MOLECULAR DYNAMICS STUDIES OF SIMPLE MODEL FLUIDS AND WATER CONFINED IN CARBON NANOTUBE

Molecular Dynamics (MD) simulation is one of the most important computational techniques with broad applications in physics, chemistry, chemical engineering, materials design and biological science. Traditional computational chemistry refers to quantum calculations based on solving Schrodinger equations. Later developed Density Functional Theory (DFT) based on solving Kohn-Sham equations became the more popular ab initio calculation technique which could deal with ~1000 atoms by explicitly considering electron interactions. In contrast, MD simulation based on solving classical mechanics equations of motion is a totally different technique in the field of computational chemistry. Electron interactions were implicitly included in the empirical atom-based potential functions and the system size to be investigated can be extended to ~106 atoms. The thermodynamic properties of model fluids are mainly determined by macroscopic quantities, like temperature, pressure, density. The quantum effects on thermodynamic properties like melting point, surface tension are not dominant. In this work, we mainly investigated the melting point, surface tension (liquid-vapor and liquid-solid) of model fluids including Lennard-Jones model, Stockmayer model and a couple of water models (TIP4P/Ew, TIP5P/Ew) by means of MD simulation. In addition, some new structures of water confined in carbon nanotube were discovered and transport behaviors of water and ions through nano-channels were also revealed.

Locus Amoenus vs. Locus Terribilis: The Spatial Dynamics of the Pastoral and the Urban in La Ceppède’s Théorèmes

The opening sonnets of Jean de La Ceppède’s Théorèmes (1613, 1622) present an urban vs. rural conflict that mirrors the dialectic between sin and salvation running throughout the work. La Ceppède’s focus for this struggle becomes the stark contrast between Jerusalem and the garden at the Mount of Olives. Jerusalem, as the place where Christ is persecuted and eventually tried, represents a Babylon-like enclave of transgression, while the garden is portrayed as a site of purity and tranquil reflection. From a literary standpoint, La Ceppède’s emphasis on the clash between dystopian and utopian settings comprises part of his adaptation of the pastoral, where this particular struggle becomes one of the genre’s principal motifs. In general, the contrast between Jerusalem and the Mount of Olives emerges as the point of departure for the poet’s figuration of nature, both human and physical. A human construct, the city of Jerusalem becomes a metaphor for human corruption. In view of humanity’s fall in paradise and the denaturation it symbolizes, the poet’s goal, on both intellectual and affective levels, is to place the reader/dévot in a position to lift her/himself from the depravity of human nature to the grace of divine nature.

Laser Optical Plankton Counter and Zooscan intercomparison in tropical and subtropical marine ecosystems

Two recently developed instruments, the Laser Optical Plankton Counter (LOPC) and the Zooscan, have been applied to study zooplankton biomass size spectra in tropical and subtropical marine ecosystems off Brazil. Both technologies rely on optical measurements of particles and may potentially be used in zooplankton monitoring programs. Vertical profiles of the LOPC installed in a 200 mu m ring net have been obtained from diverse environmental settings ranging from turbid and nearshore waters to oligotrophic open ocean conditions. Net samples were analyzed on the Zooscan and counted under a microscope. Particle biovolume in the study area estimated with the LOPC correlated with plankton displacement volume from the net samples, but there was no significant relationship between total areal zooplankton biomass determined with LOPC and the Zooscan. Apparently, normalized biomass size spectra (NBSS) of LOPC and Zooscan overlapped for particles in the size range of 500 to 1500 mu m in equivalent spherical diameter (ESD), especially at open ocean stations. However, the distribution of particles into five size classes was statistically different between both instruments at 24 of 28 stations. The disparities arise from unequal flow estimates, from different sampling efficiencies of LOPC tunnel and net for large and small particles, and possibly from the interference of non-zooplankton material in the LOPC signal. Ecosystem properties and technical differences therefore limit the direct comparability of the NBSS slopes obtained with both instruments during this study, and their results should be regarded as complementary.

Computer simulation study of collective dynamics in the glass former Ca(NO3)(2)center dot 4H(2)O

Time correlation functions of current fluctuations were calculated by molecular dynamics (MD) simulations in order to investigate sound waves of high wavevectors in the glass-forming liquid Ca(NO3)(2)center dot 4H(2)O. Dispersion curves, omega(k), were obtained for longitudinal (LA) and transverse acoustic (TA) modes, and also for longitudinal optic (LO) modes. Spectra of LA modes calculated by MD simulations were modeled by a viscoelastic model within the memory function framework. The viscoelastic model is used to rationalize the change of slope taking place at k similar to 0.3 angstrom(-1) in the omega(k) curve of acoustic modes. For still larger wavevectors, mixing of acoustic and optic modes is observed. Partial time correlation functions of longitudinal mass currents were calculated separately for the ions and the water molecules. The wavevector dependence of excitation energies of the corresponding partial LA modes indicates the coexistence of a relatively stiff subsystem made of cations and anions, and a softer subsystem made of water molecules. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4751548]

Reproductive migration and population dynamics of the blue crab Callinectes danae in an estuary in southeastern Brazil

Portunid crabs are an important resource in estuaries, and require appropriate management to guarantee their long-term availability. We investigated the population dynamics and reproduction of Callinectes danae in the Estuarine-Bay Complex of Sao Vicente, Sao Paulo, Brazil, to provide basic biological information for public policies for the management of this fishery. Monthly samples were obtained from March 2007 to February 2008 on eight transects, four in the estuary and four in the bay. A total of 2261 specimens (403 males, 1288 females, of which 570 were ovigerous) were collected. Males were significantly larger than females, and the size-frequency distribution was unimodal for males, females and ovigerous females. The sex ratio was nearly always skewed toward females (M:F - 1:4.6). C. danae showed seasonal-continuous reproduction, with high reproductive activity in the warmer season. C. danae breeds in the estuarine-bay complex, with males and juvenile females concentrated in the estuary. After copulation, fertilized females migrate to the estuary entrance and the bay, where ovigerous females are commonly found spawning in high-salinity areas. Therefore, to manage this important economic resource, both the estuary and the bay should be considered for protection, but special attention should be given to the estuary entrance during the summer months, when ovigerous females concentrate.

Decentralization and regionalization: dynamics and conditioning factors for the implementation of the Health Pact in Brazil

Decentralization and regionalization represent constitutional guidelines for the organization of the Unified Health System, which in the last 20 years has required the adoption of mechanisms to coordinate and accommodate federative tensions in Brazil's healthcare sector. This paper analyzes the national implementation of the Health Pact between 2006 and 2010 involving a strategy that reconfigures intergovernmental relations in the sector. The study involved the analysis of documents, official data and interviews with federal, state and municipal managers in the Brazilian states. The content of the national proposal is initially discussed, including its implications for health policy. The different rhythms and degrees of implementation of the Health Pact are then reviewed, with respect to adherence by states and municipalities and the formation of Regional Management Boards. Lastly, the conditioning factors for the multiplicity of experiences observed in the country are identified and the challenges facing progress toward a decentralized and regionalized health system in Brazil are discussed.

Bamboo overabundance alters forest structure and dynamics in the Atlantic Forest hotspot

With fast growth rates and clonal reproduction, bamboos can rapidly invade forest areas, drastically changing their original structure. In the Brazilian Atlantic Forest, where recent mapping efforts have shown that woody bamboos dominate large areas, the present study assessed the differences in soil and vegetation between plots dominated (>90% of bamboo coverage) and not dominated (<10% of coverage) by the native Guadua tagoara. Surface soil was physically and chemically analyzed, and trees at three size classes (seedling, sapling, and adult) were counted, identified and measured. New inventories were conducted to assess recruitment, mortality, and damage rates. Bamboo plots had more fertile soils (higher bases saturation and lower potential acidity) due to the preferential occurrence of G. tagoara on more clayey soils. Bamboo-dominated plots had lower density of adult trees (diameter >5 cm) and lower species density. In addition, overall tree diameter distribution was very different between environments, with bamboo plots having greater concentration of small-sized trees. Such differences are probably related to the general tendency of higher mortality, recruitment, and damage rates in bamboo plots. Greater physical (wind and bamboo-induced damages) and physiological stress (heat and light) in bamboo plots are probable causes of bamboo-dominated plots being more dynamic. Finally, we discuss the differences between Atlantic and Amazonian Guadua-dominated forests, causes, and possible consequences of bamboo overabundance to the Atlantic Forest conservation. (C) 2012 Elsevier Ltd. All rights reserved.

Histomorphometric analysis of inflammatory response and necrosis in re-implanted central incisor of rats treated with low-level laser therapy

Low-level laser therapy is a tool employed in the management of post-operative inflammation process and in the enhancement of reparative process. The aim of the study was to perform histological evaluation of dental and periodontal ligament of rats central upper-left incisor teeth re-implanted and irradiated with low-level laser (InGaAl, 685 nm, 50 J/cm(2)) 15, 30, and 60 days after re-implantation. Seventy-two male rats had the central upper left incisor removed and kept for 15 min on dry gauze before replantation. Laser was irradiated over the root surface and empty alveolus prior replantation and over surrounding mucosa after the re-implantation. After histological procedures, all slices were analyzed regarding external resorption area and histological aspects. We observed an increase of root resorption (p < 0.05) in the control group compared to the laser group at 15, 30, and 60 days. These results showed that the laser groups developed less root resorption areas than the control group in all experimental periods. Additionally, histological analysis revealed less inflammatory cells and necrotic areas in laser groups.

Effects of water flow on ablation rate and morphological changes in human enamel and dentin after Er:YAG laser irradiation

Purpose: To investigate the laboratory effect of Er:YAG laser on ablation rate and morphological changes in human enamel and dentin with varying water flow. Methods: 23 human third molars were sectioned in mesio-distal and buccal-lingual directions. The slabs were flattened and weighted on an analytical laboratory balance (control). A 4-mm(2) area was demarcated and the samples were randomly assigned into three groups according to water flow employed during the laser irradiation (1.0, 1.5, and 2.0 mL/minute). An Er:YAG laser was used to ablate enamel (80.22-J/cm(2), 300 mJ/4Hz) and dentin (96.26-J/cm(2), 250 mJ/4Hz). After irradiation, the samples were immersed in distilled water for 1 hour and then weighted again. The final mass was obtained and laser-irradiated substrate mass loss was calculated by the difference between the initial and final mass. Afterwards, specimens were prepared for SEM. Results: Data were submitted to ANOVA and Tukey's test (P< 0.05). It was observed that the 2.0 mL/minute resulted in a higher mass loss, 1.0 mL/minute showed a lower mass loss, and 1.5 mL/minute demonstrated intermediate results (P< 0.05). The increase of water flow promoted less melting areas and cracks. Furthermore, dentin was more ablated than enamel. It may be concluded that the water flow of Er:YAG laser and the substrates affected the ablation rate. Among the tested parameters, 2.0 mL/minute improved the ability of ablation in enamel and dentin, with less morphologic surface alteration. (Am J Dent 20 12;25:332-336).

STRUCTURE AND DYNAMICS: THE TRANSITION FROM NONEQUILIBRIUM TO EQUILIBRIUM IN INTEGRATE-AND-FIRE DYNAMICS

The transient and equilibrium properties of dynamics unfolding in complex systems can depend critically on specific topological features of the underlying interconnections. In this work, we investigate such a relationship with respect to the integrate-and-fire dynamics emanating from a source node and an extended network model that allows control of the small-world feature as well as the length of the long-range connections. A systematic approach to investigate the local and global correlations between structural and dynamical features of the networks was adopted that involved extensive simulations (one and a half million cases) so as to obtain two-dimensional correlation maps. Smooth, but diverse surfaces of correlation values were obtained in all cases. Regarding the global cases, it has been verified that the onset avalanche time (but not its intensity) can be accurately predicted from the structural features within specific regions of the map (i.e. networks with specific structural properties). The analysis at local level revealed that the dynamical features before the avalanches can also be accurately predicted from structural features. This is not possible for the dynamical features after the avalanches take place. This is so because the overall topology of the network predominates over the local topology around the source at the stationary state.

An environmentally friendly analytical procedure for nickel determination by atomic and molecular spectrometry after cloud point extraction in different samples

Cloud point extraction (CPE) was employed for separation and preconcentration prior to the determination of nickel by graphite furnace atomic absorption spectrometry (GFAAS), flame atomic absorption spectrometry (FAAS) or UV-Vis spectrophotometry. Di-2-pyridyl ketone salicyloylhydrazone (DPKSH) was used for the first time as a complexing agent in CPE. The nickel complex was extracted from the aqueous phase using the Triton X-114 surfactant. Under optimized conditions, limits of detection obtained with GFAAS, FAAS and UV-Vis spectrophotometry were 0.14, 0.76 and 1.5 mu g L-1, respectively. The extraction was quantitative and the enrichment factor was estimated to be 27. The method was applied to natural waters, hemodialysis concentrates, urine and honey samples. Accuracy was evaluated by analysis of the NIST 1643e Water standard reference material.

OSCILLATORY DYNAMICS IN SYSTEMS CONTAINING BROMATE AND 1,4-CYCLOHEXANEDIONE IN ACIDIC MEDIA. I. THE EFFECT OF TEMPERATURE.

OSCILLATORY DYNAMICS IN SYSTEMS CONTAINING BROMATE AND 1,4-CYCLOHEXANEDIONE IN ACIDIC MEDIA. I. THE EFFECT OF TEMPERATURE. We present in this work the influence of temperature on the dynamics of homogeneous chemical systems containing bromate and 1,4-cyclohexanedione (1,4-CHD) in acidic media. In particular, the following systems were studied: bromate/1,4-CHD/acid, bromate/1,4-CHD/ferroin/acid and bromate/1,4-CHD/trisbipyridine ruthenium/acid. Investigations were carried out by means of an electrochemical probe, at five temperatures between 5 and 45 degrees C. Activation energies (E-a) were estimated in different ways for the pre-oscillatory and oscillatory regimes. In any case, the E-a was found to depend on the catalyst, composition and initial concentrations. In addition, it was observed that ferroin and trisbipyridine ruthenium act as catalysts only during the transition between the induction period and oscillatory regime.

Low-level laser therapy (808 nm) reduces inflammatory response and oxidative stress in rat tibialis anterior muscle after cryolesion

Background and Objective Muscle regeneration is a complex phenomenon, involving coordinated activation of several cellular responses. During this process, oxidative stress and consequent tissue damage occur with a severity that may depend on the intensity and duration of the inflammatory response. Among the therapeutic approaches to attenuate inflammation and increase tissue repair, low-level laser therapy (LLLT) may be a safe and effective clinical procedure. The aim of this study was to evaluate the effects of LLLT on oxidative/nitrative stress and inflammatory mediators produced during a cryolesion of the tibialis anterior (TA) muscle in rats. Material and Methods Sixty Wistar rats were randomly divided into three groups (n?=?20): control (BC), injured TA muscle without LLLT (IC), injured TA muscle submitted to LLLT (IRI). The injured region was irradiated daily for 4 consecutive days, starting immediately after the lesion using a AlGaAs laser (continuous wave, 808?nm, tip area of 0.00785?cm2, power 30?mW, application time 47?seconds, fluence 180?J/cm2; 3.8?mW/cm2; and total energy 1.4?J). The animals were sacrificed on the fourth day after injury. Results LLLT reduced oxidative and nitrative stress in injured muscle, decreased lipid peroxidation, nitrotyrosine formation and NO production, probably due to reduction in iNOS protein expression. Moreover, LLLT increased SOD gene expression, and decreased the inflammatory response as measured by gene expression of NF-k beta and COX-2 and by TNF-a and IL-1 beta concentration. Conclusion These results suggest that LLLT could be an effective therapeutic approach to modulate oxidative and nitrative stress and to reduce inflammation in injured muscle. Lasers Surg. Med. 44: 726735, 2012. (c) 2012 Wiley Periodicals, Inc.

Records of sedimentary dynamics in the continental shelf and upper slope between Aveiro-Espinho (N Portugal)

The sedimentary unconsolidated cover of the Aveiro-Espinho continental shelf and upper slope (NW Portugal) records a complex interplay of processes including wave energy and currents, fluvial input, sediment transport alongshore and cross-shelf, geological and oceanographic processes and sediment sources and sinks. In order to study this record, a set of surface sediment samples was studied. Sediment grain size and composition, as well as the mineralogical composition (by XRD) of the fine (<63 mu m) and clay (<2 mu m) fractions and benthic microfaunal (foraminifera) data were analysed. Cluster analysis applied to the sedimentological data (grain size, sediment composition and mineralogy) allowed the establishment of three main zones corresponding to the: inner-, mid- and outer-shelf/upper slope. On the inner-shelf, the sedimentary coverture is composed of siliciclastic fine to very fine sand, essentially comprising modern (immature) terrigenous particles. The sediment grain size, as well as mineralogical and microfaunal composition, denote the high energetic conditions of this sector in which the alongshore transport of sand is predominantly southward and occurs mostly during the spring-summer oceanographic regime, when the main river providing sediments to this area, the River Douro, undergoes periods of drought. This effect may emphasize the erosive character of this coastal sector at present, since the Ria de Aveiro provides the shelf with few sediments. On the mid-shelf, an alongshore siliciclastic band of coarse sand and gravel can be found between the 40 m and 60 m isobaths. This gravelly deposit includes relic sediments deposited during lower sea-level stands. This structure stays on the surface due to the high bottom energy, which promotes the remobilization of the fine-grained sediments, and/or events of sediments bypassing. Benthic foraminifera density and "Benthic Foraminifera High Productivity" (BFHP) proxy values are in general low, which is consistent with the overall small supply of organic matter to the oceanic bottom in the inner- and mid-shelf. However, the Ria de Aveiro outflow, which delivers organic matter to the shelf, leaves its imprint mainly on the mid-shelf, identifiable by the increase in foraminifera density and BFHP values in front of the lagoon mouth. The higher values of BFHP along the 100 m isobath trace the present position of an oceanic thermal front whose situation may have changed in the last 3/5 ka BP. This zone marks a clear difference in the density, diversity and composition of benthic foraminifera assemblages. Here, in addition, sediment composition changes significantly, giving rise to carbonate-rich fine to medium sand in the deeper sector. The low bottom energy and the small sedimentation rate of the outer-shelf contributed to the preservation of a discontinuous carbonate-rich gravel band, between the 100 m and 140 m isobaths, also related to paleo-littorals, following the transgression that has occurred since the Last Glacial Maximum. The winter oceanographic regime favours the transport of fine grained sediments to the outer-shelf and upper slope. The inner- and mid-shelf, however, have low amounts of this kind of sediment and the Cretacic carbonated complexes Pontal da Galega and Pontal da Cartola, rocky outcrops located at the mid- and outer-shelf, act as morphological barriers to the cross-shelf transport of sediments. Thus a reduced sedimentation rate occurs in these deeper sectors, as indicated by the lower abundance of detrital minerals, which is compensated for the high sedimentary content of biogenic carbonates. The relatively high BFHP and Shannon Index values indicate water column stratification, high supply of organic matter and environmental stability, which provide favourable conditions for a diversified benthic fauna to flourish. These conditions also encourage authigenic chemical changes, favourable to glauconite formation, as well as illite and kaolinite degradation. Benthic foraminifera and clay mineral assemblages also reveal the effect of the internal waves pushing upward, and downslope losses of the sediments on the outer-shelf and upper slope.