<p>Upotrebom 50% etanola i superkritičnog ugljendioksida kao ekstragensa izvr&scaron;ena je ekstrakcija različitih vrsta pečuraka. Nakon određivanja prinosa suvih ekstrakata, u njima su određeni: sadržaj ukupnih fenola i ukupnih flavonoida, sadržaj makro- i mikro-elemenata, sadržaj adenozina, kao i sadržaj karakterističnih komponenata pistilarina i variegetične kiseline. Najveći sadržaj ukupnih fenolnih jedinjenja određen je u suvom ekstraktu pečurke <em>C. pistillaris</em>, najveći sadržaj ukupnih flavonoida u ekstraktu <em>D. confragosa</em>, a najvi&scaron;e esencijalnog cinka i selena sadrži suvi ekstrakt pečurke <em>B. edulis</em>. U odnosu na ostale suve ekstrakte ekstrakt pečurke <em>L. saccatum</em> sadrži nekoliko puta veću količinu adenozina. Antioksidativno delovanje suvih ekstrakata analizirano je primenom spektrofotometrijskih i EPR metode. Ekstrakti <em>C. pistillaris, B. edulis </em>i <em>A. mellea</em> pokazali su se kao najefikasniji skevindžeri najopasnije slobodnoradikalske vrste hidroksil radikala, dok se efikasnim u prevenciji lipidne peroksidacije mogu smatrati ekstrakti <em>B. edulis, A. mellea </em>i<em> L. saccatum</em>. Nakon određivanja prinosa supekritičnih ekstrakata ispitivanih pečuraka, u njima je analiziran sastav masnih kiselina i detektovana jedinjenja sterolnog tipa. U ispitivanim ekstraktima dominantna je nezasićena linoleinska kiselina, a značajan je udeo i oleinske nezasićene masne kiseline. Dominantno jedinjenje sterolne strukture u gotovo svim ekstraktima je ergosterol. Ispitan je uticaj superkritičnih ekstrakata pečuraka na fluidnost membrane eritrocita i na osnovu dobijenih rezultata zaključeno da bi značajnu ulogu u antihipertenzivnoj ishrani mogle imati pečurke <em>A. mellea </em>i<em> M. procera</em>.</p> / <p>Using 50% ethanol and supercritical carbon dioxide different mushroom extracts were prepared. After analysis of extraction yield, content of total phenols and total flavonoids, content of macro-elements and micro-elements, as well as content of adenosine and characteristic compounds (pistilarin and variegatic acid) were determined. Highest content od total phenols was determined in <em>C. pistillaris</em> extract, highest content of total flavonoids in<em> D. confragosa</em> and highest content of essential zinc and selenium in B. edulis dry extract. In comparsion to other extracts <em>L. saccatum</em> posses few time higher content of adenosine. Antioxidat activity was analysed by spectrophotometric and EPR methods. Extracts of <em>C. pistillaris</em>,<em> B. edulis</em> and <em>A. mellea</em> have been showed as a most efficient in scavenging of dangerous OH˙ radical. In lipid peroxidation prevention significant were mushrooms extracts of<em> B. edulis</em>, <em>A. mellea</em> and<em> L. saccatum</em>.<br />After determination of mushrooms supercritical extraction yield, fatty acid composition and sterol components were analysed. Dominant unsaturated fatty acid in investigated mushroom extracts was linoleic acid. Content of oleic fatty acid was also significant. Dominant compound of sterol structure, in almost all supercritical extracts, was ergosterole. Influence of supercritical mushroom extracts on eritrocite membrane fluidity was investigated. Acording to obtained results, mushrooms <em>A. mellea</em> and <em>M. procera</em> could have significant role in antihypertensive diet.</p>

Water quality from surface sources is fast deteriorating due to pollution from organic compounds. Among the organic compounds are chlorophenols, which are described as priority pollutants because of their detrimental effects. One way of removing them from water is by using membranes. However direct removal of chlorophenols using membranes is limited due to the inherent problem of membrane fouling. The thesis describes fabrication of thin film composite membranes modified with Ag-TiO2 and Ag-ZnO for enhancing filtration properties of the membranes for removal of 2-CP and 2,4-DCP and improving the antifouling properties of the modified membranes. Chlorophenols, 2- CP, 2,4-DCP and 2, 4, 6-TCP were determined from Vaal and Klip River using SPE- HLPC method. The SPE - HPLC method was validated by determining breakthrough volume, repeatability, reproducibility, linearity, MDL and LOQ. Nanoparticles (NPs), Ag, ZnO and TiO2 and nanocomposites (NCs), Ag-TiO2 and Ag-ZnO were synthesized using precipitation method and chemical reduction for Ag. The NPs and NCs were characterised using UV-Vis, FTIR, XRD, SEM and EDX. The synthesised NPs and NCS were evaluated for photocatalytic degradation of 2-CP and 2,4-DCP, antimicrobial activity against E.coli. and toxicity against Daphnia magna. Nanocomposites were then embedded into the PA thin film membrane surface using interfacial polymerisation and PES as a support material to produce the antifouling Ag-TiO2/PA-TFC and Ag-ZnO/PA-TFC membranes. The control PATFC membrane was prepared with no added NCs to the membrane. The membranes were characterised using ATR-FTIR, contact angle, SEM and AFM. The performance of the membranes was tested using permeation flux (using pure water and 2-CP / 2,4-DCP solutions as feed) against the neat PA-TFC membrane. Membranes were further tested for rejection of 2- CP and 2, 4 – DCP, antifouling properties and flux recoveries. The stability of the antifouling properties of the membrane was evaluated through silver release test. The performance of the membranes was tested using real water samples from Vaal and Klip Rivers. The SPE-HPLC method was repeatable, reproducible with % RSD less than 5%. Linearity range of (0.1-50 µg/ L) and recoveries of spiked water samples of more than 97% for 2-CP and 2,4-DCP but lower at 64 and 75% for 2.4.6-TCP were achieved. The Ag, TiO2 and ZnO NPs showed characteristic peaks of NPs with UV-Vis. The absorption peaks were all blue shifted due to quantum confinements. The crystalline structures were confirmed as face centred cubic, anatase and hexagonal wurzite for Ag, TiO2 and ZnO respectively. The morphology as observed from SEM showed spherically shaped nanoparticles with average sizes of 68.25 ± 4.7 and 50.92 ± 3.39 nm for Ag and TiO2 respectively. The ZnO NPs were rod -like shaped with average length = 603 nm ± 50.4 and a width = 82.92 ± 5. 40nm. Successful incorporation of silver into the TiO2 and ZnO structures was confirmed by elemental analysis, EDX. From SEM images, silver particles were distributed around TiO2 particles and ZnO rods. The presence of silver showed a remarkable improvement in photodegradation of 2-CP and 2,4-DCP from less than 40% to 86% with 2, 4- DCP. Silver modified TiO2 and ZnO showed antibacterial activity against E.coli. with minimum concentration of inhibition as low as 1.56 mg/L for both Ag-ZnO (5) and Ag-TiO2 (5). Silver was more toxic against Daphnia magna than Ag-ZnO (5) and AgTiO2 (5). The polyamide layer was confirmed by the presence of the amide I peak at 1650 cm1 and 1670 cm-1 in the Ag-TiO2/ PA-TFC and Ag-ZnO/ PA-TFC membranes. The appearance of NCs particles spread across the surface of the thin layer of the membranes as observed from surface SEM images confirming their incorporation into the PA layer. The presence of the NCs in the membranes improved water flux, water permeation, rejection of 2- CP, and 2,4-DCP, antifouling properties of the membranes and flux recoveries of more than 93 % was achieved. Silver release test revealed that Ag-ZnO/PA-TFC membrane performed better than AgTiO2/PA-TFC membrane because of the steady release of silver, which shows long lasting antifouling properties. When applied to real water samples from Vaal and Klip River, the prepared membranes showed better antifouling properties than the neat PA-TFC membrane

No description available.

Geosorption processes play an important role as retardation mechanism in subsurface transport of organic water constituents. Geosorption behaviour of Ionisable Hydrophobic Organic compounds (IHOCs) especially influence of dissolved natural organic materials on their sorption coefficients is poorly investigated. In this study influence of pH and NOM on the sorption of three different phenols (2-methyl-4,6-dinitrophenol, 2,4,6-trichlorophenol and pentachlorophenol) on a natural sandy aquifer material collected from a bank filtration site was studied in flow through column experiments. In first step the sorption coefficients of investigated phenols from NOM-free solutions with different pH values were determined. Single as well as multi (mixed) solutes experiments confirmed that there was no competition effect among the phenols investigated. An increasing sorption/retardation was observed with decreasing pH. A linear model was used to resolve the apparent sorption coefficient into an ionised species and neutral species component. This model allows a prediction of apparent sorption coefficients for any pH value. Analysis of data also revealed that the anion of 2-M-4,6-DNP show no significant sorption and a simple model based on the neutral form sorption coefficient was useful in predicting the apparent sorption coefficient over the entire pH range investigated. For 2,4,6-TCP and PCP, the anion sorption is much lower than that of the neutral species but cannot be neglected completely. For PCP, the anion sorption is even as high as the sorption of neutral 2,4,6-TCP. Thus for such hydrophobic phenols prediction of sorption based only on the partitioning of non-dissociated species may lead to an error, especially at high pH values (&amp;gt; pKa), where ionised form is present predominantly. On the other hand prediction of sorption based on the partitioning of non-dissociated species is useful at pH &amp;lt; pKa or in cases where the anion sorption can be neglected. The advantage of this prediction is that it allows predicting the pH-dependent sorption only on the basis of LFER correlations. It was shown that the organic carbon normalized sorption coefficients of the neutral forms of the phenols can be predicted better by solubility based regression correlations than by n-octanol-water partition coefficient based correlations. In second step the apparent sorption coefficients of investigated phenols from NOM-containing solutions (mixed solution of phenols dissolved in natural river water) with different pH values were determined; the sorption coefficients obtained from this step were compared with the results of the first step examinations. Analysis of data revealed that binding of 2-M-4,6-DNP by dissolved humic substances (DHS) reduces the sorption coefficient significantly. In contrast to it, the sorption of the more hydrophobic chlorinated phenols was not affected by DHS. A strong reduction of sorption onto aquifer material caused by complex formation with DHS was also observed for a second nitrophenol (2,4-DNP) and seems to be typically for nitrophenols. A combined sorption and complex formation model was proposed which could be used successfully to describe the effect of pH and NOM concentration on sorption reduction and to estimate binding constants. The binding constant found for 2-M-4,6-DNP is much higher than those reported by Ohlenbusch and Frimmel, 2001, for chlorophenols associated with Aldrich humic acid. This can be interpreted as a result of specific interactions between the nitrophenol and DHS. This phenomenon may cause an increase of the amount of nitrophenols, which can be transported with the groundwater flow and has to be considered in transport modelling, especially in cases where pH is lower than pKa. The models developed here are a useful tool to describe the influence of pH and NOM on geosorption processes and to estimate the Kd values which have to be used in transport models.

Novel sol-gel titania-poly(dimethylsiloxane) (TiO2-PDMS) and titania-silica-N-(triethoxysilylpropyl)-O-polyethylene oxide urethane (TiO2-SiO2-TESP-PEO) coatings were developed for capillary microextraction (CME) to perform on-line preconcentration and HPLC analysis of trace impurities in aqueous samples. Due to chemical inertness of titania, effective covalent binding of a suitable organic ligand to its surface is difficult via conventional surface modification methods. In this research, sol-gel chemistry was employed to chemically bind hydroxy-terminated poly(dimethylsiloxane) (PDMS) and N-(triethoxysilylpropyl)-O-polyethylene oxide urethane (TESP-PEO) to sol-gel titania and sol-gel titania-silica network, respectively. A method is presented describing in situ preparation of the titania-based sol-gel PDMS and TESP-PEO coatings and their immobilization on the inner surface of a fused-silica microextraction capillary. To perform on-line CME-HPLC, the sol-gel TiO2-PDMS or TiO2-SiO2-TESP-PEO capillarywas installed in the HPLC injection port as an external sampling loop, and a conventionalHPLC separation column was used for the liquid chromatographic separation. The sol-gel TiO2-PDMS-coated microextraction capillary was used for on-line CME-HPLC analysis of non-polar and moderately polar analytes, and the sol-gel coatings showed excellent pH (1-13), and solvent (acetonitrile and methanol) stabilities under elevated temperatures (150 C) over analogous non-sol-gel silica-based coatings. Extraction of highly polar analytes, especially from aqueous phases is not an easy task. However, the sol-gel TiO2-SiO2-TESP-PEO-coated capillaries showed excellent capability of extracting underivatized highly polar analytes from aqueous samples. This opens the possibility to employ sol-gel titania-based polar coatings for solvent-free extraction and trace analysis of target analytes in environmental and biomedical matrices. To our knowledge, this is the first research on the use of sol-gel titania (or titania-silica)-based organic-inorganic materials as a sorbent in capillary microextraction. The newly developed sol-gel titania (or titania-silica)-based organic-inorganic hybrid extraction media provides an effective solution to coupling CME with HPLC (CME-HPLC), and this can be expected to become a powerful analytical tool in environmental investigations, proteomic research, early disease diagnosis and biomarker research. Being a combination of a highly efficient solvent free sample preconcentration technique (CME) and a powerful separation method (HPLC), CME-HPLC poses to become a key analytical tool in solving complex chemical, environmental, and biomedical problems involving complex matrices.

Terpenes and phenols are of importance in conifer defense against insects and pathogens. Knowledge about tree chemical defense is vital for developing practical methods to maintain healthy forests. With the aims of characterizing the defensive chemical induction in Norway spruce Picea abies and demonstrating its ecological function to spruce bark beetle Ips typographus, we measured the terpenoid and phenolic content in the bark of mature Norway spruce trees suffering windstorm, inoculated with Ceratocystis polonica, or treated with methyl jasmonate (MeJA), and investigated the colonization and pheromone emission of I. typographus. All three stressors altered the chemical profile in the bark of Norway spruce. Trees damaged by windstorm had lower proportions of (+)-3-carene and two unidentified stilbenes, and a higher taxifolin glycoside content than trees without apparent windstorm damage; C. polonica inoculation induced extremely strong quantitative terpene accumulation in the wound reaction zone, but only increased the levels of (+)-3-carene, sabinene and terpinolene in the bark near the reaction zone; MeJA treatment generally elicited quantitative terpene accumulation, but the induction differed extensively between individual trees. In addition, logs from MeJA-treated tree showed much stronger wounding response compared to control logs. The chemical profile of Norway spruce affected the colonization and pheromone emission of I. typographus. In response to fungal inoculation, terpene present in the reaction zone inhibited the colonization of I. typographus in a dose-dependent manner. Host defense elicited by MeJA treatment reduced emissions of 2-methyl-3-buten-2-ol and (S)-cis-verbenol, the two key aggregation pheromone components of I. typographus, and altered the ratio between the two components. / QC 20110503

A significant focus of nucleic acids research is on the reactivity of electrophilic species with DNA to form addition products (adducts). Phenols are known to be able to form adducts at the C8 site of deoxyguanosine (dG). This dissertation studies the oxygen (O)-linked class of phenolic dG adducts for their hydrolytic stability as well as their structural impact on the DNA duplex. To determine the effect of C8 O-linked phenolic dG adducts on glycosidic bond stability spectrophotometric determination of hydrolysis kinetics was performed. The kinetics establish the adducts to be less stable than native dG in acid, but surprisingly stable under physiological conditions. Then to assess the modified duplex structure, a C8 O-linked phenolic dG adduct was incorporated into a DNA duplex. Thermal melting analysis establish the adduct as having a destabilizing effect on the regularly paired duplex and the conformational analysis suggests the phenolic lesion to be weakly mutagenic. / NSERC

This study quantifies discolouration on the surface of Pinus radiata boards during kiln drying, particularly kiln brown stain (KBS), and models it as a function of chemical compounds present in the wood closest to the surface. The discolouration was investigated with two experimental factors: drying time, which consisted in drying at 70/120 ℃ for 0, 8, 16 and 24 hours; and leaching, done at three levels, noleaching, mild and severe, to reduce the soluble compounds present in wood suspected of developing coloured compounds. The colour change was quantified using a reflectance photometer (colour system CIE Yxy, brightness) and by the analysis of digital photographs (colour system CIE Lab). The chemical analysis of the wood closest to the surface of the boards determined fructose, glucose, sucrose (HPLC), total sugar (sum of fructose, glucose and sucrose), total nitrogen (combustion gas analysis), and phenols discriminated by molecular weight (Folin-Ciocalteu method). In the cause-effect analysis, colour was the dependent variable, and drying time and the determinations of chemical compounds were independent variables. After statistical analysis (ANOVA and MANOVA) the dependent variables to be included in the models were luminance factor (Y), brightness (R457 and the blue-to-yellow scale of CIE Lab (b); and the independent variables were drying time, nitrogen, total sugar, and high-molecular-weight phenols. Linear (multivariate regression) and non-linear models (Neural Networks) showed that discolouration during kiln drying was best predicted when the luminance factor (Y) was used to quantify colour change as a function of the content of nitrogen-containing compounds and drying time. Furthermore, the data were fitted into an empirical model based on simple reaction kinetics that considered the rate of discolouration as a function of nitrogen concentration. The results suggest that nitrogen could act as a limiting reactant in Maillard-type reactions that produce colour during kiln drying.

The amount of organic carbon (OC) present in Siberian Arctic permafrost soils is estimated at twice the amount of carbon currently in the atmosphere. The shelf seas of the Arctic Ocean receive large amounts of this terrestrial OC from Eurasian Arctic rivers and from coastal erosion. Degradation of this land-derived material in the sea would result in the production of dissolved carbon dioxide and may then add to the atmospheric carbon dioxide reservoir. Observations from the Siberian Arctic suggest that transfer of carbon from land to the marine environment is accelerating. However, it is not clear how much of the transported OC is degraded and oxidized, nor how much is removed from the active carbon cycle by burial in marine sediment. Using bulk geochemical parameters, total OC, d13C and D14C isotope composition, and specific molecular markers of plant wax lipids and lignin phenols, the abundance and composition of OC was determined in both dissolved and particulate carrier phases: the colloidal OC (COC; part of the dissolved OC), particulate OC (POC), and sedimentary OC (SOC). Statistical modelling was used to quantify the relative contribution of OC sources to these phases. Terrestrial OC is derived from the seasonally thawing top layer of permafrost soil (topsoil OC) and frozen OC derived from beneath the active layer eroded at the coast, commonly identified as yedoma ice complex deposit OC (yedoma ICD-OC). These carbon pools are transported differently in the aquatic conduits. Topsoil OC was found in young DOC and POC, in the river water, and the shelf water column, suggesting long-distance transport of this fraction. The yedoma ICD-OC was found as old particulate OC that settles out rapidly to the underlying sediment and is laterally transported across the shelf, likely dispersed by bottom nepheloid layer transport or via ice rafting. These two modes of OC transport resulted in different degradation states of topsoil OC and yedoma ICD-OC. Terrestrial CuO oxidation derived biomarkers indicated a highly degraded component in the COC. In contrast, the terrestrial component of the SOC was much less degraded. In line with earlier suggestions the mineral component in yedoma ICD functions as weight and surface protection of the associated OC, which led to burial in the sediment, and limited OC degradation. The degradability of the terrestrial OC in shelf sediment was also addressed in direct incubation studies. Molecular markers indicate marine OC (from primary production) was more readily degraded than terrestrial OC. Degradation was also faster in sediment from the East Siberian Sea, where the marine contribution was higher compared to the Laptev Sea. Although terrestrial carbon in the sediment was degraded slower, the terrestrial component also contributed to carbon dioxide formation in the incubations of marine sediment. These results contribute to our understanding of the marine fate of land-derived OC from the Siberian Arctic. The mobilization of topsoil OC is expected to grow in magnitude with climate warming and associated active layer deepening. This translocated topsoil OC component was found to be highly degraded, which suggests degradation during transport and a possible contribution to atmospheric carbon dioxide. Similarly, the yedoma ICD-OC (and or old mineral soil carbon) may become a stronger source with accelerated warming, but slow degradation may limit its impact on active carbon cycling in the Siberian Shelf Seas. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.</p>

A invasibilidade do capim-annoni-2 em agroecossistemas tem sido atribuída as suas características biológicas e relações ecológicas. A ecologia da germinação da espécie e a interação alelopática são pouco compreendidas. Este trabalho objetivou determinar a influência de fatores ambientais na germinação, a fitotoxicidade de extratos de capim-annoni-2, identificar e quantificar aleloquímicos fenólicos presentes em suas frações, determinar a influência da degradação da fitomassa e do solo na fitotoxicidade do extrato aquoso, monitorar a degradação dos compostos presentes nos extratos e identificar e quantificar aleloquímicos no solo de área contaminada. Foram realizados experimentos em laboratório utilizando materiais coletados a campo. As sementes germinaram em temperaturas constantes de 15 até 40 °C, mas as percentagens de germinação foram superiores a 94 % apenas em temperaturas alternadas. A exposição à luz aumentou a frequência de plântulas normais. A germinação aumentou com incremento no potencial de água e o número de plantas normais diminuiu com aumento na concentração de cloreto de sódio. A maior taxa de emergência foi observada com as sementes colocadas na superfície do solo, enquanto que nenhuma emergência ocorreu a 4 cm. Foram identificados e quantificados nove compostos fenólicos com potencial aleloquímico nas frações dos extratos de capim-annoni-2: ácido caféico, ácido cumárico, ácido ferúlico, ácido gálico, ácido vanílico, catequina, epicatequina, resveratrol e rutina. A ordem decrescente de fitotoxicidade geral dos extratos brutos no desenvolvimento de plântulas de trigo e alfafa foi acetato de etila, metanólico, aquoso e hexânico. Foi identificada correlação inversamente proporcional entre concentração de ácido vanílico e comprimento de radícula e total de plântulas de alfafa. A simulação da degradação da fitomassa e do solo ocasionou aumento na fitotoxicidade dos extratos sobre a germinação e o desenvolvimento de plântulas, comprovando a liberação dos aleloquímicos e a influência do solo no aumento de sua fitotoxicidade. Extratos etéreos da fitomassa e do solo incubados apresentaram modificações em seus respectivos cromatogramas do primeiro até o sétimo dia de incubação, enquanto a mistura de fitomassa + solo apresentou maiores modificações apenas entre o primeiro e o terceiro dia de degradação. Foram identificados quatro compostos fenólicos com potencial aleloquímico no solo da área infestada com capim-annoni-2: ácido cumárico, ácido ferúlico, catequina e epicatequina. A concentração destes compostos foi maior na superfície do solo e horizontalmente próximo às plantas de capim-annoni-2, evidenciando associação entre as concentrações dos aleloquímicos com a proximidade da planta. / The invasiveness of South African lovegrass in agroecosystems has been attributed to its biological characteristics and the ecological relations. The ecology of species germination and allelopathic interaction are poorly understood. The objective of this work was to determine the influence of environmental factors on germination, phytotoxicity of South African lovegrass extracts, to identify and quantify phenolic allelochemicals present in their fractions, to determine the influence of phytomass and soil degradation on the phytotoxicity of the aqueous extract, to monitor the degradation of the compounds present in the extracts and to identify and quantify allelochemicals in a infested soil. Experiments were carried out in the laboratory using materials collected in the field. Seeds germinated at constant temperatures of 15 to 40 ° C, but the percentages of germination were greater than 94 % only at alternating temperatures. Exposure to light increased the frequency of normal seedlings. Germination increased with increasing water potential and the number of normal plants decreased with increasing sodium chloride concentration. The highest emergence rate was observed with the seeds placed on the soil surface, whereas no emergence occurred at 4 cm. A total of nine phenolic compounds with allelochemical potential were identified in the fractions of extracts of South African lovegrass: caffeic acid, coumaric acid, ferulic acid, gallic acid, vanillic acid, catechin, epicatechin, resveratrol and rutin. The general decreasing order of general phytotoxicity of crude extracts in the development of wheat and alfalfa seedlings was ethyl, methanolic, aqueous and hexane acetate. An inversely proportional correlation was identified between vanillic acid concentration and root and total alfalfa seedlings length. The simulation of phytomass and soil degradation caused an increase in the phytotoxicity of the extracts on germination and seedling development, proving the release of the allelochemicals and the influence of the soil in the increase of its phytotoxicity. The ether extracts of the straw and soil showed changes in their chromatograms from the first to the seventh day of incubation, while the mixture of straw + soil showed greater changes only between the first and third day of degradation. Four phenolic compounds with allelochemical potential were identified in the South African lovegrass infested soil: coumaric acid, ferulic acid, catechin and epicatechin. The concentration of these compounds was higher at the soil surface and horizontally near the South African lovegrass plants, showing an association between concentrations of allelochemicals and plant distance.