DMSO-Induced Denaturation of Hen Egg White Lysozyme

We report on the size, shape, structure, and interactions of lysozyme in the ternary system lysozyme/DMSO/water at low protein concentrations. Three structural regimes have been identified, which we term the ""folded"" (0 < phi(DMSO) < 0.7), ""unfolded"" (0.7 <= phi(DMSO) < 0.9), and ""partially collapsed"" (0.9 <= phi(DMSO) < 1.0) regime. Lysozyme resides in a folded conformation with an average radius of gyration of 1.3 +/- 0.1 nm for phi(DMSO) < 0.7 and unfolds (average R(g) of 2.4 +/- 0.1 nm) above phi(DMSO) > 0.7. This drastic change in the protein`s size coincides with a loss of the characteristic tertiary structure. It is preceded by a compaction of the local environment of the tryptophan residues and accompanied by a large increase in the protein`s overall flexibility. In terms of secondary structure, there is a gradual loss of alpha-helix and concomitant increase of beta-sheet structural elements toward phi(DMSO) = 0.7, while an increase in phi(DMSO) at even higher DMSO volume fractions reduces the presence of both a-helix and beta-sheet secondary structural elements. Protein-protein interactions remain overall repulsive for all values of phi(DMSO) An attempt is made to relate these structural changes to the three most important physical mechanisms that underlie them: the DMSO/water microstructure is strongly dependent on the DMSO volume fraction, DMSO acts as a strong H-bond acceptor, and DMSO is a bad solvent for the protein backbone and a number of relatively polar side groups, but a good solvent for relatively apolar side groups, such as tryptophan.

Raman spectra of acetonitrile in imidazolium ionic liquids

Raman spectra of dilute solutions of acetonitrile in ionic liquids reveal the characteristic features of ionic liquids` polarity. This is accomplished by investigating the Raman bandshape of the nu (CN) band, corresponding to the CN stretching mode of CH(3)CN, which is a very sensitive probe of the local environment. The amphiphilic nature of the CH(3)CN molecule allows us to observe the effect of electron pair acceptor and electron pair donor characteristics on ionic liquids. It has been found that the overall polarity of nine different ionic liquids based on 1-alkyl-3-methylimidazolium cations is more dependent on the anion than cation. The observed wavenumber shift of the nu (CN) band of CH(3)CN in ionic liquids containing alkylsulfate anions agrees with the significant different values previously measured for the dielectric constant of these ionic liquids. The conclusions obtained from the analysis of the nu (CN) band were corroborated by the analysis of the symmetric nu(1) (CD(3)) stretching mode of deuterated acetonitrile in different ionic liquids. Copyright (C) 2010 John Wiley & Sons, Ltd.

For profit social entrepreneurship: milestones to develop an efficient social venture

Inúmeras questões terríveis e alarmantes são ainda mal resolvidas, apesar da mobilização de ONGs para aliviá-los. Por muito tempo, o setor privado deu as costas a preocupações tal qual estas. Ate que um novo tipo de empreendedor revolucionário apareceu com um novo conceito para combater a pobreza. Mohamed Yunus desbravou empreendedorismo social quando criou a Grameen Bank 36 anos atrás: ele desafiou regras convencionais e estritas alugando dinheiro para Bengalis desmerecidos de credito, tudo isso obtendo lucro no mesmo tempo. Hoje, empreendedorismo social esta um fenômeno mas a maioria dos empreendedores do setor dos e meia ainda enfrentam dificuldades. A pesquisa acadêmica sobre o empreendedorismo social com fins lucrativos ainda está hesitante. O presente trabalho é uma modesta tentativa de analisar quais são os desafios que um empreendedor social com fins lucrativos enfrentará ao longo do caminho para criar seu empreendimento e sustentar os seus objetivos. O exame da literatura mostra que as dificuldades enfrentadas pelos empreendedores são devido a vários fatores, compreendo questões diretamente relacionadas a incerteza do mercado e o contexto local, questões organizacionais, de financiamento, de ética e questões relacionadas a resistência do modelo de negocio. As proposições derivando do exame da literatura foram confrontadas a casos concretos através de entrevistas com empreendedores sociais, investidores de impacto e instituições de apoio. Resultados da pesquisa corroboram as proposições do inicio mas enfatizam necessidade de resolver, com consideração cuidadosa, as questões relacionadas a incerteza do mercado e ao desenho duma governança adequada. A respeito da incerteza do mercado, a identificação das partes interessadas no empreendimento social e a adoção duma mentalidade eficaz para ajustar suposições iniciais para a realidade local, são um padrão chave de sucesso para o empreendimento social. No nível organizacional, a constituição dum time perito e comprometido junto com o desenho duma governança certa para equilibrar o desejo de obter lucro e a necessidade de sustentabilidade financeira é uma garantia de sucesso para o empreendedor social.

Uma proposta de slam com determinação de informações geométricas do ambiente

PEDROSA, Diogo P. F. ; MEDEIROS, Adelardo A. D. ; ALSINA, Pablo J. . Uma Proposta de SLAM com Determinação de Informações Geométricas do Ambiente. In: CONGRESSO BRASILEIRO DE AUTOMÁTICA, 16, Salvador, BA, 2006. Anais... Salvador: CBA, 2006. v. 1. p. 1704-1709

Efeitos das variáveis ambientais locais sobre a abundância, a riqueza e a biomassa da macrofauna de solo em um ecossistema semiárido no estado do rio grande do norte, nordeste do brasil

The soil macrofauna is influenced to several biotic and abiotic environmental factors, from changes in the physical environment to a variety of interactions among the species involved, affecting the patterns of biodiversity of soil fauna. The power and specificity of the mechanisms that act on soil organisms vary greatly depending on environmental conditions at different scales of space and time. The Caatinga has great spatial heterogeneity of vegetation, climate and soil, so the soil macrofauna would follow this local spatial variation in the environment? This study aimed to investigate the effects of local environmental variables on biological parameters (taxa richness, total abundance and biomass) of soil macrofauna in a fragment of caatinga in João Câmara, Rio Grande Norte, Northeast Brazil. The study was conducted in the Cauaçu farm, where a grid of 2000m x 500m was drawn, and later, 30 sampling points were randomly selected. The methodology used to collect the macrofauna was the TSBF method. We tested the effects of 10 environmental variables on macrofauna across the plots and across the layers of soil. The hypothesis that macrofauna soil responds to changes in the environment was not supported throughout the plots, but was confirmed to soil layers. The soil macrofauna shows a pattern of concentration in the surface layer and decreases considerably in the deeper layers. This pattern had significant and positive relationship with the aerial plant biomass and fine root stock. The aerial plant biomass releases plant necromass that accumulates in the surface layer, providing an important source of resource and shelter for soil macrofauna, explaining their greater abundance in this layer. The roots are used as a means for the arrival of nutrients to the soil from the primary production, thus a greater amount of root conditions higher food intake for macrofauna, especially the herbivores

Mapeamento de ambientes estruturados com extração de informações geométricas através de dados sensoriais

The objective of this thesis is proposes a method for a mobile robot to build a hybrid map of an indoor, semi-structured environment. The topological part of this map deals with spatial relationships among rooms and corridors. It is a topology-based map, where the edges of the graph are rooms or corridors, and each link between two distinct edges represents a door. The metric part of the map consists in a set of parameters. These parameters describe a geometric figure which adapts to the free space of the local environment. This figure is calculated by a set of points which sample the boundaries of the local free space. These points are obtained with range sensors and with knowledge about the robot s pose. A method based on generalized Hough transform is applied to this set of points in order to obtain the geomtric figure. The building of the hybrid map is an incremental procedure. It is accomplished while the robot explores the environment. Each room is associated with a metric local map and, consequently, with an edge of the topo-logical map. During the mapping procedure, the robot may use recent metric information of the environment to improve its global or relative pose

Prevalência e susceptibilidade antimicrobiana de Staphylococcusspp. em quadros de saúde e doença periodontal

The aim of this study was determine the prevalence and antimicrobial susceptibility of Staphylococcus spp. from patients with periodontal disease and periodontally healthy, correlate them with factors to host, local environment and traits of the diseases. To this, thirty adults from 19 to 55 years old were selected. They had not periodontal treatment and no antibiotic or antimicrobial was administered during three previous months. From these individuals, sites periodontally healthy, with chronic gingivitis and/or periodontitis were analyzed. Eighteen subgingival dental biofilm samples were collected through sterile paper points being six from each tooth randomly selected, representing conditions mentioned. They were transported to Oral Microbiology laboratory, plated onto Mannitol Salt Agar (MSA) and incubated at 370C in air for 48 h. Staphylococcus spp. were identified by colonial morphology, Gram stain, catalase reaction, susceptibility to bacitracin and coagulase activity. After identification, strains were submitted to the antibiotic susceptibility test with 12 antimicrobials, based on Kirby-Bauer technique. To establish the relation between coagulase-negative Staphylococcus (CSN) presence and their infection levels and host factors, local environment and traits of diseases were used Chi-square, Mann-Whitney and Kruskal-Wallis tests to a confidence level of 95%. 86,7% subjects harbored CSN in 11,7% periodontal sites. These prevalence were 12,1% in healthy sites, 11,7% in chronic gingivitis, 13,5% in slight chronic periodontitis, 6,75% in moderate chronic periodontitis and in sites with advance chronic periodontitis was not isolated CSN, without difference among them (p = 0,672). There was no significant difference to presence and infection levels of CSN as related to host factors, local environm ent and traits of the diseases. Amongst the 74 samples of CSN isolated, the biggest resistance was observed to penicillin (55,4%), erythromycin (32,4%), tetracycline (12,16%) and clindamycin (9,4%). 5,3% of the isolates were resistant to oxacilin and methicillin. No resistance was observed to ciprofloxacin, rifampicin and vancomycin. It was concluded that staphylococci are found in low numbers in healthy or sick periodontal sites in a similar ratio. However, a trend was observed to a reduction in staphylococci occurrence toward more advanced stages of the disease. This low prevalence was not related to any variables analyzed. Susceptibility profile to antibiotics demonstrates a raised resistance to penicillin and a low one to methicillin. To erythromycin, tetracycline and clindamycin was observed a significant resistance

A contribuição da asstênia técnica no desenvolvimento desenvolvimento de projetos de assentamento no estado do Rio Grande do Norte

The public policies must have as their aimed the primordial at improving quality of life of families of a given population, however, its performance must be constantly monitored and evaluated scoped to ascertain whether these policies are reaching those goals. This work consisted in search of bibliographies and analysis that addressed the historical evolution of the debate on the subject of agrarian reform in Brazil as public policy and on the policy of technical assistance and rural extension, and collecting data in loco, in order to assess whether the actions implemented under this latter contribute to improvements in local development of settlements projects (PA) land reform in the state of Rio Grande do Norte (RN), this given the constant presented criticisms regarding their effectiveness, considering that it is difficult to empirically differentiate settlements they received of those who did not receive the technical assistance services. In this way, was held the data collection for comparison of characteristics (social organization, relationship with the local environment, form of producing and evaluation of technical assistance services) of two settlements in RN, being one you have received the technical assistance services and another who has not had access to these services in the past five years, at least, to confirm whether those who had access to the above services presents best features of social organization and the relationship with the local environment, mainly, which was confirmed in the results obtained, which still demonstrated that no significant differences on the forma to produce and of commercialization in PA studied. It was also found that the problems faced by families settled in PA studied resemble those seen verified in many other Brazilian states, especially as to how to use natural resources in the areas of land reform and the instability of the availability of technical assistance services. Should be guaranteed at continuity and universality of technical assistance services to settlements, seeking a higher focus on productive issues, which provide the income necessary for families settled can have a better quality of life

Erbium-activated silica-zirconia planar waveguides prepared by sol-gel route

Er(3+) doped (100-x)SiO(2)-xZrO(2) planar waveguides were prepared by the sol-gel route, with x ranging from 10 up to 30 mol%. Multilayer films doped with 0.3 mol% Er(3+) ions were deposited on fused quartz substrates by the dip-coating technique. The thickness and refractive index were measured by m-line spectroscopy at different wavelengths. The fabrication protocol was optimized in order to confine one propagating mode at 1.5 mu m. Photoluminescence in the near and visible region indicated a crystalline local environment for the Er(3+) ion. (c) 2007 Elsevier B.V. All rights reserved.

Visible and near-infrared luminescent Eu3+ or Er3+ doped laponite-derived xerogels and thick films: Structural and spectroscopic properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Structure and crystallization of lanthanum fluorozirconate glasses

Glasses with compositions (1-x)ZrF4-xLnF(3), 0.2 less than or equal to x less than or equal to 0.4 and Ln = La or La, Eu have been synthesized and investigated using differential scanning calorimetry, X-ray diffraction, Raman scattering and Eu3+ optical spectroscopy. Single-phase polycrystalline lanthanum fluorozirconates with Zr/Ln ratio equal to 1, 2 and 3 have been investigated using the same techniques for comparison. The crystalline phases LnZrF(7), LnZr(2)F(11), LT-LnZr(3)F(15) (orthorhombic) and HT-LnZr(3)F(15) (trigonal) have been characterized in the recrystallized glasses and in samples spontaneously crystallized from the melt. Another phase has also been observed but remains undefined, the Raman scattering spectra of the vitreous samples are related to the vibration modes of [ZrF6] isolated octahedra, and of [ZrF7] and [ZrF8] structural units with bridging fluorine ions. The Eu3+ fluorescence data are related to a predominant local environment of the lanthanide ions in the glasses similar to that of the lanthanide in LnZrF(7).

Structural organization and thermal properties of the Sb2O3-SbPO4 glass system

The structural organization of Sb2O3-SbPO4 glasses has been studied by FTIR, Raman, P-31 MAS and spin echo NMR, Mossbauer and X-ray absorption spectroscopy (EXAFS and XANES at K and L-3,L-1-Sb edges). The combined results can be explained in terms of two potential mechanisms describing the change of the Sb(m) local environment upon incorporation of Q((4))-type phosphate. The formation of the latter species requires anionic compensation that may be adjusted by (a) formation of non bridging oxygen or (b) formation of SbO4E- groups (E = non-bonding electron pair). The second model is favored.

EXAFS, SAXS and Eu3+ luminescence spectroscopy of sol-gel derived siloxane-polyethyleneoxide hybrids

Hybrid Eu3+-doped silica-poliethyleneoxide (PEO) nanocomposites with covalent bonds between the inorganic (siloxane) and organic (PEO) phases have been obtained by sol-gel process. These materials are transparent, flexible and present high Eu3+ luminescence output. Their luminescence properties, local environment around europium ions and structure have been investigated as a function of europium content. EXAFS measurements indicate that the increase in Eu-doping induces a decrease in Eu3+ coordination number. An increase in symmetry degree around the metal ion is also observed for increasing Eu3+ concentration, while non radiative decay paths from the D-5(0) excited state become more important. SAXS results suggest the preferential interaction of europium ions with ether-type oxygens of the polymer chains. However, the existence of interactions between the cations and the carbonyl groups from urea bridges located at the siloxane-PEO interface can not be excluded.

White light emission of Eu3+-based hybrid xerogels

The luminescence spectra and extended x-ray-absorption fine-structure (EXAFS) measurements of a series of Eu3+-based organic/inorganic xerogels were reported and related to the local coordination of the lanthanide cations. The hybrid matrix of these organically modified silicates, classed as U(2000) ureasils, is a siliceous network to which short organic chains containing oxyethylene units are covalently grafted by means of urea bridges. The luminescent centers were incorporated as europium triflate, Eu(CF3SO3)3, and europium bromide, EuBr3, with concentrations 200≥n≥20 and n=80, 40, and 30, respectively - where n is the number of ether oxygens in the polymer chains per Eu3+ cation. EXAFS measurements were carried out in some of the U(2000)nEu(CF3SO3)3 xerogels (n=200, 80, 60, and 40). The obtained coordination numbers N ranging from 12.8, n=200, to 9.7, n=40, whereas the average Eu3+ first neighbors distance R is 2.48-2.49 Å. The emission spectra of these multiwavelength phosphors superpose a broad green-blue band to a series of yellow-red narrow 5D0→7F0-4 Eu3+ lines and to the eye the hybrids appeared to be white, even at room temperature. The ability to tune the emission of the xerogels to colors across the chromaticity diagram is achieved by changing the excitation wavelength and the amount of salt incorporated in the hybrid host. The local environment of Eu3+ is described as a continuous distribution of closely similar low-symmetry network sites. The cations are coordinated by the carbonyl groups of the urea moieties, water molecules, and, for U(2000)nEu(CF3SO3)3, by the SO3 end groups of the triflate anions. No spectral evidences have been found for the coordination by the ether oxygens of the polyether chains. A mean radius for the first coordination shell of Eu3+ is calculated on the basis of the emission energy assignments. The results obtained for U(2000)nEu(CF3SO3)3, 2.4 Å for 90 ≥n≥40 and 2.6 and 2.5 Å for n=30 and 20, respectively, are in good agreement with the values calculated from EXAFS measurements. The energy of the intraconfigurational charge-transfer transitions, the redshift of the 5D0→7F0 line, with respect to the value calculated for gaseous Eu3+, and the hypersensitive ratio between the 5D0→7F2 and 5D0→7F1 transitions, point out a rather low covalency nature of the Eu3+ first coordination shell in these xerogels, comparing to the case of analogous polymer electrolytes modified by europium bromide. ©1999 The American Physical Society.

Coordination of Eu3+ ions in siliceous nanohybrids containing short polyether chains and bridging urea cross-links

Infrared and photoluminescence spectroscopies have been used to investigate the local environment of the Eu3+ ions in luminescent sol-gel derived materials-di-ureasils-based on a hybrid framework represented by U(600). This host is composed of a siliceous backbone grafted, through urea cross-links, to both ends of polymer segments incorporating 8.5 oxyethylene repeat units. The active centers have been introduced as europium perchlorate, Eu(ClO4)3. Samples with compositions n = 232, 62, 23, 12, and 6 (where n denotes the ratio of (OCH2CH2) moieties per lanthanide ion) have been examined. The combination of the information retrieved from the analysis of characteristic bands of the FTIR spectra-the perchlorate and the Amide I/Amide II features-with that obtained from the photoluminescence data demonstrates that at compositions n = 232 and 62 the anions are free, whereas the Eu3+ ions are complexed by the heteroatoms of the polyether chains. At higher salt concentration, the cations are bonded, not only to the ClO4 - ions, but also to the ether oxygen atoms of the organic segments and to the carbonyl oxygen atoms of the urea linkages. The dual behavior of U(600) with respect to cation coordination has been attributed to the presence in this nanohybrid of strong hydrogen-bonded urea-urea structures, which, at low salt content, cannot be disrupted, thus inhibiting the formation of Eu3+-O=C(urea) contacts and promoting the interaction between the lanthanide ions and the (OCH2CH2) moieties. The present work substantiates the claim that the activation of the coordinating sites of the di-ureasil framework can be tuned by varying either the guest salt concentration at constant chain length or the length of the.organic segments at constant salt concentration. This relevant property opens challenging new prospects in the fields of application of this class of hybrids. © 2001 American Chemical Society.