Institute of Chemistry, Technology and Metallurgy

The formation of hydroxyl radical and long-living chemical species (H2O2, O-3, NO3- and NO2-) generated in the liquid phase of a water falling film dielectric barrier discharge in dependence on the gas atmosphere (air, nitrogen, oxygen, argon and helium) was studied. The chemical molecular probe dimethyl sulfoxide was employed for quantification of. OH, and the influence of hydroxyl radical scavenging on formation of reactive oxygen and nitrogen species was investigated. In addition to liquid analysis, plasma diagnostics was applied to indicate possible reaction pathways of plasma-liquid interaction. The highest. OH production rate of 1.19 x 10 (5) mol l (1) s (1) was found when water was treated in oxygen, with a yield of 2.75 x 10(-2) molecules of. OH per 100 eV. Formation of hydrogen peroxide in air, nitrogen and argon discharges is determined by recombination reaction of hydroxyl radicals, reaching the highest yield of about 0.7 g kWh(-1) when distilled water was treated in argon discharge. Ozone formation was dominant in oxygen and air discharges. Strong acidification along with formation of reactive nitrogen species was detected in water treated in air and nitrogen discharges.

A large part of Central Serbia experiences continual shortage of sufficient ground water resources. For that reason, more than 20 reservoirs serve as drinking water suppliers. Significant and persistent cyanobacterial "blooms" have been recognized in nine of them. Samples for cyanotoxin analyses were taken during and after "blooms" in Celije Reservoir and from Krusevac town-supplied tap water from that reservoir two days later. Concentration of microcystin-LR was 650 microg L(-1) in the reservoir, while the tap water contained 2.5 microg L(-1). In the two investigated periods, the high primary liver cancer (PLC) mortality of 11.6 from 1980-1990 and extremely high PLC incidence of 34.7 from 2000-2002 were observed in the regions affected by heavy cyanobacterial "blooms." In contrast, PLC mortality and incidence rates were substantially lower in the regions not affected by cyanobacterial blooms: in 1980-1990 the rate of PLC mortality amounted to 2.7 in Kosovo, 7.6 in Vojvodina, and 8.3 in the non-affected regions of Central Serbia; while in 2000-2002 PLC incidence amounted to 4.1 in Kosovo, 5.2 in Vojvodina, and 13.6 in the non- or less-affected regions of Central Serbia. Keeping in mind that the most affected PLC regions in Central Serbia (Toplicki, Niski, and Sumadijski regions) have the water supply systems based on six reservoirs found regularly in bloom during summer months and that some of the regions are also connected with two boundary "blooming" reservoirs, representing a total of eight of nine blooming reservoirs, it is easy to presume that the PLC incidence could be related to drinking water quality. The uneven geographic distribution of liver cancer in Serbia is conspicuous and hot spots could be related to drinking water supply. It is very clear that the high-risk regions for PLC occurrence correspond with drinking water reservoirs continually found with cyanobacterial blooms, and the low risk regions correspond with water supplies not affected by cyanobacteria.

san ai, as a biosurfactant producer with multidegradative capacity for hydrocarbons, can be used in an improved strategy for environmental bioremediation of hydrocarbon-contaminated sites, including extreme habitats characterized by low or elevated temperatures, acidic or alkaline pH or high concentrations of heavy metals.

Hydrolates, also referred to as hydrosols, floral or distillate waters, as well as aromatic waters, are produced in the same isolation process with essential oils by steam distillation. A small amount of essential oil constituents is dissolved in hydrolates providing specific organoleptic properties and flavor, as well as biological activity which makes them useful as raw material in many industries. Their popularity is still on the rise, especially in aromatherapy. The objective in this review is to analyze the chemical compositions of hydrolates and their corresponding essential oils, as well as biological activity of hydrolates (antimicrobial, antioxidant and antiinflamatory) and potential uses, not only in food industry for flavoring, and preservation of fresh-cut fruits and vegetables, but also as functional (soft) drinks. However, hydrolates can be used in aromatherapy and cosmetics, as well as in organic agriculture and aquaculture.

Eggshell waste is among the most abundant waste materials coming from food processing technologies. Despite the unique properties that both its components (eggshell, ES, and eggshell membrane, ESM) possess, it is very often discarded without further use. This review article aims to summarize the recent reports utilizing eggshell waste for very diverse purposes, stressing the need to use a mechanochemical approach to broaden its applications. The most studied field with regards to the potential use of eggshell waste is catalysis. Upon proper treatment, it can be used for turning waste oils into biodiesel and moreover, the catalytic effect of eggshell-based material in organic synthesis is also very beneficial. In inorganic chemistry, the eggshell membrane is very often used as a templating agent for nanoparticles production. Such composites are suitable for application in photocatalysis. These bionanocomposites are also capable of heavy metal ions reduction and can be also used for the ozonation process. The eggshell and its membrane are applicable in electrochemistry as well. Due to the high protein content and the presence of functional groups on the surface, ESM can be easily converted to a high-performance electrode material. Finally, both ES and ESM are suitable for medical applications, as the former can be used as an inexpensive Ca 2+ source for the development of medications, particles for drug delivery, organic matrix/mineral nanocomposites as potential tissue scaffolds, food supplements and the latter for the treatment of joint diseases, in reparative medicine and vascular graft producing. For the majority of the above-mentioned applications, the pretreatment of the eggshell waste is necessary. Among other options, the mechanochemical pretreatment has found an inevitable place. Since the publication of the last review paper devoted to the mechanochemical treatment of eggshell waste, a few new works have appeared, which are reviewed here to underline the sustainable character of the proposed methodology. The mechanochemical treatment of eggshell is capable of producing the nanoscale material which can be further used for bioceramics synthesis, dehalogenation processes, wastewater treatment, preparation of hydrophobic filters, lithium-ion batteries, dental materials, and in the building industry as cement.

Polyethylene terephthalate (PET) is widely used material and as such became highly enriched in nature. It is generally considered inert and safe plastic, but due to the recent increased efforts to break-down PET using biotechnological approaches, we realized the scarcity of information about structural analysis of possible degradation products and their ecotoxicological assessment. Therefore, in this study, 11 compounds belonging to the group of PET precursors and possible degradation products have been comprehensively characterized. Seven of these compounds including 1-(2-hydroxyethyl)-4-methylterephthalate, ethylene glycol bis(methyl terephthalate), methyl bis(2-hydroxyethyl terephtahalate), 1,4-benzenedicarboxylic acid, 1,4-bis[2-[[4-(methoxycarbonyl)benzoyl]oxy]ethyl] ester and methyl tris(2-hydroxyethyl terephthalate) corresponding to mono-, 1.5-, di-, 2,5- and trimer of PET were synthetized and structurally characterized for the first time. In-silico druglikeness and physico-chemical properties of these compounds were predicted using variety of platforms. No antimicrobial properties were detected even at 1000 μg/mL. Ecotoxicological impact of the compounds against marine bacteria Allivibrio fischeri proved that the 6 out of 11 tested PET-associated compounds may be classified as harmful to aquatic microorganisms, with PET trimer being one of the most toxic. In comparison, most of the compounds were not toxic on human lung fibroblasts (MRC-5) at 200 μg/mL with inhibiting concentration (IC50) values of 30 μg/mL and 50 μg/mL determined for PET dimer and trimer. Only three of these compounds including PET monomer were toxic to nematode Caenorhabditis elegans at high concentration of 500 μg/mL. In terms of the applicative potential, PET dimer can be used as suitable substrate for the screening, identification and characterization of novel PET-depolymerizing enzymes.

Bioremediation, a process that utilizes the capability of microorganism to degrade toxic waste, is emerging as a promising technology for the treatment of soil and groundwater contamination. The technology is very effective in dealing with petroleum hydrocarbon contamination. The aim of this study was to examine the composition of the microbial consortium during the ex situ experiment of bioremediation of soil heavily contaminated with crude oil and its products from the Oil Refinery Pancevo, Serbia. After a 5.5-month experiment with biostimulation and bioventilation, the concentration of the total petroleum hydrocarbons (TPH) had been reduced from 29.80 to 3.29 g/kg (89 %). In soil, the dominant microorganism population comprised Gram-positive bacteria from actinomycete-Nocardia group. The microorganisms which decompose hydrocarbons were the dominant microbial population at the end of the process, with a share of more than 80 % (range 107 CFU/g). On the basis of the results, it was concluded that a stable microbial community had been formed after initial fluctuations.

In this study we analysed mineral composition of bee pollen of different plant origin collected across Serbia using inductively coupled plasma - optical emission spectrometry. The most abundant elements were potassium, calcium, and magnesium. The samples were also exceptionally rich in iron and zinc, which are very important as nutrients. Judging by our findings, mineral composition of bee pollen much more depends on the type of pollen-producing plant than on its geographical origin.

Conglutins represent the major peanut allergens and are renowned for their resistance to gastro-intestinal digestion. Our aim was to characterize the digestion-resistant peptides (DRPs) of conglutins by biochemical and biophysical methods followed by a molecular dynamics simulation in order to better understand the molecular basis of food protein allergenicity. We have mapped proteolysis sites at the N- and C-termini and at a limited internal segment, while other potential proteolysis sites remained unaffected. Molecular dynamics simulation showed that proteolysis only occurred in the vibrant regions of the proteins. DRPs appeared to be conformationally stable as intact conglutins. Also, the overall secondary structure and IgE-binding potency of DRPs was comparable to that of intact conglutins. The stability of conglutins toward gastro-intestinal digestion, combined with the conformational stability of the resulting DRPs provide conditions for optimal exposure to the intestinal immune system, providing an explanation for the extraordinary allergenicity of peanut conglutins.

Fungal polysaccharides attract a lot of attention due to their multiple challenging biological properties, such as: anti-tumor, anti-viral, anticomplementary, anticoagulant, hypolipidemic and immunomodulatory and immune-stimulatory activities, which all together make them suitable for application in many quite distinctive areas, such as food industry, biomedicine, cosmetology, agriculture, environmental protection and waste water management. This article presents results with respect to biological properties, structure and procedures related to the isolation and activation of polysaccharides of higher fungi. It is considered and presented along with a review of the critical antioxidative activity and possible influence of the structural composition of polysaccharide extracts (isolated from these higher fungi) upon their antioxidative properties.

Anticancer activities of various extracts of the medicinal mushroom, Ganoderma lucidum, have been widely demonstrated and are mainly associated with the presence of different bioactive polysaccharides and triterpenoids. We have evaluated and compared in vitro and in vivo the antitumor effects of two preparations from Ganoderma lucidum: a methanol extract containing total terpenoids (GLme) and a purified methanol extract containing mainly acidic terpenoids (GLpme). Both extracts inhibited tumor growth of B16 mouse melanoma cells inoculated subcutaneously into syngeneic C57BL/6 mice and reduced viability of B16 cells in vitro, whereby GLme exhibited stronger effect. Furthermore, anticancer activity of GLme was demonstrated for the first time against two other rodent tumor cell lines, L929-mouse fibrosarcoma and C6-rat astrocytoma. The mechanism of antitumor activity of GLme comprised inhibition of cell proliferation and induction of caspase-dependent apoptotic cell death mediated by upregulated p53 and inhibited Bcl-2 expression. Moreover, the antitumor effect of the GLme was associated with intensified production of reactive oxygen species, whereas their neutralization by the antioxidant, N-acetyl cysteine, resulted in partial recovery of cell viability. Thus, our results suggest that GLme might be a good candidate for treatment of diverse forms of cancers.

The aromaticity of the chelate rings of acetylacetonato (acac) and o-benzoquinonediimine (bqdi) ligands was investigated theoretically by calculating nucleus-independent chemical shifts (NICS). The calculations were done for the complexes with various metals and various other ligands. The results show that acac chelate rings in none of the complexes satisfy this magnetic criterion for aromaticity. According to the results for bqdi chelate rings, there is only the Ru2+-bqdi chelate ring with large negative NICS values, indicating possible aromaticity by magnetic criterion.

Today, the occurrence of harmful cyanobacterial blooms is a common phenomenon and a potential global health problem. Cyanobacteria can produce metabolites highly toxic to humans. More than 80% of reservoirs used for water supply in Central Serbia have bloomed over the past 80 years. A 10-year epidemiological study showed a significant increase in the incidence of primary liver cancer (PLC) in the regions where water from the blooming reservoirs was used for human consumption. At the same time, no correlation was found between the incidence of PLC and other risk factors, such as cirrhosis and hepatitis viruses. Given the strong association with PLC induction and various known possible mechanisms of carcinogenic action, it is highly possible that, cyanotoxins--acting as initiator and promoter--may be the major risk factor that acts synergistically with other risk factors to cause increased incidence of PLC. However, at present, it is still not certain whether cyanotoxins alone were sufficient to induce PLC. Therefore, additional assessment of the health risks that may arise from human exposure to cyanotoxins is advisable.

The sesquiterpene hydroquinone avarol (1) was isolated from the marine sponge Dysidea avara, whereas the corresponding quinone, avarone (2), was obtained by oxidation of avarol, and the significantly more lipophilic compounds [3'-(p-chloro-phenyl)avarone (3), 3',4'-ethylenedithioavarone (4), 4'-isopropylthioavarone (5), 4'-tert-butylthioavarone (6), 4'-propylthioavarone (7), 4'-octylthioavarone (8)] were obtained by nucleophilic addition of thiols or p-chloroaniline to avarone. All these compounds were tested, at concentrations ranging from 0.5 to 50 microg/mL, for their effect on the settlement of the cyprid stage of Balanus amphitrite, for toxicity to both nauplii and cyprids and for their growth inhibitory activity on marine bacteria (Cobetia marina, Marinobacterium stanieri, Vibrio fischeri and Pseudoalteromonas haloplanktis) and marine fungi (Halosphaeriopsis mediosetigera, Asteromyces cruciatus, Lulworthia uniseptata and Monodictys pelagica).

The problem of endemic malaria continues unabated globally. Malaria affects 40 % of the global population, causing an estimated annual mortality of 1.5-2.7 million people. The World Health Organization (WHO) estimates that 90 % of these deaths occur in sub-Saharan Africa among infants under the age of five. While a vaccine against malaria continues to be elusive, chemotherapy remains the most viable alternative towards treatment of the disease. During last years, the situation has become urgent in many ways, but mainly because of the development of chloroquine-resistant (CQR) strains of Plasmodium falciparum (Pf). The discovery that artemisinin (ART, 1), an active principle of Artemisia annua L., expresses a significant antimalarial activity, especially against CQR strains, opened new approaches for combating malaria. Since the early 1980s, hundreds of semi-synthetic and synthetic peroxides have been developed and tested for their antimalarial activity, the results of which were extensively reviewed. In addition, in therapeutic practice, there is no reported case of drug resistance to these antimalarial peroxides. This review summarizes recent achievements in the area of peroxide drug development for malaria chemotherapy.

The Mediterranean blue mussel Mytilus galloprovincialis was used as a pollution level indicator in the Boka Kotorska Bay of the southeastern Adriatic on the Montenegrin coast. The ever-increasing urbanization and industrialization, combined with a poor sewage system, an increase in both marine and inland traffic, as well as insufficient water circulation in the Bay itself have resulted in some level of pollution. Since heavy metals are extremely toxic and do not easily undergo biodecomposition, the results of this study supply valuable information concerning the metal pollution of the marine environment in Boka Kotorska Bay. The concentrations of the investigated metals and nonmetals accumulated in the mussels were determined during the fall of 2007 using Atomic Absorption Spectroscopy (AAS) for Cr, Mn, Co, Ni, Cu, Cd, Hg, Pb, Sn and V, and Energy Dispersive X-ray Fluorescence (ED-XRF) to determine the concentrations of Fe, Zn, Si, P, S, Cl, K and Ca. ED-XRF was also used to determine the levels of non-metals and elements present in high concentrations. Comparing the data from this study in relation to data from other regions for Mytilus galloprovincialis, the mussel sampled from the Boka Kotorska Bay showed a moderate level of pollution.

Seed extracts from eight grape cultivars (Vitis vinifera) growing in Serbia were screened for their polyphenolic composition by means of HPLC/PDA/ESI/MS analysis. The study revealed 34 phenolic compounds belonging to the following groups: flavan-3-ol monomers, proanthocyanidins, flavonols, hydroxycinnamic acids and hydroxybenzoic acid derivatives. The quantities of the main constituents were determined using PDA/HPLC. Qualitative and quantitative differences among the cultivars were observed.

Oil extracts of Hypericum perforatum L. (Oleum Hyperici) were prepared in three different ways according to the prescriptions from traditional medicine. Variability of constituents and biological activity were evaluated in the obtained oil extracts. The carrageenan-induced rat paw edema test has been used for screening the antiinflammatory activity, while the indomethacin-induced rat gastric mucosa damage test was used for evaluation of gastroprotective activity. All examined oil extracts possessed antiinflammatory and gastroprotective activity. Among them, the oil extract prepared by maceration with 96% ethanol, followed by extraction with sunflower oil by heating on a water bath (extract 2), in a dose of 1.25 mL/kg p.o., exhibited the highest antiinflammatory effect (95.24 +/- 11.66%) and gastroprotective activity (gastric damage score of 0.21 +/- 0.12). The same oil extract had the highest content of quercetin and I3,II8-biapigenin (129 +/- 9 microg/mL and 52 +/- 4 microg/mL, respectively). Quercetin and I3,II8-biapigenin exhibited antiinflammatory activity similar to those of indomethacin as well as significant gastroprotective activity. The results provide evidence for the usage of Oleum Hyperici as an antiinflammatory and gastroprotective agent, which has been based previously only on ethnopharmacological claims.

The chemical composition of Rhodobryum ontariense (Kindb.) Kindb. has not been previously investigated. Fatty acids of this moss were analysed qualitatively and quantitatively with an aim to identify its corresponding pattern. A total of eight fatty acids were identified including two acetylenic ones: 9,12,15-octadecatrien-6-ynoic acid (42.26%), α-linolenic acid (20.32%), palmitic acid (14.31%), 9,12-octadecadienoic-6-ynoic acid (13.31%), linoleic acid (5.25%), oleic acid (2.47%), stearic acid (1.14%) and γ-linolenic acid (0.92%). To our knowledge, this is the first record of acetylenic fatty acids in the genus Rhodobryum. In general, acetylenic fatty acids vary considerably among different moss groups and have been used as a chemotaxonomic character in bryophyte classifications. Other species of Rhodobryum from Asia have been traditionally used in ethno medicine by indigenous cultures. Two fatty acids of those reported here, 9,12,15-octadecatrien-6-ynoic and α-linolenic acid, have known cardio protective activity, which supports respective claims of traditional herbal use of these mosses.

Abstract This research examined the distribution features of red beds and 1,100 Danxia landform sites across China, while probing the relationship between these spatial patterns and geological elements. This study is based on geological and tectonic maps of China. ArcGIS software was used to process the adjacent index, then perform a spatial analysis of Danxia landforms and red beds, and a coupling analysis of Danxia landforms and red beds with tectonics. Based on a point pattern analysis of Danxia landforms, the adjacent index is 0.31, and the coefficient of variation verified by Thiessen polygon reaches 449%. These figures reflect the clustered distribution pattern of the Danxia landforms. Across the country, Danxia landforms are concentrated into three areas, namely, the Southeast China region, the Sichuan Basin region and the Qilian-Liupan region. The exposure of red beds covers 9.16 × 10 5 km 2 , which accounts for 9.5% of the total land area of China. With this research background, the geological elements of tectonics and their effects on the distribution, number, and spatial pattern of Danxia landforms and red beds were analyzed.