In vitro gas production and nitrogen degradability of tannin-containing tree fruits in response to incremental levels of polyethylene glycol

This study was designed to determine the response of in vitro fermentation parameters to incremental levels of polyethylene glycol (PEG) when tanniniferous tree fruits (Dichrostachys cinerea, Acacia erioloba, A. erubiscens, A. nilotica and Piliostigma thonningii) were fermented using the Reading Pressure Technique. The trivalent ytterbium precipitable phenolics content of fruit substrates ranged from 175 g/kg DM in A. erubiscens to 607 g/kg DM in A. nilotica, while the soluble condensed tannin content ranged from 0.09 AU550nm/40mg in A. erioloba to 0.52 AU550nm/40 mg in D. cinerea. The ADF was highest in P. thonningii fruits (402 g/kg DM) and lowest in A. nilotica fruits (165 g/kg DM). Increasing the level of PEG caused an exponential rise to a maximum (asymptotic) for cumulative gas production, rate of gas production and nitrogen degradability in all substrates except P. thonningii fruits. Dry matter degradability for fruits containing higher levels of soluble condensed tannins (D. cinerea and P. thonningii), showed little response to incremental levels of PEG after incubation for 24 h. The minimum levels of PEG required to maximize in vitro fermentation of tree fruits was found to be 200 mg PEG/g DM of sample for all tree species except A. erubiscens fruits, which required 100 mg PEG/g DM sample. The study provides evidence that PEG levels lower than 1 g/g DM sample can be used for in vitro tannin bioassays to reduce the cost of evaluating non-conventional tanniniferous feedstuffs used in developing countries in the tropics and subtopics. The use of in vitro nitrogen degradability in place of the favoured dry matter degradability improved the accuracy of PEG as a diagnostic tool for tannins in in vitro fermentation systems.

Effect of water-soluble polymers, polyethylene glycol and poly(vinylpyrrolidone),on the gelation of aqueous micellar solutions of Pluronic copolymer F127

The micellization of F127 (E98P67E98) in dilute aqueous solutions of polyethylene glycol (PEG6000 and PEG35000) and poly(vinylpyrrolidone) (PVP K30 and PVP K90) is studied. The average hydrodynamic radius (rh,app) obtained from the dynamic light scattering technique increased with increase in PEG concentration but decreased on addition of PVP, results which are consistent with interaction of the micelles with PEG and the formation of micelles clusters, but no such interaction occurs with PVP. Tube inversion was used to determine the onset of gelation. The critical concentration of F127 for gelation increased on addition of PEG and of PVP K30 but decreased on addition of PVP K90. Small-angle X-ray scattering (SAXS) was used to show that the 30 wt% F127 gel structure (fcc) was independent of polymer type and concentration, as was the d-spacing and so the micelle hard-sphere radius. The maximum elastic modulus (G0 max) of 30 wt% F127 decreased from its value for water alone as PEG was added, but was little changed by adding PVP. These results are consistent with the packed-micelles in the 30 wt% F127 gel being effectively isolated from the polymer solution on the microscale while, especially for the PEG, being mixed on the macroscale.

The development of organized structures in polyethylene crystallized from a sheared melt, analyzed by WAXS and TEM

The development of global orientation and morphological features in linear polyethylene crystallizing from a sheared melt are studied using in-situ time-resolving wide angle X-ray scattering (WAXS) and ex-situ transmission electron microscopy. It is found that samples subjected to a shear rate above a critical value of ~1s-1 result in macroscopically oriented structures in the crystallized sample. This critical shear rate appears to be independent of the differences in molecular weight distribution of the samples studied although the morphologies which develop are sensitive to quite small differences in molecular weight distributions. The presence of shish kebabs in the morphology is shown to differ markedly according to variations in the upper molecular weight fraction of the molecular weight distribution, even though the resulting global orientation does not. The WAXS also reveals that areas which evidence no row nucleated structures still realize high degrees of molecular orientation. It is proposed that the formation of shish kebab or lamellar morphologies in these samples is dependent on the critical density of contiguous elongated crystallization nuclei rather than any specific global criteria.

A complete atomistic model of molten polyethylene from neutron scattering data: a new methodology for polymer structure

A new approach to the study of the local organization in amorphous polymer materials is presented. The method couples neutron diffraction experiments that explore the structure on the spatial scale 1–20 Å with the reverse Monte Carlo fitting procedure to predict structures that accurately represent the experimental scattering results over the whole momentum transfer range explored. Molecular mechanics and molecular dynamics techniques are also used to produce atomistic models independently from any experimental input, thereby providing a test of the viability of the reverse Monte Carlo method in generating realistic models for amorphous polymeric systems. An analysis of the obtained models in terms of single chain properties and of orientational correlations between chain segments is presented. We show the viability of the method with data from molten polyethylene. The analysis derives a model with average C-C and C-H bond lengths of 1.55 Å and 1.1 Å respectively, average backbone valence angle of 112, a torsional angle distribution characterized by a fraction of trans conformers of 0.67 and, finally, a weak interchain orientational correlation at around 4 Å.

Carbon nanotubes in electrospun polyethylene oxide nanofibres: a potential route to conducting nanofibres

Polyethylene oxide solution containing multi-walled carbon nanotubes have been electrospun onto a rotating collector to produce highly aligned arrays of electrospun nanofibers ranging in diameters from (200 – 360) nanometres. The addition of a surfactant (Triton X-100)is highly effective in dispersing carbon nanotube within an aqueous solution of polyethylene oxide and the resulting mixture can be electrospun without excessive clumping to produce nanofibers containing high loadings of nanotubes; in this case up to 5% wt thereby providing an effective route to electrically conductive nanofibres.

Determination of volatile organic compounds in recycled polyethylene terephthalate and high-density polyethylene by headspace solid phase microextraction gas chromatography mass spectrometry to evaluate the efficiency of recycling processes

A method for the determination of volatile organic compounds (VOCs) in recycled polyethylene terephthalate and high-density polyethylene using headspace sampling by solid-phase microextraction and gas chromatography coupled to mass spectrometry detection is presented. This method was used to evaluate the efficiency of cleaning processes for VOC removal from recycled PET. In addition, the method was also employed to evaluate the level of VOC contamination in multilayer packaging material containing recycled HDPE material. The optimisation of the extraction procedure for volatile compounds was performed and the best extraction conditions were found using a 75 mu m carboxen-polydimethylsiloxane (CAR-PDMS) fibre for 20 min at 60 degrees C. The validation parameters for the established method were linear range, linearity, sensitivity, precision (repeatability), accuracy (recovery) and detection and quantification limits. The results indicated that the method could easily be used in quality control for the production of recycled PET and HDPE. (C) 2011 Elsevier B.V. All rights reserved.

Investigation by Combined Solid-State NMR and SAXS Methods of the Morphology and Domain Size in Polystyrene-b-Polyethylene Oxide-b-Polystyrene Triblock Copolymers

The microphase structure of a series of polystyrene-b-polyethylene oxide-b-polystyrene (SEOS) triblock copolymers with different compositions and molecular weights has been studied by solid-state NMR, DSC, wide and small angle X-ray scattering (WAXS and SAXS). WAXS and DSC measurements were used to detect the presence of crystalline domains of polyethyleneoxide (PEO) blocks at room temperature as a function of the copolymer chemical composition. Furthermore, DSC experiments allowed the determination of the melting temperatures of the crystalline part of the PEO blocks. SAXS measurements, performed above and below the melting temperature of the PEO blocks, revealed the formation of periodic structures, but the absence or the weakness of high order reflections peaks did not allow a clear assessment of the morphological structure of the copolymers. This information was inferred by combining the results obtained by SAXS and (1)H NMR spin diffusion experiments, which also provided an estimation of the size of the dispersed phases of the nanostructured copolymers. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48:55-64,2010

Surface esterification of cellulose fibres: Processing and characterisation of low-density polyethylene/cellulose fibres composites

Low-density polyethylene was filled with cellulose fibres from sugar cane bagasse obtained from organosolv/supercritical carbon dioxide pulping process. The fibres were also used after chemical modification with octadecanoyl and dodecanoyl chloride acids. The morphology, thermal properties, mechanical properties in both the linear and nonlinear range, and the water absorption behaviour of ensuing composites were tested. The evidence of occurrence of the chemical modification was checked by X-ray photoelectron spectrometry. The degree of polymerisation of the fibres and their intrinsic properties (zero tensile strength) were determined. It clearly appeared that the surface chemical modification of cellulose fibres resulted in improved interfacial adhesion with the matrix and higher dispersion level. However, composites did not show improved mechanical performances when compared to unmodified fibres. This surprising result was ascribed to the strong lowering of the degree of polymerisation of cellulose fibres (as confirmed by the drastic decrease of their zero tensile strength) after chemical treatment despite the mild conditions used. (c) 2007 Elsevier Ltd. All rights reserved.

Extrusion and characterization of functionalized cellulose whiskers reinforced polyethylene nanocomposites

The surface of ramie cellulose whiskers has been chemically modified by grafting organic acid chlorides presenting different lengths of the aliphatic chain by an esterification reaction. The occurrence of the chemical modification was evaluated by FTIR and X-ray photoelectron spectroscopies, elemental analysis and contact angle measurements. The crystallinity of the particles was not altered by the chain grafting, but it was shown that covalently grafted chains were able to crystallize at the cellulose surface when using C18. Both unmodified and functionalized nanoparticles were extruded with low density polyethylene to prepare nanocomposite materials. The homogeneity of the ensuing nanocomposites was found to increase with the length of the grafted chains. The thermomechanical properties of processed nanocomposites were studied by differential scanning calorimetry (DSC), dynamical mechanical analysis (DMA) and tensile tests. A significant improvement in terms of elongation at break was observed when sufficiently long chains were grafted on the surface of the nanoparticles. It was ascribed to improved dispersion of the nanoparticles within the LDPE matrix. (C) 2009 Elsevier Ltd. All rights reserved.

Análise de contratos de private equity & venture capital : o alinhamento dos interesses entre fundos investidores de PE/VC e empresários nas empresas investidas no contexto institucional brasileiro

Nas economias desenvolvidas, especialmente nos Estados Unidos, a indústria de Private Equity & Venture Capital, que vive o seu segundo ciclo de expansão no Brasil, representa importante fonte de crescimento e dinamização da atividade econômica, através do fomento do empreendedorismo e da inovação tecnológica. Como tal, o estudo da adaptabilidade deste mecanismo a diferentes ambientes jurídico-institucional merece crescente atenção. A complexidade dos chamados contratos incompletos pelas incertezas e assimetrias de informações intrínsecas a estas operações, aliado ao estabelecimento de estruturas de incentivos ótimas que remunerem e protejam adequadamente tanto o investidor quanto o empreendedor, pode ser um fator limitante da expansão do modelo de PE/VC em determinadas geografias. Estas limitações seriam maiores nos países com sistemas legais e instituições menos adaptáveis ao modelo norte-americano de PE/VC. O objetivo central deste trabalho é estudar modelos de financial contract praticados no Brasil entre fundos de PE/VC e empresas investidas em diferentes estágios de maturação; visando a identificar como, se é que existem, condições impeditivas do nosso ambiente jurídico-institucional à celebração de contratos mais eficientes. À luz das teorias em financial contracting e das peculiaridades do ambiente jurídico-institucional brasileiro avaliar-se-á a adequação das estruturas contratuais mais utilizadas em operações de PE/VC no Brasil comparadas aos modelos e às estruturas contratuais mais praticados internacionalmente. De posse destes insights, aplicar-se-á questionário junto a operadores da indústria (gestores de fundos de PE/VC) para identificar suas percepções no tocante às limitações impostas pelo ambiente jurídico-institucional. E se há, na visão deles, um modelo / estrutura de contrato mais recomendado para operações de PE/VC.

Novel catalyst systems based on Ni(II), Ti(IV), and Cr(III) complexes for oligo-and polymerization of ethylene

The complex of Brookhart Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6- diisopropylphenyl)-acenaphthenediimine) has been characterized after impregnation on silica (S1) and MAO-modified silicas (4.0, 8.0 and 23.0 wts.% Al/SiO2 called S2, S3 and S4, respectively). The treatment of these heterogeneous systems with MAO produces some active catalysts for the polymerization of the ethylene. A high catalytic activity has been gotten while using the system supported 1/S3 (196 kg of PE/mol[Ni].h.atm; toluene, Al/Ni = 1000, 30ºC, 60 min and atmospheric pressure of ethylene). The effects of polymerization conditions have been tested with the catalyst supported in S2 and the best catalytic activity has been gotten with solvent hexane, MAO as cocatalyst, molar ratio Al/Ni of 1000 and to the temperature of 30°C (285 kg of PE/mol[Ni].h.atm). When the reaction has been driven according to the in situ methodology, the activity practically doubled and polymers showed some similar properties. Polymers products by the supported catalysts showed the absence of melting fusion, results similar to those gotten with the homogeneous systems by DSC analysis. But then, polymers gotten with the transplanted system present according to the GPC’s curves the polydispersity (MwD) varies between 1.7 and 7.0. A polyethylene blend (BPE/LPE) was prepared using the complex Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {TpMs*}TiCl3 (2) (TpMs* = hydridobis(3-mesitylpyrazol-1-yl)(5-mesitylpyrazol-1-yl)) supported in situ on MAO-modified silica (4.0 wts. -% Al/SiO2, S2). Reactions of polymerization of ethylene have been executed in the toluene in two different temperatures (0 and 30°C), varying the molars fraction of nickel (xNi), and using MAO as external cocatalyst. To all temperatures, the activities show a linear variation tendency with xNi and indicate the absence of the effect synergic between the species of nickel and the titanium. The maximum of activity have been found at 0°C. The melting temperature for the blends of polyethylene produced at 0 °C decrease whereas xNi increases indicating a good compatibility between phases of the polyethylene gotten with the two catalysts. The melting temperature for the blends of polyethylene showed be depend on the order according to which catalysts have been supported on the MAO-modified silica. The initial immobilization of 1 on the support (2/1/S2) product of polymers with a melting temperature (Tm) lower to the one of the polymer gotten when the titanium has been supported inicially (1/2/S2). The observation of polyethylenes gotten with the two systems (2/1/S2 and 1/2/S2) by scanning electron microscopy (SEM) showed the spherical polymer formation showing that the spherical morphology of the support to been reproduced. Are described the synthesis, the characterization and the catalytic properties for the oligomerization of the ethylene of four organometallics compounds of CrIII with ligands ([bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine] chromium (III) chloride (3a), [bis[2-(3,5- dimethyl-l-pyrazolyl)ethyl]benzylamine] chromium (III) chloride (3b), [bis[2-(3,5-dimethyl-lpyrazolyl) ethyl]ether] chromiun(III)chloride (3c), [bis[2-(3-phenyl-lpyrazolyl) ethyl]ether]chromiun(III)chloride (3d)). In relation of the oligomerization, at exception made of the compounds 3a, all complex of the chromium showed be active after activation with MAO and the TOF gotten have one effect differentiated to those formed with CrCl3(thf)3. The coordination of a tridentate ligand on the metallic center doesn't provoke any considerable changes on the formation of the C4 and C6, but the amount of C8 are decrease and the C10 and C12+ have increased. The Polymers produced by the catalyst 3a to 3 and 20 bar of ethylene have, according to analyses by DSC, the temperatures of fusion of 133,8 and 136ºC respectively. It indicates that in the two cases the production of high density polyethylene. The molar mass, gotten by GPC, is 46647 g/mols with MwD = 2,4 (3 bar). The system 3c/MAO showed values of TOF, activity and selectivity to different α-olefins according to the pressure of ethylene uses. Himself that shown a big sensibility to the concentration of ethylene solubilized.

O Instituto da Ouvidoria como ferramenta para a melhoria da gestão pública : experiência do METROREC e DETRAN-PE

Diante do crescimento do número de ouvidorias dentro das instituições brasileiras e em particular, nas empresas públicas, a pesquisa realizada abordou as relações entre a sociedade e o Estado, destacando, como tema central, o instituto da ouvidoria como ferramenta para melhoria da gestão pública. A pesquisa investigou as ouvidorias do DETRAN-PE e do METROREC ressaltando o tratamento dado às manifestações do cidadão. Os resultados dos estudos, baseados na revisão da literatura sobre o instituto da ouvidoria, envolvendo conceitos, objetivos e um modelo conceitual sobre ouvidoria, apontam caminhos de participação social e indicam que há ações implementadas decorrentes, gerando benefícios para a sociedade e para as instituições. A análise de elementos como o histórico de criação de suas ouvidorias, a estrutura de funcionamento, formas de atuações e indicadores no tratamento das demandas, permitiu realizar comparações sobre o desempenho das ouvidorias nessas duas organizações. O presente trabalho também fez observações sobre alguns aspectos de dissonância encontrados entre o modelo conceitual do instituto da ouvidoria e as ouvidorias pesquisadas, havendo a necessidade de reflexão sobre suas práticas institucionais vigentes. O estudo possibilitou um panorama sobre o instituto da ouvidoria nas instituições DETRAN-PE e METROREC, observando suas interações com os atores sociais, aproximando a gestão pública de uma vertente mais social, mediante a efetiva participação do cidadão, colocando o instituto da ouvidoria a serviço da sociedade e da instituição, como ferramenta para a melhoria da gestão pública.

A tecnologia da informação como instrumento para gestão estratégica hospitalar: um estudo de caso sobre a contribuição do Prontuário Eletrônico do Paciente - PEP - para a gestão hospitalar do hospital beneficente Maria Vitória - PE

O presente estudo teve objetivo identificar qual a percepção e expectativas que os Gestores da Sociedade Hospitalar Maria Vitória localizada no Estado de Pernambuco tem acerca da contribuição do Prontuário Eletrônico do Paciente – PEP – para a gestão estratégica do Hospital. Este trabalho está focado em três importantes pilares, a saber: Administração Hospitalar e suas principais características, a Tecnologia da Informação – TI como ferramenta estratégica para a gestão e a utilização do Prontuário Eletrônico do Paciente e suas peculiaridades. No que se refere à metodologia aplicada trata-se de um estudo de caso, o tipo de pesquisa utilizado, quanto aos meios, foram bibliográfica, documental e de campo. As conclusões suscitadas servirão no sentido de contribuir para o avanço em matéria de administração pública, mais especificamente, a percepção dos gestores da potencial contribuição do PEP como ferramenta estratégica na gestão do Hospital Maria Vitória.

Remuneração dos fundos de PE&VC: um estudo empírico no Brasil

Este trabalho procurou investigar os fatores que influenciam a remuneração dos fundos de Private Equity e Venture Capital (PE/VC) no Brasil. O estudo empírico foi realizado utilizando-se uma amostra de 55 fundos com dados do “Primeiro Censo Brasileiro de PE/VC”. Os resultados obtidos indicam que organizações gestoras mais antigas recebem uma remuneração fixa significativamente maior do que as organizações mais novas. Fundos especializados em empresas de alta tecnologia e em estágios iniciais de desenvolvimento também recebem uma compensação fixa maior do que os fundos com foco em empresas de outros setores e em outros estágios de desenvolvimento. Estas evidências são um misto das premissas derivadas dos modelos de aprendizado e de sinalização. Não foram encontrados resultados significativos que expliquem os fatores que influenciam a sensibilidade da compensação dos gestores ao desempenho dos fundos sob sua administração. A falta de constatação empírica de algumas das hipóteses testadas pode ser um indicativo de que as organizações gestoras de PE/VC ainda estão em processo de formação de sua reputação no mercado brasileiro.

A nova regra eleitoral que põe medo em boa parte dos partidos

Pesquisador da DAPP, Luis Felipe da Graça, comenta a resolução do Tribunal Superior Eleitoral que obriga partidos a terem diretório municipal constituído nas cidades onde pretendem lançar candidato a prefeito