In situ solid state NMR observation of the methanol-to-hydrocarbons (MTH) process over nanosized and microsized HZSM-5 zeolites

The formation of surface alkoxy species on nanosized HZSM-5 and microsized HZSM-5, after exposure to methanol and subsequent conversion to olefins, has been investigated by in situ solid state NMR. Compared to microsized HZSM-5 zeolite, the nanosized HZSM-5 zeolite was found to exhibit a higher affinity for trapping methanol species. Activation of the adsorbed methanol species resulted in the formation of various surface alkoxy species with different rigid characters, including the carboxylate-like surface species, as evidenced by deconvolution of the related spectra. The present results support the existence of the so-called carbon-pool in the conversion of methanol, which serves as the reaction precursor not only for the coupling of the species to form olefins, but also for uncontrolled polymerization to give coke on the surface. The nanosized HZSM-5 shows a distinct resistance to the formation of carbonaceous deposits on the surface.

The stability of nanosized HZSM-5 zeolite: a high-resolution solid-state NMR study

The thermal and hydrothermal stabilities of HZSM-5 zeolites with crystal sizes less than 100 nm have been studied by multinuclear solid-state NMR, combined with BET and XRD. As evidenced by Al-27 and Si-29 MAS as well as their corresponding cross-polarization/MAS NMR investigations, the thermal stability of nanosized HZSM-5 is not so good as that of microsized HZSM-5. This is due to two processes concerning dealumination and desilicification involved in the calcination of nanosized HZSM-5, while only the dealumination process is conducted in microsized HZSM-5 under the similar calcination process. The hydrothermal stability of nanosized HZSM-5 is, contrary to what was expected, not so bad as that of the microsized HZSM-5 in the course of steam treatment. The actual resistance of the hydrothermal stability to the crystal size of HZSM-5 can be ascribed to an active reconstruction of zeolitic framework through an effective filling of amorphous Si species into nanosized HZSM-5 during hydrothermal treatment. (C) 2001 Published by Elsevier Science B.V.

Effect of variations in acid properties of HZSM-5 on the coking behavior and reaction stability in butene aromatization

In order to investigate the effect of acid properties on the coke behavior and stability of butene aromatization, we prepared the AHZSM-5 samples with various acid properties by the methods of hydrothernial treatment and K addition. The reaction of butene aromatization was carried out at 350 degrees C and 0.5 MPa in a continuous flow fixed bed. The characterization of the fresh/coked catalysts with NH3-TPD, N-2 adsorption-desorption measurement, and TG techniques has shown that a large amount of acid sites (high acid density) of the AHZMS-5 catalyst can cause a large quantity of coke deposit and serious channel blockage, and so result in a rapid loss of aromatization activity. On the contrary, after a great reduction in strong acid sites of AHZSM-5 catalyst resulting from some K-modification, the presence of only many weak acid sites also could not lessen the formation of coke nor improve the reaction stability of butene aromatization. Interestingly, the simultaneous reduction in the strong and weak acid sites to a desirable level by hydrothermal treating the AHZSM-5 catalyst at a proper temperature can effectively suppress the coke formation and channel blockage, and thus improve its olefin aromatization stability. (c) 2005 Elsevier B.V. All rights reserved.

Comparação de interpoladores espaciais multivariados para precipitação pluvial anual no Estado de São Paulo.

O objetivo deste trabalho é incorporar a altitude como variável auxiliar na determinação do mapa de variabilidade espacial de precipitação pluvial para o Estado de São Paulo através da comparação de dois interpoladores geoestatístico multivariados (cokrigagem ordinária e cokrigagem colocalizada).

Caracterização dos solos da microbacia do Ribeirão Barro Branco, município de São José de Ubá - RJ.

O presente estudo refere-se à caracterização dos solos da microbacia do ribeirão Barro Branco no município de São José de Ubá, Rio de Janeiro, abrangendo uma área de cerca de 550 ha, como parte integrante do Projeto Modelagem Hidrológica apoiado pela FAPERJ. O resultado final deste estudo consistiu no Mapa Semidetalhado de Solos da microbacia de acordo com as normas preconizadas pela Embrapa Solos, com a utilização de geotecnologias e técnicas de mapeamento digital. Consiste na caracterização dos solos visando contribuir para o planejamento do uso e ocupação das terras de forma racional e sustentável. Como material básico, utilizou-se uma aerorrestituição na escala 1:10.000 que foi empregada para a geração de um modelo digital de elevação (MDE), tendo ainda o apoio de imagens do Sensor Geoeye-1 de 2010. Os resultados obtidos, além de permitirem uma visão geral sobre as características ambientais da área, contêm todos os critérios utilizados para distinção e classificação dos solos e uma descrição das principais classes de solos da área estudada, cuja distribuição espacial é representada em um mapa na escala 1:10.000. Este mapa é constituído por 25 unidades de mapeamento, que compõem uma legenda de identificação dos solos, individualizados até o 5º nível categórico do Sistema Brasileiro de Classificação de Solos (SiBCS), seguido de textura, tipo de horizonte A, fases de vegetação, relevo e, para solos pouco evoluídos, substrato geológico. As principais classes de solos identificadas foram: Argissolos Vermelhos; Argissolos Vermelho-Amarelos; Gleissolos, Argissolos Amarelos; Afloramentos de Rocha e Luvissolos. Os primeiros apresentando grande predomínio sobre as demais classes da área com ocorrência superior a 42% do total. O principal tipo de utilização agrícola nessa microbacia é com pastagens, em sua maioria em estágio avançado de degradação, devido à baixa capacidade de retenção de água no solo, a baixa fertilidade e o baixo nível de utilização de insumos e práticas de conservação de solos na área.

Evolução das exportações de manga e uva produzidas no Submédio do Vale do São Francisco no período de 2010-2014.

O objetivo deste trabalho foi analisar as estatísticas disponíveis para aferir a evolução, nos últimos 5 anos (2010-2014), das exportações das frutas de maior importância econômica para o Submédio do Vale do São Francisco, enfocando tanto o comportamento agregado quanto o mercado europeu e o americano. A base de dados usada foi a do sistema Aliceweb2, do Ministério do Desenvolvimento, Indústria e Comércio Exterior, (MDIC).

Early determinants of overweight and obesity at 5 years old in preschoolers from inner of Minas Gerais, Brazil

Introduction: Brazil is experiencing a nutritional transition characterized by a reduction in the prevalence of nutritional deficits and an increase in overweight and obesity, not only in adults but also in children and adolescents.Objectives: This study was designed to evaluate the factors associated with overweight and obesity in Brazilian 5-year-old preschoolers.Methods: A cross-sectional study of a cohort of 232 preschoolers born in Diamantina/Minas Gerais, Brazil, was undertaken. the data, including socioeconomic status, anthropometry, diet, previous history of the preschoolers and family history, were collected between July of 2009 and July of 2010. To identify the factors associated with overweight and obesity, a logistic regression and a hierarchical model were undertaken.Results: Overweight and obesity occurred in 17.2% of the preschoolers. After adjusting for mother's obesity, per capita income, protective food intake, weight gain at age 0-4 months and time spent playing, the factors associated with overweight and obesity that reached statistical significance were mother's obesity [OR = 3.12 (95% CI 1.41-6.91), P = 0.01], weight gain of more than 0.85 kg/month in the first four months of life [OR = 2.16 (95% CI 1.01-4.64), P = 0.041 and lower per capita income [OR = 0.32 (95 %CI 0.13-0.79), P = 0.01].Conclusion: the results show that more weight gain during the first four months of life and being born of mothers with obesity increased the odds of overweight/obesity in the preschoolers, while lower per capita income was a protective factor.

Cancer is essentially due to bad luck...but not so much if you don’t exercise or are overweight

2.241 JCR (2015) Q3, 140/213 Oncology, 45/80 Nutrition & dietetics

So different, yet so similar: meta-analysis and policy modeling of willingness to participate in clinical trials among Brazilians and Indians.

BACKGROUND: With the global expansion of clinical trials and the expectations of the rise of the emerging economies known as BRICs (Brazil, Russia, India and China), the understanding of factors that affect the willingness to participate in clinical trials of patients from those countries assumes a central role in the future of health research. METHODS: We conducted a systematic review and meta-analysis (SRMA) of willingness to participate in clinical trials among Brazilian patients and then we compared it with Indian patients (with results of another SRMA previously conducted by our group) through a system dynamics model. RESULTS: Five studies were included in the SRMA of Brazilian patients. Our main findings are 1) the major motivation for Brazilian patients to participate in clinical trials is altruism, 2) monetary reimbursement is the least important factor motivating Brazilian patients, 3) the major barrier for Brazilian patients to not participate in clinical trials is the fear of side effects, and 4) Brazilian patients are more likely willing to participate in clinical trials than Indians. CONCLUSION: Our study provides important insights for investigators and sponsors for planning trials in Brazil (and India) in the future. Ignoring these results may lead to unnecessary fund/time spending. More studies are needed to validate our results and for better understanding of this poorly studied theme.

5-α reductase inhibitors and prostate cancer prevention: where do we turn now?

With the lifetime risk of being diagnosed with prostate cancer so great, an effective chemopreventive agent could have a profound impact on the lives of men. Despite decades of searching for such an agent, physicians still do not have an approved drug to offer their patients. In this article, we outline current strategies for preventing prostate cancer in general, with a focus on the 5-α-reductase inhibitors (5-ARIs) finasteride and dutasteride. We discuss the two landmark randomized, controlled trials of finasteride and dutasteride, highlighting the controversies stemming from the results, and address the issue of 5-ARI use, including reasons why providers may be hesitant to use these agents for chemoprevention. We further discuss the recent US Food and Drug Administration ruling against the proposed new indication for dutasteride and the change to the labeling of finasteride, both of which were intended to permit physicians to use the drugs for chemoprevention. Finally, we discuss future directions for 5-ARI research.

Tillin, H. & Tyler-Walters, H., 2014. Assessing the sensitivity of subtidal sedimentary habitats to pressures associated with marine activities. Phase 2 Report – Literature review and sensitivity assessments for ecological groups for circalittoral and offshore Level 5 biotopes. JNCC Report No. 512B, 260 pp.

Human activities within the marine environment give rise to a number of pressures on seabed habitats. Improved understanding of the sensitivity of subtidal sedimentary habitats is required to underpin the management advice provided for Marine Protected Areas, as well as supporting other UK marine monitoring and assessment work. The sensitivity of marine sedimentary habitats to a range of pressures induced by human activities has previously been systematically assessed using approaches based on expert judgement for Defra Project MB0102 (Tillin et al. 2010). This previous work assessed sensitivity at the level of the broadscale habitat and therefore the scores were typically expressed as a range due to underlying variation in the sensitivity of the constituent biotopes. The objective of this project was to reduce the uncertainty around identifying the sensitivity of selected subtidal sedimentary habitats by assessing sensitivity, at a finer scale and incorporating information on the biological assemblage, for 33 Level 5 circalittoral and offshore biotopes taken from the Marine Habitat Classification of Britain and Ireland (Connor et al. 2004). Two Level 6 sub-biotopes were also included in this project as these contain distinctive characterising species that differentiate them from the Level 5 parent biotope. Littoral, infralittoral, reduced and variable salinity sedimentary habitats were excluded from this project as the scope was set for assessment of circalittoral and offshore sedimentary communities. This project consisted of three Phases. • Phase 1 - define ecological groups based on similarities in the sensitivity of characterising species from the Level 5 and two Level 6 biotopes described above. • Phase 2 - produce a literature review of information on the resilience and resistance of characterising species of the ecological groups to pressures associated with activities in the marine environment. • Phase 3 - to produce sensitivity assessment ‘proformas’ based on the findings of Phase 2 for each ecological group. This report outlines results of Phase 2. The Tillin et al., (2010) sensitivity assessment methodology was modified to use the best available scientific evidence that could be collated within the project timescale. An extensive literature review was compiled, for peer reviewed and grey literature, to examine current understanding about the effects of pressures from human activities on circalittoral and offshore sedimentary communities in UK continental shelf waters, together with information on factors that contribute to resilience (recovery) of marine species. This review formed the basis of an assessment of the sensitivity of the 16 ecological groups identified in Phase 1 of the project (Tillin & Tyler-Walters 2014). As a result: • the state of knowledge on the effects of each pressure on circalittoral and offshore benthos was reviewed; • the resistance, resilience and, hence, sensitivity of sixteen ecological groups, representing 96 characteristic species, were assessed for eight separate pressures; • each assessment was accompanied by a detailed review of the relevant evidence; Assessing the sensitivity of subtidal sedimentary habitats to pressures associated with human activities • knowledge gaps and sources of uncertainty were identified for each group; • each assessment was accompanied by an assessment of the quality of the evidence, its applicability to the assessment and the degree of concordance (agreement) between the evidence, to highlight sources of uncertainty as an assessment of the overall confidence in the sensitivity assessment, and finally • limitations in the methodology and the application of sensitivity assessments were outlined. This process demonstrated that the ecological groups identified in Phase 1 (Tillin & Tyler-Walters 2014) were viable groups for sensitivity assessment, and could be used to represent the 33 circalittoral and offshore sediments biotopes identified at the beginning of the project. The results of the sensitivity assessments show: • the majority of species and hence ecological groups in sedimentary habitats are sensitive to physical change, especially loss of habitat and sediment extraction, and change in sediment type; • most sedimentary species are sensitive to physical damage, e.g. abrasion and penetration, although deep burrowing species (e.g. the Dublin Bay prawn - Nephrops norvegicus and the sea cucumber - Neopentadactyla mixta) are able to avoid damaging effects to varying degrees, depending on the depth of penetration and time of year; • changes in hydrography (wave climate, tidal streams and currents) can significantly affect sedimentary communities, depending on whether they are dominated by deposit, infaunal feeders or suspension feeders, and dependant on the nature of the sediment, which is itself modified by hydrography and depth; • sedentary species and ecological groups that dominate the top-layer of the sediment (either shallow burrowing or epifaunal) remain the most sensitive to physical damage; • mobile species (e.g. interstitial and burrowing amphipods, and perhaps cumaceans) are the least sensitive to physical change or damage, and hydrological change as they are already adapted to unstable, mobile substrata; • sensitivity to changes in organic enrichment and hence oxygen levels, is variable between species and ecological groups, depending on the exact habitat preferences of the species in question, although most species have at least a medium sensitivity to acute deoxygenation; • there is considerable evidence on the effects of bottom-contact fishing practices and aggregate dredging on sedimentary communities, although not all evidence is directly applicable to every ecological group; • there is lack of detailed information on the physiological tolerances (e.g. to oxygenation, salinity, and temperature), habitat preferences, life history and population dynamics of many species, so that inferences has been made from related species, families, or even the same phylum; • there was inadequate evidence to assess the effects of non-indigenous species on most ecological groups, and Assessing the sensitivity of subtidal sedimentary habitats to pressures associated with human activities • there was inadequate evidence to assess the effects of electromagnetic fields and litter on any ecological group. The resultant report provides an up-to-date review of current knowledge about the effects of pressures resulting from human activities of circalittoral and offshore sedimentary communities. It provides an evidence base to facilitate and support the provision of management advice for Marine Protected Areas, development of UK marine monitoring and assessment, and conservation advice to offshore marine industries. However, such a review will require at least annual updates to take advantage of new evidence and new research as it becomes available. Also further work is required to test how ecological group assessments are best combined in practice to advise on the sensitivity of a range of sedimentary biotopes, including the 33 that were originally examined.

La evolución de destinos turísticos litorales consolidados. Análisis comparado de Balneario Camnoriú (Brasil) y Benidorm (España)

El objetivo de este trabajo consiste en estudiar la evolución de los destinos turísticos litorales consolidados a partir del análisis comparado entre Balneario Camboriú y Benidorm. Se trata de dos destinos localizados en contextos territoriales y turísticos diferentes, en los que se contrastan de manera empírica los indicadores de evolución de los destinos y se vinculan las dinámicas evolutivas con el modelo territorial-turístico resultante en cada destino. El análisis realizado permite contrastar los postulados de los modelos evolutivos clásicos (Butler, 1980) e incorporar los nuevos planteamientos de la geografía económica evolutiva. La investigación delimita cronológicamente los periodos de desarrollo de ambos destinos para identificar los factores con mayor incidencia en la evolución de los mismos. Una evolución marcada, fundamentalmente, por la ubicación geográfica, la planificación y gestión urbanoturística a diferentes escalas, la dependencia de determinados mercados emisores y la influencia de factores macroeconómicos. Un conjunto de factores interrelacionados que dibujan trayectorias dispares para los destinos analizados.

SO and CS observations of molecular clouds - II. Analysis and modelling of the abundance ratios - probing O-2/CO with SO/CS?

We here analyse the observational SO and CS data presented in Nilsson ct al. (2000). The SO/CS integrated intensity ratio maps are presented for 19 molecular clouds, together with tables of relevant ratios at strategic positions, where we have also observed (SO)-S-34 and/or (CS)-S-34. The SO/CS abundance ratio as calculated from an LTE analysis is highly varying within and between the sources. Our isotopomer observations and Monte Carlo simulations verify that this is not an artifact due to optical depth problems. The variation of the maximum SO/CS abundance ratio between the clouds is 0.2-7. The largest variations within a cloud are found for the most nearby objects, possibly indicating resolution effects. We have also performed time dependent chemical simulations. We compare the simulations with our observed SO/CS abundance ratios and suggest a varying oxygen to carbon initial abundance, differing temporal evolution, density differences and X-ray sources associated with young stellar objects as possible explanations to the variations. In particular, the observed variation of the maximum SO/CS abundance ratio between the clouds can be explained by using initial O/C+ abundance ratios in the range 1.3-2.5. We finally derive a relationship between the SO/CS and O-2/CO abundance ratios, which may be used as a guide to find the most promising interstellar O-2 search targets.

Enantioselective Rhodium-Catalyzed Alkylative Desymmetrization of 3,5-Dimethylglutaric Anhydride

A rhodium-catalyzed enantioselective cross-coupling of sp³ organozinc reagents and 3,5-dimethylglutaric anhydride has been developed to afford the corresponding products, syn-deoxypolypropionates, in excellent yields and enantioselectivities. This reaction has been developed so that both commercially available and in situ prepared organozinc reagents are competent coupling partners.