Índice de aromaticidade baseado na deslocalização, degenerescência e densidade (D3BIA) para acenos e moléculas homoaromáticas

The aromaticity index is an important tool for the investigation of aromatic molecules. This work consists on new applications of the aromaticity index developed by teacher Caio Lima Firme, so-called D3BIA (density, delocalization, degeneracy-based index of aromaticity). It was investigated its correlation with other well-known aromaticity indexes, such as HOMA (harmonic oscillator model of aromaticity), NICS (nucleus independent chemical shielding), PDI (para-delocalization index), magnetic susceptibility (), and energetic factor in the study of aromaticity of acenes and homoaromatic species based on bisnoradamantanyl cage. The density functional theory (DFT) was used for optimization calculations and for obtaining energetic factors associated with aromaticity and indexes HOMA and NICS. From quantum theory of atoms in molecules (QTAIM) it was obtained the indexes D3BIA, PDI and . For acenes, when the over-mentioned indexes were applied it was observed no correlation except for D3BIA and HOMA (R2=0.752). For bisnoradamantenyl dication and its derivatives, it was obtained a good correlation between D3BIA and NICS. Moreover, it was evaluated solely one of the factors used on D3BIA calculation, the delocalization index uniformity (DIU), so as to investigate its possible influence on stability of chemical species. Then, the DIU was compared with the formation Gibbs free energy of some pairs of carbocations, isomers or not, which each pair had small difference in point group symmetry and no difference among other well-known stability factors. The obtained results indicate that DIU is a new stability factor related to carbocations, that is, the more uniform the electron density delocalization, the more stable the is carbocation. The results of this work validate D3BIA and show its importance on the concept of aromaticity, indicating that it can be understood from degeneracy of atoms belonging the aromatic site, the electronic density in the aromatic site and the degree of uniformity of electron delocalization

Estudos de sorção de um corante aniônico modelo em partículas de quitosana reticulada

Textile activity results in effluents with a variety of dyes. Among the several processes for dye-uptaking from these wastewaters, sorption is one of the most effective methods, chitosan being a very promising alternative for this end. The sorption of Methyl Orange by chitosan crosslinked particles was approached using equilibrium and kinetic analyses at different pH s. Besides the standard pseudo-order analysis normally effectuated (i.e. pseudo-first-order and pseudo-second-order), a novel approach involving a pseudo-nth-order kinetics was used, nbeing determined via non-linear regression, using the Levenberg-Marquardt method. Zeta potential measurements indicated that electrostatic interactions were important for the sorption process. Regarding equilibrium experiments, data were well fitted to a hybrid Langmuir-Freundlich isotherm, and estimated Gibbs free energy of adsorption as a function of mass of dye per area of chitosan showed that the process of adsorption becomes more homogeneous as the pH of the continuous phase decreased. Considering the kinetics of sorption, although a pseudo-nth-order description yielded good fits, a kinetic equation involving diffusion adsorption phenomena was found to be more consistent in terms of a physicochemical description of the sorption process

Avaliação da remoção catalítica de compostos orgânicos monoaromáticos em água utilizando materiais nanoestruturados de sílica

Statistics of environmental protection agencies show that the soil has been contaminated with problems often resulting from leaks, spills and accidents during exploration, refining, transportation and storage oil operations and its derivatives. These, gasoline noteworthy, verified by releasing, to get in touch with the groundwater, the compounds BTEX (benzene, toluene, ethylbenzene and xylenes), substances which are central nervous system depressants and causing leukemia. Among the processes used in remediation of soil and groundwater contaminated with organic pollutants, we highlight those that use hydrogen peroxide because they are characterized by the rapid generation of chemical species of high oxidation power, especially the hydroxyl radical ( OH), superoxide (O2 -) and peridroxil (HO2 ), among other reactive species that are capable of transforming or decomposing organic chemicals. The pH has a strong effect on the chemistry of hydrogen peroxide because the formation of different radicals directly depends on the pH of the medium. In this work, the materials MCM-41 and Co-MCM-41 were synthesized and used in the reaction of BTEX removal in aqueous media using H2O2. These materials were synthesized by the hydrothermal method and the techniques used to characterize were: XRD, TG/DTG, adsorption/desorption N2, TEM and X-Ray Fluorescence. The catalytic tests were for 5 h of reaction were carried out in reactors of 20 mL, which was accompanied by the decomposition of hydrogen peroxide by molecular absorption spectrophotometry in the UV-Vis, in addition to removal of organic compounds BTEX was performed as gas chromatography with detection photoionization and flame ionization and by static headspace sampler. The characterizations proved that the materials were successfully synthesized. The catalytic tests showed satisfactory results, and the reactions containing BTEX + Co-MCM-41 + H2O2 at pH = 12.0 had the highest percentages of removal for the compounds studied

Entropia de bloco no formalismo estatístico generalizado de Kaniadakis

A posição que a renomada estatí stica de Boltzmann-Gibbs (BG) ocupa no cenário cientifíco e incontestável, tendo um âmbito de aplicabilidade muito abrangente. Por em, muitos fenômenos físicos não podem ser descritos por esse formalismo. Isso se deve, em parte, ao fato de que a estatística de BG trata de fenômenos que se encontram no equilíbrio termodinâmico. Em regiões onde o equilíbrio térmico não prevalece, outros formalismos estatísticos devem ser utilizados. Dois desses formalismos emergiram nas duas ultimas décadas e são comumente denominados de q-estatística e k-estatística; o primeiro deles foi concebido por Constantino Tsallis no final da década de 80 e o ultimo por Giorgio Kaniadakis em 2001. Esses formalismos possuem caráter generalizador e, por isso, contem a estatística de BG como caso particular para uma escolha adequada de certos parâmetros. Esses dois formalismos, em particular o de Tsallis, nos conduzem também a refletir criticamente sobre conceitos tão fortemente enraizados na estat ística de BG como a aditividade e a extensividade de certas grandezas físicas. O escopo deste trabalho esta centrado no segundo desses formalismos. A k -estatstica constitui não só uma generalização da estatística de BG, mas, atraves da fundamentação do Princípio de Interação Cinético (KIP), engloba em seu âmago as celebradas estatísticas quânticas de Fermi- Dirac e Bose-Einstein; além da própria q-estatística. Neste trabalho, apresentamos alguns aspectos conceituais da q-estatística e, principalmente, da k-estatística. Utilizaremos esses conceitos junto com o conceito de informação de bloco para apresentar um funcional entrópico espelhado no formalismo de Kaniadakis que será utilizado posteriormente para descrever aspectos informacionais contidos em fractais tipo Cantor. Em particular, estamos interessados em conhecer as relações entre parâmetros fractais, como a dimensão fractal, e o parâmetro deformador. Apesar da simplicidade, isso nos proporcionará, em trabalho futuros, descrever estatisticamente estruturas mais complexas como o DNA, super-redes e sistema complexos

Termoestatística quântica: uma abordagem via estatísticas não-gaussianas

Considering a quantum gas, the foundations of standard thermostatistics are investigated in the context of non-Gaussian statistical mechanics introduced by Tsallis and Kaniadakis. The new formalism is based on the following generalizations: i) Maxwell- Boltzmann-Gibbs entropy and ii) deduction of H-theorem. Based on this investigation, we calculate a new entropy using a generalization of combinatorial analysis based on two different methods of counting. The basic ingredients used in the H-theorem were: a generalized quantum entropy and a generalization of collisional term of Boltzmann equation. The power law distributions are parameterized by parameters q;, measuring the degree of non-Gaussianity of quantum gas. In the limit q

Macrofauna de ambientes não consolidados adjacentes à recifes da área de proteção ambiental dos recifes de corais Rio Grande do Norte, Brasil

This study aimed to characterize, for the first time, the benthic invertebrates that inhabit the region of soft bottoms adjacent to the APARC reefs in order to situate them as an important component of infralittoral coastal areas of Northeast Brazil. Soft bottoms areas of APARC corresponds to infralittoral zones vegetated by seagrass Halodule wrightii and unvegetated infralittoral zones, both subjected to substantial hydrodynamic stress. Through scuba diving, biological and sedimentary samples of both habitats were analyzed, with a cylindrical sampler. We identified 6160 individuals belonging to 16 groups and 224 species. The most abundant macrofaunal group was Polychaeta (43%), followed by Mollusca (25%) and Crustacea (14%), what was expected for these environments. In the first chapter, regarding vegetated areas, we tested three hypotheses: the existence of differences in the faunal structure associated with H. wrightii banks submitted to different hydrodynamic conditions; the occurrence of minor temporal variations on the associated macrofauna of banks protected from hydrodynamic stress; and if the diversity of macrofauna is affected by both benthophagous predators and H. wrightii biomass. It was observed that macrofauna associated at the Exposed bank showed differences in structure when comparing the Protected bank, the granulometry of the sediments, that co-varies with the hydrodynamism, was the cause of these variations. The results also pointed to a lower temporal variation in the macrofaunal structure on the Protected bank and a negative relation between macrofaunal and benthophagous fish abundance. At the Exposed bank, a greater faunal diversity was observed, probably due to the higher seagrass biomass. The second chapter compares the vegetated and non-vegetated areas in order to test the hypothesis that due to greater seasonal stability in tropical environments, seagrass structure would act to distinguish the vegetated and non-vegetated areas macrofauna, over time. It was also expected that depositivores were the most representative invertebrates on non-vegetated environments, on the assumption that the seagrass bank would work as a source of debris to adjacent areas, enriching them. Considering all sampling periods, the total macrofauna abundance and diversity were higher in vegetated areas, when compared to non-vegetated ones. Seasonally, the structural complexity provided by Halodule differentiated more clearly the fauna from vegetated and non-vegetated areas, but only at the climatic extremes, i.e. Dry season (extreme climatic stability, with low hydronamism variation) and Rainy season (great hydrodynamism variation and probably vegetated bank burial). Furthermore, the high organic matter levels measured in the sandy banks coincided with an outstanding trophic importance of deposit feeders, proving the debris-carrying hypothesis. The last chapter focused on the non-vegetated areas, where we tested that the hypothesis infaunal halo in tropical reefs depending on local granulometry. In this context, we also tested the hypothesis that benthophagous fish predation would have an effect on the low abundance of macrofaunal groups due to the high hydrographic stress, thus allowing other predatory groups to have greater importance in these environments. Proving the hypothesis, no spatial variation, both on abundance families neither on community structure, occur along distance of the edge reefs. However, we found that complex combinations of physical factors (grain size and organic matter levels originated from local hydronamic conditions) covary with the distance from the reefs and has stronger influence on macrofauna than considered biological factors, such as predation by benthophagous fishes. Based on the main results, this study shows that unconsolidated areas around APARC reefs are noteworthy from an ecological and conservational point of view, as evidenced by the biota-environment and organismal relations, never before described for these areas

Análise hidrodinâmica e morfodinâmica do complexo estuarino do Rio Piranhas-Açu/RN, Nordeste do Brasil

The aim of this study was the seasonal characterization of the morphology, sedimentology and hydrodynamic of the Açu, Cavalos and Conchas estuaries. These estuaries are inserted in a semi-arid climate area and form the mouth of the hydrographic basin of the Piranhas-Açu river, that represent the discharge of the largest watershed in the state. They are embedded in an environment consisting of a fluvial-marine floodplain, mangrove ecosystem, sandbanks, fields of dunes, spits and sandy beaches. Adjacent to the natural units are the main local socioeconomic activities (oil industry, salt industry, shrimp farming, fishing and tourism) are dependent on this river and its conservation. The environmental monitoring is necessary because it is an area under constant action of coastal processes and at high risk of oil spill. The acquisition and interpretation of hydrodynamic, sonographic and sediment data was conducted in two campaigns, dry season (2010) and rainy season (2011), using respectively the current profiler ADCP Doppler effect, the side-scan sonar and Van Veen sampler. In these estuaries: Açu, Cavalos and Conchas were identified the following types of bedforms: flatbed and Dunes 2-D and 3-D (small to medium size), generated at lower flow regime (Froude number <1). Structures such as ripples were observed in the Açu estuary mouth. The higher values of flow discharge and velocity were recorded in the Açu estuary (434,992 m³.s-¹ and 0,554 m.s-¹). In rainy season, despite the record of highest values of discharge and flow velocities at the mouth, the energy rates upstream did not differ much from the data of the dry season. However, in all estuaries were recorded an increase in speed and flow, with reservation to the flow in the Açu estuary and flow at the mouth of the Conchas estuary. Sediment grain sizes tend to increase towards the mouth of the estuary and these ranged from very fine sand to very coarse sand, medium sand fraction being the most recurrent. Based on the data acquired and analyzed, the estuaries Açu, Cavalos and Conchas are classified as mixed , dominated by waves and tides. According to their morphology, they are classified as estuaries constructed by bar and according to the classification by salinity, estuaries Conchas and Cavalos were ranked as hypersaline estuaries, and Açu as hypersaline and vertically well mixed type C