Tailored SERS substrates obtained with cathodic arc plasma ion implantation of gold nanoparticles into a polymer matrix

This manuscript reports on the fabrication of plasmonic substrates using cathodic arc plasma ion implantation, in addition to their performance as SERS substrates. The technique allows for the incorporation of a wide layer of metallic nanoparticles into a polymer matrix, such as PMMA. The ability to pattern different structures using the PMMA matrix is one of the main advantages of the fabrication method. This opens up new possibilities for obtaining tailored substrates with enhanced performance for SERS and other surface-enhanced spectroscopies, as well as for exploring the basic physics of patterned metal nanostructures. The architecture of the SERS-active substrate was varied using three adsorption strategies for incorporating a laser dye (rhodamine): alongside the nanoparticles into the polymer matrix, during the polymer cure and within nanoholes lithographed on the polymer. As a proof-of-concept, we obtained the SERS spectra of rhodamine for the three types of substrates. The hypothesis of incorporation of rhodamine molecules into the polymer matrix during the cathodic arc plasma ion implantation was supported by FDTD (Finite-Difference Time-Domain) simulations. In the case of arrays of nanoholes, rhodamine molecules could be adsorbed directly on the gold surface, then yielding a well-resolved SERS spectrum for a small amount of analyte owing to the short-range interactions and the large longitudinal field component inside the nanoholes. The results shown here demonstrate that the approach based on ion implantation can be adapted to produce reproducible tailored substrates for SERS and other surface-enhanced spectroscopies.

Aerosol and precipitation chemistry measurements in a remote site in Central Amazonia: the role of biogenic contribution

In this analysis a 3.5 years data set of aerosol and precipitation chemistry, obtained in a remote site in Central Amazonia (Balbina, (1A degrees 55' S, 59A degrees 29' W, 174 m a.s.l.), about 200 km north of Manaus) is discussed. Aerosols were sampled using stacked filter units (SFU), which separate fine (d < 2.5 mu m) and coarse mode (2.5 mu m < d < 10.0 mu m) aerosol particles. Filters were analyzed for particulate mass (PM), Equivalent Black Carbon (BCE) and elemental composition by Particle Induced X-Ray Emission (PIXE). Rainwater samples were collected using a wet-only sampler and samples were analyzed for pH and ionic composition, which was determined using ionic chromatography (IC). Natural sources dominated the aerosol mass during the wet season, when it was predominantly of natural biogenic origin mostly in the coarse mode, which comprised up to 81% of PM10. Biogenic aerosol from both primary emissions and secondary organic aerosol dominates the fine mode in the wet season, with very low concentrations (average 2.2 mu g m(-3)). Soil dust was responsible for a minor fraction of the aerosol mass (less than 17%). Sudden increases in the concentration of elements as Al, Ti and Fe were also observed, both in fine and coarse mode (mostly during the April-may months), which we attribute to episodes of Saharan dust transport. During the dry periods, a significant contribution to the fine aerosols loading was observed, due to the large-scale transport of smoke from biomass burning in other portions of the Amazon basin. This contribution is associated with the enhancement of the concentration of S, K, Zn and BCE. Chlorine, which is commonly associated to sea salt and also to biomass burning emissions, presented higher concentration not only during the dry season but also for the April-June months, due to the establishment of more favorable meteorological conditions to the transport of Atlantic air masses to Central Amazonia. The chemical composition of rainwater was similar to those ones observed in other remote sites in tropical forests. The volume-weighted mean (VWM) pH was 4.90. The most important contribution to acidity was from weak organic acids. The organic acidity was predominantly associated with the presence of acetic acid instead of formic acid, which is more often observed in pristine tropical areas. Wet deposition rates for major species did not differ significantly between dry and wet season, except for NH4+, citrate and acetate, which had smaller deposition rates during dry season. While biomass burning emissions were clearly identified in the aerosol component, it did not present a clear signature in rainwater. The biogenic component and the long-range transport of sea salt were observed both in aerosols and rainwater composition. The results shown here indicate that in Central Amazonia it is still possible to observe quite pristine atmospheric conditions, relatively free of anthropogenic influences.

Alzheimer random walk model: Two previously overlooked diffusion regimes

A non-Markovian one-dimensional random walk model is studied with emphasis on the phase-diagram, showing all the diffusion regimes, along with the exactly determined critical lines. The model, known as the Alzheimer walk, is endowed with memory-controlled diffusion, responsible for the model's long-range correlations, and is characterized by a rich variety of diffusive regimes. The importance of this model is that superdiffusion arises due not to memory per se, but rather also due to loss of memory. The recently reported numerically and analytically estimated values for the Hurst exponent are hereby reviewed. We report the finding of two, previously overlooked, phases, namely, evanescent log-periodic diffusion and log-periodic diffusion with escape, both with Hurst exponent H = 1/2. In the former, the log-periodicity gets damped, whereas in the latter the first moment diverges. These phases further enrich the already intricate phase diagram. The results are discussed in the context of phase transitions, aging phenomena, and symmetry breaking.

Use of levoglucosan, potassium, and water-soluble organic carbon to characterize the origins of biomass-burning aerosols

Three chemical species related to biomass burning, levoglucosan, potassium and water-soluble organic carbon (WSOC), were measured in aerosol samples collected in a rural area on the outskirts of the municipality of Ourinhos (Sao Paulo State, Brazil). This region is representative of the rural interior of the State, where the economy is based on agro-industrial production, and the most important crop is sugar cane. The manual harvesting process requires that the cane be first burned to remove excess foliage, leading to large emissions of particulate materials to the atmosphere. Most of the levoglucosan (68-89%) was present in small particles (<1.5 mu m), and its concentration in total aerosol ranged from 25 to 1186 ng m(-3). The highest values were found at night, when most of the biomass burning occurs. In contrast, WSOC showed no diurnal pattern, with an average concentration of 5.38 +/- 2.97 mu g m(-3) (n = 27). A significant linear correlation between levoglucosan and WSOC (r = 0.54; n = 26; p < 0.0001) confirmed that biomass burning was in fact an important source of WSOC in the study region. A moderate (but significant) linear correlation between levoglucosan and potassium concentrations (r = 0.62; n = 40; p < 0.0001) was indicative of the influence of other sources of potassium in the study region, such as soil resuspension and fertilizers. When only the fine particles (<1.5 pm; typical of biomass burning) were considered, the linear coefficient increased to 0.91 (n = 9). In this case, the average levoglucosan/K+ ratio was 0.24, which may be typical of biomass burning in the study region. This ratio is about 5 times lower than that previously found for Amazon aerosol collected during the day, when flaming combustion prevails. This suggests that the levoglucosan/K+ ratio may be especially helpful for characterization of the type of vegetation burned (such as crops or forest), when biomass-burning is the dominant source of potassium. The relatively high concentrations of WSOC (and inorganic ions) suggest an important influence on the formation of cloud condensation nuclei, which is likely to affect cloud formation and precipitation patterns. (C) 2012 Elsevier Ltd. All rights reserved.

A new Pennsylvanian Oriocrassatellinae from Brazil and the distribution of the genus Oriocrassatella in space and time

Oriocrassatella Etheridge Jr., 1907 is a long range crassatellid bivalve genus well recognized in shallow waters of epeiric seas throughout the upper part of Paleozoic. The first occurrences of this genus are recorded in the sedimentary successions of the Gondwana, both in Australia and South America. However, the geographic and age distribution of Oriocrassatella in Late Mississippian deposits of Australia and Argentina may indicate an earliest Visean or even a pre-Visean origin for the genus. Following its origin in Early Carboniferous a complex paleobiogeographic history from Southern to Northern Hemisphere took place in the Permian. During its initial dispersal phase from Late Carboniferous to the Early Permian the genus thrived in cold water environments associated to the Late Paleozoic Gondwana glaciation. Shallow-water bottoms of the warm waters of the central Gondwana fringe and Laurussia were colonized by Oriocrassatella only during Early Permian times when the genus became cosmopolitan. A new species of this genus is described herein, Oriocrassatella piauiensis n. sp., recorded from the Piaui Formation, Pennsylvanian of the Parnaiba Basin. This new species may represent an early adaptation to warm waters. However, based on available data, species of this genus seem to have adapted definitely to warm water environments probably related the Late Pennsylvanian interglacial phases. In these phases, climatic barrier were interrupted allowing the faunal interchange and larval dispersion following a South to North migration route through the eastern margins of Gondwana and the eastern Paleotethys.

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.

Structural properties and energetics of diffuse Rb-87 clusters in three-dimension

A correlated two-body basis function is used to describe the three-dimensional bosonic clusters interacting via two-body van der Waals potential. We calculate the ground state and the zero orbital angular momentum excited states for Rb-N clusters with up to N = 40. We solve the many-particle Schrodinger equation by potential harmonics expansion method, which keeps all possible two-body correlations in the calculation and determines the lowest effective many-body potential. We study energetics and structural properties for such diffuse clusters both at dimer and tuned scattering length. The motivation of the present study is to investigate the possibility of formation of N-body clusters interacting through the van der Waals interaction. We also compare the system with the well studied He, Ne, and Ar clusters. We also calculate correlation properties and observe the generalised Tjon line for large cluster. We test the validity of the shape-independent potential in the calculation of the ground state energy of such diffuse cluster. These are the first such calculations reported for Rb clusters. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4730972]

Self-organized criticality in MHD driven plasma edge turbulence

We analyze long-range time correlations and self-similar characteristics of the electrostatic turbulence at the plasma edge and scrape-off layer in the Tokamak Chauffage Alfven Bresillien (TCABR), with low and high Magnetohydrodynamics (MHD) activity. We find evidence of self-organized criticality (SOC), mainly in the region near the tokamak limiter. Comparative analyses of data before and during the MHD activity reveals that during the high mHD activity the Hurst parameter decreases. Finally, we present a cellular automaton whose parameters are adjusted to simulate the analyzed turbulence SOC change with the MHD activity variation. (C) 2011 Published by Elsevier B.V.

On the Origin of the Trigger-Angle Dependence of the Ridge Structure

The origin of the trigger-angle dependence of the ridge structure in two-hadron long-range correlations, as observed at RHIC, is discussed as due to an interplay between the elliptic flow caused by the initial state global geometry and flow produced by fluctuations.

A theoretical study of SnF2+, SnCl2+, and SnO2+ and their experimental search

We present a detailed theoretical study of the stability of the gas-phase diatomic dications SnF2+, SnCl2+, and SnO2+ using ab initio computer calculations. The ground states of SnF2+, SnCl2+, and SnO2+ are thermodynamically stable, respectively, with dissociation energies of 0.45, 0.30, and 0.42 eV. Whereas SnF2+ dissociates into Sn2+ + F, the long range behaviour of the potential energy curves of SnCl2+ and SnO2+ is repulsive and wide barrier heights due to avoided crossing act as a kind of effective dissociation energy. Their equilibrium internuclear distances are 4.855, 5.201, and 4.852 a(0), respectively. The double ionisation energies (T-e) to form SnF2+, SnCl2+, and SnO2+ from their respective neutral parents are 25.87, 23.71, and 25.97 eV. We combine our theoretical work with the experimental results of a search for these doubly positively charged diatomic molecules in the gas phase. SnO2+ and SnF2+ have been observed for prolonged oxygen (O-16(-)) ion beam sputtering of a tin metal foil and of tin (II) fluoride (SnF2) powder, respectively, for ion flight times of about 10(-5) s through a magnetic-sector mass spectrometer. In addition, SnCl2+ has been detected for O-16(-) ion surface bombardment of stannous (tin (II)) chloride (SnCl2) powder. To our knowledge, SnF2+ is a novel gas-phase molecule, whereas SnCl2+ had been detected previously by electron-impact ionization mass spectrometry, and SnO2+ had been observed before by spark source mass spectrometry as well as by atom probe mass spectrometry. We are not aware of any previous theoretical studies of these molecular systems. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4758475]

Influence of the network modifier on the characteristics of MSnO3 (M=Sr and Ca) thin films synthesized by chemical solution deposition

CaSnO3 and SrSnO3 alkaline earth stannate thin films were prepared by chemical solution deposition using the polymeric precursor method on various single crystal substrates (R- and C-sapphire and 100-SrTiO3) at different temperatures. The films were characterized by X-ray diffraction (θ-2θ, ω- and φ-scans), field emission scanning electron microscopy, atomic force microscopy, micro-Raman spectroscopy and photoluminescence. Epitaxial SrSnO3 and CaSnO3 thin films were obtained on SrTiO3 with a high crystalline quality. The long-range symmetry promoted a short-range disorder which led to photoluminescence in the epitaxial films. In contrast, the films deposited on sapphire exhibited a random polycrystalline growth with no meaningful emission regardless of the substrate orientation. The network modifier (Ca or Sr) and the substrate (sapphire or SrTiO3) influenced the crystallization process and/or the microstructure. Higher is the tilts of the SnO6 octahedra, as in CaSnO3, higher is the crystallization temperature, which changed also the nucleation/grain growth process.