Anatomia ecológica do lenho de espécies arbustivas e arbóreas que ocorrem naturalmente em bosques com drástico gradiente de precipitação ao Noroeste da Patagônia, Argentina

A utilização de gradientes ambientais no estudo de comunidades vegetais possibilita a eleição de sítios onde há a predominância de um fator abiótico que determina o sucesso ou o fracasso de espécies ao longo de sua extensão. Entre as inúmeras ferramentas utilizadas no estudo de gradientes climáticos, se destaca a anatomia do lenho, pois, é um ramo da ciência que permite analisar, além dos aspectos espaciais, os aspectos temporais dos sítios por meio dos anéis de crescimento. Além disso, a ampla distribuição das plantas lenhosas ao longo do globo possibilita análises em praticamente todos os tipos de biomas e ecossistemas terrestres. Dentro desse contexto estão os bosques andino-patagônicos de Araucaria araucana (Pehuén) ao norte de sua distribuição na Argentina. Esses bosques ocupam territórios caracterizados por um acentuado gradiente de precipitação, que vai de cerca de 3000 a 100 milímetros anuais, entre a cordilheira do Andes e a estepe patagônica, que os define como bosques mésicos e xéricos, com diferenças ecológicas que condicionam a formação vegetal, dinâmica, estrutura, relações com o clima e vulnerabilidade em cenários de mudanças ambientais. O objetivo do projeto foi descrever e analisar comparativamente a estrutura anatômica do lenho de 33 espécies arbóreas e arbustivas ocorrentes ao longo de um gradiente de precipitação, entre a encosta da cordilheira dos Andes e a estepe Patagônica, para verificar possíveis alterações anatômicas que permitam a determinação de tendências e elucidem os limites de distribuição das espécies. Foram coletadas amostras não destrutivas de lenho durante três expedições para a Patagônia entre 2012 e 2014, seguidas de procedimentos laboratoriais de confeccção de lâminas histológicas, preparo de amostras para análises dendrocronológicas, captura de imagens com câmeras acopladas a microscópios óptico e eletrônico de varredura, mensurações, descrições e análises comparativas com o auxílio de softwares. Foram identificados caracteres anatômicos exclusivos de sítios secos e úmidos que permitiram a caracterização, posicionamento ao longo do gradiente de precipitação e grupamento de espécies xerófitas e mesófitas; A ultra-estrutura das pontoações de traqueídeos de Araucaria araucana apresentou diferenças marcantes na frequência e porosidade de suas membranas, sendo maior e menos porosas em sítios xéricos, e menor e mais porosas nos mésicos; a chave dicotômica microscópica permitiu a identificação das 32 espécies arbustivas, as espécies Chuquiraga oppositifolia e Nothofagus antarctica apresentaram potencial dendrocronológico, e foram identificadas tendências anatômicas latitudinais influenciadas pelo clima nos extremos da América do Sul. A anatomia do lenho se mostrou uma ferramenta confiável no estudo de um gradiente de precipitação na Patagônia argentina, e os resultados apontam para riscos de embolismos e morte induzida por falha no sistema hidráulico de Araucaria araucana ao longo de todo o gradiente, em função do atual cenário climático, e suas projeções em médio e longo prazos.

Cotunneling theory of atomic spin inelastic electron tunneling spectroscopy

We propose cotunneling as the microscopic mechanism that makes possible inelastic electron tunneling spectroscopy of magnetic atoms in surfaces for a wide range of systems, including single magnetic adatoms, molecules, and molecular stacks. We describe electronic transport between the scanning tip and the conducting surface through the magnetic system (MS) with a generalized Anderson model, without making use of effective spin models. Transport and spin dynamics are described with an effective cotunneling Hamiltonian in which the correlations in the magnetic system are calculated exactly and the coupling to the electrodes is included up to second order in the tip MS and MS substrate. In the adequate limit our approach is equivalent to the phenomenological Kondo exchange model that successfully describes the experiments. We apply our method to study in detail inelastic transport in two systems, stacks of cobalt phthalocyanines and a single Mn atom on Cu2N. Our method accounts for both the large contribution of the inelastic spin exchange events to the conductance and the observed conductance asymmetry.

Synthesis, Characterization and Conducting Properties of Nanocomposites of Intercalated 2-Aminophenol with Aniline in Sodium-Montmorillonite

A simple method was used to synthesize poly(2-aminophenol), poly(2-aminophenol-co-Aniline) and polyaniline nanocomposites with sodium-montmorillonite (Na-M) using in situ intercalative oxidative polymerization. Morphology and thermal properties of the synthesized nanocomposites were examined by transmission electron microscopy (TEM) and thermogravimetric analysis. The thermal analysis shows an improved thermal stability of the nanocomposites in comparison with the pure poly(2-aminophenol). The intercalation of polymers into the clay layers was confirmed by X-ray diffraction studies, TEM images and FTIR spectroscopy. In addition, the room temperature conductivity values of these nanocomposites varied between 8.21 × 10−5 and 6.76 × 10−4 S cm−1. The electrochemical behavior of the polymers extracted from the nanocomposites, has been analyzed by cyclic voltammetry. Good electrochemical response has been observed for polymer films; the observed redox processes indicate that the polymerization into Na-M produces electroactive polymers.

Evidence of Intracrystalline Mesostructured Porosity in Zeolites by Advanced Gas Sorption, Electron Tomography and Rotation Electron Diffraction

The small size of micropores (typically <1 nm) in zeolites causes slow diffusion of reactant and product molecules in and out of the pores and negatively impacts the product selectivity of zeolite based catalysts, for example, fluid catalytic cracking (FCC) catalysts. Size-tailored mesoporosity was introduced into commercial zeolite Y crystals by a simple surfactant-templating post-synthetic mesostructuring process. The resulting mesoporous zeolite Y showed significantly improved product selectivity in both laboratory testing and refinery trials. Advanced characterization techniques such as electron tomography, three-dimensional rotation electron diffraction, and high resolution gas adsorption coupled with hysteresis scanning and density functional theory, unambiguously revealed the intracystalline nature and connectivity of the introduced mesopores. They can be considered as molecular highways that help reactant and product molecules diffuse quickly to and away from the catalytically active sites within the zeolite crystals and, thus, shift the selectivity to favor the production of more of the valuable liquid fuels at reduced yields of coke and unconverted feed.

Generation of nitrogen functionalities on activated carbons by amidation reactions and Hofmann rearrangement: Chemical and electrochemical characterization

Nitrogen functionalization of a highly microporous activated carbon (BET surface area higher than 3000 m2/g) has been achieved using the following sequence of treatments: (i) chemical oxidation using concentrated nitric acid, (ii) amidation by acyl chloride substitution with NH4NO3 and (iii) amination by Hoffman rearrangement. This reaction pathway yielded amide and amine functional groups, and a total nitrogen content higher than 3 at.%. It is achieved producing only a small decrease (20%) of the starting microporosity, being most of it related to the initial wet oxidation of the activated carbon. Remarkably, nitrogen aromatic rings were also formed as a consequence of secondary cyclation reactions. The controlled step-by-step modification of the surface chemistry allowed to assess the influence of individual nitrogen surface groups in the electrochemical performance in 1 M H2SO4 of the carbon materials. The largest gravimetric capacitance was registered for the pristine activated carbon due to its largest apparent surface area. The nitrogen-containing activated carbons showed the highest surface capacitances. Interestingly, the amidated activated carbon showed the superior capacitance retention due to the presence of functional groups (such as lactams, imides and pyrroles) that enhance electrical conductivity through their electron-donating properties, showing a capacitance of 83 F/g at 50 A/g.

Characterization and electrochemical properties of conducting nanocomposites synthesized from p-anisidine and aniline with titanium carbide by chemical oxidative method

A novel polymer/TiC nanocomposites “PPA/TiC, poly(PA-co-ANI)/TiC and PANI/TiC” was successfully synthesized by chemical oxidation polymerization at room temperature using p-anisidine and/or aniline monomers and titanium carbide (TiC) in the presence of hydrochloric acid as a dopant with ammonium persulfate as oxidant. These nanocomposites obtained were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and thermogravimetric analysis (TGA). XRD indicated the presence of interactions between polymers and TiC nanoparticle and the TGA revealed that the TiC nanoparticles improve the thermal stability of the polymers. The electrical conductivity of nanocomposites is in the range of 0.079–0.91 S cm−1. The electrochemical behavior of the polymers extracted from the nanocomposites has been analyzed by cyclic voltammetry. Good electrochemical response has been observed for polymer films; the observed redox processes indicate that the polymerisation on TiC nanoparticles produces electroactive polymers. These nanocomposite microspheres can potentially used in commercial applications as fillers for antistatic and anticorrosion coatings.

Characterization of histopathological lesions in a biological model for environmental studies: Eisenia andrei Bouché. Preliminar results

Introduction The strong expansion of the world production of plastics caused a severe accumulation of plastic debris in the environment, which makes them one of the most important contaminants, growing as a global environmental problem. Although the production in Europe has been relatively constant in the last 10 years, world plastic production continues to increase, affecting soil biota and their functions. Objectives Thus, in order to evaluate the effects of MP in soil-dwelling organisms, earthworms (Eisenia andrei Bouché), were exposed to standard artificial soil mixed with MPs and the authors documented, using microscopic figures, the pathological lesions found in this biological model. Material and Methods Eight adult earthworms extracted from soils contaminated with different concentrations of MP (mg/kgdw) with sizes ranging between 250-1000 m, were fixed in 10% neutral-buffered formalin and processed for routine histopathological diagnosis. Results and discussion Contrary to what would be expected, MP were not found throughout the GI tube of earthworms but several lesions were found in the individuals extracted from the soils with high MP concentrations, when compared with control group, namely epithelial intestinal atrophy and evidences of inflammatory responses to this stress agent. Conclusion Earthworms have probably avoided the consumption of the biggest MPs. However, evidences point for lesions that were likely caused by the smallest MPs that were likely egested during the depuration phase.

Particel size distribution and microstructures of sediments from ODP Leg 205 sites (Table 1)

Ocean Drilling Program Legs 170 and 205 offshore Costa Rica provide structural observations which support a new model for the geometry and deformation response to the seismic cycle of the frontal sedimentary prism and decollement. The model is based on drillcore, thin section, and electron microscope observations. The decollement damage zone is a few tens of meters in width, it develops mainly within the frontal prism. A clear cm-thick fault core is observed 1.6 km from the trench. The lower boundary of the fault core is coincident with the lithological boundary between the frontal prism and the hemipelagic and pelagic sediment of the Cocos plate. Breccia clast distributions in the upper portion of the decollement damage zone were studied through fractal analysis. This analysis shows that the fractal dimension changes with brecciated fragment size, implying that deformation was not accommodated by self-similar fracturing. A higher fractal dimensionality correlates with smaller particle size, which indicates that different or additional grain-size reduction processes operated during shearing. The co-existence of two distinct fracturing processes is also confirmed by microscopic analysis in which extension fracturing in the upper part of the damage zone farthest from the fault core is frequent, while both extension and shear fracturing occur approaching the fault core. The coexistence of extensional and shear fracturing seems to be best explained by fluid pressure variations in response to variations of the compressional regime during the seismic cycle. During the co-seismic event, sub-horizontal compression and fluid pressure increase, triggering shear fracturing and fluid expulsion. Fractures migrate upward with fluids, contributing to the asymmetric shape of the decollement, while slip propagates. In the inter-seismic interval the frontal prismrelaxes and fluid pressure drops. The frontal prismgoes into diffuse extension during the intervalwhen plate convergence is accommodated by creep along the ductile fault core. The fault core is typically a barrier to deformation, which is explained by its weak, but impermeable, nature. The localized development of a damage zone beneath the fault core is characterized by shear fracturing that appears as the result of local strengthening of the detachment.

Towards Accurate and Efficient Description of Excited States

Thesis (Ph.D.)--University of Washington, 2016-06

Structural Insights into Viral Membrane Fusion Machinery via Cryo-Electron Tomography: Influenza Virus and Human Parainfluenza Virus

Thesis (Ph.D.)--University of Washington, 2016-06

Kinetic and phylogenetic characterization of an anaerobic dechlorinating microbial community

The reductive dechlorination (RD) of tetrachloroethene (PCE) to vinyl chloride (VC) and, to a lesser extent, to ethene (ETH) by an anaerobic microbial community has been investigated by studying the processes and kinetics of the main physiological components of the consortium. Molecular hydrogen, produced by methanol-utilizing acetogens, was the electron donor for the PCE RD to VC and ETH without forming any appreciable amount of other chlorinated intermediates and in the near absence of methanogenic activity. The microbial community structure of the consortium was investigated by preparing a 1 6S rDNA clone library and by fluorescence in situ hybridization (FISH). The PCR primers used in the clone library allowed the harvest of 16SrDNA from both bacterial and archaeal members in the community. A total of 616 clones were screened by RFLP analysis of the clone inserts followed by the sequencing of RFLP group representatives and phylogenetic analysis. The clone library contained sequences mostly from hitherto undescribed bacteria. No sequences similar to those of the known RD bacteria like 'Dehalococcoides ethenogenes' or Dehalobacter restrictus were found in the clone library, and none of these bacteria was present in the RD consortium according to FISH. Almost all clones fell into six previously described phyla of the bacterial domain, with the majority (56(.)6%) being deep-branching members of the Spirochaetes phylum. Other clones were in the Firmicutes phylum (18(.)5%), the Chloroflexi phylum (16(.)4%), the Bacteroidetes phylum (6(.)3%), the Synergistes genus (11(.)1%) and a lineage that could not be affiliated with existing phyla (11(.)1%). No archaeal clones were found in the clone library. Owing to the phylogenetic novelty of the microbial community with regard to previously cultured microorganisms, no specific microbial component(s) could be hypothetically affiliated with the RD phenotype. The predominance of Spirochaetes in the microbial consortium, the main group revealed by clone library analysis, was confirmed by FISH using a purposely developed probe.

TEM characterization of nanostructure and chemistry of semiconductor quantum structures

The power of advanced transmission electron microscopy in determining the nanostructures and chemistry of nanosized materials on the applications in semiconductor quantum structures was demonstrated.

Intra- vs intermolecular photoinduced electron transfer reactions of a macrocyclic donor-acceptor dyad

The synthesis, structural characterization, and photophysical behavior of a 14-membered tetraazamacrocycle with pendant 4-dimethylaminobenzyl (DMAB) and 9-anthracenylmethyl groups is reported (L-3, 6-((9-anthracenylmethyl)amino)-trans-6,13-dimethyl-13-((4-dimethylaminobenzyl)amino)-1,4,8,11-tetraaza-cyclotetradecane). In its free base form, this compound displays rapid intramolecular photoinduced electron transfer (PET) quenching of the anthracene emission, with both the secondary amines and the DMAB group capable of acting as electron donors. When complexed with Zn(II), the characteristic fluorescence of the anthracene chromophore is restored as the former of these pathways is deactivated by coordination. Importantly, it is shown that the DMAB group, which remains uncoordinated and PET active, acts only very weakly to quench emission, by comparison to the behavior of a model Zn complex lacking the pendant DMAB group, [ZnL2](2+) (Chart 1). By contrast, Stern-Volmer analysis of intermolecular quenching of [ZnL2](2+) by N,N-dimethylaniline (DMA) has shown that this reaction is diffusion limited. Hence, the pivotal role of the bridge in influencing intramolecular PET is highlighted.

Dimeric allylpalladium(II) complexes with pyrazolate bridges: Synthesis, characterization, structure and thermal behaviour

The synthesis, characterization and thermal behaviour of some new dimeric allylpalladium (II) complexes bridged by pyrazolate ligands are reported. The complexes [Pd(mu-3, 5-R'(2)pz)(eta(3)-CH2C(R)CH2)](2) [R = H; R'= CH(CH3)(2) (1a); R = H, R' = C(CH3)(3) (1b), R = H; R' = CF3 (1c); R = CH3, R' = CH(CH3)(2) (2a); R = CH3, R' = C(CH3)(3) (2b); and R = CH3, R' = CF3 (2c)] have been prepared by the room temperature reaction of [Pd(eta(3)-CH2C(R)CH2)(acac)](acac = acetylacetonate) with 3,5-disubstituted pyrazoles in acetonitrile solution. The complexes have been characterized by NMR (H-1, C-13{H-1}), FT-IR, and elemental analyses. The structure of a representative complex, viz. 2c, has been established by single-crystal X-ray diffraction. The dinuclear molecule features two formally square planar palladium centres which are bridged by two pyrazole ligands and the coordination of each metal centre is completed by allyl substituents. The molecule has non-crystallographic mirror symmetry. Thermogravimetric studies have been carried out to evaluate the thermal stability of these complexes. Most of the complexes thermally decompose in argon atmosphere to give nanocrystals of palladium, which have been characterized by XRD, SEM and TEM. However, complex 2c can be sublimed in vacuo at 2 mbar without decomposition. The equilibrium vapour pressure of 2c has been measured by the Knudsen effusion technique. The vapour pressure of the complex 2c could be expressed by the relation: In (p/Pa)(+/- 0.06) = -18047.3/T + 46.85. The enthalpy and entropy of vapourization are found to be 150.0 +/- 3 kJ mol(-1) and 389.5 +/- 8 J K-1 mol(-1), respectively. (c) 2005 Elsevier B.V. All rights reserved.

Characterization of heat-treated porous carbons using argon adsorption

The microstructural variation of Norit RI Extra activated carbon, progressively heated at 1373 K, was explored in terms of pore size and pore wall thickness distributions, for various periods of heating time, determined by argon adsorption at 87 K, both using an infinite as well as and finite wall thickness model. The latter approach has recently been developed in our laboratory and has been applied to several virgin carbons. The current results show significant variations in small pore size regions (< 7 angstrom) in association with strong growth of thick walls having at least three carbon sheets, as a result of heat treatment. In particular, shrinkage of the smallest pores due to strong interaction between their opposite walls as well as smoothening of carbon wall surfaces due to an increase in graphitization degree under thermal treatment have been found. Further, the results of pore wall thickness distribution are well corroborated by X-ray diffraction. The results of pore size and pore wall thickness distributions are also shown to be consistent with transmission electron microscopy analyses. (c) 2005 Elsevier Ltd. All rights reserved.