Highly swollen liquid crystals as new reactors for the synthesis of nanomaterials

Synthesis and self-assembly of nanomaterials can be controlled by the properties of soft matter. on one hand, dedicated nanoreactors such as reverse microemulsions or miniemulsions can be designed. on the other hand, direct shape control can be provided by the topology of liquid crystals that confine the reacting medium within a specific geometry. In the first case, the preparation of micro- or miniemulsions generally requires energetic mechanical stirring. The second approach uses thermodynamically stable systems, but it remains usually limited to binary (water + surfactant) systems. We report the preparation of different families of materials in highly ordered quaternary mediums that exhibit a liquid crystal structure with a high cell parameter. They were prepared with the proper ratios of salted water, nonpolar solvent, surfactant. and cosurfactants that form spontaneously swollen hexagonal phases. These swollen liquid crystals can be prepared from all classes of surfactants (cationic, anionic, and nonionic). They contain a regular network of parallel cylinders, whose diameters can be swollen with a nonpolar solvent, that are regularly spaced in a continuous aqueous salt solution. We demonstrate in the present report that both aqueous and organic phases can be used as nanoreactors for the preparation of materials. This property is illustrated by various examples such as the synthesis of platinum nanorods prepared in the aqueous phase or zirconia needles or the photo- or gamma-ray-induced polymerization of polydiacetylene in the organic phase. In all cases, materials can be easily extracted and their final shapes are directed by the structure-directing effect imposed by the liquid crystal.

Foraminiferal ecological zonation along a Brazilian mangrove transect: Diversity, morphotypes and the influence of subaerial exposure time.

Two foraminiferal associations comprising only arenaceous species define two distinct environments in a 340 m-long mangrove transect at Cardoso Island, Trapande Bay (Cananeia-Iguape estuarine system, SP, Brazil). The "lower muddy flat" (LMF), from the outer mangrove fringe inwards towards land (100 m), is positioned in the lower plain between 0.04 and 0.23 m above the mean sea level (msl), and remains subaerially exposed between 48.5 and 65.6% of the time. This environment is characterized by higher foraminiferal diversity and evenness (McIntosh's D = 0.54 [plus or minus] 0.21 and Pielou's E = 0.68 [plus or minus] 0.25, respectively) and is dominated by Arenoparrella mexicana and Trochammina inflata, and to a lesser extent by Ammotium directum and Textularia earlandi. The mangrove plant of this segment is a Rhizophoretum with average height of 8.4 [plus or minus] 1.2 m. The sediment is characterized by higher concentration of organic matter (93.5 [plus or minus] 32.3 g dm-3) and metals (e.g. V = 53.4 [plus or minus] 21.8 ppm and Zn = 46.4 [plus or minus] 21.3 ppm). The "upper sandy flat" (USF), 240 m wide along the transect, is positioned in the upper plain between 0.28 and 0.89 m above the msl, and remains subaerially exposed between 69.7 and 98.5% of the time. This environment is characterized by a lower diversity and evenness (D = 0.33 [plus or minus] 0.17 and E = 0.49 [plus or minus] 0.20, respectively). The association is dominated by species T. inflata and Miliammina fusca. The Rhizophoretum exhibits a lower average height of 3.6 [plus or minus] 0.6 m. The sediment is poorer in organic matter (39.3 [plus or minus] 15.0 g dm-3) and metals (e.g. V = 13.0 [plus or minus] 6.8 ppm and Zn = 6.9 [plus or minus] 3.7 ppm). Whereas "elongate" tests (uniserial, biserial and planospiral followed by a uniserial portion) are restricted to the LMF, "spiraled" species dominate the USF. Subaerial exposure time seems to exert a primary influence on species distribution, in addition to salinity and sediment type. Species may be adapted to different exposure times, a factor dependent on their position on the intertidal zone and the tidal regime, which should be taken into account in relative sea level reconstructions based on intertidal foraminifera. These patterns have important implications for studies investigating the ecology and paleoecology of foraminifera and subtle fluctuations in relative sea level during the Quaternary.

The antibacterial effects for Salmonella Enteritidis phage type 4 of different chemical disinfectants and cleaning agents tested under different conditions

A selection of commercially available disinfectants, sanitizers and water sanitizers based on iodophor, quaternary ammonium compounds (QACs) and phenolic compounds were tested for their activity against a phage type 4 strain of Salmonella serotype Enteritidis in the presence of a variety of organic materials. In general the phenolic preparations were the most effective followed by the QACs and the iodophors. They were all inactivated to different degrees by chick fluff, chicken faeces, feed and wood shavings. The inactivation was greatest when Salmonella organisms were pre-dried in feed. Under these conditions formaldehyde and glutaraldehyde were still active. There was some evidence that induced resistance to stress conditions including culture at 42°C and anaerobic culture increased resistance to one of the water sanitizers.

The use of shallow seismic reflection technique in near surface exploration of urban sites: An evaluation in the city of SãO Paulo, Brazil

In order to evaluate the use of shallow seismic technique to delineate geological and geotechnical features up to 40 meters depth in noisy urban areas covered with asphalt pavement, five survey lines were conducted in the metropolitan area of São Paulo City. The data were acquired using a 24-bit, 24-channel seismograph, 30 and 100 Hz geophones and a sledgehammer-plate system as seismic source. Seismic reflection data were recorded using a CMP (common mid point) acquisition method. The processing routine consisted of: prestack band-pass filtering (90-250 Hz); automatic gain control (AGC); muting (digital zeroin) of dead/noisy traces, ground roll, air-wave and refracted-wave; CMP sorting; velocity analyses; normal move-out corrections; residual static corrections; f-k filtering; CMP stacking. The near surface is geologically characterized by unconsolidated fill materials and Quaternary sediments with organic material overlying Tertiary sediments with the water table 2 to 5 m below the surface. The basement is composed of granite and gneiss. Reflections were observed from 40 milliseconds to 65 ms two-way traveltime and were related to the silt clay layer and fine sand layer contact of the Tertiary sediments and to the weathered basement. The CMP seismic-reflection technique has been shown to be useful for mapping the sedimentary layers and the bedrock of the São Paulo sedimentary basin for the purposes of shallow investigations related to engineering problems. In spite of the strong cultural noise observed in these urban areas and problems with planting geophones we verified that, with the proper equipment, field parameters and particularly great care in data collection and processing, we can overcome the adverse field conditions and to image reflections from layers as shallow as 20 meters.

Aplicação do Índice Relaçáo Declividade-Extensão - RDE Na Bacia do Rio do Peixe (SP) para Detecção de Deformações Neotectô nicas

This paper presents the identification of tectonic deformation through the application of the stream-gradient index (slope x length) method in the Rio do Peixe hydrographic basin, located in western State of Sã o Paulo. The main principle used is that river valleys are the best tools for this type of analysis because of their fast adjustment to even the most gentle crustal deformations. This type of analysis for structural studies is extremely useful in the western region of the State of São Paulo, where deep chemical weathering results in a thick regolith and scarce outcrops. The stream length index is the ratio of the altimetric amplitude of each drainage and the natural logarithm of its length. The value obtained is plotted on maps at the median point of each drainage, allowing the drawings of lines with the same values (isodefs). Three anomalies (A, B and C) were identified along the Rio do Peixe valley representing uplift sectors indicated by the formation and distribution of Upper Quaternary deposits in terraces and modern fluvial plains and alluvial fans. In correlation with known tectonic data for this region it is possible to attribute the A and B anomalies to the Ribeirão Preto and Presidente Prudente crustal sutures, respectively. The smaller C anomaly needs further field investigation, but it could be associated with the Três Lagoas crustal suture. It must be emphasised that these sutures are inherited from the Precambrian Basement which had a strong influence on the Phanerozoic evolution in the whole sedimentary and volcanic stratigraphic pile of the Paraná Basin and on the dominant structural lineaments directions developed therein .The A, Band C anomalies are suggestive of renewed uplift as a result of neotectonic action in modern times.

Water relations of cut inflorescences of Alpinia purpurata treated with seven pulsing solutions

Alpinia purpurata (Vieill) K. Schum, common name red ginger belongs to Zingiberaceae family, and is a perennial, with nice inflorescences composed of layers of bracts arranged in spirals. The utilization of keeping-quality solutions seeks to prolong vase-life and to maintain the quality of cut flowers. This research was performed to evaluate the effect of seven pulsing solutions (during 24 hours) on water relations, quality (turgor, browning and curvature) and the longevity of cut red ginger. The experiment followed complete randomized design, in factorial arrangement. The following treatments were studied: 1) distilled water (control), 2) sucrose 2% + 8-hidroxyquinoline citrate 200 ppm, 3) sucrose 2%, 4) sucrose 2% + citric acid, 5) benzyladenine 10 μM, 6) benzyladenine 10 μmol + sucrose 2%, 7) quaternary ammonia 0,5 mL/L. There was no significant (P>0.05) reduction of the relative water content (RWC) of the inflorescence bracts, among solutions, in the first period (7 days) and in the second period (14 days) and, between the two periods for all treatments. Significant differences among RWC of some treatments were recorded after 16 days of vase life. The utilization of benzyladenine, benzyladenine plus sucrose and sucrose plus citric acid, in the pulsing solution, allowed to keep the flowers quality for longer periods than the other treatments.

Detecção de prováveis deformações neotectônicas no Vale do Rio do Peixe, Região Ocidental Paulista, mediante aplicaçao de Índices RDE (Relac̈ão Declividade-Extensão) em segmentos de drenagem

Running water is one of the most important of all the physical processes which fashion the landscape, allowing gravity to operate along the valley floors. Besides this, the streams show a fast adjustment to the crustal deformations, even to the most gentle ones. This geologic behavior turns them a potential tool for neotectonic studies, specially the analysis of morphotnetric parameters associated with hydraulic gradient and discharge, this second factor being directly proportional to the extension of the streams. Both elements, gradient and stream length, can be combined in the SL index. The purpose of this paper is to show the RDE index application in the neotectonics analysis of the Rio do Peixe hydrographic basin and to compare the obtained values with the geologic basement incised by the streams. This basement encompasses Cretaceous sedimentary rocks of post-Serra Oeral Formation magmatism (Caiuá and Bauru groups) and Quaternary deposits that include chiefly recent alluvial plains and some Pleistocene terrace deposits. In the final part of this paper, an attempt is made in order to correlate the RDE results and the neotectonic framework admitted to this portion of the São Paulo State territory, as well as with field geologic, seismologic and paleoseismologic known elements. The results indicate the presence of two groups of anomalies: The first set corresponds to the Marília-Exaporã Plateau border, and the second one, located in the central portion of the hydrographic basin, is correlated to the Presidente Prudente seimogenic zone.

Orphan nuclear receptor NGFI-B forms dimers with nonclassical interface

The orphan receptor nerve growth factor-induced B (NGFI-B) is a member of the nuclear receptor's subfamily 4A (Nr4a). NGFI-B was shown to be capable of binding both as a monomer to an extended half-site containing a single AAAGGTCA motif and also as a homodimer to a widely separated everted repeat, as opposed to a large number of nuclear receptors that recognize and bind specific DNA sequences predominantly as homo- and/or heterodimers. To unveil the structural organization of NGFI-B in solution, we determined the quaternary structure of the NGFI-B LBD by a combination of ab initio procedures from small-angle X-ray scattering (SAXS) data and hydrogen-deuterium exchange followed by mass spectrometry. Here we report that the protein forms dimers in solution with a radius of gyration of 2.9 nm and maximum dimension of 9.0 nm. We also show that the NGFI-B LBD dimer is V-shaped, with the opening angle significantly larger than that of classical dimer's exemplified by estrogen receptor (ER) or retinoid X receptor (RXR). Surprisingly, NGFI-B dimers formation does not occur via the classical nuclear receptor dimerization interface exemplified by ER and RXR, but instead, involves an extended surface area composed of the loop between helices 3 and 4 and C-terminal fraction of the helix 3. Remarkably, the NGFI-B dimer interface is similar to the dimerization interface earlier revealed for glucocorticoid nuclear receptor (GR), which might be relevant to the recognition of cognate DNA response elements by NGFI-B and to antagonism of NGFI-B-dependent transcription exercised by GR in cells. Published by Cold Spring Harbor Laboratory Press. Copyright © 2007 The Protein Society.

A grande colisão pré-cambriana do sudeste brasileiro e a estruturação regional

This paper presents a review on the geotectonic framework of the Southeastern Brazil and neighborhoods, and its importance in the regional geologic evolution, which was exposed as a main conference at the XI Symposium of Southeast Geology (São Pedro, SP, 2009). Although the geologic history dates back to the Archean, and Paleo to Mesoproterozoic processes related to the evolution of the Columbia and Rodinia supercontinents occurred, it was in the Neoproterozoic that the most important structural features developed due to collisional tectonics. The collisions began in the Brasiliano I (900-700 Ma), but mainly developed during the Brasiliano II (670-530 Ma) and ended in the Brasiliano III (580-490 Ma), resulting the orogenic systems of Mantiqueira and Tocantins. The final consolidation resulted in Gondwana, around 460 My in the part which correspond to the South America Platform. The structural features represent an important heritage that controlled much the Phanerozic geologic and tectonic processes: the formation of the Paraná Basin in the Ordovician-Jurassic, the South Atlantian reactivation (active magmatism and Paraná LIP, rifting, morphogenesis and the Atlantic opening), and the Neogene-Quaternary intraplate discrete neotectonism.

O papel das argininas alfa-92 e alfa-141 na regulação das propriedades funcionais de hemoglobinas por íons cloreto

The oxygenation of human Hb (HbA) demands a three state model: two deoxy states To and Tx, free and complexed with anions respectively, and an oxy R state. The regulation between these states is modulated by the presence of anions, such as chloride, that binds to T state. The b inding if chloride, however, remains controversial. The aim of this work is the study of arginines 92a (a1ß2 interface) and 141a (C-terminal) as chloride binding sites. To investigate that, we have studied 92 and 141 site directed mutant species: natural mutants Hb J-Cape-Town (R92Q), desArg (R141Δ), Chesapeake (R92L), and the constructed Chesapeake desArg (R92L,141Δ). We expressed Hbs in Escherichia coli and purified. Through oxygen binding curves we measured affinity and cooperativity, in function of water effect and Bohr effect in presence and absence of chloride. Structural features were obtained through 1H NMR spectroscopy Oxygen binding properties and Bohr effect measured indicated a higher affinity and lower cooperativity in absence and presence of chloride for all mutants. Structural changes represent functional aspects of mutant Hbs, such as a significant rise in affinity or a change in cooperativity. Water activity studies conducted as a function of chloride concentration showed that the only Hb desArg follows the thre state model. The other mutant Hbs do not exhibit the Tx state, a fact confirmed by the number of water molecules bound to each Hb during the deoxy-oxy transition. This behavior suggests that the Arginine 92 site could be responsible for chloride binding to Hb, since oxygenation of 92 mutant Hbs cannot be adjusted by the three state model. However, Bohr effect showed that all mutant Hbs released~1 proton in chloride presence, different from HbA that releases ~2, suggesting a role for 141 arginine in the tertiary and quaternary Bohr effect.

Evolução do rifteamento e paleogeografia da margem Atlântica Equatorial do Brasil: Triássico ao Holoceno

The Equatorial Atlantic Margin evolved from three rift systems recorded by a complex set of sedimentary basins developed since Upper Triassic to the Lower Cretaceous (Albian). The first rift system formed Foz do Amazonas Basin in Upper Triassic; the second phase formed Marajó Basin in Berriasian, a new rift in Foz do Amazonas Basin in Valanginian and Bragança-Viseu, Ilha Nova, São Luís e Barreirinhas basins in Aptian; the third phase formed Barreirinhas and Pará- Maranhão basins and a new rifting in the Foz do Amazonas Basin between the Aptian and Albian and evolved to continental break up. The main paleostress field during rift evolution was NE-SW and after the continental break up took the E-W direction, from the development of transform zones in the oceanic crust. From Miocene, South America was subjected to intraplate tectonics, which resulted in formation of E-W transcurrent faults that generated transtensive and transpressive segments that formed sedimentary basins and hills, resulting in changes in the drainage network. In Quaternary the landscape was modified by the last ice age that changed the sea level; the coastal drainage network was drowning resulting in the formation of the current line coast.

O rio Paraguai no megaleque do Nabileque, sudoeste do Pantanal mato-grossense, MS

The Nabileque fluvial fan is a Quaternary depositional system located along the southwestern border of the Pantanal, covering an area of approximately 9,100 km 2. It is a peculiar alluvial system because it is not associated with inflow from adjacent plateaus. The Nabileque megafan is formed by the Paraguay River at the exit of the Pantanal wetland, coalescing with the Pilcomayo megafan of the Chaco basin. A geomorphological zonation analysis was performed making use of remote sensing data with field verification. Most of the area is a vast alluvial plain made of Pleistocene deposits, whose surface is marked by the presence of an intricate network of distributary paleochannels. Areas blanketed by Pleistocene deposits are dissected by erosional streams and subject to frequent flooding events. The Paraguay River flows in a meander belt constrained by NE fractures associated with the Transbrasiliano Lineament, but deflects towards the SSE after the Negro River confluence composing the system's peripheral drainage. An abandoned meander belt is preserved within a remarkable N-S incised-valley that is interpreted as the ancient Paraguay River course. Processes of avulsion and river capture are suggested to explain the observed changes of the river course. The Nabileque River is an underfit stream within the incised-valley, cutting paleomeanders and point bars of the previous Paraguay River course.

Identificação de paleocanais na região da confluência entre os rios Ivaí e Paraná com o uso de dados de sensoriamento remoto e reconhecimento de fácies sedimentares

The confluence of Ivaí River together with the Paraná one is located near Icaraíma city on the Northwest of Paraná State. In this region, several paleochannels showed quaternary dynamic of Ivaí and Paraná Rivers floodplain. The aim of study was to apply multispectral indices and a data transformation of Landsat 5 TM data, associated with fieldwork and sedimentary facies to identify paleochannels. The results of the Normalized Difference Vegetation, Normalized Difference Water e Modificated Normalized Difference Water indices did not show satisfactory gains. However, the Tasseled Cap Wetness has provided an important gain of information on recognizing paleochannels facies. Through the remote sensing results sediment cores were realized and the sedimentary facies showed its correspondence with remote sensing interpretation.

Crystallographic portrayal of different conformational states of a Lys49 phospholipase A2 homologue: Insights into structural determinants for myotoxicity and dimeric configuration

Catalytically inactive phospholipase A2 (PLA2) homologues play key roles in the pathogenesis induced by snake envenomation, causing extensive tissue damage via a mechanism still unknown. Although, the amino acid residues directly involved in catalysis are conserved, the substitution of Asp49 by Arg/Lys/Gln or Ser prevents the binding of the essential calcium ion and hence these proteins are incapable of hydrolyzing phospholipids. In this work, the crystal structure of a Lys49-PLA2 homologue from Bothrops brazili (MTX-II) was solved in two conformational states: (a) native, with Lys49 singly coordinated by the backbone oxygen atom of Val31 and (b) complexed with tetraethylene glycol (TTEG). Interestingly, the TTEG molecule was observed in two different coordination cages depending on the orientation of the nominal calcium-binding loop and of the residue Lys49. These structural observations indicate a direct role for the residue Lys49 in the functioning of a catalytically inactive PLA2 homologue suggesting a contribution of the active site-like region in the expression of pharmacological effects such as myotoxicity and edema formation. Despite the several crystal structures of Lys49-PLA2 homologues already determined, their biological assembly remains controversial with two possible conformations. The extended dimer with the hydrophobic channel exposed to the solvent and the compact dimer in which the active site-like region is occluded by the dimeric interface. In the MTX-II crystal packing analysis was found only the extended dimer as a possible stable quaternary arrangement. © 2012 Elsevier B.V.

Effect of molybdenum on the formation of Ti6Si2B in mechanically alloyed Ti-Mo-Si-B powders

This paper discusses on effect of molybdenum on the Ti6Si2B formation in mechanically alloyed and hot-pressed Ti-xMo-22Si-11B (x= 2, 5, 7 and 10 at%) alloys. High-energy ball milling and hot pressing were utilized to produce homogeneous and dense materials, which were characterized by scanning electron microscopy, X-ray diffraction, electron dispersive spectrometry, and Vickers hardness. The excessive agglomeration during milling was more pronounced in Moricher powders, which was minimized with the formation of brittle phases. Hot pressing of mechanically alloyed Ti-xMo-22Si-11B powders produced dense samples containing lower pore amounts than 1%. Ti6Si2B was formed in microstructure of the hot-pressed Ti-2Mo-22Si-11B alloy only. In Mo-richer quaternary alloys, the Ti3Si and Ti5Si3 phases were preferentially formed during hot pressing. Oppositely to the ternary phase, the Ti3Si phase dissolved a significant Mo amount. Vickers hardness values were reduced in hot-pressed Ti-xMo-22Si-11B alloys containing larger Mo amounts, which were dissolved preferentially in Ti solid solution. © (2012) Trans Tech Publications, Switzerland.