Study of the carbon dioxide chemical fixation-activation by guanidines

Fixation of CO(2) is one of the most important priorities of the scientific community dedicated to reduce global warming. In this work, we propose new methods for the fixation of CO2 using the guanidine bases tetramethylguanidine (TMG) and 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]-pyrimidine (TBD). In order to understand the reactions occurring during the CO(2) fixation and release processes, we employed several experimental methods, including solution and solid-state NMR, FTIR, and coupled TGA-FTIR. Quantum mechanical NMR calculations were also carried out. Based on the results obtained, we concluded that CO(2) fixation with both TMG and TBD guanidines is a kinetically reversible process, and the corresponding fixation products have proved to be useful as transcarboxylating compounds. Afterward, CO(2) thermal releasing from this fixation product with TBD was found to be an interesting process for CO(2) capture and isolation purposes. (C) 2008 Elsevier Ltd. All rights reserved.

Isolation and characterization of four type 2 ribosome inactivating pulchellin isoforms from Abrus pulchellus seeds

Abrus pulchellus seeds contain at least seven closely related and highly toxic type 2 ribosome-inactivating pulchellins, each consisting of a toxic A-chain linked to a sugar binding B-chain. In the present study, four pulchellin isoforms (termed P I, P II, P III and P IV) were isolated by affinity, ion exchange and chromatofocusing chromatographies, and investigated with respect to toxicity and sugar binding specificity. Half maximal inhibitory concentration and median lethal dose values indicate that P I and P II have similar toxicities and that both are more toxic to cultured HeLa cells and mice than P III and P IV. Interestingly, the secondary structural characteristics and sugar binding properties of the respective pairs of isoforms correlate well with the two toxicity levels, in that P I/P II and P III/P IV form two specific subgroups. From the deduced amino acids sequences of the four isoforms, it is clear that the highest similarity within each subgroup is found to occur within domain 2 of the B-chains, suggesting that the disparity in toxicity levels might be attributed to subtle differences in B-chain-mediated cell surface interactions that precede and determine toxin uptake pathways.

Isolation, chemical composition and anti-inflammatory activity of Copaifera langsdorffii desf. fruit peels essential oil according to successive hydrodistillations

In this study, the isolation and characterization of chemical composition of C. langsdorffii (copaiba) fruit peel volatile oil from Alfenas - MG was carried out according to successive hydrodistillations, likewise the anti-inflammatory activity was evaluated by rat paw edema model. The chemical composition of the oil was determined by GC-MS analysis. The major components were (E)-caryophyllene, germacrene B, 1,5-epoxysalvial-4(14)-ene, caryophyllene oxide and isospathulenol. The inflammatory process was inhibited in 39 +/- 6 % (p<0.05, Tukey-Kramer) by one sample of essential oil. The C. langsdorffii fruit peel is a rich source of essential oil (3.8% w/w), and due to potential industrial interest of its components this ecotype presents feasible crop seeking productivity and it could constitutes in a good alternative to the sustainable use of this specie.

The development of blowouts and foredunes in the Ilha Comprida barrier (Southeastern Brazil): the influence of Late Holocene climate changes on coastal sedimentation

Middle to Late Holocene barriers are conspicuous landforms in southeastern and southern Brazilian regions. The barriers in the coastal zones of northern Santa Catarina, Parana and Sao Paulo states (27 degrees 19`-24 degrees 00`S) are formed mainly by beach ridge alignments and many barriers present foredune and blowout alignments in their seaward portion. The development of these eolian landforms appears to record a regional shift in coastal dynamics and barrier building. In this context, the Ilha Comprida barrier stands out for its well-developed and well-preserved foredunes and blowouts. Based on the presence or not and type of eolian landforms, the Ilha Comprida barrier can be divided seaward into inner, middle and outer units. The inner unit is formed entirely by beach ridges. The middle unit comprises a narrow belt of blowouts (up to 15 m high) aligned alongshore. Blowout lobes pointing NNW are indicative of their generation by southern winds. The outer unit is represented by low (<= 1 m high) active or stabilized foredunes and a small transgressive dunefield (similar to 1 km(2)). Twenty-seven luminescence ages (SAR protocol) obtained for the beach ridges, foredunes, and blowouts of these three units allow definition of a precise chronology of these landforms and calculation of rates of coastal progradation. The inner unit presents ages greater than 1004 +/- 88 years. The blowouts of the middle unit show ages from 575 +/- 47 to 172 +/- 18 years. The ages of the outer unit are less than 108 +/- 10 years. Rates of coastal progradation for the inner and outer units are 0.71-0.82 m/year and 0.86-2.23 m/year, respectively. The main phase of blowout development correlates well with the Little Ice Age (LIA) climatic event. These results indicate that southern winds in subtropical Brazil became increasingly more intense and/or frequent during the LIA. These conditions persist to the present and are responsible for the development of the eolian landforms in the outer unit. Thus, barrier geomorphology can record global climatic events. The sensitivity of barrier systems in subtropical Brazil to Late Holocene climate changes was favored by the relative sea level stillstand during this time. Luminescence dating makes it possible to analyze barrier geomorphology during Late Holocene climate changes operating on timescales of a hundred to thousand years. These results improve our knowledge of barrier building and will help in the evaluation of the impact of future climate changes on coastal settings. (C) 2008 Elsevier Ltd. All rights reserved.

Controls of heavy minerals and grain size in a holocene regressive barrier (Ilha Comprida, southeastern Brazil)

Ilha Comprida is a regressive barrier island located in southeastern Brazil that was formed essentially by Quaternary sandy sediments. Ilha Comprida sediments were analyzed to assess heavy mineral indices and grain size variables. The spatial variation of heavy minerals and grain size was interpreted in terms of the present barrier dynamics and the barrier`s evolution since the Middle Holocene. These analyses allowed for the identification of the main factors and processes that control the variation of heavy minerals and grain size on the barrier. Rutile and zircon (RZi) and tourmaline and hornblende (THi) are significantly sensitive to provenance and exhibit the contributions of the Ribeira de Iguape River sediments, which reach the coast next to the northeastern end of Ilha Comprida. In addition to the influence of provenance, TZi responds mainly to hydraulic sorting processes. This agrees with a sediment transport pattern characterized by a divergence of two resultant net alongshore drifts southwest of the barrier. The sediments from the Ribeira de Iguape River reach the barrier directly through the river mouth and indirectly after temporary storage in the inner shelf. The combination of grain size and heavy mineral analyses is a reliable method for determining sediment transport patterns and provenance. (C) 2010 Elsevier Ltd. All rights reserved.

Palythine-threonine, a major novel mycosporine-like amino acid (MAA) isolated from the hermatypic coral Pocillopora capitata

Using a high-resolution reverse-phase liquid chromatography method we found that the tissues of the hermatypic coral Pocillopora capitato (collected in Santiago Bay, Mexico) contain a high diversity of primary and secondary mycosporine-like amino acids (MAAs) typical of some reef-building coral species: mycosporine-glycine, shinorine, porphyra-334, mycosporine-methylamine-serine, mycosporine-methylamine-threonine, palythine-serine, palythine and one additional novel predominant MAA, with an absorbance maximum of 320 nm. Here we document the isolation and characterization of this novel MAA from the coral A capitata. Using low multi-stage mass analyses of deuterated and non deuterated compounds, high-resolution mass analyses (Time of Flight, TOF) and other techniques, this novel compound was characterized as palythine-threonine. Palythine-threonine was also present in high concentrations in the corals Pocillopora eydouxi and Stylophora pistillata indicating a wider distribution of this MAA among reef-building corals. From structural considerations we suggest that palythine-threonine is formed by decarboxylation of porphyra-334 followed by demethylation of mycosporine-methylamine-threonine. (C) 2008 Elsevier B.V. All rights reserved.

Square wave adsorptive cathodic stripping voltarnmetry automated by sequential injection analysis - Potentialities and limitations exemplified by the determination of methyl parathion in water samples

This paper describes the development and evaluation of a sequential injection method to automate the determination of methyl parathion by square wave adsorptive cathodic stripping voltammetry exploiting the concept of monosegmented flow analysis to perform in-line sample conditioning and standard addition. Accumulation and stripping steps are made in the sample medium conditioned with 40 mmol L-1 Britton-Robinson buffer (pH 10) in 0.25 mol L-1 NaNO3. The homogenized mixture is injected at a flow rate of 10 mu Ls(-1) toward the flow cell, which is adapted to the capillary of a hanging drop mercury electrode. After a suitable deposition time, the flow is stopped and the potential is scanned from -0.3 to -1.0 V versus Ag/AgCl at frequency of 250 Hz and pulse height of 25 mV The linear dynamic range is observed for methyl parathion concentrations between 0.010 and 0.50 mgL(-1), with detection and quantification limits of 2 and 7 mu gL(-1), respectively. The sampling throughput is 25 h(-1) if the in line standard addition and sample conditioning protocols are followed, but this frequency can be increased up to 61 h(-1) if the sample is conditioned off-line and quantified using an external calibration curve. The method was applied for determination of methyl parathion in spiked water samples and the accuracy was evaluated either by comparison to high performance liquid chromatography with UV detection, or by the recovery percentages. Although no evidences of statistically significant differences were observed between the expected and obtained concentrations, because of the susceptibility of the method to interference by other pesticides (e.g., parathion, dichlorvos) and natural organic matter (e.g., fulvic and humic acids), isolation of the analyte may be required when more complex sample matrices are encountered. (C) 2007 Elsevier B.V. All rights reserved.

ACE inhibition by astilbin isolated from Erythroxylum gonocladum (Mart.) OE Schulz

Erythroxylum species have several traditional uses in different countries, including the treatment of hypertension. The ethanol extract from E. gonocladum aerial parts, a species endemic to the Brazilian cerrado, elicited a concentration-dependent inhibition of angiotensin converting enzyme (ACE) (pIC(50)=4.53 +/- 0.05). Extract fractionation led to the isolation of two compounds, whose structures were assigned by spectrometric data as astilbin and beta-sitosterol, along with a mixture of palmitic, stearic and linolenic acids. This is the first report on the occurrence of these compounds on E. gonocladum. Astilbin promoted significant ACE inhibition in vitro (pIC(50)=5.86 +/- 0.33) and its activity did not differ from captopril, when both compounds were assayed at 10 mu M concentration. (C) 2009 Elsevier GmbH. All rights reserved.

Anticorrosive cerium-based coatings prepared by the sol-gel method

The development of efficient anti-corrosion and environmentally friendly coating systems are needed for the replacement of the highly toxic Cr-based conversion coatings for corrosion protection of aluminum alloys. In this study, we demonstrate that the direct application of ceramic cerium-based sol-gel coatings to AA7075-T6 substrates produces high-performance anti-corrosion layers. Electrochemical experiments and analyses of the microstructure demonstrate that the protective layers are very efficient for the passivation of the alloy surfaces operating as both passive and active barrier for corrosion protection.

Leakage current, ferroelectric and structural properties in Pb(1-x)Ba(x)TiO(3) thin films prepared by chemical route

Single-phase perovskite structure Pb(1-x)Ba(x)TiO(3) thin films (x = 0.30, 0.50 and 0.70) were deposited on Pt/Ti/SiO(2)/Si substrates by the spin-coating technique. The dielectric study reveals that the thin films undergo a diffuse type ferroelectric phase transition, which shows a broad peak. An increase of the diffusivity degree with the increasing Barium contents was observed, and it was associated to a grain decrease in the studied composition range. The temperature dependence of the phonon frequencies was used to characterize the phase transition temperatures. Raman modes persist above tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive. The origin of these modes was interpreted in terms of breakdown of the local cubic symmetry by chemical disorder. The absence of a well-defined transition temperature and the presence of broad bands in some interval temperature above FE-PE phase transition temperature Suggested a diffuse type phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in these thin films. The leakage Current density of the PBT thin films was studied at different temperatures and the data follow the Schottky emission model. Through this analysis the Schottky barrier height values 0.75, 0.53 and 0.34 eV were obtained to the PBT70, PBT50 and PBT30 thin films, respectively. (C) 2008 Elsevier Ltd. All rights reserved.

Immobilized analogues of sunflower trypsin inhibitor-1 constitute a versatile group of affinity sorbents for selective isolation of serine proteases

Sunflower trypsin inhibitor-1 (SFI-1), a natural 14-residue cyclic peptide, and some of its synthetic acyclic variants are potent protease inhibitors displaying peculiar inhibitory profiles. Here we describe the synthesis and use of affinity sorbents prepared by coupling SFTI-1 analogues to agarose resin. Chymotrypsinand trypsin-like proteases could then be selectively isolated from pancreatin; similarly, other proteases were obtained from distinct biological sources. The binding capacity of [Lys5]-SFTI-1-agarose for trypsin was estimated at over 10 mg/mL of packed gel. SFTI-1-based resins could find application either to improve the performance of current purification protocols or as novel protease-discovery tools in different areas of biological investigation. (C) 2009 Elsevier B.V. All rights reserved.

Improved Road Design for Future Maintenance - Analysis of Road Barrier Repair Costs

The cost of a road construction over its service life is a function of the design, quality of construction, maintenance strategies and maintenance operations. Unfortunately, designers often neglect a very important aspect which is the possibility to perform future maintenance activities. The focus is mainly on other aspects such as investment costs, traffic safety, aesthetic appearance, regional development and environmental effects. This licentiate thesis is a part of a Ph.D. project entitled “Road Design for lower maintenance costs” that aims to examine how the life-cycle costs can be optimized by selection of appropriate geometrical designs for the roads and their components. The result is expected to give a basis for a new method used in the road planning and design process using life-cycle cost analysis with particular emphasis on road maintenance. The project started with a review of literature with the intention to study conditions causing increased needs for road maintenance, the efforts made by the road authorities to satisfy those needs and the improvement potential by consideration of maintenance aspects during planning and design. An investigation was carried out to identify the problems which obstruct due consideration of maintenance aspects during the road planning and design process. This investigation focused mainly on the road planning and design process at the Swedish Road Administration. However, the road planning and design process in Denmark, Finland and Norway were also roughly evaluated to gain a broader knowledge about the research subject. The investigation was carried out in two phases: data collection and data analysis. Data was collected by semi-structured interviews with expert actors involved in planning, design and maintenance and by a review of design-related documents. Data analyses were carried out using a method called “Change Analysis”. This investigation revealed a complex combination of problems which result in inadequate consideration of maintenance aspects. Several urgent needs for changes to eliminate these problems were identified. Another study was carried out to develop a model for calculation of the repair costs for damages of different road barrier types and to analyse how factors such as road type, speed limits, barrier types, barrier placement, type of road section, alignment and seasonal effects affect the barrier damages and the associated repair costs. This study was carried out using a method called the “Case Study Research Method”. Data was collected from 1087 barrier repairs in two regional offices of the Swedish Road Administration, the Central Region and the Western Region. A table was established for both regions containing the repair cost per vehicle kilometre for different combinations of barrier types, road types and speed limits. This table can be used by the designers in the calculation of the life-cycle costs for different road barrier types.

Study of Proteinuria: Isolation of Proteins from the Nephrotic Syndrome

One of the most puzzling phenomena of abnormal renal physiology is the occurrence of the nephrotic syndrome. The syndrome has been defined by a collection of clinical and pathological symptoms, but there is no correlation between the clinical and pathological symptoms nor is the etiology of the syndrome known. Proteinuria is probably the most distinguishing feature in the nephrotic syndrome, and there are two possible explanations for its occurrence: (1) the excessive amounts of protein found in nephrotic urine could be due to an increased basement membrane permeability in the glomerulus of the kidney or (2) dysproteinemia. An attempt has been made to evaluate the theory of dysproteinemia in connection with the syndrome. The albumin fractions of nephrotic urine have been studied for their amino acid composition by separating them from the urine by paper electrophoresis, hydrolyzing them, and identifying the amino acids present by two-dimensional chromatography. There seem to be no variations in the qualitative makeup of nephrotic albumin from that of normal albumin, but the literature shows that there are some slight variations in the quantitative amino acid composition of nephrotic albumin compared with normal albumin. More extensive and highly developed experimentation along the lines of protein structure and composition must be done before it can conclusively be stated that dysproteinemia is of importance in the nephrotic syndrome.

O exame neurológico do recém-nascido pré-termo não complicado: avaliação pela escala de saint-anne dargassies, e screening pelas escalas de amiel-barrier-shnider modificada e prechtl ao termo

This study compared the evolution of posture, tone and neonatal reflexes in preterm infants without clinical or neurological complications before and after the age of term using the scale of Saint-Anne Dargassies. To reach the age of the term, was applied Scales Amiel-Barrier-Shnider changed and the Prechtl, traditionally used in the evaluation of term newborns, looking for possible changes to the term, while also evaluating the sensitivity of these scales. We studied 20 non-complicated preterm infants, both sexes aged 32-36 weeks, born in Januário Cicco Maternity School, from August 2006 to August 2007. Was applied to the scale of Saint-Anne Dargassies every two weeks until reach the term, and the range of Amiel-Barrier-Shnider changed and the Prechtl, after reaching 39 and 41 weeks. The evaluation result of articular angles was subjected to the test of Friedman ANOVA, significant differences between the three measurements of the scale of Saint-Anne Dargassies only for angles heel-to-ear to term. Neonatal reflexes changed in the period of prematurity were the cardinal points reflexes, Moro reflexes, cross extensions reflex and the automatic walking reflexes. The posture was the parameter which remained unchanged in the three scales. Considering a significance level of 5% by applying Cochran Q Test, it was found that the scale of Saint-Anne Dargassies is more sensitive to detect suspects. With this methodology and the results it was possible to prepare a manuscript: The neurological examination of non-complicated preterm newborns using the Sanit-Anne Dargssies Scale from birth to term: normal or altered? In which we describe that despite the good clinical condition, the RNP show changes in tone and neonatal reflexes. These data are important because though non-complicated RNP need further attention its maturation process, enabling us to detect and intervene early. With these results we can build a scale simplified neurological assessment made with items found most altered during the application of three scales. The development of this project has a multidisciplinary approach, because it involved Paediatric Neurologist, Physiotherapist and Neonatologist, as recommended by PPGCSA

Isolation and characterization of Flavobacterium columnare (Bernardet et al. 2002) from four tropical fish species in Brazil

Flavobacterium columnare é o agente etiológico da columnariose em peixes de água doce, ocasionando enfermidade na pele e nas brânquias, provocando freqüentemente um grande número de mortalidade. O objetivo deste estudo foi o isolamento e a caracterização de Flavobacterium columnare em peixes tropicais no Brasil. Piracanjuba (Brycon orbignyanus), pacu (Piaractus mesopotamicus), tambaqui (Colossoma macropomum) e cascudo (Hypostomus plecostomus) foram examinados externamente com relação a sinais característicos de columnariose, como manchas acinzentadas na cabeça, região dorsal e pedúnculo caudal dos peixes. A amostragem compreendeu a coleta de 50 exemplares de peixes, representando as quatro diferentes espécies escolhidas para este estudo. Amostras para o isolamento foram obtidas através de raspado com swab estéril das lesões e do rim dos peixes clinicamente diagnosticados como acometidos por columnarios e imediatamente semeados em meios de culturas artificiais (líquido e sólido) próprios para o estudo de Flavobacterium segundo Carlson e Pacha (1968). No meio líquido, houve o desenvolvimento de microrganismos que observados em gota pendente apresentaram a forma de bacilos finos, longos, móveis por deslizamento. Através da coloração de Gram, apresentaram morfologia de bacilos finos, Gram negativos, agrupados em colunas. em meio sólido, as colônias eram pequenas, cinza-amareladas, com borda em forma de raiz. No total, foram obtidos quatro isolamentos: 01 cepa de Brycon orbignyanus; 01 cepa de Piaractus mesopotamicus; 01 cepa de Colossoma macropomum; e 01 cepa de Hypostomus plecostomus. A caracterização bioquímica das amostras, como absorção do vermelho Congo, produção de flexirrubina, produção de H2S e redução do nitrato, sugere que os isolamentos poderiam ser classificados como Flavobacterium columnare.