal component analysis. The analysis of four isotope ratios (206Pb/207Pb, 208Pb/206Pb, 206Pb/204Pb, and 207Pb/204Pb) indicated that the analyzed M. procera accumulates lead from the first two fractions of topsoil layers.

Content and distribution of major and trace elements as a tool to assess the genotypes, harvesting time, and cultivation systems of potato.

The effects of organic versus integral and conventional crop management on content and distribution of major and trace elements in different varieties of potato were investigated in a three year field trial. A set of 48 potato tubers of four varieties with different harvesting times, cultivated in three types of agricultural systems: conventional (C), integral (I), and organic (O) were characterized based on the composition of the elements of their bulk and peel. A total of 16 elements were quantified. In order to determine the source of variation among the types of production, parts of potato and varieties, multivariate analysis of variance (MANOVA) was conducted. The results indicate that Ca, Mg, and K may be considered as important indicators of the type of production, genotypes of potato, and harvesting time. Additionally, the analyses show that ten microelements are able to distinguish between production types and genotypes of potato.

Elemental Analysis and Phenolic Profiles of Selected Italian Wines.

The study of the chemical composition of wines is nowadays a topic of great interest because of the importance of this market, especially in Italy, and also considering the numerous cases of falsification of famous and very expensive wines. The present paper focused on the analysis of metals and polyphenols in Italian wines belonging to different provenance and types. At this purpose 20 elements were quantified by inductively coupled plasma optical emission spectrometry (ICP-OES) and ICP mass spectrometry (ICP-MS). Regarding polyphenols, a total of 32 were quantified, among 6 were anthocyanins. Furthermore, in 4 samples (1 rosè and 3 red wines) 42 anthocyanins and related compounds were identified by ultra-high performance liquid chromatography (UHPLC)-Orbitrap MS technique (among these, 6 were also quantified). Non-anthocyanins were determined using UHPLC coupled with a diode array detector and triple-quadrupole mass spectrometer (UHPLC-DAD-QqQ-MS). Total phenolic content (TPC) and radical scavenging activity (RSA) were measured using spectrophotometric methods. The results obtained by elemental techniques were submitted to principal components analysis (PCA) allowing to get information on both geographical and botanical origin of the examined wine samples. Some polyphenols have been detected in higher concentrations only in a certain type of wine, as for example in the case of Grechetto wine. Most of the identified anthocyanin derivatives (pyranoanthocyanins) are formed during the aging of wine by reaction with the other wine components.

Chemical Content of Five Molluscan Bivalve Species Collected from South Korea: Multivariate Study and Safety Evaluation.

Bivalves are a good source of nutrients but also a potential source of environmental contaminants, which could pose a risk for consumers. The aims of this study were: the determination of 16 elements by ICP-MS in 48 samples of five bivalve species purchased from market in Korea; the identification of elements useful for species classification using multivariate analyses; and the benefit-risk evaluation associated to the consumption of these bivalves. The highest difference among content of elements between species was found for Cd, Mn, Ni, Zn, and Fe. Partial last squares discriminant analysis revealed elements with a VIP score >1 which were considered as the most relevant for explaining certain species. As, Cd, Co, and Ni were found as taxonomical markers of V. philippinarum; Mn, Zn, Mg, and Na of A. irradians; and Cd, Ni, and Fe of M. yessoensis. These species could serve as good dietary sources of essential elements. Cd exposure by consumption of Manila clams is not representing a health risk for the Korean population; however, through consumption of Yesso scallops, 5.3% of the Korean population has a potential health risk. Removal of the digestive gland before eating will drastically reduce the amount of Cd ingested.

Protective Effect of an Exopolysaccharide Produced by Lactiplantibacillus plantarum BGAN8 Against Cadmium-Induced Toxicity in Caco-2 Cells.

Cadmium (Cd) ranks seventh on the list of most significant potential threats to human health based on its suspected toxicity and the possibility of exposure to it. It has been reported that some bacterial exopolysaccharides (EPSs) have the ability to bind heavy metal ions. We therefore investigated the capacity of eight EPS-producing lactobacilli to adsorb Cd in the present study, and Lactiplantibacillus plantarum BGAN8 was chosen as the best candidate. In addition, we demonstrate that an EPS derived from BGAN8 (EPS-AN8) exhibits a high Cd-binding capacity and prevents Cd-mediated toxicity in intestinal epithelial Caco-2 cells. Simultaneous use of EPS-AN8 with Cd treatment prevents inflammation, disruption of tight-junction proteins, and oxidative stress. Our results indicate that the EPS in question has a strong potential to be used as a postbiotic in combatting the adverse effects of Cd. Moreover, we show that higher concentrations of EPS-AN8 can alleviate Cd-induced cell damage.

Geochemical distribution of selected elements in flotation tailings and soils/sediments from the dam spill at the abandoned antimony mine Stolice, Serbia.

Materials held within mine tailings pose a serious risk to the environment in cases of tailings dam failure. Collapse of the tailing dam at the Stolice antimony mine in West Serbia caused a spilling of tailing slurry into the nearby river watersheds. Medium-term effects of As, Pb, Sb, Zn, and Cd from the tailings material that remained in the flooded zone 3 years after the initial exposure were evaluated. Mobility of these elements was determined by analyzing their distribution between exchangeable, reducible, oxidizable, and residual phases. Results indicate that Fe-Mn oxides represent important sinks for As, Cd, Pb, and Sb. Multivariate statistical analysis revealed that concentrations of the analyzed elements were related to sand-sized fractions, as they tended to adsorb or co-precipitate as coatings on larger particles (particularly feldspar and quartz) upon the change of redox conditions. Assessment of the most relevant physico-chemical factors, metal(loid) concentration, and mobility can be used as tool to characterize the degree of contamination of impacted sites. Percentage of sand-sized particles, content of investigated metal(loid)s, and their amount in the reducible fractions are factors determining the best remediation techniques for the area impacted by tailing spill.

Association between oxidative stress biomarkers and concentrations of some metal ions in the blood of patients with brain tumors and hydrocephalus.

INTRODUCTION: Any substance that induces production of free radicals can be a potential cause of brain damage. The aim of our study was to investigate the relationship between some metal ions and oxidative stress biomarkers in the blood of patients with brain tumor and hydrocephalus. MATERIAL AND METHODS: Our study included 27 control subjects, 24 patients with brain tumor and 21 patients with hydrocephalus. The activities of superoxide dismutase (CuZn SOD), catalase (CAT), glutathione peroxidase (GSH-Px), glutathione reductase (GR), glutathione S-transferase (GST) and acetyl cholinesterase (AChE), as well as concentrations of reduced glutathione (GSH), lipid peroxides (TBARS) and sulfhydryl groups (SH) were analyzed in the plasma and red blood cells (RBCs) of patients. We also determined the concentrations of Mn, Ni, Co, Cu, Zn, As, Se, Cd, Hg and Fe. RESULTS: The higher activity of SOD and concentration of GSH in both investigated groups could indicate higher oxidative stress. We also observed decreased levels of SH groups in both groups of patients. In both groups of patients we detected decreased concentrations of Ni, Co, Zn and Fe (and Mn in brain tumor patients) and increased concentrations of As, Se and Cd in the blood. Interestingly, we observed a higher concentration of Cd in both plasma and RBCs of hydrocephalus patients compared to the patients with brain tumor. CONCLUSIONS: There are strong correlations between some metal ion concentrations and certain oxidative stress biomarkers in the blood of patients, which supports our hypothesis, but the observed trend needs to be further investigated.

Phenolic Profiles of Leaves, Grapes and Wine of Grapevine Variety Vranac (Vitis vinifera L.) from Montenegro.

Vranac, an old autochthonous red grapevine variety of Montenegro, was first mentioned in a historical document published in the 15th century. As currently the study of indigenous varieties is of particular importance, the subject of this work was detailed characterization of phenolic compounds in the autochthonous grapevine variety Vranac, from the Montenegrin Podgorica subregion. Phenolic profiles of leaves, berries (skin, seeds, and pulp were examined separately) and young monovarietal wine were determined using ultra-high performance liquid chromatography (UHPLC) with linear trap quadrupole (LTQ)-Orbitrap XL mass spectrometry (MS). Total phenolic content (TPC) and radical scavenging activity (RSA) were higher for the grape seeds extracts, followed by extracts of grape skins and pulps. As expected, the total anthocyanin content (TAC) was higher in grape skin than in wine. A total of one hundred twenty nine compounds (forty two phenolic acids and their derivatives, twenty three flavan-3-ols, twenty one flavanols, five stilbenes and thirty eight anthocyanins) were identified in the investigated extracts. To our best knowledge, this is the first report of tentative identification of (epi)catechin 3-O-coumarate in grape seed and chalcan-flavan 3-ol dimers in wine and grape seed.