THE PYROCHLORE SUPERGROUP OF MINERALS: NOMENCLATURE

A new scheme of nomenclature for the pyrochlore supergroup, approved by the CNMNC-IMA, is based on the ions at the A, B and Y sites. What has been referred to until now as the pyrochlore group should be referred to as the pyrochlore supergroup, and the subgroups should be changed to groups. Five groups are recommended, based on the atomic proportions of the B atoms Nb, Ta, Sb, Ti, and W. The recommended groups are pyrochlore, microlite, romite, betafite, and elsmoreite, respectively. The new names are composed of two prefixes and one root name (identical to the name of the group). The first prefix refers to the dominant anion (or cation) of the dominant valence [or H(2)O or rectangle] at the Y site. The second prefix refers to the dominant cation of the dominant valence [or H(2)O or rectangle] at the A site. The prefix "" keno-"" represents "" vacancy"". Where the first and second prefixes are equal, then only one prefix is applied. Complete descriptions are missing for the majority of the pyrochlore-supergroup species. Only seven names refer to valid species on the grounds of their complete descriptions: oxycalciopyrochlore, hydropyrochlore, hydroxykenomicrolite, oxystannomicrolite, oxystibiomicrolite, hydroxycalcioromite, and hydrokenoelsmoreite. Fluornatromicrolite is an IMA-approved mineral, but the complete description has not yet been published. The following 20 names refer to minerals that need to be completely described in order to be approved as valid species: hydroxycalciopyrochlore, fluornatropyrochlore, fluorcalciopyrochlore, fluorstrontiopyrochlore, fluorkenopyrochlore, oxynatropyrochlore, oxyplumbopyrochlore, oxyyttropyrochlore-(Y), kenoplumbopyrochlore, fluorcalciomicrolite, oxycalciomicrolite, kenoplumbomicrolite, hydromicrolite, hydrokenomicrolite, oxycalciobetafite, oxyuranobetafite, fluornatroromite, fluorcalcioromte, oxycalcioromite, and oxyplumboromite. For these, there are only chemical or crystalstructure data. Type specimens need to be defined. Potential candidates for several other species exist, but are not sufficiently well characterized to grant them any official status. Ancient chemical data refer to wet-chemical analyses and commonly represent a mixture of minerals. These data were not used here. All data used represent results of electron-microprobe analyses or were obtained by crystal-structure refinement. We also verified the scarcity of crystal-chemical data in the literature. There are crystalstructure determinations published for only nine pyrochlore-supergroup minerals: hydropyrochlore, hydroxykenomicrolite, hydroxycalcioromite, hydrokenoelsmoreite, hydroxycalciopyrochlore, fluorcalciopyrochlore, kenoplumbomicrolite, oxycalciobetafite, and fluornatroromite. The following mineral names are now discarded: alumotungstite, bariomicrolite, bariopyrochlore, bindheimite, bismutomicrolite, bismutopyrochlore, bismutostibiconite, calciobetafite, ceriopyrochlore-(Ce), cesstibtantite, ferritungstite, jixianite, kalipyrochlore, monimolite, natrobistantite, partzite, plumbobetafite, plumbomicrolite, plumbopyrochlore, stannomicrolite, stetefeldtite, stibiconite, stibiobetafite, stibiomicrolite, strontiopyrochlore, uranmicrolite, uranpyrochlore, yttrobetafite-(Y), and yttropyrochlore-(Y).

Diphtheria toxoid conformation in the context of its nanoencapsulation within liposomal particles sandwiched by chitosan

Chitosan (alpha alpha-(1-4)-amino-2-deoxy-beta beta-D-glucan) is a deacetylated form of chitin, a polysaccharide from crustacean shells. Its unique characteristics, such as positive charge, biodegradability, biocompatibility, nontoxicity, and rigid structure, make this macromolecule ideal for an oral vaccine delivery system. We prepared reverse-phase evaporation vesicles (REVs) sandwiched by chitosan (Chi) and polyvinylic alcohol (PVA). However, in this method, there are still some problems to be circumvented related to protein stabilization. During the inverted micelle phase of protein nanoencapsulation, hydrophobic interfaces are expanded, leading to interfacial adsorption, followed by protein unfolding and aggregation. Here, spectroscopic and immunological techniques were used to ascertain the effects of the Hoffmeister series ions on diphtheria toxoid (Dtxd) stability during the inverted micelle phase. A correlation was established between the salts used in aqueous solutions and the changes in Dtxd solubility and conformation. Dtxd alpha alpha-helical content was quite stable, which led us to conclude that encapsulation occurred without protein aggregation or without exposition of hydrophobic residues. Dtxd aggregation was 98% avoided by the kosmotropic, PO

Predicting and characterizing new molecular species at a high-level theoretical approach: HSeCl, HClSe, and SeCl

New molecular species HSeCl, HClSe, and SeCl were investigated at a high level of theory, CCSD(T), with a series of correlation consistent basis sets with extrapolation to the CBS limit. Account has been taken for valence-only and core-valence correlation effects, and of anharmonic effects on the vibrational frequencies. HSeCl is 43.25 kcal mol (1) more stable than HClSe. A barrier (Delta G(#)) of 47.20 kcal mol (1) separates these species. Internuclear distances are generally overestimated by 0.008 angstrom in the valence-only correlation calculations. Inclusion of anharmonicity leads to much improved vibrational frequencies. For SeCl, we estimate Delta H(f) (0 K) = 23.96 and Delta H(f) (298.15 K) = 24.64 kcal mol (1); for HSeCl, we had 4.20 and 4.97 kcal mol (1), respectively. (C) 2010 Elsevier B.V. All rights reserved.

Structural and spectroscopic properties of the diazocarbene radical (CNN) and its ions CNN(+) and CNN(-): a high-level theoretical investigation

The diazocarbene radical, CNN, and the ions CNN(+) and CNN(-) were investigated at a high level of theory. Very accurate structural parameters for the states X(3)Sigma(-) and A(3)Pi of CNN, and X(2)Pi of both CNN(+) and CNN(-) were obtained with the UCCSD(T) method using correlated-consistent basis functions with extrapolations to the complete basis set limit, with valence only and also with all electrons correlated. Harmonic and anharmonic frequencies were obtained for all species and the Renner parameter and average frequencies evaluated for the Pi states. At the UCCSD(T)/CBS(T-5) level of theory, Delta(f)H(0 K) = 138.89 kcal/mol and Delta(f)H(298 K) = 139.65 kcal/mol were obtained for diazocarbene; for the ionization potential and the electron affinity of CNN, 10.969 eV (252.95 kcal/mol), and 1.743 eV (40.19 kcal/mol), respectively, are predicted. Geometry optimization was also carried out with the CASSCF/MRCI/CBS(T-5) approach for the states X(3)Sigma(-) A(3)Pi, and a(1)Delta of CNN, and with the CASSCF/MRSDCI/aug-cc-pVTZ approach for the states b(1)Sigma(+), c(1)Pi, d(1)Sigma(-), and B(3)Sigma(-), and excitation energies (T(e)) evaluated. Vertical energies were calculated for 15 electronic states, thus improving on the accuracy of the five transitions already described, and allowing for a reliable overview of a manifold of other states, which is expected to guide future spectroscopic experiments. This study corroborates the experimental assignment for the vertical transition X (3)Sigma(-) <- E (3)Pi.

Thiothionyl bromide (S=SBr2): The elusive isomer of dibromodisulfane (BrSSBr)

CCSD(T) with a series of correlation consistent basis up to quadruple-zeta is used to investigate the structures, vibrational spectra, relative stability, heats of formation, and barrier to isomerization of S=SBr2 and BrSSBr. It represents the most accurate and detailed characterization of these molecules to date. We show that the frequency mode at 302 cm(-1), detected in various studies and assigned to impurities by some authors, and to the anti-symmetric SBr stretch in BrSSBr by others, thus in fact corresponds to the anti-symmetric SBr stretch in the elusive S=SBr2 species; it thus corroborates and complements an earlier partial IR spectra study attributable to S=SBr2. Including corrections for relativistic and core-valence correlation effects, we also predict 26.33 (12.74) kcal/mol for Delta H-f (298.15 K) of S=SBr2 (BrSSBr). For the S=SBr2 -> BrSSBr reaction, our best estimates for the Gibbs free energy and the enthalpy of the reaction at 298.15 K are -13.71 and -13.44 kcal/mol, respectively. For a value of Delta G(#) equal to 23.52 kcal/mol, we estimate a TST rate constant, at 298.15 K, of 3.57 x 10(-5) s(-1). (c) 2007 Elsevier B.V. All rights reserved.

Reaction of a model siderophore with Ni(II), Co(II) and Zn(II) in aqueous solution: Kinetics and spectroscopy

A spectroscopic study was performed showing that the [Fe(III)(L(2-))(2)](1-) (L(2-) = dopacatecholate) complex reacts with Ni(II), Co(II) and Zn(II) in an aqueous solution containing S(2)O(3)(2-) resulting in the soluble [M(L(1-))(3)](1-) (L(1-) = dopasemiquinone; M = Ni(II), Co(II) or Zn(II) complex species. The Raman and IR spectra of the [CTA][M(L(1-))(3)] complexes, CTA hexadecyltrimethylammonium cation, in the solid state were obtained. The kinetic constants for the metal substitution reactions were determined at four different temperatures, providing values for Delta W(not equal) Delta S(not equal) and Delta G(not equal). The reactions were slow (k = 10(-1)1 M s(-1)) and endothermic. The system investigated can be considered as a simplified model to explain some aspects of siderophore chemistry. (c) 2007 Elsevier Inc. All rights reserved.

Effects of the partial replacement of La by M (M=Ce, Ca and Sr) in La(2-x)M(x)CuO(4) perovskites on catalysis of the water-gas shift reaction

The performance of La(2-x)M(x)CuO(4) perovskites (where M = Ce, Ca or Sr) as catalysts for the water-gas shift reaction was investigated at 290 degrees C and 360 degrees C. The catalysts were characterized by EDS, XRD, N(2) adsorption-desorption, XPS and XANES. The XRD results showed that all the perovskites exhibited a single phase (the presence of perovskite structure), suggesting the incorporation of metals in the perovskite structure. The XPS and XANES results showed the presence of Cu(2+) on the surface. The perovskites that exhibited the best catalytic performance were La(2-x)Ce(x)CuO(4) perovslcites, with CO conversions of 85%-90%. Moreover, these perovskites have higher surface areas and larger amounts of Cu on the surface. And Ce has a higher filled energy level than the other metals, increasing the energy of the valence band of Ce and providing more electrons for the reaction. Besides, the La(1.80)Ca(0.20)CuO(4) perovskite showed a good catalytic performance.

SEM, EPR and ToF-SIMS analyses applied to unravel the technology employed for pottery-making by pre-colonial Indian tribes from Pantanal, Brazil

The present work aims at elucidating the technology applied in the fabrication of ceramic objects by the ancient ceramists that inhabited the western border of Pantanal, Mato-Grosso do Sul, with the help of a multidisciplinary approach making use of chemical and physical methods of analysis. The potshards under study show the presence of different types of additives, as determined by scanning electron microscopy (SEM) and time of flight secondary ion mass spectrometry (ToF-SIMS). The dispersion of the additives within the ceramic matrix was also addressed by SEM, which shed light on the mounting technique used by the potters to assemble the ceramic vessels. Moreover, the tensile strength conferred to the pottery by the use of a specific type of additive was evaluated by applying a mechanical test. These results were correlated with the firing temperature of the potshards, determined by means of electron paramagnetic resonance (EPR). (C) 2010 Elsevier Ltd. All rights reserved.

Determinantes emocionais do compartilhamento entre consumidores online

O objetivo desta tese é contribuir com a análise das emoções, a partir dos papéis da valência e da excitação emocional, como influenciadoras do compartilhamento de informação entre consumidores online. Pessoas compartilham onversando ou utilizando ferramentas de compartilhamento de conteúdo na internet, como as redes sociais virtuais. O compartilhamento de conteúdo na internet leva a uma maior difusão, fazendo com que eles se viralizem, ou seja, sejam retransmitidos diversas vezes, atingindo diferentes públicos (HO; DEMPSEY, 2010). Ainda há dúvidas na literatura sobre as causas desta viralização, e o quanto as emoções influenciam o processo, articularmente se as pessoas tendem a compartilhar mais o que lhes é positivo, o que lhes causa mais excitação (BERGER; MILKMAN, 2012) ou se há um perfil específico de consumidor que se engaja mais nessas ações, como os chamados advogados de marca, e como tal perfil se comporta. Para investigar isso, foram conduzidos quatro experimentos: o primeiro comparou a propensão a compartilhar notícias de valências emocionais e excitações diferentes, o segundo relacionou a propensão a compartilhar propagandas e notícias com valências diferentes, o terceiro analisou como advogados de marca declarados agem com relação a conteúdo de diferentes valências e o quarto comparou a propensão a compartilhar de propagandas com diferentes valências e estímulos ao compartilhamento (nenhum, dica de um amigo ou participação em um sorteio). Os conteúdos de valência positiva que geraram maior excitação ou tidos como mais úteis seriam mais compartilhados, enquanto advogados de marca deram ênfase em suas respostas ao conteúdo negativo, negando-o, justificando-o ou se abstendo, e foram mais intensos ao reclamar de problemas que eles próprios sofreram. Os principais achados desta tese são que a) conteúdo online de valência positiva e de alta excitação tem maior probabilidade de ser compartilhado, porém b) conteúdo online de valência negativa é tido como mais útil e gera maior excitação. Além disso, c) se o conteúdo for referente a uma marca com que o consumidor é engajado, ele reagirá com respostas mais circunstanciadas e d) se o conteúdo lhe for indicado por um amigo, ele tem maior chance de compartilhar. A principal contribuição desta tese é auxiliar na compreensão, teórica e gerencial, do compartilhamento entre usuários, avaliando o 9 impacto de conteúdo excitante ou útil, seja de valência positiva ou negativa, permitindo às organizações dimensionar seus esforços de comunicação e de relacionamento com clientes, com vistas a selecionar as abordagens mais adequadas às mensagens

A culpa das mães como antecedente do consumo

A culpa, uma emoção de valência negativa, é objeto de interesse da literatura científica em comportamento do consumidor desde os anos 1990. Um grupo de pessoas especialmente susceptível ao sentimento de culpa são as mães, e o pressuposto desta dissertação é que esta emoção influencia suas decisões de consumo. O objetivo aqui é investigar se a culpa pode ser um antecedente do consumo, e para isso a pesquisa foi realizada por meio de métodos mistos sequenciais com mães de crianças entre 3 e 12 anos. A primeira fase foi um estudo exploratório qualitativo e a segunda foram dois experimentos em que foram testadas hipóteses sobre as relações entre: 1) Culpa da mãe em relação ao bem estar do filho e influência do filho nas decisões de consumo; 2) Culpa da mãe em relação ao bem estar do filho e atendimento aos pedidos de compra do filho; 3) Culpa da mãe em relação ao bem estar do filho e frequência com que a mãe compra produtos supérfluos para o filho; sendo estas últimas duas relações moderadas pelo estilo de consumo da mãe e pelo poder de insistência do filho. O primeiro experimento (técnica projetiva) comprovou as três hipóteses e o segundo experimento (questionamento direto) comprovou a terceira hipótese e sua moderação. Os diferentes resultados devem-se à escolha da estratégia de pesquisa utilizada, sendo que a técnica projetiva reduz as defesas das respondentes quando o tema abordado está sujeito a normas sociais (Fisher, 1998). Este estudo tem relevância pois trouxe evidências empíricas de que a culpa é um antecedente de consumo. Pode trazer insights para as mães e para os gestores sobre a relação entre culpa e consumo.

Aparências da forma e forma do espaço: análise da configuração espacial de residências unifamiliares dos anos 1970 em João Pessoa PB

Assuming that the form of a building shell and its content the spatial form are distinct dimensions of architecture - however indivisible and interdependent -, this study focus, in the light of the Social Logic of Space (HILLIER; HANSON, 1984), on the intrinsic properties through which domestic space was structured in a sample of single-family dwellings built in João Pessoa (PB) during the 1970s - when the vocabulary of modern architecture still prevailed in Brazil though sharing the urban scene with other architectural trends -, in order to investigate regularities or divergences underlying their conception. These dwellings were originally classified (ARAÚJO, 2010a) in five categories defined according to the form of their building shells and to their prevailing construction techniques: (1) Brazilian modern legacy (considered as truly Brazilian modern style); (2) Paulista architecture (that refers to the modern production of São Paulo, Brazil, from the 1950s through the 1970s); (3) experiences of rationalization and prefabrication ; (4) experiences of adaptation to the climate (referring to a design strongly influenced by the hot and humid climate of North-eastern Brazil); and (5) hybrid (to account for a kind of stylistic hybridism that includes formal attributes, which evoke our colonial past). This study aims to determine, through the analyses of nineteen cases that represent each category, whether this taxonomy corresponds to distinct modes of spatial configuration. This research therefore proposes an approach to the classification of domestic architecture based on topological properties. The dwellings spatial organization was represented, quantified and analyzed, their spatial properties explored in consonance with one another and with the literature. Results pointed out that there is no evidence of a reciprocal relationship between the formal look of the built shells and their respective spatial structures

Growth of the hermit crab Clibanarius vittatus (Bosc, 1802) (Crustacea, Anomura, Diogenidae) at São Vicente, São Paulo, Brazil

O presente estudo teve como objetivo analisar o crescimento de machos e fêmeas do ermitão Clibanarius vittatus (Bosc, 1802), da região de São Vicente, São Paulo, Brasil. Foram realizadas coletas mensais de maio/2001 a abril/2003, na Praia dos Pescadores em São Vicente. Os 2.501 animais capturados foram identificados, determinados quanto ao sexo e mensurados quanto ao seu comprimento de escudo cefalotorácico (CEC). Para o estudo sazonal do crescimento, a população foi dividida em classes de tamanho de 5mm de (CEC), e analisada pelo método de Bertalanffy, com o auxílio do software Fisat II. Foram obtidos 703 indivíduos machos e 1.798 fêmeas, com média de tamanho de 8.94±1.80 e 6.61±1.13mm, respectivamente. Constatou-se um padrão de crescimento sazonal, com machos atingindo um tamanho assintótico (14.92mm) superior ao das fêmeas (13.85mm), além de iniciarem o processo de crescimento aproximadamente cinco meses antes destas. Desta forma, é provável que este seja um padrão que auxilia na diminuição da disputa intra-específica por conchas, uma vez que os machos atingiram maior tamanho e estariam disponibilizando conchas menores para as fêmeas.

Biological features of a puzzling symbiotic association between the hermit crab Dardanus insignis and the porcellanid crab Porcellana Sayana (Crustacea)

The symbiotic lifestyle is widespread among porcellanid crabs, which maintain ecological and co-evolutionary associations with annelid polychaetes, poriferans, cnidarians, echinoderms, gastropod. mollusks, and other crustaceans such as shrimps and hermit crabs, among others. We investigated the ecological association between the hermit crab Dardanus insignis and the porcellanid Porcellana sayana, in southeastern Brazil. Porcellanid crabs, hermit crabs, and available shells were collected monthly from July 2001 to June 2003, with a shrimp boat equipped with two double-rig trawl nets. The majority of P. sayana specimens were collected in shells occupied by D. insignis (96.6%); a few were found in empty shells (3.4%). The catch of both symbionts and hosts increased with increasing depth, with the highest occurrence at 35 m. The F. sayana crabs of various sizes could be found solitary or forming aggregations of up to 14 individuals per host, showing no sex or size segregation. In spite of the high diversity of shell species occupied by the hermit crabs and also available in the field, only a few of them were also utilized by P. sayana. The majority (93%) of shells utilized by P. sayana also hosted other symbiont species, constituting the basis of extensive symbiotic complexes. Thus, the ecological relationship between D. insignis and P. sayana may be classified as a non-obligate and non-specific symbiosis that may also involve other facultative organisms such as sea anemones. (C) 2008 Elsevier B.V. All rights reserved.

Um estudo de aplicação das teorias da expectativa e da ancoragem na motivação para o desempemho de alunos do ensino médio

This thesis presents a study on Tversky & Kahneman s (1974) Anchoring theory, and Vroom s (1964) Expectance theory in the context of education and students motivation. It is surveyed 424 students of a secondary and agricultural technical school in Brazil Northeast (EAJ). The survey form try to capture the Vroom s Expectance Theory constructs of Valence, Instrumentality, Expectation and Motivational Force, and also the Tversky and Kahneman Anchoring effect in terms of grade expected. The main findings suggest that the minimum grade required by the school is much strong in driving the students motivation and performance than the Expectancy Theory. It was found that the different grades required drive the students to pursue different grade in the same way

Preparação e caracterização de um material híbrido, à base de vermiculita modificada com quitosana, para a remoção de íons de chumbo presentes em efluentes sintéticos

Actually, surveys have been developed for obtaining new materials and methodologies that aim to minimize environmental problems due to discharges of industrial effluents contaminated with heavy metals. The adsorption has been used as an alternative technology effectively, economically viable and potentially important for the reduction of metals, especially when using natural adsorbents such as certain types of clay. Chitosan, a polymer of natural origin, present in the shells of crustaceans and insects, has also been used for this purpose. Among the clays, vermiculite is distinguished by its good ion exchange capacity and in its expanded form enhances its properties by greatly increasing its specific surface. This study aimed to evaluate the functionality of the hybrid material obtained through the modification of expanded vermiculite with chitosan in the removal of lead ions (II) in aqueous solution. The material was characterized by infrared spectroscopy (IR) in order to evaluate the efficiency of modification of matrix, the vermiculite, the organic material, chitosan. The thermal stability of the material and the ratio clay / polymer was evaluated by thermogravimetry. To evaluate the surface of the material was used in scanning electron microscopy (SEM) and (BET). The BET analysis revealed a significant increase in surface area of vermiculite that after interaction with chitosan, was obtained a value of 21, 6156 m2 / g. Adsorption tests were performed according to the particle size, concentration and time. The results show that the capacity of removal of ions through the vermiculite was on average 88.4% for lead in concentrations ranging from 20-200 mg / L and 64.2% in the concentration range of 1000 mg / L. Regarding the particle size, there was an increase in adsorption with decreasing particle size. In fuction to the time of contact, was observed adsorption equilibrium in 60 minutes with adsorption capacity. The data of the isotherms were fitted to equation Freundlich. The kinetic study of adsorption showed that the pseudo second- order model best describes the adsorption adsorption, having been found following values K2=0,024 g. mg-1 min-1and Qmax=25,75 mg/g, value very close to the calculated Qe = 26.31 mg / g. From the results we can conclude that the material can be used in wastewater treatment systems as a source of metal ions adsorbent due to its high adsorption capacity