Polarization effect on the two-photon absorption of a chiral compound

In this report, we investigate the polarization effect (linear, elliptical and circular) on the two-photon absorption (2PA) properties of a chiral compound based in azoaromatic moieties using the femtosecond Z-scan technique with low repetition rate and low pulse energy. We observed a strong 2PA modulation between 800 nm and 960 nm as a function the polarization changes from linear through elliptical to circular. Such results were interpreted employing the sum-over-essential states approach, which allowed us to model the 2PA circular-linear dichroism effect and to identifier the overlapping of the excited electronic states responsible by the 2PA allowed band. (C) 2012 Optical Society of America

Experimental and Theoretical Study on the One- and Two-Photon Absorption Properties of Novel Organic Molecules Based on Phenylacetylene and Azoaromatic Moieties

This Article reports a combined experimental and theoretical analysis on the one and two-photon absorption properties of a novel class of organic molecules with a pi-conjugated backbone based on phenylacetylene (JCM874, FD43, and FD48) and azoaromatic (YB3p2S) moieties. Linear optical properties show that the phenylacetylene-based compounds exhibit strong molar absorptivity in the UV and high fluorescence quantum yield with lifetimes of approximately 2.0 ns, while the azoaromatic-compound has a strong absorption in the visible region with very low fluorescence quantum yield. The two-photon absorption was investigated employing nonlinear optical techniques and quantum chemical calculations based on the response functions formalism within the density functional theory framework. The experimental data revealed well-defined 2PA spectra with reasonable cross-section values in the visible and IR. Along the nonlinear spectra we observed two 2PA allowed bands, as well as the resonance enhancement effect due to the presence of one intermediate one-photon allowed state. Quantum chemical calculations revealed that the 2PA allowed bands correspond to transitions to states that are also one-photon allowed, indicating the relaxation of the electric-dipole selection rules. Moreover, using the theoretical results, we were able to interpret the experimental trends of the 2PA spectra. Finally, using a few-energy-level diagram, within the sum-over-essential states approach, we observed strong qualitative and quantitative correlation between experimental and theoretical results.

A palaeobiologist's guide to 'virtual' micro-CT preparation

This paper provides a brief but comprehensive guide to creating, preparing and dissecting a 'virtual' fossil, using a worked example to demonstrate some standard data processing techniques. Computed tomography (CT) is a 3D imaging modality for producing 'virtual' models of an object on a computer. In the last decade, CT technology has greatly improved, allowing bigger and denser objects to be scanned increasingly rapidly. The technique has now reached a stage where systems can facilitate large-scale, non-destructive comparative studies of extinct fossils and their living relatives. Consequently the main limiting factor in CT-based analyses is no longer scanning, but the hurdles of data processing (see disclaimer). The latter comprises the techniques required to convert a 3D CT volume (stack of digital slices) into a virtual image of the fossil that can be prepared (separated) from the matrix and 'dissected' into its anatomical parts. This technique can be applied to specimens or part of specimens embedded in the rock matrix that until now have been otherwise impossible to visualise. This paper presents a suggested workflow explaining the steps required, using as example a fossil tooth of Sphenacanthus hybodoides (Egerton), a shark from the Late Carboniferous of England. The original NHMUK copyrighted CT slice stack can be downloaded for practice of the described techniques, which include segmentation, rendering, movie animation, stereo-anaglyphy, data storage and dissemination. Fragile, rare specimens and type materials in university and museum collections can therefore be virtually processed for a variety of purposes, including virtual loans, website illustrations, publications and digital collections. Micro-CT and other 3D imaging techniques are increasingly utilized to facilitate data sharing among scientists and on education and outreach projects. Hence there is the potential to usher in a new era of global scientific collaboration and public communication using specimens in museum collections.

The processing of polyelectrolyte-covered magnetite nanoparticles in the form of nanostructured thin films

Magnetic nanoparticles are promising for a variety of applications, such as biomedical devices, spin electronics, magnetic data storage media, to name a few. However, these goals may only be reached if stable and organized structures are fabricated. In this article, we report on a single-step synthetic route with the coprecipitation method, in which iron oxide magnetic nanoparticles (Fe3O4 NPs) were stabilized in aqueous media using the poly(diallyldimethylammonium chloride) (PDAC) polyelectrolyte. The Fe3O4 NPs had a diameter of ca. 5 nm, according to transmission electron microscopy (TEM) images, being arranged in an inverse spinel structure typical of magnetite. An investigation with infrared spectroscopy indicated that the mechanisms of stabilization in the polymer matrix were based on the interaction between quaternary amide groups from PDAC and the nanoparticle surface. The Fe3O4-PDAC NPs exhibited considerable magnetic susceptibility, with a monotonic increase in the magnetization with decreasing temperature. These Fe3O4-PDAC NPs were immobilized in layer-by-layer (LbL) films, being alternated with layers of poly(vinylsulfonic acid) (PVS). The LbL films were much rougher than typical films made with polyelectrolytes, and Fe3O4-PDAC NPs have been responsible for the high electrocatalytic activity toward H2O2 reduction, with an overpotential shift of 0.69 V. Overall, the stability, magnetic properties and film-forming ability indicate that the Fe3O4-PDAC NPs may be used for nanoelectronics and bioelectrochemical devices requiring reversible and magnetic redox materials.

Influence of salinity on the interannual heat storage trends in the Atlantic estimated from altimeters and Pilot Research Moored Array in the Tropical Atlantic data

Changes in the oceanic heat storage (HS) can reveal important evidences of climate variability related to ocean heat fluxes. Specifically, long-term variations in HS are a powerful indicator of climate change as HS represents the balance between the net surface energy flux and the poleward heat transported by the ocean currents. HS is estimated from sea surface height anomaly measured from the altimeters TOPEX/Poseidon and Jason 1 from 1993 to 2006. To characterize and validate the altimeter-based HS in the Atlantic, we used the data from the Pilot Research Moored Array in the Tropical Atlantic (PIRATA) array. Correlations and rms differences are used as statistical figures of merit to compare the HS estimates. The correlations range from 0.50 to 0.87 in the buoys located at the equator and at the southern part of the array. In that region the rms differences range between 0.40 and 0.51 x 10(9) Jm(-2). These results are encouraging and indicate that the altimeter has the precision necessary to capture the interannual trends in HS in the Atlantic. Albeit relatively small, salinity changes can also have an effect on the sea surface height anomaly. To account for this effect, NCEP/GODAS reanalysis data are used to estimate the haline contraction. To understand which dynamical processes are involved in the HS variability, the total signal is decomposed into nonpropagating basin-scale and seasonal (HS(l)) planetary waves, mesoscale eddies, and small-scale residual components. In general, HS(l) is the dominant signal in the tropical region. Results show a warming trend of HS(l) in the past 13 years almost all over the Atlantic basin with the most prominent slopes found at high latitudes. Positive interannual trends are found in the halosteric component at high latitudes of the South Atlantic and near the Labrador Sea. This could be an indication that the salinity anomaly increased in the upper layers during this period. The dynamics of the South Atlantic subtropical gyre could also be subject to low-frequency changes caused by a trend in the halosteric component on each side of the South Atlantic Current.

Detecting an abnormality in a recovery boiler using dynamic multivariate data analysis with parallel coordinate plots

Data visualization techniques are powerful in the handling and analysis of multivariate systems. One such technique known as parallel coordinates was used to support the diagnosis of an event, detected by a neural network-based monitoring system, in a boiler at a Brazilian Kraft pulp mill. Its attractiveness is the possibility of the visualization of several variables simultaneously. The diagnostic procedure was carried out step-by-step going through exploratory, explanatory, confirmatory, and communicative goals. This tool allowed the visualization of the boiler dynamics in an easier way, compared to commonly used univariate trend plots. In addition it facilitated analysis of other aspects, namely relationships among process variables, distinct modes of operation and discrepant data. The whole analysis revealed firstly that the period involving the detected event was associated with a transition between two distinct normal modes of operation, and secondly the presence of unusual changes in process variables at this time.

VALIDATION OF THE LAND WATER STORAGE FROM GRAVITY RECOVERY AND CLIMATE EXPERIMENT (GRACE) WITH GAUGE DATA IN THE AMAZON BASIN

The Amazon basin is a region of constant scientific interest due to its environmental importance and its biodiversity and climate on a global scale. The seasonal variations in water volume are one of the examples of topics studied nowadays. In general, the variations in river levels depend primarily on the climate and physics characteristics of the corresponding basins. The main factor which influences the water level in the Amazon Basin is the intensive rainfall over this region as a consequence of the humidity of the tropical climate. Unfortunately, the Amazon basin is an area with lack of water level information due to difficulties in access for local operations. The purpose of this study is to compare and evaluate the Equivalent Water Height (Ewh) from GRACE (Gravity Recovery And Climate Experiment) mission, to study the connection between water loading and vertical variations of the crust due to the hydrologic. In order to achieve this goal, the Ewh is compared with in-situ information from limnimeter. For the analysis it was computed the correlation coefficients, phase and amplitude of GRACE Ewh solutions and in-situ data, as well as the timing of periods of drought in different parts of the basin. The results indicated that vertical variations of the lithosphere due to water mass loading could reach 7 to 5 cm per year, in the sedimentary and flooded areas of the region, where water level variations can reach 10 to 8 m.

An online data access prediction and optimization approach for distributed systems

Current scientific applications have been producing large amounts of data. The processing, handling and analysis of such data require large-scale computing infrastructures such as clusters and grids. In this area, studies aim at improving the performance of data-intensive applications by optimizing data accesses. In order to achieve this goal, distributed storage systems have been considering techniques of data replication, migration, distribution, and access parallelism. However, the main drawback of those studies is that they do not take into account application behavior to perform data access optimization. This limitation motivated this paper which applies strategies to support the online prediction of application behavior in order to optimize data access operations on distributed systems, without requiring any information on past executions. In order to accomplish such a goal, this approach organizes application behaviors as time series and, then, analyzes and classifies those series according to their properties. By knowing properties, the approach selects modeling techniques to represent series and perform predictions, which are, later on, used to optimize data access operations. This new approach was implemented and evaluated using the OptorSim simulator, sponsored by the LHC-CERN project and widely employed by the scientific community. Experiments confirm this new approach reduces application execution time in about 50 percent, specially when handling large amounts of data.

Validation of the land water storage from gravity recovery and climate experiment (GRACE) with gauge data in the amazon basin

The Amazon basin is a region of constant scientific interest due to its environmental importance and its biodiversity and climate on a global scale. The seasonal variations in water volume are one of the examples of topics studied nowadays. In general, the variations in river levels depend primarily on the climate and physics characteristics of the corresponding basins. The main factor which influences the water level in the Amazon Basin is the intensive rainfall over this region as a consequence of the humidity of the tropical climate. Unfortunately, the Amazon basin is an area with lack of water level information due to difficulties in access for local operations. The purpose of this study is to compare and evaluate the Equivalent Water Height (Ewh) from GRACE (Gravity Recovery And Climate Experiment) mission, to study the connection between water loading and vertical variations of the crust due to the hydrologic. In order to achieve this goal, the Ewh is compared with in-situ information from limnimeter. For the analysis it was computed the correlation coefficients, phase and amplitude of GRACE Ewh solutions and in-situ data, as well as the timing of periods of drought in different parts of the basin. The results indicated that vertical variations of the lithosphere due to water mass loading could reach 7 to 5 cm per year, in the sedimentary and flooded areas of the region, where water level variations can reach 10 to 8 m.

Optical storage in azobenzene-containing epoxy polymers processed as Langmuir Blodgett films

In this study, azocopolymers containing different main-chain segments have been synthesized with diglycidyl ether of bisphenol A (DGEBA, DER 332, n=0.03) and the azochromophore Disperse Orange 3 (DO3) cured with twomonoamines, viz. benzylamine (BA) and m-toluidine (MT). The photoinduced birefringence was investigated in films produced with these azopolymers using the spin coating (SC) and Langmuir Blodgett (LB) techniques. In the LB films, birefringence increased with the content of azochromophore and the film thickness, as expected. The nanostructured nature of the LB films led to an enhanced birefringence and faster dynamics in the writing process, compared to the SC films. In summary, the combination of azocopolymers and the LBmethod may allow materials with tuned properties for various optical applications, including in biological systems were photoisomerization may be used to trigger actions such as drug delivery.