Incorporation of PbF2 into Heavy Metal Oxide Borate Glasses. Structural Studies by Solid State NMR

A series of heavy metal oxide (HMO) glasses with composition 26.66B(2)O(3)-16GeO(2)-4 Bi2O3-(53.33-x)PbO-xPbF2 (0 <= x <= 40) were prepared and characterized with respect to their bulk (glass transition and crystallization temperatures, densities, molar volumes) and spectroscopic properties. Homogeneous glasses are formed up to x = 30, while crystallization of beta-PbF2 takes place at higher contents. Substitution of PbO by PbF2 shifts the optical band gap toward higher energies, thereby extending the UV transmission window significantly toward higher frequencies. Raman and infrared absorption spectra can be interpreted in conjunction with published reference data. Using B-11 and F-19 high-resolution solid state NMR as well as B-11/F-19 double resonance methodologies, we develop a quantitative structural description of this material. The fraction of four-coordinate boron is found to be moderately higher compared to that in glasses with the same PbO/B2O3 ratios, suggesting some participation of PbF2 in the network transformation process. This suggestion is confirmed by the F-19 NMR spectra. While the majority of the fluoride ions is present as ionic fluoride, similar to 20% of the fluorine inventory acts as a network modifier, resulting in the formation of four-coordinate BO3/2F- units. These units can be identified by F-19{B-11} rotational echo double resonance and B-11{F-19} cross-polarization magic angle spinning (CPMAS) data. These results provide the first unambiguous evidence of B-F bonding in a PbF2-modified glass system. The majority of the fluoride ions are found in a lead-dominated environment. F-19-F-19 homonuclear dipolar second moments measured by spin echo decay spectroscopy are quantitatively consistent with a model in which these ions are randomly distributed within the network modifier subdomain consisting of PbO, Bi2O3, and PbF2. This model, which implies both the features of atomic scale mixing with the network former borate species and some degree of fluoride ion clustering is consistent with all of the experimental data obtained on these glasses.

Investigation of Ground- and Excited-State Photophysical Properties of 5,10,15,20-Tetra(4-pyridyl)-21H,23H-porphyrin with Ruthenium Outlying Complexes

The present work employs a set of complementary techniques to investigate the influence of outlying Ru(II) groups on the ground- and excited-state photophysical properties of free-base tetrapyridyl porphyrin (H(2)TPyP). Single pulse and, pulse train Z-scan techniques used M association with laser flash photolysis, absorbance and fluorescence spectroscopy, and fluorescence decay measurements, allowed us to conclude that the presence of outlying Ru(II) groups causes significant changes on both electronic structure and vibrational properties of porphyrin. Such modifications take place mainly due to the activation of. nonradiative decay channels responsible for the emission, quenching, as well as by favoring some vibrational modes in the light absorption process, It is also observed that, differently from what happens when the Ru(II) is placed at the center of the macrocycle, the peripheral groups cause an increase of the intersystem crossing processes, probably due to the structural distortion of the ring that implies a worse spin orbit coupling, responsible for the intersystem crossing mechanism.

Synthesis of Carbon Nanomaterials through Up-Cycling Agricultural and Municipal Solid Wastes

This work addresses the synthesis of carbon nanomaterials (CNMs) by up-cycling common solid wastes. These feedstocks could supersede the use of costly and often toxic or highly flammable chemicals, such as hydrocarbon gases, carbon monoxide, and hydrogen, which are commonly used as feedstocks in current nanomanufacturing processes for CNMs. Agricultural sugar cane bagasse and corn residues, scrap tire chips, and postconsumer polyethylene (PE) and polyethylene terephthalate (PET) bottle shreddings were either thermally treated by sole pyrolysis or by sequential pyrolysis and partial oxidation. The resulting gaseous carbon-bearing effluents were then channeled into a heated reactor. CNMs, including carbon nanotubes, were catalytically synthesized therein on stainless steel meshes. This work revealed that the structure of the resulting CNMs is determined by the feedstock type, through the disparate mixtures of carbon-bearing gases generated when different feedstocks are pyrolyzed. CNM characterization was conducted by scanning and transmission electron microscopy as well as by Raman spectroscopy and by thermogravimetric analysis. Gas chromatography was used to characterize the gases in the synthesis chamber. This work demonstrated an alternative method for efficient manufacturing of CNMs using both biodegradable and nonbiodegradable agricultural and municipal carbonaceous wastes.

Evaluation of the capability of decentralized management of epidemiological surveillance in the state of Bahia

Evaluative research into the capability of decentralized management of epidemiological vigilance (EV) was conducted in the operational, organizational and sustainable dimensions in the state of Bahia, Brazil. The quantitative approach was used in the construction of a baseline, with primary data obtained through an online questionnaire answered by thirty-eight municipal EV managers. In the qualitative approach to analyze the context and assess the management capability of municipalities in two case studies, techniques adapted to the analysis of discursive practices were used. This was done through semi-structured interviews with managers of regional and municipal government, health workers and representatives of the municipal health council. The case studies showed that the municipality with enhanced management capability is that in which the manager has the greatest potential of using the resources of his position, in addition to his ability to control, negotiate and coordinate with other actors. Due to decentralization of EV, considering the shared nature of management between the three spheres of government, there is a marked variation in the management capability of municipalities, determined by social, economic, political inequalities and management mechanisms adopted.

Metropolitan and regional health planning: dilemmas of the Pact for Health in the Baixada Santista Metropolitan Area, Sao Paulo State, Brazil

This paper focuses on the relationship between metropolitan and regional health planning based on the processes of regionalization and the Pact for Health in the Baixada Santista Metropolitan Area, Sao Paulo State, Brazil. The method used was a case study in two stages, namely during initial implementation of the Pact for Health (2007) and the Regional Administration Committees (CGR) and in 2010. Municipal and regional health systems managers and the director of the Metropolitan Agency were interviewed, and records were analyzed from ten years of meetings of the Regional Inter-Administration Committee and the Regional Development Council. Four issues emerged: financing and infrastructure; health services utilization; inefficiency of the Regional Health Administration's instruments and decision-making levels; and the relationship between different levels in the Administration. Metropolitan health management remained as an underlying issue, appearing only incidentally or tangentially to regional management. Despite some limitations, the CGR has been legitimized as a space for regional health management.

On the Mechanisms of Triplet Excited State Population in 8-Azaadenine

The photophysics of 8-azaadenine (8-AA) has been studied with the CASPT2//CASSCF protocol and ANO-L double-zeta basis sets. Stationary equilibrium structures, surface crossings, minimum energy paths, and linear interpolations have been used to study possible mechanisms to populate the lowest triplet state, T-1 (3)(pi pi*), capable of sensitizing molecular oxygen. Our results show that two main mechanisms can occur after photoexcitation to the S-2 (1)(pi pi*) state. The first one is through the S-2/S-1 conical intersection (((1)pi pi*/(1)n pi*)(Cl)), leading to the S-1 ((1)n pi*) state minimum, (S-1 ((1)n pi*))(min), where a singlet-triplet crossing, ((1)n pi*/(3)pi pi*)(STC), is accessible. The second one starts with the ((1)pi pi*/(3)n pi*)(STC) at the (S-2((1)pi pi*))(min), from which the system can evolve to the (T-2 ((3)n pi*))(min), with subsequent population of the T-1 excited electronic state, due to the ((3)n pi*/(3)pi pi*)(Cl) conical intersection.

The dynamical state of galaxy groups and their luminosity content

We analyse the dependence of the luminosity function (LF) of galaxies in groups on group dynamical state. We use the Gaussianity of the velocity distribution of galaxy members as a measurement of the dynamical equilibrium of groups identified in the Sloan Digital Sky Survey Data Release 7 by Zandivarez & Martinez. We apply the Anderson-Darling goodness-of-fit test to distinguish between groups according to whether they have Gaussian or non-Gaussian velocity distributions, i.e. whether they are relaxed or not. For these two subsamples, we compute the (0.1)r-band LF as a function of group virial mass and group total luminosity. For massive groups, , we find statistically significant differences between the LF of the two subsamples: the LFs of groups that have Gaussian velocity distributions have a brighter characteristic absolute magnitude (similar to 0.3 mag) and a steeper faint-end slope (similar to 0.25). We detect a similar effect when comparing the LF of bright [M-0.1r(group) - 5log(h) < -23.5] Gaussian and non-Gaussian groups. Our results indicate that, for massive/luminous groups, the dynamical state of the system is directly related to the luminosity of its galaxy members.

Impact of the Manaus urban plume on trace gas mixing ratios near the surface in the Amazon Basin: Implications for the NO-NO2-O-3 photostationary state and peroxy radical levels

We measured the mixing ratios of NO, NO2, O-3, and volatile organic carbon as well as the aerosol light-scattering coefficient on a boat platform cruising on rivers downwind of the city of Manaus (Amazonas State, Brazil) in July 2001 (Large-Scale Biosphere-Atmosphere Experiment in Amazonia-Cooperative LBA Airborne Regional Experiment-2001). The dispersion and impact of the Manaus plume was investigated by a combined analysis of ground-based (boat platform) and airborne trace gas and aerosol measurements as well as by meteorological measurements complemented by dispersion calculations (Hybrid Single-Particle Lagrangian Integrated Trajectory model). For the cases with the least anthropogenic influence (including a location in a so far unexplored region similar to 150 km west of Manaus on the Rio Manacapuru), the aerosol scattering coefficient, sigma(s), was below 11 Mm(-1), NOx mixing ratios remained below 0.6 ppb, daytime O-3 mixing ratios were mostly below 20 ppb and maximal isoprene mixing ratios were about 3 ppb in the afternoon. The photostationary state (PSS) was not established for these cases, as indicated by values of the Leighton ratio, Phi, well above unity. Due to the influence of river breeze systems and other thermally driven mesoscale circulations, a change of the synoptic wind direction from east-northeast to south-southeast in the afternoon often caused a substantial increase of ss and trace gas mixing ratios (about threefold for sigma(s), fivefold for NOx, and twofold for O-3), which was associated with the arrival of the Manaus pollution plume at the boat location. The ratio F reached unity within its uncertainty range at NOx mixing ratios of about 3 ppb, indicating "steady-state" conditions in cases when radiation variations, dry deposition, emissions, and reactions mostly involving peroxy radicals (XO2) played a minor role. The median midday/afternoon XO2 mixing ratios estimated using the PSS method range from 90 to 120 parts per trillion (ppt) for the remote cases (sigma(s) < 11 Mm(-1) and NOx < 0.6 ppb), while for the polluted cases our estimates are 15 to 60 ppt. These values are within the range of XO2 estimated by an atmospheric chemistry box model (Chemistry As A Box model Application-Module Efficiently Calculating the Chemistry of the Atmosphere (CAABA/MECCA)-3.0).

Strategies and results of the oral cancer prevention campaign among the elderly in Sao Paulo, Brazil, 2001 to 2009

Objective. To describe the strategies and results obtained by the early diagnosis and prevention of an oral cancer campaign targeting the population aged 60 years or older developed since 2001 in the state of Sao Paulo. Methods. The main strategies used to develop the campaign were described based on the review of documents issued by the Health Ministry, National Cancer Institute, Sao Paulo State Health Department, Oncocentro Foundation of Sao Paulo, Sao Paulo City Health Department, School of Public Health at the University of Sao Paulo (USP), and Santa Marcelina Health Care Center. The impact of the campaign on the incidence of new cases of oral cancer in the target population was evaluated. Results. In 2001, 90 886 elderly were examined vs. 629 613 in 2009. The following strategies were identified: training of professionals, development of printed materials to guide municipal governments in developing the campaign and using standardized codes and criteria, guidelines for data consolidation, establishment of patient referral flows, practical training with a specialist at the basic health care unit after the follow-up examination of individuals presenting changes in soft tissues, and increase in the number of oral diagnosis services. Between 2005 and 2009, there was a significant reduction in the rate of confirmed cases of oral cancer per 100 000 individuals examined, from 20.89 to 11.12 (P = 0.00003). Conclusions. The campaign was beneficial to the oral health of the elderly and could be extended to include other age groups and regions of the country. It may also provide a basis for the development of oral cancer prevention actions in other countries, as long as local characteristics are taken into account.

Conhecimento histórico e crianças pequenas: parques infantis e escola municipal de educação infantil

Este artigo relata a experiência com o projeto "Os parques infantis de Mário de Andrade ontem e hoje", empreendido por todos os profissionais e crianças de uma escola municipal de Educação Infantil da cidade de São Paulo. A preocupação com o conhecimento histórico e as crianças da primeira infância e suas especificidades, numa perspectiva não-escolarizante e não-antecipatória do Ensino Fundamental, foi a tônica e um desafio. Procura aliar história e memória, estabelecendo relações entre História da Educação, história da escolarização de crianças pequenas e formação docente.

Epidemiological aspects of American cutaneous leishmaniasis and phlebotomine sandfly population, in the municipality of Monte Negro, State of Rondônia, Brazil

INTRODUCTION: This work was carried out on the purpose of identifying the species of phlebotomine sandflies in the municipality of Monte Negro, state of Rondonia, Brazil, that may have been transmitting the American cutaneous leishmaniasis (ACL), and concisely describe epidemiological aspects of disease. METHODS: The epidemiologic and socioeconomical indicators were obtained from government institutions and the local Municipal Secretary of Health. Phlebotomine sandflies were captured using CDC light traps between July 2006 to July 2008. The total of 1,240 of female sandflies were examined by PCR method directed to k-DNA. RESULTS: There has been a significant decrease in the incidence of ACL of about 50% over the last ten years in the municipality. A total of 1,935 specimens of 53 sandfly species were captured, three of the genus Brumptomyia genus and 50 of the genus Lutzomyia. The predominant species was Lutzomyia acanthopharynx, Lutzomyia whitmani, Lutzomyia geniculata and Lutzomyia davisi. None were positive for Leishmania sp. CONCLUSIONS: Four sandflies species were found in the State of Rondonia for the first time: Brumptomyia brumpti, Lutzomyia tarapacaensis, Lutzomyia melloi and Lutzomyia lenti. The presence of Lutzomyia longipalpis, was also captured. Socioeconomical improvement of Brazilian economy and the increase of environmental surveillance in the last 15 years collaborated in the decrease of people exposed to vectors, reducing the incidence of ACL.