Synthesis and evaluation of lipophilic BTBP ligands for An/Ln separation in nuclear waste treatment: the effect of alkyl substitution on extraction properties and implications for ligand design

Four new 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) ligands, which contain either additional alkyl groups on the pyridine rings or seven-membered aliphatic rings attached to the triazine rings, have been synthesized, and the effects of the additional alkyl substitution in the 4- and 4′-positions of the pyridine rings on their extraction properties with LnIII and AnIII cations in simulated nuclear waste solutions have been studied. The speciation of ligand 13 with some trivalent lanthanide nitrates was elucidated by 1H NMR spectroscopic titrations and ESI-MS. Although 13 formed both 1:1 and 1:2 complexes with LaIII and YIII, only 1:2 complexes were observed with EuIII and CeIII. Quite unexpectedly, both alkyl-substituted ligands 12 and 13 showed lower solubilities in certain diluents than the unsubstituted ligand CyMe4-BTBP. Compared to CyMe4-BTBP, alkyl-substitution was found to decrease the rates of metal-ion extraction of the ligands in both 1-octanol and cyclohexanone. A highly efficient (DAm > 10) and selective (SFAm/Eu > 90) extraction was observed for 12 and 13 in cyclohexanone and for 13 in 1-octanol in the presence of a phase-transfer agent. The implications of these results for the design of improved extractants for radioactive waste treatment are discussed.

The "Fair trade nation": market-oriented development in devolved European regions

Scholars have largely ignored the roles played by government and public sector institutions in the fair trade movement. This article addresses the knowledge gap through examining government involvement in fair trade networks in the context of European devolution and the localization of international development action. Proposing a relational view of fair trade networks, and considering the Fair Trade Nation as a social category for development, it highlights how power sources outside the centralized nation-state permit a political community to associate itself with fair trade. Research from Wales demonstrates that government acts in a leadership role rather than as regulator, conferring political voice and finance while enhancing its international credentials and contributing to the politics of nation-building. Our conclusion is cautious; campaigners celebrate political commitment to fair trade embodied within the category of the Fair Trade Nation, but evidence suggests that government reliance on the market as a vehicle for decentralized development action is limited by how the Fair Trade Nation is currently executed.

Environmental oestrogens and breast cancer: long-term low-dose effects of mixtures of various chemical combinations

The incidence of breast cancer has risen worldwide to unprecedented levels in recent decades, making it now the major cancer of women in many parts of the world.1 Although diet, alcohol, radiation and inherited loss of BRCA1/2 genes have all been associated with increased incidence, the main identified risk factors are life exposure to hormones including physiological variations associated with puberty/pregnancy/menopause,1 personal choice of use of hormonal contraceptives2 and/or hormone replacement therapy.3–6 On this basis, exposure of the human breast to the many environmental pollutant chemicals capable of mimicking or interfering with oestrogen action7 should also be of concern.8 Hundreds of such environmental chemicals have now been measured in human breast tissue from a range of dietary and domestic exposure sources7 ,9 including persistent organochlorine pollutants (POPs),10 polybrominated diphenylethers and polybromobiphenyls,11 polychlorinated biphenyls,12 dioxins,13 alkyl phenols,14 bisphenol-A and chlorinated derivatives,15 as well as other less lipophilic compounds such as parabens (alkyl esters of p-hydroxybenzoic acid),16 but studies investigating any association between raised levels of such compounds and the development of breast cancer remain inconclusive.7–16 However, the functionality of these chemicals has continued to be assessed on the basis of individual chemicals rather than the environmental reality of long-term low-dose exposure to complex mixtures. This misses the potential for individuals to have high concentrations of different compounds but with a common mechanism of action. It also misses the complex interactions between chemicals and physiological hormones which together may act to alter the internal homeostasis of the oestrogenic environment of mammary tissue.

Laurdan Spectrum Decomposition as a Tool for the Analysis of Surface Bilayer Structure and Polarity: a Study with DMPG, Peptides and Cholesterol

The highly hydrophobic fluorophore Laurdan (6-dodecanoyl-2-(dimethylaminonaphthalene)) has been widely used as a fluorescent probe to monitor lipid membranes. Actually, it monitors the structure and polarity of the bilayer surface, where its fluorescent moiety is supposed to reside. The present paper discusses the high sensitivity of Laurdan fluorescence through the decomposition of its emission spectrum into two Gaussian bands, which correspond to emissions from two different excited states, one more solvent relaxed than the other. It will be shown that the analysis of the area fraction of each band is more sensitive to bilayer structural changes than the largely used parameter called Generalized Polarization, possibly because the latter does not completely separate the fluorescence emission from the two different excited states of Laurdan. Moreover, it will be shown that this decomposition should be done with the spectrum as a function of energy, and not wavelength. Due to the presence of the two emission bands in Laurdan spectrum, fluorescence anisotropy should be measured around 480 nm, to be able to monitor the fluorescence emission from one excited state only, the solvent relaxed state. Laurdan will be used to monitor the complex structure of the anionic phospholipid DMPG (dimyristoyl phosphatidylglycerol) at different ionic strengths, and the alterations caused on gel and fluid membranes due to the interaction of cationic peptides and cholesterol. Analyzing both the emission spectrum decomposition and anisotropy it was possible to distinguish between effects on the packing and on the hydration of the lipid membrane surface. It could be clearly detected that a more potent analog of the melanotropic hormone alpha-MSH (Ac-Ser(1)-Tyr(2)-Ser(3)-Met(4)-Glu(5)-His(6)-Phe(7)-Arg(8)-Trp(9)-Gly(10)-Lys(11)-Pro(12)-Val(13)-NH(2)) was more effective in rigidifying the bilayer surface of fluid membranes than the hormone, though the hormone significantly decreases the bilayer surface hydration.

Emplacement mechanism of the main granite pluton of the Lavras do Sul intrusive complex, South Brazil, determined by magnetic anisotropies

Magnetic fabric and rock magnetism studies were performed on apparently isotropic granite facies from the main intrusion of the Lavras do Sul Intrusive Complex pluton (LSIC, Rio Grande do Sul, South Brazil). This intrusion is roughly circular (similar to 12 x 13.5 km), composed of alkali-calcic and alkaline granitoids, with the latter occupying the margin of the pluton. Magnetic fabrics were determined by applying both anisotropy of low-field magnetic susceptibility (AMS) and anisotropy of anhysteretic remanent magnetization (AARM). The two fabrics are coaxial. The parallelism between AMS and AARM tensors excludes the presence of a single domain (SD) effect on the AMS fabric of the granites. Several rock-magnetism experiments performed in one specimen from each sampled site show that for all sites the magnetic susceptibility is dominantly carried by ferromagnetic minerals, while mainly magnetite carries the magnetic fabrics. Lineations and foliations in the granite facies were successful determined by applying magnetic methods. Magnetic lineations are gently plunging and roughly parallel to the boundaries of the pluton facies, except at the few sites in the central facies which have a radial orientation pattern. In contrast, the magnetic foliations tend to follow the contacts between the different granite facies. They are gently outerward-dipping inside the pluton, and become either steeply southwesterly dipping or vertical towards its margin. The lack of solid-state and subsolidus deformations at outcrop scale and in thin sections precludes deformation after full crystallization of the pluton. This evidence allows us to interpret the observed magnetic fabrics as primary in origin (magmatic) acquired when the rocks were solidified as a result of processes reflecting magma flow. The foliation pattern displays a dome-shaped form for the main LSIC-pluton. However, the alkaline granites which outcrop in the southern part of the studied area have an inward-dipping foliation, and the steeply plunging magnetic lineation suggests that this area could be part of a feeder zone. The magma ascent probably occurred due to ring-diking. (C) 2008 Elsevier B.V. All rights reserved.

Alkaloids from the Bark of Guatteria hispida and Their Evaluation as Antioxidant and Antimicrobial Agents

Phytochemical investigation of the bark of Guatteria hispida afforded three new alkaloids, 9-methoxy-O-methylmoschatoline (1), 9-methoxyisomoschatoline (2), and isocerasonine (3), along with 10 known alkaloids, 8-oxopseudopalmatine (4), O-methylmoschatoline (5), lysicamine (6), liriodenine (7), 10-methoxyliriodenine (8), nornuciferine (9), anonaine (10), xylopine (11), coreximine (12), and isocoreximine (13). The major compounds, 2, 6, 12, and 13, showed significant antioxidant capacity in the ORAC(FL), assay. Compounds 5, 6, and 7 were active against S. epidermidis and C. dubliniensis, with MIC values in the range 12.5-100 mu g mL(-1).

Low levels of methylmercury induce DNA damage in rats: protective effects of selenium

In this study we examined the possible antigenotoxic effect of selenium (Se) in rats chronically exposed to low levels of methylmercury (MeHg) and the association between glutathione peroxidase (GSH-Px) activity and DNA lesions (via comet assay) in the same exposed animals. Rats were divided into six groups as follows: (Group I) received water; (Group II) received MeHg (100 mu g/day); (Group III) received Se (2 mg/L drinking water); (Group IV) received Se (6 mg/L drinking water); (Group V) received MeHg (100 mu g/day) and Se (2 mg/L drinking water); (Group VI) received MeHg (100 mu g/day) and Se (6 mg/L drinking water). Total treatment time was 100 days. GSH-Px activity was determined spectrophotometrically and DNA damage was determined by comet assay. Mean GSH-Px activity in groups I, II, III, IV, V and VI were, respectively: 40.19 +/- A 17.21; 23.63 +/- A 6.04; 42.64 +/- A 5.70; 38.50 +/- A 7.15; 34.54 +/- A 6.18 and 41.39 +/- A 11.67 nmolNADPH/min/gHb. DNA damage was represented by a mean score from 0 to 300; the results for groups I, II, III, IV, V and VI were, respectively: 6.87 +/- A 3.27; 124.12 +/- A 13.74; 10.62 +/- A 3.81; 13.25 +/- A 1.76; 86.87 +/- A 11.95 and 76.25 +/- A 7.48. There was a significant inhibition of GSH-Px activity in group II compared with group I (P < 0.05). Groups V and VI did not show a difference in enzyme activity compared with groups III and IV, showing the possible protective action of Se. Comet assay presented a significant difference in DNA migration between group II and group I (P < 0.0001). Groups V and VI showed a significant reduction in MeHg-induced genotoxicity (P < 0.001) when compared with group II. A negative correlation (r = -0.559, P < 0.05) was found between GSH-Px activity and DNA lesion, showing that the greater the DNA damage, the lower the GSH-Px activity. Our findings demonstrated the oxidative and genotoxic properties of MeHg, even at low doses. Moreover, Se co-administration reestablished GSH-Px activity and reduced DNA damage.

Crystal and molecular structures of three 2-sulphur-substituted cyclohexanones studied by X-ray crystallography and by ab initio molecular orbital calculations

The conformational features of three 2-sulphur-substituted cyclohexanone derivatives, which differ in the number of sulphur-bound oxygen atoms, i.e. zero (I), one (II) and two (III), were investigated by single crystal X-ray crystallography and geometry optimized structures determined using Hartree-Fock method. In each of (I)-(III) an intramolecular S center dot center dot center dot O(carbonyl) interaction is found with the magnitude correlated with the oxidation state of the sulphur atom, i.e. 2.838(3) angstrom in (I) to 2.924(2) angstrom in (II) to 3.0973(18) angstrom in (III). There is an inverse relationship between the strength of this interaction and the magnitude of the carbonyl bond. The supramolecular aggregation patterns are primarily determined by C-H center dot center dot center dot O contacts and are similarly influenced by the number of oxygen atoms in the molecular structures. Thus, a supramolecular chain is found in the crystal structure of (I). With an additional oxygen atom available to participate in C-H center dot center dot center dot O interactions, as in (II), a two-dimensional array is found. Finally, a three-dimensional network is found for (III). Despite there being differences in conformations between the experimental structures and those calculated in the gas-phase, the S center dot center dot center dot O interactions persist. The presence of intermolecular C-H center dot center dot center dot O interactions involving the cyclohexanone-carbonyl group in the solid-state, disrupts the stabilising intramolecular C-H center dot center dot center dot O interaction in the energetically-favoured conformation. (I): C(12)H(13)NO(3)S, triclinic space group P (1) over bar with a = 5.392(3) angstrom b = 10.731(6) angstrom, c = 11.075(6) angstrom, alpha = 113.424(4)degrees, beta = 94.167(9)degrees, gamma = 98.444(6)degrees, V = 575.5(6) angstrom(3), Z = 2, R(1) = 0.052; (II): C(12)H(13)NO(4)S, monoclinic P2(1)/n, a = 7.3506(15) angstrom, b = 6.7814(14) angstrom, c = 23.479(5) angstrom, beta = 92.94(3)degrees, V = 1168.8(4) angstrom(3), Z = 4, R(1) = 0.046; (III): C(12)H(13)NO(5)S, monoclinic P2(1)/c, a = 5.5491(11) angstrom, b = 24.146(3) angstrom, c = 11.124(3) angstrom, beta = 114.590(10)degrees, V = 1355.3(5) angstrom(3), Z = 4, R(1) = 0.051.

Shiro, Burt and Phyllis, interviewed by Sam Levine on January 17, 2010: Audio Recording

Some of the themes discussed are: • Occupation—store, The Jefferson Hotel (2, 4-6, 11, 17-18) • Food (2) • Colby—Greek life (3, 7) • Military service (3-4) • Bar Mitzvah (6, 12) • Life in Waterville—Circus (6) • Anti-semitism (10-12) • Occupation—law (8-9) • Occupation—legislature (14) • Jewish education (12) • Synagogue (13) • Civic engagement—United Way (15) • Civic engagement (26-28) • Camp—Modin (18) • College—attendance (19) • Colby—football (20-21, 23, 30)

Shiro, Burt, and Phyllis, interviewed by Sam Levine on January 17, 2010: Transcript

Some of the themes discussed are: • Occupation—store, The Jefferson Hotel (2, 4-6, 11, 17-18) • Food (2) • Colby—Greek life (3, 7) • Military service (3-4) • Bar Mitzvah (6, 12) • Life in Waterville—Circus (6) • Anti-semitism (10-12) • Occupation—law (8-9) • Occupation—legislature (14) • Jewish education (12) • Synagogue (13) • Civic engagement—United Way (15) • Civic engagement (26-28) • Camp—Modin (18) • College—attendance (19) • Colby—football (20-21, 23, 30)

Avaliação dos serviços da rede Accor Hospitality na região do Grande ABC Paulista

Dissertação de Mestrado apresentada ao Programa de Pós-Graduação em Administração da Universidade Municipal de São Caetano do Sul - USCS

Julgamento moral pró-social de meninos e meninas de rua

A socialização e a educação contribuem na formação dos indivíduos e favorecem o desenvolvimento do julgamento moral pró-social. Tal enunciado tem sido apresentado por estudos realizados com indivíduos de nível sócio-econômico médio em países desenvolvidos. O desenvolvimento do julgamento moral pró-social de indivíduosde nível sócio-econômico baixo e de países subdesenvolvidos ainda precisa ser investigada. Portanto, este estudo tem como objetivos: (a) investigar o julgamento moral pró-social de indivíduos que vivem nas ruas e não frequentam escolas comparando-os com indivíduos de nível sócio-econômico baixo, que frequentam escolas; (b) investigar os índices de ajuda diferencial dos indivíduos entre os potenciais receptores de ajuda. Quarenta meninos(as) de rua e 40 meninos(as) de escolas da Rede Municipal, de 9-12 e 13-16 anos de idade, metade de cada gênero, foram submetidos, individualmente, à Entrevista de Julgamento Moral Pró-social de Eisenberg. Algumas questões adicionais foram incluídas para avaliar os índices de ajuda diferencial entre os receptores de ajuda. Foram obtidos dados de identificação dos sujeitos por meio de uma Entrevista Inicial. Os dados coletados foram submetidos a análises quantitativas (frequências e ANOVAs). Os resultados revelaram que há diferença significativa no nível de julgamento moral pró-social de meninos(as) de rua e de escola (F[1,72] = 5.80; p< .05). Há, ainda, diferença significativa no índice de ajuda diferencial entre os receptores de ajuda (F[5,360]= 116.91; p<.OOI) e uma interação significativa de condição de vida e faixa etária (F[I,72]= 10.56; p<.Ol). Algumas análises extra-hipóteses foram realizadas, investigando a ocorrência e a clareza de expressão do julgamento moral pró-social. Os resultados são discutidos e comparados à literatura da área e a conclusão apresenta uma proposta para educação pró-social dos indivíduos aplicada à escola e às instituições de atendimento aos(às) meninos(as) de ruas.

Perfil do atletismo do Rio Grande do Sul: características somáticas e motoras das categorias pré-mirim, mirim e menor

Este estudo teve por objetivo verificar as variáveis somato-motoras dos atletas de atletismo do Estado do Rio Grande do Sul, nas categorias pré-mirim (12 e 13 anos de idade), mirim (14 e 15 anos de idade) e menor (16 e 17 anos de idade), em ambos os sexos. Os atletas da amostra (63 do sexo masculino e 48 do sexo feminino) foram divididos em 3 grupos de provas: potência de membros inferiores (PMI), potência de membros superiores (PMS) e resistência (R), seguindo como critério os resultados obtidos em competições no ano de 2001. Foram realizadas 11 medidas somáticas, incluindo estatura, envergadura, massa corporal, pregas de adiposidade subcutâneas, diâmetros e perímetros. O somatotipo foi determinado de acordo com o método de Heath-Carter. Entre os testes utilizados, estão o teste do quadrado (agilidade), salto horizontal (força explosiva de membros inferiores), corrida de 20 metros (velocidade), arremesso de medicine ball de 2 kg (força explosiva de membros superiores), teste de sentar e alcançar – “sit and reach” (mobilidade articular), sit-ups (força-resistência abdominal 60 segundos). Para descrever os resultados foi utilizado a estatística descritiva usual, com médias e desvios-padrão; para as análises inferenciais, foi utilizada a analise de variância ANOVA. O programa estatístico utilizado foi o SPSS 8.0. No sexo feminino os resultados foram muito semelhantes, sugerindo um grupo muito homogêneo entre as atletas. Os atletas do sexo masculino apresentaram diferenças estatísticas, principalmente entre as categorias pré-mirim e mirim e entre as categorias pré-mirim e menor. As diferenças entre as categorias mirim e menor foram mínimas. Recomenda-se uma atenção maior para a variável de flexibilidade que apresentou valores inferiores aos das avaliações do Projeto Esporte Brasil (PROESP-BR). As variáveis somáticas são os principais fatores para a determinação dos grupos de provas, quando os atletas ingressam na categoria pré-mirim. Na mesma categoria,houve diferenças estatisticamentesignificantes em relação às variáveis motoras entre os grupos de provas (PMI, PMS, R).

Análise do processo de convergência de renda nos estados brasileiros: 1970-2005

Este artigo examina a hipótese de convergência de renda per capita entre os estados brasileiros no período de 1970 a 2005. Comentam-se os resultados encontrados para sigmaconvergência medida através de indicadores de desigualdade, como o índice de Theil e coeficiente de variação. Para testar a existência ou não de convergência aplica-se além da metodologia tradicional de beta convergência baseada em regressões de cross-section, a técnica de estimação de GMM em primeira diferença para painel dinâmico. Além disso, com a finalidade de obter a distribuição de renda de longo prazo da economia, utiliza-se a metodologia de cadeia de Markov proposta por Quah (1993). A conclusão do estudo é de que os estados brasileiros já estão muito próximos ao seu steady-state. A velocidade de convergência quando se utiliza o método de GMM eleva-se para 15%, enquanto os resultados obtidos para estudos de cross-section giram por volta de 1%.

Utilização do ultra-som para predição de características de carcaça em bovinos

Foram utilizados cento sessenta e dois animais, avaliados em dois anos para determinar a acurácia do ultra-som em estimar a espessura de gordura subcutânea (EGSC) e a área do músculo longissimus (AOLC) no sítio anatômico entre a 12ª e 13ª costelas. Dentro de vinte quatro horas antes do abate, foi medida por ultra-som a espessura de gordura subcutânea (EGSUS) e a área de músculo longissimus (AOLUS) utilizando uma eco câmera da Marca Aloka SSD 500V equipado com um transdutor de 17,2cm e 3,5MHz, no primeiro ano e de um Pie Medical Falcon 100 com transdutor de 18 cm e 3,5MHz no segundo ano. Os coeficientes de correlação simples entre as características medidas por ultra-som e a espessura de gordura subcutânea e área do músculo longissimus da carcaça foram de 0,95 e 0,96, respectivamente, considerando todos os animais. Correlações para EGSUS e EGSC foram iguais (0,95) entre os anos, enquanto as relações entre AOLUS e AOLC foram estreitamente relacionadas, de 0,96 no ano 1 e de 0,97, no ano 2. Diferenças entre medidas ultra-sônicas e da carcaça foram expressas em base atual (EDIFF e ADIFF) e em base absoluta (EDEV e ADEV). As médias da EDIFF e ADIFF indicaram que o ultra-som superestima a EGSC em 0,16mm e subestima a AOLC em 0,26cm² considerando ambos os anos. As médias globais da EDEV e ADEV, que são indicações da taxa média de erro, foram 0,34mm e 1,28cm², respectivamente.