megaTAL-mediated Gene Editing at the CCR5 locus

Thesis (Ph.D.)--University of Washington, 2016-08

Effects of IFRS adoption on the financial statements of Nigerian listed entities: the case of oil and gas companies

On 28 July 2010, the Nigerian Federal Executive Council approved January 1, 2012 as the effective date for the convergence of Nigerian Statement of Accounting Standards (SAS) or Nigerian GAAP (NG-GAAP) with International Financial Reporting Standards (IFRS). By this pronouncement, all publicly listed companies and significant public interest entities in Nigeria were statutorily required to issue IFRS based financial statements for the year ended December, 2012. This study investigates the impact of the adoption of IFRS on the financial statements of Nigerian listed Oil and Gas entities using six years of data which covers three years before and three years after IFRS adoption in Nigeria and other African countries. First, the study evaluates the impact of IFRS adoption on the Exploration and Evaluation (E&E) expenditures of listed Oil and Gas companies. Second, it examines the impact of IFRS adoption on the provision for decommissioning of Oil and Gas installations and environmental rehabilitation expenditures. Third, the study analyses the impact of the adoption of IFRS on the average daily Crude Oil production cost per Barrel. Fourth, it examines the extent to which the adoption and implementation of IFRS affects the Key Performance Indicators (KPIs) of listed Oil and Gas companies. The study further explores the impact of IFRS adoption on the contractual relationships between Nigerian Government and Oil and Gas companies in terms of Joint Ventures (JVs) and Production Sharing Contracts (PSCs) as it relates to taxes, royalties, bonuses and Profit Oil Split. A Paired Samples t-test, Wilcoxon Signed Rank test and Gray’s (Gray, 1980) Index of Conservatism analyses were conducted simultaneously where the accounting numbers, financial ratios and industry specific performance measures of GAAP and IFRS were computed and analysed and the significance of the differences of the mean, median and Conservatism Index values were compared before and after IFRS adoption. Questionnaires were then administered to the key stakeholders in the adoption and implementation of IFRS and the responses collated and analysed. The results of the analyses reveal that most of the accounting numbers, financial ratios and industry specific performance measures examined changed significantly as a result of the transition from GAAP to IFRS. The E&E expenditures and the mean cost of Crude Oil production per barrel of Oil and Gas companies increased significantly. The GAAP values of inventories, GPM, ROA, Equity and TA were also significantly different from the IFRS values. However, the differences in the provision for decommissioning expenditures were not statistically significant. Gray’s (Gray, 1980) Conservatism Index shows that Oil and Gas companies were more conservative under GAAP when compared to the IFRS regime. The Questionnaire analyses reveal that IFRS based financial statements are of higher quality, easier to prepare and present to management and easier to compare among competitors across the Oil and Gas sector but slightly more difficult to audit compared to GAAP based financial statements. To my knowledge, this is the first empirical research to investigate the impact of IFRS adoption on the financial statements of listed Oil and Gas companies. The study will therefore make an enormous contribution to academic literature and body of knowledge and void the existing knowledge gap regarding the impact and implications of IFRS adoption on the financial statements of Oil and Gas companies.

Environmental impacts of freshwater use and suspended solids in life cycle assessment

Perturbation of natural ecosystems, namely by increasing freshwater use and its degradative use, as well as topsoil erosion by water of land-use production systems, have been emerging as topics of high environmental concern. Freshwater use has become a focus of attention in the last few years for all stakeholders involved in the production of goods, mainly agro-industrial and forest-based products, which are freshwater-intensive consumers, requiring large inputs of green and blue water. This thesis presents a global review on the available Water Footprint Assessment and Life Cycle Assessment (LCA)-based methods for measuring and assessing the environmental relevance of freshwater resources use, based on a life cycle perspective. Using some of the available midpoint LCA-based methods, the freshwater use-related impacts of a Portuguese wine (white ‘vinho verde’) were assessed. However, the relevance of environmental green water has been neglected because of the absence of a comprehensive impact assessment method associated with green water flows. To overcome this constraint, this thesis helps to improve and enhance the LCA-based methods by providing a midpoint and spatially explicit Life Cycle Impact Assessment (LCIA) method for assessing impacts on terrestrial green water flow and addressing reductions in surface blue water production caused by reductions in surface runoff due to land-use production systems. The applicability of the proposed method is illustrated by a case study on Eucalyptus globulus conducted in Portugal, as the growth of short rotation forestry is largely dependent on local precipitation. Topsoil erosion by water has been characterised as one of the most upsetting problems for rivers. Because of this, this thesis also focuses on the ecosystem impacts caused by suspended solids (SS) from topsoil erosion that reach freshwater systems. A framework to conduct a spatially distributed SS delivery to freshwater streams and a fate and effect LCIA method to derive site-specific characterisation factors (CFs) for endpoint damage on aquatic ecosystem diversity, namely on algae, macrophyte, and macroinvertebrates organisms, were developed. The applicability of this framework, combined with the derived site-specific CFs, is shown by conducting a case study on E. globulus stands located in Portugal as an example of a land use based system. A spatially explicit LCA assessment was shown to be necessary, since the impacts associated with both green water flows and SS vary greatly as a function of spatial location.

Distribuição dos metais nas poeiras colhidas em Estarreja: estudo da mobilidade e impacto potencial dos metais no ambiente

As poeiras urbanas, vulgarmente designadas na literatura por street dusts ou road dusts, são misturas heterogêneas de partículas minerais do solo e partículas resultantes do tráfego, formando um material com características únicas e específicas de cada local. Estas partículas, geralmente enriquecidas com elementos potencialmente tóxicos, quando inaladas ou ingeridas poderão ser um risco para a saúde das populações. Neste trabalho foram recolhidas 21 amostras de poeiras urbanas na cidade de Estarreja assim como amostras representativas de partículas relacionados com o tráfego (poeiras resultante do desgaste dos travões e das marcações dos pavimentos e estradas) com o objetivo de investigar a contribuição relativa destas partículas no comportamento geoquímico dessas amostras e o risco associado para as populações locais. Para a concretização do objetivo proposto caracterizou-se química e mineralogicamente as amostras de poeiras urbanas e as partículas relacionadas com o tráfego e avaliou-se a disponibilidade e bioacessibilidade para três elementos considerados potencialmente tóxicos (Cu, Pb e Zn) usando uma combinação de ensaios: (a) digestão ácida; (b) extração sequencial para identificar o fracionamento do Cu, Pb e Zn nas diferentes fases-suporte dos metais, e (c) bioaccessibilidade oral in vitro. Os resultados da análise química mostram que as poeiras dos travões apresentam concentrações elevadas em Fe, Cu, Zn, Mn, Ba, Sb, Cr e Ni sendo de referir diferenças composicionais significativas entre as amostras estudadas. A amostra de tinta contém teores elevados de Ba, Ca, Ti e Pb e também pode conter outros elementos tais como Co, Cr, Cu, Mn. Mineralogicamente constata-se que as amostras de poeiras dos travões tem uma composição mineralógica semelhante mostrando que são constituídas por uma elevada percentagem de material de baixa cristalinidade, grafite e óxidos/hidróxidos de Fe amorfos. A amostra de tinta de marcação dos pavimentos das estradas é composta por material mais cristalino do que a poeira dos travões e é essencialmente constituída por carbonatos (maioritariamente dolomite) e também por barite (em menor quantidade). Os resultados obtidos nas amostras de poeiras urbanas indicam a existência de associações de elementos que definem claramente a componente geogénica e/ou antropogénica e apontam para diferenças entre essas associações nas duas frações estudadas (250 m e 63 m). A heterogeneidade das poeiras é revelada pela existência de partículas com origem geogénica (por exemplo quartzo e aluminossilicatos), de partículas com características marcadamente antropogénicas (partículas enriquecidas em Fe, Pb, Zn e Cu) ou ainda de partículas com origem mista (óxidos de Fe e Ti). Os resultados da extração química seletiva sequencial permitiu concluir que, nas amostras em estudo, as fases de troca e ácido-solúveis são as fases suporte mais importantes para o Cu, Pb e Zn Os resultados dos ensaios de bioacessibilidade mostraram também que uma percentagem significativa de Cu, Pb e Zn total está disponível para absorção gástrica. Este estudo destaca também a necessidade de se caracterizar em detalhe as propriedades intrínsecas das partículas antrópicas presentes nas poeiras urbanas, de forma a compreender as variações da fração bioacessível nos diferentes elementos estudados assim como nas diferentes frações.

The dynamic decode-and-forward channel: SNR allocation.

In the half-duplex relay channel applying the decode-and-forward protocol the relay introduces energy over random time intervals into the channel as observed at the destination. Consequently, during simulation the average signal power seen at the destination becomes known at run-time only. Therefore, in order to obtain specific performance measures at the signal-to-noise ratio (SNR) of interest, strategies are required to adjust the noise variance during simulation run-time. It is necessary that these strategies result in the same performance as measured under real-world conditions. This paper introduces three noise power allocation strategies and demonstrates their applicability using numerical and simulation results.

A multitracer approach to assess the spatial contamination pattern of hake (Merluccius merluccius) in the French Mediterranean

Chemical contamination levels and stable isotope ratios provide integrated information about contaminant exposure, trophic position and also biological and environmental influences on marine organisms. By combining these approaches with otolith shape analyses, the aim of the present study was to document the spatial variability of Hg and PCB contamination of the European hake (Merluccius merluccius) in the French Mediterranean, hypothesizing that local contaminant sources, environmental conditions and biological specificities lead to site-specific contamination patterns. High Hg concentrations discriminated Corsica (average: 1.36 ± 0.80 μg g− 1 dm) from the Gulf of Lions (average values < 0.5 μg g− 1 dm), where Rhône River input caused high PCB burdens. CB 153 average concentrations ranged between 4.00 ± 0.64 and 18.39 ± 12.38 ng g− 1 dm in the Gulf of Lions, whatever the sex of the individuals, whereas the highest values in Corsica were 6.75 ± 4.22 ng g− 1 dm. Otolith shape discriminated juveniles and adults, due to their different habitats. The use of combined ecotracers was revealed as a powerful tool to discriminate between fish populations at large and small spatial scale, and to enable understanding of the environmental and biological influences on contamination patterns.

STRUCTURAL ANALYSIS OF RIBOSOME BINDING ELEMENTS OF THE 3´ UTR IN TWO POSITIVE-STRAND PLANT RNA VIRUSES

Turnip crinkle virus (TCV) and Pea enation mosaic virus (PEMV) are two positive (+)-strand RNA viruses that are used to investigate the regulation of translation and replication due to their small size and simple genomes. Both viruses contain cap-independent translation elements (CITEs) within their 3´ untranslated regions (UTRs) that fold into tRNA-shaped structures (TSS) according to nuclear magnetic resonance and small angle x-ray scattering analysis (TCV) and computational prediction (PEMV). Specifically, the TCV TSS can directly associate with ribosomes and participates in RNA-dependent RNA polymerase (RdRp) binding. The PEMV kissing-loop TSS (kl-TSS) can simultaneously bind to ribosomes and associate with the 5´ UTR of the viral genome. Mutational analysis and chemical structure probing methods provide great insight into the function and secondary structure of the two 3´ CITEs. However, lack of 3-D structural information has limited our understanding of their functional dynamics. Here, I report the folding dynamics for the TCV TSS using optical tweezers (OT), a single molecule technique. My study of the unfolding/folding pathways for the TCV TSS has provided an unexpected unfolding pathway, confirmed the presence of Ψ3 and hairpin elements, and suggested an interconnection between the hairpins and pseudoknots. In addition, this study has demonstrated the importance of the adjacent upstream adenylate-rich sequence for the formation of H4a/Ψ3 along with the contribution of magnesium to the stability of the TCV TSS. In my second project, I report on the structural analysis of the PEMV kl-TSS using NMR and SAXS. This study has re-confirmed the base-pair pattern for the PEMV kl-TSS and the proposed interaction of the PEMV kl-TSS with its interacting partner, hairpin 5H2. The molecular envelope of the kl-TSS built from SAXS analysis suggests the kl-TSS has two functional conformations, one of which has a different shape from the previously predicted tRNA-shaped form. Along with applying biophysical methods to study the structural folding dynamics of RNAs, I have also developed a technique that improves the production of large quantities of recombinant RNAs in vivo for NMR study. In this project, I report using the wild-type and mutant E.coli strains to produce cost-effective, site-specific labeled, recombinant RNAs. This technique was validated with four representative RNAs of different sizes and complexity to produce milligram amounts of RNAs. The benefit of using site-specific labeled RNAs made from E.coli was demonstrated with several NMR techniques.

Conversion of sub-tropical native vegetation to introduced conifer forest: Impacts on below-ground and above-ground carbon pools

Land-use change can have a major influence on soil organic carbon (SOC) and above-ground C pools. We assessed a change from native vegetation to introduced Pinus species plantations on C pools using eight paired sites. At each site we determined the impacts on 0–50 cm below-ground (SOC, charcoal C, organic matter C, particulate organic C, humic organic C, resistant organic C) and above-ground (litter, coarse woody debris, standing trees and woody understorey plants) C pools. In an analysis across the different study sites there was no significant difference (P > 0.05) in SOC or above-ground tree C stocks between paired native vegetation and pine plantations, although significant differences did exist at specific sites. SOC (calculated based on an equivalent soil mass basis) was higher in the pine plantations at two sites, higher in the native vegetation at two sites and did not differ for the other four sites. The site to site variation in SOC across the landscape was far greater than the variation observed with a change from native vegetation to introduced Pinus plantation. Differences between sites were not explained by soil type, although tree basal area was positively correlated with 0–50 cm SOC. In fact, in the native vegetation there was a significant linear relationship between above-ground biomass and SOC that explained 88.8% of the variation in the data. Fine litter C (0–25 mm diameter) tended to be higher in the pine forest than in the adjacent native vegetation and was significantly higher in the pine forest at five of the eight paired sites. Total litter C (0–100 mm diameter) increased significantly with plantation age (R2 = 0.64). Carbon stored in understorey woody plants (2.5–10 cm DBH) was higher in the native vegetation than in the adjacent pine forest. Total site C varied greatly across the study area from 58.8 Mg ha−1 at a native heathland site to 497.8 Mg ha−1 at a native eucalypt forest site. Our findings suggest that the effects of change from native vegetation to introduced Pinus sp. forest are highly site-specific and may be positive, negative, or have no influence on various C pools, depending on local site characteristics (e.g. plantation age and type of native vegetation).

A biochemical analysis into the co-translational folding of a G protein-coupled receptor; GPR35

The folding and targeting of membrane proteins poses a major challenge to the cell, as they must remain insertion competent while their highly hydrophobic transmembrane (TM) domains are transferred from the ribosome, through the aqueous cytosol and into the lipid bilayer. The biogenesis of a mature membrane protein takes place through the insertion and integration into the lipid bilayer. A number of TM proteins have been shown to gain some degree of secondary structure within the ribosome tunnel and to retain this conformation throughout maturation. Although studies into the folding and targeting of a number of membrane proteins have been carried out to date, there is little information on one of the largest class of eukaryotic membrane proteins; the G-protein-coupled receptors (GPCRs). This project studies the early folding events of the human ortholog of GPR35. To analyse the structure of the 1st TM domain, intermediates were generated and assessed by the biochemical method of pegylation (PEG-MAL). A structurally-similar microbial opsin (Bacterioopsin) was also used to investigate the differences in the early protein folding within eukaryotic and prokaryotic translation systems. Results showed that neither the 1st TM domain of GPR35 nor Bacterioopsin were capable of compacting in the ribosome tunnel before their N-terminus reached the ribosome exit point. The results for this assay remained consistent whether the proteins were translated in a eukaryotic or prokaryotic translation system. To examine the communication mechanism between the ribosome, the nascent chain and the protein targeting pathway, crosslinking experiments were carried out using the homobifunctional lysine cross-linker BS3. Specifically, the data generated here show that the nascent chain of GPR35 reaches the ribosomal protein uL23 in an extended conformation and interacts with the SRP protein as it exits the ribosome tunnel. This confirms the role of SRP in the co-translational targeting of GPR35. Using these methods insights into the early folding of GPCRs has been obtained. Further experiments using site-directed mutagenesis to reduce hydrophobicity in the 1st TM domain of GPR35, highlighted the mechanisms by which GPCRs are targeted to the endoplasmic reticulum. Confirming that hydrophobicity within the signal anchor sequence is essential of SRP-dependent targeting. Following the successful interaction of the nascent GPR35 and SRP, GPR35 is successfully targeted to ER membranes, shown here as dog pancreas microsomes (DPMs). Glycosylation of the GPR35 N-terminus was used to determine nascent chain structure as it is inserted into the ER membrane. These glycosylation experiments confirm that TM1 has obtained its compacted state whilst residing in the translocon. Finally, a site-specific cross-linking approach using the homobifunctional cysteine cross-linker, BMH, was used to study the lateral integration of GPR35 into the ER. Cross-linking of GPR35 TM1 and TM2 could be detected adjacent to a protein of ~45kDa, believed to be Sec61α. The loss of this adduct, as the nascent chain extends, showed the lateral movement of GPR35 TM1 from the translocon was dependent on the subsequent synthesis of TM2.

Synthetic biology in droplet-based microfluidics

Droplet microfluidics is an active multidisciplinary area of research that evolved out of the larger field of microfluidics. It enables the user to handle, process and manipulate micrometer-sized emulsion droplets on a micro- fabricated platform. The capability to carry out a large number of individual experiments per unit time makes the droplet microfluidic technology an ideal high-throughput platform for analysis of biological and biochemical samples. The objective of this thesis was to use such a technology for designing systems with novel implications in the newly emerging field of synthetic biology. Chapter 4, the first results chapter, introduces a novel method of droplet coalescence using a flow-focusing capillary device. In Chapter 5, the development of a microfluidic platform for the fabrication of a cell-free micro-environment for site-specific gene manipulation and protein expression is described. Furthermore, a novel fluorescent reporter system which functions both in vivo and in vitro is introduced in this chapter. Chapter 6 covers the microfluidic fabrication of polymeric vesicles from poly(2-methyloxazoline-b-dimethylsiloxane-b-2-methyloxazoline) tri-block copolymer. The polymersome made from this polymer was used in the next Chapter for the study of a chimeric membrane protein called mRFP1-EstA∗. In Chapter 7, the application of microfluidics for the fabrication of synthetic biological membranes to recreate artificial cell- like chassis structures for reconstitution of a membrane-anchored protein is described.

O desenho que providencia um contexto

Com o presente artigo pretende-se mostrar a expressão da linha como elemento da linguagem do desenho e, simultaneamente, perceber a relação que a linha estabelece com o espaço. Toma-se como referência a obra do artista Lewitt enquanto marco de origem concetual do desenho na relação que ele estabelece com o espaço. Consideraremos as obras dos artistas Sandback, Gego, Derdyk e Grzymala, cujo trabalho usa o espaço como suporte do desenho e, a partir daí, procuraremos perceber que relações se estabelecem entre o espaço – que corporiza a obra - e o espectador. Com base neste pressuposto procuramos interpretar a obra como instalação ou site-specific, resultado da integração do desenho num determinado espaço. Para tal, abordaremos metodologicamente três momentos: 1. a contextualização, 2. a clarificação do conceito, 3. a experiência do artista e 4. o envolvimento e participação do espectador na obra. Procuraremos concluir acerca da presença instigadora do desenho quanto à participação do espectador na obra.

Ecological effects of flow and temperature regimes on fish communities in temperate rivers

Les organismes aquatiques sont adaptés à une grande variabilité hydrique et thermique des rivières. Malgré ceci, la régulation des eaux suscite des changements aux débits qui peuvent provoquer des impacts négatifs sur la biodiversité et les processus écologiques en rivière. Celle-ci peut aussi causer des modifications au niveau des régimes thermiques et des caractéristiques de l’habitat du poisson. Des données environnementales et biologiques décrivant l’habitat du poisson existent, mais elles sont incomplètes pour plusieurs rivières au Canada et de faible qualité, limitant les relations quantitatives débit-température-poissons à un petit nombre de rivières ou à une région étudiée. La recherche menée dans le cadre de mon doctorat concerne les impacts de la génération d'hydroélectricité sur les rivières; soit les changements aux régimes hydriques et thermiques reliés à la régulation des eaux sur la variation des communautés ichtyologiques qui habitent les rivières régulées et naturelles au Canada. Suite à une comparaison d’échantillonnage de pêche, une méthode constante pour obtenir des bons estimés de poisson (richesse, densité et biomasse des espèces) a été établie pour évaluer la structure de la communauté de poissons pour l’ensemble des rivières ciblées par l’étude. Afin de mieux comprendre ces changements environnementaux, les principales composantes décrivant ces régimes ont été identifiées et l’altération des régimes hydriques pour certaines rivières régulées a été quantifiée. Ces résultats ont servi à établir la relation significative entre le degré de changement biotique et le degré de changement hydrique pour illustrer les différences entre les régimes de régulation. Pour faire un complément aux indices biotiques déjà calculés pour l’ensemble des communautés de poissons (diversité, densité et biomasse des espèces par rivière), les différences au niveau des guildes de poissons ont été quantifiées pour expliquer les divers effets écologiques dus aux changements de régimes hydriques et thermiques provenant de la gestion des barrages. Ces derniers résultats servent à prédire pour quels traits écologiques ou groupes d’espèces de poissons les composantes hydriques et thermiques sont importantes. De plus, ces derniers résultats ont servi à mettre en valeur les variables décrivant les régimes thermiques qui ne sont pas toujours inclues dans les études hydro-écologiques. L’ensemble des résultats de cette thèse ont des retombées importantes sur la gestion des rivières en évaluant, de façon cohérente, l’impact de la régulation des rivières sur les communautés de poissons et en développant des outils de prévision pour la restauration des écosystèmes riverains.

Dual Quorum Quenching Capsules: Disrupting two bacterial communication pathways that lead to virulence

Healthcare Associated Infections (HAIs) in the United States, are estimated to cost nearly $10 billion annually. And, while device-related infections have decreased, the 60% attributed to pneumonia, gastrointestinal pathogens and surgical site infections (SSIs) remain prevalent. Furthermore, these are often complicated by antibacterial resistance that ultimately cause 2 million illnesses and 23,000 deaths in the US annually. Antibacterial resistance is an issue increasing in severity as existing antibiotics are losing effectiveness, and fewer new antibiotics are being developed. As a result, new methods of combating bacterial virulence are required. Modulating communications of bacteria can alter phenotype, such as biofilm formation and toxin production. Disrupting these communications provides a means of controlling virulence without directly interacting with the bacteria of interest, a strategy contrary to traditional antibiotics. Inter- and intra-species bacterial communication is commonly called quorum sensing because the communication molecules have been linked to phenotypic changes based on bacterial population dynamics. By disrupting the communication, a method called ‘quorum quenching’, bacterial phenotype can be altered. Virulence of bacteria is both population and species dependent; each species will secrete different toxic molecules, and total population will affect bacterial phenotype9. Here, the kinase LsrK and lactonase SsoPox were combined to simultaneously disrupt two different communication pathways with direct ties to virulence leading to SSIs, gastrointestinal infection and pneumonia. To deliver these enzymes for site-specific virulence prevention, two naturally occurring polymers were used, chitosan and alginate. Chitosan, from crustacean shells, and alginate, from seaweed, are frequently studied due to their biocompatibility, availability, self-assembly and biodegrading properties and have already been verified in vivo for wound-dressing. In this work, a novel functionalized capsule of quorum quenching enzymes and biocompatible polymers was constructed and demonstrated to have dual-quenching capability. This combination of immobilized enzymes has the potential for preventing biofilm formation and reducing bacterial toxicity in a wide variety of medical and non-medical applications.

Structural and Biochemical Characterization of Peroxiredoxin Q beta from Xylella fastidiosa CATALYTIC MECHANISM and HIGH REACTIVITY

The phytopathogenic bacterium Xylella fastidiosa is the etiological agent of various plant diseases. To survive under oxidative stress imposed by the host, microorganisms express antioxidant proteins, including cysteine-based peroxidases named peroxiredoxins. This work is a comprehensive analysis of the catalysis performed by PrxQ from X. fastidiosa (XfPrxQ) that belongs to a peroxiredoxin class still poorly characterized and previously considered as moderately reactive toward hydroperoxides. Contrary to these assumptions, our competitive kinetics studies have shown that the second-order rate constants of the peroxidase reactions of XfPrxQ with hydrogen peroxide and peroxynitrite are in the order of 107 and 106 M(-1) s(-1), respectively, which are as fast as the most efficient peroxidases. The XfPrxQ disulfides were only slightly reducible by dithiothreitol; therefore, the identification of a thioredoxin system as the probable biological reductant of XfPrxQ was a relevant finding. We also showed by site-specific mutagenesis and mass spectrometry that an intramolecular disulfide bond between Cys-47 and Cys-83 is generated during the catalytic cycle. Furthermore, we elucidated the crystal structure of XfPrxQ C47S in which Ser-47 and Cys-83 lie similar to 12.3 angstrom apart. Therefore, significant conformational changes are required for disulfide bond formation. In fact, circular dichroism data indicated that there was a significant redox-dependent unfolding of alpha-helices, which is probably triggered by the peroxidatic cysteine oxidation. Finally, we proposed a model that takes data from this work as well data as from the literature into account.

Contamination of port zone sediments by metals from Large Marine Ecosystems of Brazil

Sediment contamination by metals poses risks to coastal ecosystems and is considered to be problematic to dredging operations. In Brazil, there are differences in sedimentology along the Large Marine Ecosystems in relation to the metal distributions. We aimed to assess the extent of Al, Fe, Hg, Cd, Cr, Cu, Ni, Pb and Zn contamination in sediments from port zones in northeast (Mucuripe and Pecem) and southeast (Santos) Brazil through geochemical analyses and sediment quality ratings. The metal concentrations found in these port zones were higher than those observed in the continental shelf or the background values in both regions. In the northeast, metals were associated with carbonate, while in Santos, they were associated with mud. Geochemical analyses showed enrichments in Hg, Cd, Cu, Ni and Zn, and a simple application of international sediment quality guidelines failed to predict their impacts, whereas the use of site-specific values that were derived by geochemical and ecotoxicological approaches seemed to be more appropriate in the management of the dredged sediments. (C) 2012 Elsevier Ltd. All rights reserved.