Theoretical study of one- and two-photon absorption spectra of azoaromatic compounds

In this study, the one- and two-photon absorption spectra of seven azoaromatic compounds (five pseudostilbenes-type and two aminoazobenzenes) were theoretically investigated using the density functional theory combined with the response functions formalism. The equilibrium molecular structure of each compound was obtained at three different levels of theory: Hartree-Fock, density functional theory (DFT), and Moller-Plesset 2. The effect of solvent on the equilibrium structure and the electronic transitions of the compounds were investigated using the polarizable continuum model. For the one-photon absorption, the allowed pi ->pi(*) transition energy showed to be dependent on the molecular structures and the effect of solvent, while the n ->pi(*) and pi ->pi(*)(n) transition energies exhibited only a slight dependence. An inversion between the bands corresponding to the pi ->pi(*) and n ->pi(*) states due to the effect of solvent was observed for the pseudostilbene-type compounds. To characterize the allowed two-photon absorption transitions for azoaromatic compounds, the response functions formalism combined with DFT using the hybrid B3LYP and PBE0 functionals and the long-range corrected CAM-B3LYP functional was employed. The theoretical results support the previous findings based on the three-state model. The model takes into account the ground and two electronic excited states and has already been used to describe and interpret the two-photon absorption spectrum of azoaromatic compounds. The highest energy two-photon allowed transition for the pseudostilbene-type compounds shows to be more effectively affected (similar to 20%) by the torsion of the molecular structure than the lowest allowed transition (similar to 10%). In order to elucidate the effect of the solvent on the two-photon absorption spectra, the lowest allowed two-photon transition (dipolar transition) for each compound was analyzed using a two-state approximation and the polarizable continuum model. The results obtained reveal that the effect of solvent increases drastically the two-photon cross-section of the dipolar transition of the pseudostilbene-type compounds. In general, the features of both one- and two-photon absorption spectra of the azoaromatic compounds are well reproduced by the theoretical calculations.

Extending Bell's beables to encompass dissipation, decoherence, and the quantum-to-classical transition through quantum trajectories

In this paper, employing the Ito stochastic Schrodinger equation, we extend Bell's beable interpretation of quantum mechanics to encompass dissipation, decoherence, and the quantum-to-classical transition through quantum trajectories. For a particular choice of the source of stochasticity, the one leading to a dissipative Lindblad-type correction to the Hamiltonian dynamics, we find that the diffusive terms in Nelsons stochastic trajectories are naturally incorporated into Bohm's causal dynamics, yielding a unified Bohm-Nelson theory. In particular, by analyzing the interference between quantum trajectories, we clearly identify the decoherence time, as estimated from the quantum formalism. We also observe the quantum-to-classical transition in the convergence of the infinite ensemble of quantum trajectories to their classical counterparts. Finally, we show that our extended beables circumvent the problems in Bohm's causal dynamics regarding stationary states in quantum mechanics.

Nonclassical correlation in NMR quadrupolar systems

The existence of quantum correlation (as revealed by quantum discord), other than entanglement and its role in quantum-information processing (QIP), is a current subject for discussion. In particular, it has been suggested that this nonclassical correlation may provide computational speedup for some quantum algorithms. In this regard, bulk nuclear magnetic resonance (NMR) has been successfully used as a test bench for many QIP implementations, although it has also been continuously criticized for not presenting entanglement in most of the systems used so far. In this paper, we report a theoretical and experimental study on the dynamics of quantum and classical correlations in an NMR quadrupolar system. We present a method for computing the correlations from experimental NMR deviation-density matrices and show that, given the action of the nuclear-spin environment, the relaxation produces a monotonic time decay in the correlations. Although the experimental realizations were performed in a specific quadrupolar system, the main results presented here can be applied to whichever system uses a deviation-density matrix formalism.

Chemical and in vitro study of the potential of 3-(aryl)-2-sulfanylpropenoic acids and their Zn(II) complexes as protective agents against cadmium toxicity

The free H(2)xspa ligands [xspa = pspa, Clpspa, tspa or fspa where p = 3-(phenyl), Clp = 3-(2-chlorophenyl), t = 3-(2-thienyl), f = 3-(2-furyl) and spa = 2-sulfanylpropenoato], their Zn(II) complexes of formula [HQ](2)[Zn(xspa)(2)] (HQ=diisopropylammonium) and the Cd(II) equivalents were prepared and characterized by elemental analysis and by IR, Raman and NMR ((1)H, (13)C) spectroscopy. X-Ray studies of the crystal structures of [HQ](2)[Zn(pspa)(2)], [HQ](2)[Zn(Clpspa)2], [HQ](2)[Zn(tspa)(2)] and [HQ](2)[Zn(fspa)(2)] show that the zinc atom is coordinated to two O atoms and two S atoms of the ligands in a distorted tetrahedral ZnO(2)S(2) environment. In the structures of [HQ](2)[Cd(pspa)(2)] and [HQ](2)[Cd(Clpspa)(2)] the cadmium atom is coordinated to three S atoms and two carboxylato O atoms of the ligands in a distorted trigonal bipyramidal environment. The interchange of ligands between Zn( II) and Cd( II) was studied by (113)Cd NMR spectroscopy. The in vitro protective effect of H(2)xspa and their Zn( II) complexes against Cd toxicity was investigated using the human hepatocarcinoma HepG2 cell line and the pig renal proximal tubule LLC-PK1 cell line. The incorporation of Zn( II) was found to be relevant in the case of H(2)pspa, with an increase observed in the cell viability of the LCC-PK1 cells with respect to the value for the free ligand.

NMR quadrupolar system described as Bose-Einstein-condensate-like system

This paper presents a description of nuclear magnetic resonance (NMR) of quadrupolar systems using the Holstein-Primakoff (HP) formalism and its analogy with a Bose-Einstein condensate (BEC) system. Two nuclear spin systems constituted of quadrupolar nuclei I=3/2 ((23)Na) and I=7/2 ((133)Cs) in lyotropic liquid crystals were used for experimental demonstrations. Specifically, we derived the conditions necessary for accomplishing the analogy, executed the proper experiments, and compared with quantum mechanical prediction for a Bose system. The NMR description in the HP representation could be applied in the future as a workbench for BEC-like systems, where the statistical properties may be obtained using the intermediate statistic, first established by Gentile. The description can be applied for any quadrupolar systems, including new developed solid-state NMR GaAS nanodevices.

Chemical analyses confirm a rare case of seed dispersal by bees

It has been suggested that dispersal of seeds of Coussapoa asperifolia magnifolia could have endozoochoric dispersal by frugivorous birds and monkeys because the fruits are red when ripe, or exozoochoric dispersal, because the exocarp is mucilaginous and sticky. However, our field observations showed only stingless bees collecting the exocarp with seeds of C. asperifolia magnifolia, which are used for building and repairing their nests, from which the plants sprout. This paper aimed to determine the fruit chemical composition, since we postulated that C. asperifolia magnifolia is neither consumed by birds nor monkeys due to being very sticky and apparently resinous. Apolar extract analyses revealed the fruits are not resinous but extremely rich in waxes ( mainly esterified triglycerides), and polar extract analyses revealed the sugar content to be close to the sensorial minimum level. This probably accounts for why only stingless bees are seen visiting fruits and dispersing seeds.

CHEMICAL AND PHYSICO-CHEMICAL CHARACTERIZATION OF LIGNINS OBTAINED FROM ETHANOL-WATER FRACTIONATION OF BAGASSE

Organosolv lignins can replace petroleum chemicals such as phenol either partially or totally in various applications. Eight lignins, seven of which corresponded to the ethanol-water fractionation of bagasse and the other to a reference lignin (Alcell (R)) were analyzed with the aim to evaluate their chemical and physicochemical characteristics. The purity of the lignin fractions was determined by high pressure liquid chromatography (HPLC) and by ash content. Fourier Transform-Infrared Spectroscopy (FTIR) techniques and differential UV spectroscopy were applied to identify the chemical groups in the lignin samples. The molecular weight distribution was determined by size exclusion chromatography (HPSEC). Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques were used to determine the mass loss due to the high temperature treatment. The lignins studied showed the presence of p-hydroxyphenyl (H unit) and a greater proportion of guaiacyl (G unit) moieties, lower purity, similar or greater amount of phenolic hydroxyl groups, and higher degradation temperatures, than the Alcell (R) lignin.

Excitation energies from ground-state density-functionals by means of generator coordinates

The generator-coordinate method is a flexible and powerful reformulation of the variational principle. Here we show that by introducing a generator coordinate in the Kohn-Sham equation of density-functional theory, excitation energies can be obtained from ground-state density functionals. As a viability test, the method is applied to ground-state energies and various types of excited-state energies of atoms and ions from the He and the Li isoelectronic series. Results are compared to a variety of alternative DFT-based approaches to excited states, in particular time-dependent density-functional theory with exact and approximate potentials.

Total soil carbon and chemical attributes under different land uses in the Brazilian savanna

Total soil carbon and chemical attributes under different land uses in the Brazilian savanna. The Brazilian savanna region (Cerrado) is one of the largest cultivated areas of the world. The different land uses in the region can effectively change the quantities of soil organic matter and the cycling of nutrients. I-lie objective of this study was to evaluate the effect of different land use management systems on the relationship between soil organic carbon and the soil chemical attributes of a Red Latosol (Oxisol) under Cerrado in Rio Verde (Goias state). The treatments studied were native vegetation (cerrado), low-productivity pasture, conventional tillage with soybean, and no-tillage with soybean and maize. The smallest values for pH, available P, K, Ca and Mg were observed for the Cerradao treatment, even if the relatively high C levels increased the potential soil cation exchange capacity. The pasture, conventional tillage and no-tillage treatments showed higher K, Ca, Mg, available 13, and S concentrations in the soil. In the areas where soil tillage did not take place and lime and fertilizers were applied superficially, the stratification of the soil organic carbon provides the retention of the elements near to the surface, with significance correlations with the soil chemicals attributes.

Effects of land cover on chemical characteristics of streams in the Cerrado region of Brazil

The Cerrado is the second largest Brazilian biome and contains the headwaters of three major hydrological basins in Brazil. In spite of the biological and ecological relevance of this biome, there is little information about how land use changes affect the chemistry of low-order streams in the Cerrado. To evaluate these effects streams that drain areas under natural, rural, and urban land cover were sampled near Brasilia, Brazil. Water samples were collected between September 2004 and December 2006. Chemical concentrations generally followed the pattern of Urban > Rural > Natural. Median conductivity of stream water of 21.6 (interquartile: 22.7) mu S/cm in urban streams was three and five-fold greater relative to rural and natural areas, respectively. In the wet season, despite of increasing discharge, concentration of many solutes were higher, particularly in rural and natural streams. Streams also presented higher total dissolved N (TDN) loads from natural to rural and urban although DIN:DON ratios did not differ significantly. In natural and urban streams TDN was 80 and 77% dissolved organic N, respectively. These results indicate that alterations in land cover from natural to rural and urban are changing stream water chemistry in the Cerrado with increasing solute concentrations, in addition to increased TDN output in areas under urban cover, with potential effects on ecosystem function.

k(0)-INAA for determining chemical elements in bird feathers

The k(0)-method instrumental neutron activation analysis (k(0)-INAA) was employed for determining chemical elements in bird feathers. A collection was obtained taking into account several bird species from wet ecosystems in diverse regions of Brazil. For comparison reason, feathers were actively sampled in a riparian forest from the Marins Stream, Piracicaba, Sao Paulo State, using mist nets specific for capturing birds. Biological certified reference materials were used for assessing the quality of analytical procedure. Quantification of chemical elements was performed using the k(0)-INAA Quantu Software. Sixteen chemical elements, including macro and micronutrients, and trace elements, have been quantified in feathers, in which analytical uncertainties varied from 2% to 40% depending on the chemical element mass fraction. Results indicated high mass fractions of Br (max=7.9 mgkg(-1)), Co (max= 0.47 mg kg(-1)), Cr (max =68 mg kg(-1)), Hg (max =2.79 mg kg(-1)), Sb (max= 0.20 mg kg(-1)), Se (max=1.3 mg kg(-1)) and Zn (max =192 mg kg(-1)) in bird feathers, probably associated with the degree of pollution of the areas evaluated. In order to corroborate the use of k(0)-INAA results in biomonitoring studies using avian community, different factor analysis methods were used to check chemical element source apportionment and locality clustering based on feather chemical composition. (C) 2010 Elsevier B.V. All rights reserved.

Chemical changes in bromeliad leaves at different vegetative stages

Studies concerning the accumulating capacity of native epiphytic bromeliads are of utmost relevance, due to the continuous incorporation of chemical elements provided by these organisms in the ecosystems. Bromeliad species from diverse So Paulo State conservation units, Brazil, were sampled for young, mature and old leaves using a sustainable sampling method. By applying INAA, the accumulation of ten chemical elements, i.e. Br, Ca, Co, Fe, K, Na, Rb, Sc, Sr and Zn, was investigated in different leaf vegetative stages. The bromeliads showed divergent chemical element distribution patterns, demonstrating a real complexity in the accumulation and translocation mechanisms utilized by these plants.

Native bromeliads as biomonitors of airborne chemical elements in a Brazilian restinga forest

Epiphytic bromeliads have been used as biomonitors of air pollution since they have specialized structures in leaves for absorbing humidity and nutrients available in the atmosphere. Leaves of five bromeliad species were collected in the conservation unit Parque Estadual Ilha do Cardoso, Sao Paulo State, Brazil, and analyzed by INAA. Vriesea carinata was the species showing most accumulation, with the highest mass fractions of K, Na, Rb and Zn. Similar results were previously found for the same species collected in the dense ombrophilous forest. Chemical composition of bromeliads provided an indication of the atmosphere status in the conservation unit.

Status of chemical elements in Atlantic Forest tree species near an industrial complex

Environmental quality assessment studies have been conducted with tree species largely distributed in the Atlantic Forest. Leaf and soil samples were collected in the conservation unit Parque Estadual da Serra do Mar (PESM) nearby the industrial complex of Cubatao, Sao Paulo State, Brazil, and analyzed for chemical elements by instrumental neutron activation analysis. Results were compared to background values obtained in the Parque Estadual Carlos Botelho (PECB). The higher As, Fe, Hg and Zn mass fractions in the tree leaves of PESM indicated anthropogenic influence on this conservation unit.

Chemical characterization of agricultural supplies applied to organic tomato cultivation

The agricultural supplies used in the organic system to control pests and diseases as well as to fertilize soil are claimed to be beneficial to plants and innocuous to human health and to the environment. The chemical composition of six agricultural supplies commonly used in the organic tomato culture, was evaluated by instrumental neutron activation analysis (INAA). Results were compared to the maximum limits established by the Environment Control Agency of the Sao Paulo State (CETESB) and the Guidelines for Organic Quality Standard of Instituto Biodinamico (IBD). Concentrations above reference values were found for Co, Cr and Zn in compost, Cr and Zn in cattle manure and Zn in rice bran.