Model studies of Ziegler-Natta olefin polymerization using group 3 and group 4 metallocenes

Evidence for the stereochemical isomerization of a variety of ansa metallocene compounds is presented. For the scandocene allyl derivatives described here, we have established that the process is promoted by a variety of salts in both ether and hydrocarbon solvents and is not accelerated by light. A plausible mechanism based on an earlier proposal by Marks, et al., is offered as an explanation of this process. It involves coordination of anions and/or donor solvents to the metal center with cation assistance to encourage metalcyclopentadienyl bond heterolysis, rotation about the Si-Cp bond of the detached cyclopentadienide and recoordination of the opposite face. Our observations in some cases of thermodynamic racemic:meso ratios under the reaction conditions commonly used for the synthesis of the metallocene chlorides suggests that the interchange is faster than metallation, such that the composition of the reaction mixture is determined by thermodynamic, not kinetic, control in these cases.

Two new ansa-scandocene alkenyl compounds react with olefins resulting in the formation of η³-allyl complexes. Kinetics and labeling experiments indicate a tuck-in intermediate on the reaction pathway; in this intermediate the metal is bound to the carbon adjacent to the silyllinker in the rear of the metallocene wedge. In contrast, reaction of permethylscandocene alkenyl compounds with olefins results, almost exclusively, in vinylic C-H bond activation. It is proposed that relieving transition state steric interactions between the cyclopentadienyl rings and the olefin by either linking the rings together or using a larger lanthanide metal may allow for olefin coordination, stabilizing the transition state for allylic σ-bond metathesis.

A selectively isotopically labeled propylene, CH₂CD(¹³CH₃), was synthesized and its polymerization was carried out at low concentration in toluene solution using isospecific metallocene catalysts. Analysis of the NMR spectra (¹³C, ¹H, and ²H) of the resultant polymers revealed that the production of stereoerrors through chain epimerization proceeds exclusively by the tertiaryalkyl mechanism. Additionally, enantiofacial inversion of the terminally unsaturated polymer chain occurs by a non-dissociative process. The implications of these results on the mechanism of olefin polymerization with these catalysts is discussed.

The Flocculation of E. coli with Polyethyleneimine

A comprehensive study was made of the flocculation of dispersed E. coli bacterial cells by the cationic polymer polyethyleneimine (PEI). The three objectives of this study were to determine the primary mechanism involved in the flocculation of a colloid with an oppositely charged polymer, to determine quantitative correlations between four commonly-used measurements of the extent of flocculation, and to record the effect of varying selected system parameters on the degree of flocculation. The quantitative relationships derived for the four measurements of the extent of flocculation should be of direct assistance to the sanitary engineer in evaluating the effectiveness of specific coagulation processes.

A review of prior statistical mechanical treatments of absorbed polymer configuration revealed that at low degrees of surface site coverage, an oppositely- charged polymer molecule is strongly adsorbed to the colloidal surface, with only short loops or end sequences extending into the solution phase. Even for high molecular weight PEI species, these extensions from the surface are theorized to be less than 50 Å in length. Although the radii of gyration of the five PEI species investigated were found to be large enough to form interparticle bridges, the low surface site coverage at optimum flocculation doses indicates that the predominant mechanism of flocculation is adsorption coagulation.

The effectiveness of the high-molecular weight PEI species 1n producing rapid flocculation at small doses is attributed to the formation of a charge mosaic on the oppositely-charged E. coli surfaces. The large adsorbed PEI molecules not only neutralize the surface charge at the adsorption sites, but also cause charge reversal with excess cationic segments. The alignment of these positive surface patches with negative patches on approaching cells results in strong electrostatic attraction in addition to a reduction of the double-layer interaction energies. The comparative ineffectiveness of low-molecular weight PEI species in producing E. coli flocculation is caused by the size of the individual molecules, which is insufficient to both neutralize and reverse the negative E.coli surface charge. Consequently, coagulation produced by low molecular weight species is attributed solely to the reduction of double-layer interaction energies via adsorption.

Electrophoretic mobility experiments supported the above conclusions, since only the high-molecular weight species were able to reverse the mobility of the E. coli cells. In addition, electron microscope examination of the seam of agglutination between E. coli cells flocculation by PEI revealed tightly- bound cells, with intercellular separation distances of less than 100-200 Å in most instances. This intercellular separation is partially due to cell shrinkage in preparation of the electron micrographs.

The extent of flocculation was measured as a function of PEl molecular weight, PEl dose, and the intensity of reactor chamber mixing. Neither the intensity of mixing, within the common treatment practice limits, nor the time of mixing for up to four hours appeared to play any significant role in either the size or number of E.coli aggregates formed. The extent of flocculation was highly molecular weight dependent: the high-molecular-weight PEl species produce the larger aggregates, the greater turbidity reductions, and the higher filtration flow rates. The PEl dose required for optimum flocculation decreased as the species molecular weight increased. At large doses of high-molecular-weight species, redispersion of the macroflocs occurred, caused by excess adsorption of cationic molecules. The excess adsorption reversed the surface charge on the E.coli cells, as recorded by electrophoretic mobility measurements.

Successful quantitative comparisons were made between changes in suspension turbidity with flocculation and corresponding changes in aggregate size distribution. E. coli aggregates were treated as coalesced spheres, with Mie scattering coefficients determined for spheres in the anomalous diffraction regime. Good quantitative comparisons were also found to exist between the reduction in refiltration time and the reduction of the total colloid surface area caused by flocculation. As with turbidity measurements, a coalesced sphere model was used since the equivalent spherical volume is the only information available from the Coulter particle counter. However, the coalesced sphere model was not applicable to electrophoretic mobility measurements. The aggregates produced at each PEl dose moved at approximately the same vlocity, almost independently of particle size.

PEl was found to be an effective flocculant of E. coli cells at weight ratios of 1 mg PEl: 100 mg E. coli. While PEl itself is toxic to E.coli at these levels, similar cationic polymers could be effectively applied to water and wastewater treatment facilities to enhance sedimentation and filtration characteristics.

Tão perto, tão longe: a vivência do enfermeiro na construção/desenvolvimento da relação mãe/recém-nascido na Unidade Terapia Intensiva Neonatal

Não há duvidas sobre a grandeza e intensidade que pode existir no relacionamento entre mãe e filho, porém, quando esse recém nascido é um bebê prematuro e/ou necessita de hospitalização em uma Unidade de Terapia Intensivo Neonatal (UTIN) pode haver um pode haver um choque, uma grande decepção, pois essa mãe não poderá interagir de forma plena com seu filho, não poderá amamentar e nem cuidar dele da forma habitual que se espera. Neste sentido, esse estudo propõe uma reflexão sobre a atuação do enfermeiro quanto à relação mãe/recém-nascido na UTIN. Assim sendo, tem-se como objeto A vivência do enfermeiro na construção/desenvolvimento da relação mãe/recém-nascido na UTIN. E como objetivo Compreender o significado da ação do enfermeiro na aproximação mãe/recém-nascido. Para o embasamento teórico foi necessário pensar sobre a prática do enfermeiro na UTIN, no que diz respeito a sua assistência, o processo de humanização neste ambiente e na inserção da família nos cuidados. Outro conceito fundamental discutido foi a interação, destacando o pensamento fenomenológico de Alfred Schutz. Estudo do tipo descritivo, desenvolvido com abordagem qualitativa e o referencial teórico-metodológico da fenomenologia. O cenário para sua realização foi a UTIN de um grande hospital da rede pública, localizado no subúrbio da cidade do Rio de Janeiro e foram sujeitos 16 enfermeiros lotados nesta unidade. A entrevista fenomenológica foi a técnica utilizada para captar as vivências profissionais e em seguida realizou-se a análise compreensiva tendo em vista a categorização. Como resultado chegou-se a 3 categorias do vivido; (1) ambientar as mães na UTIN: o começo da relação,(2) aproximar através do toque: usando os sentidos para se relacionar e (3) melhorar a relação entre mãe/recém-nascido: pensando no futuro. Além dessas categorias foi possível a apreensão do contexto vivencial das experiências dos enfermeiros no relacionamento com as mães de recém-nascidos na UTIN. Conclui-se que os enfermeiros que trabalham em UTIN têm a percepção de quão fundamental é promover a aproximação entre mãe e filho nesse ambiente. Contudo, essa ação ainda acontece de forma intuitiva, sem nenhum embasamento, e ainda muitas vezes é desprestigiada em detrimento da grande carga de trabalho deste setor, ou a gravidade do recém-nascido. É preciso que haja um maior engajamento por parte dos enfermeiros, em aprimorar as estratégias de aproximação entre mãe e recém-nascido, visando sempre um relacionamento mais saudável e harmonioso no futuro. Deste modo, o estudo contribui para enriquecer esta temática e despertar nos enfermeiros neonatologistas um olhar que compreenda não só os aspectos biológicos, mas também os psicossocias e torne, assim, a assistência ao recém nascido e sua família mais plena.

Optimisation of the first principle code Octopus for massive parallel architectures: application to light harvesting complexes

150 p.

Integralidade no cuidado à saúde da mulher: refletindo sobre a atuação dos profissionais em unidades básicas de saúde do município de Toledo PR

Este estudo tem como objetivo entender como as práticas de saúde das mulheres são desenvolvidas pelos profissionais de saúde, frente ao princípio de integralidade, em unidades básicas de saúde de um município do Estado do Paraná. O estudo teve como suporte teórico a integralidade da atenção, não só como princípio do SUS, mas também como exercício de boas práticas de produção de cuidado que devem estar presentes no atendimento das necessidades de saúde das mulheres, em busca da conquista de uma saúde mais digna e solidária para todos. O Sistema Único de Saúde deve estar orientado e capacitado para a atenção integral à saúde da mulher, numa perspectiva que contempla a promoção da saúde, a proteção e a prevenção às necessidades de saúde da população feminina, o controle de patologias mais prevalentes nesse grupo e a garantia do direito à saúde. Por esta razão, a humanização e a qualidade da atenção implicam promoção, reconhecimento e respeito aos direitos humanos, garantindo a saúde integral e seu bem-estar. A metodologia envolveu uma abordagem qualitativa realizada em duas unidades básicas de saúde do município de Toledo-PR. Utilizou-se como técnica de coleta de dados a observação a 15 atendimentos médicos a mulheres em ginecologia e clínico geral e entrevista com 10 mulheres freqüentadoras de duas unidades de saúde. A análise do material produzido foi organizada em torno de certos aspectos-chave de certas categorias. Identificamos, nos atendimentos observados, que há uma cordialidade desintegral dos profissionais que atendem às mulheres com certa gentileza, mas que ao mesmo tempo são desatentos a certos aspectos fundamentais de um atendimento integral. Deixam a desejar do ponto de vista técnico, comprometendo a integralidade do atendimento, focando sua atenção na queixa principal trazida pela mulher, com atendimentos restritos somente na conversa, ou exame clínico centrado na queixa principal, não explorando aspectos para a prevenção. Tornam, assim, o atendimento seletivo e centralizado, mas cercado por uma cordialidade junto às mulheres, que classificam tal cordialidade como uma sensação de bom atendimento, satisfação ilusória do ponto de vista técnico, em que a atenção clínica não responde a suas necessidades. Estas mulheres não reconhecem esta má prática, relatando uma resolutividade no atendimento diante da resolução da queixa imediata, como o acesso a alguns exames, medicamentos. Identificamos também que algumas mulheres sonham com um atendimento integral, e em alguns atendimentos se percebe a tentativa do profissional de buscar uma atenção que vá além da queixa principal, buscando entender com se dá o modo de andar a vida de certas mulheres. Concluímos que desafios ainda são colocados quando olhamos para a organização dos serviços de saúde na perspectiva da atenção integral. Considera-se fundamental a organização dos serviços de saúde para estarem pautados em cuidados efetivos à saúde da mulher, em busca da produção da integralidade que será traduzida em mais saúde para as mulheres.

Community management of coastal resources, southern Thailand

The involvement of communities with the assistance and support of government and non government organizations on the management of the coastal resources in Southern Thailand are discussed. The 3 most important resources, mangrove, seagrass and coral, create a complex coastal ecology. Several man-made activities causing the deterioration of this resources are also presented.

The Programme for Integrated Development of Artisanal Fisheries in West Africa

The Programme for Integrated Development of Artisanal Fisheries in West Africa (IDAF) was initiated in 1983 to help some 20 coastal states from Mauritiana to Angola which wished to develop and manage their artisanal fisheries through participatory and integrated approaches. IDAF was initially financed by Denmark and Norway. The second phase of the programme which started in January 1989 and its third phase, July 1984 are entirely financed by Denmark through the Danish International Development Assistance (DANIDA). IDAF objectives and activities to meet its goals are briefly discussed together with its beneficiaries and accomplishments.

Census of Active Commercial Fishermen in Puerto Rico: 2008

The implementation of Puerto Rican Regulation No. 6768, which overhauled the existing fishery management framework, generated considerable hostility towards local managers. Among the controversial management measures adopted in 2004 were the assignment of fishing licenses based on fishing income, the establishment of closed seasons, and new minimum size restrictions for commercially valuable species. Though tensions have subsided, considerable opposition to these regulations remains. This paper provides a characterization of the current population of active small-scale fishermen, discusses their perceptions about the biological and socio-economic condition of the fishery, and describes their attitudes towards the new management framework. This study revealed that the number of active fishermen decreased from 1,731 in 1988 to 868 in 2008. Although a declining resource base was one of the main drivers behind these waning participation statistics, rising fuel costs and burdensome regulations exacerbated the rate of attrition. The majority of the fishermen were middleaged men (50 years) with moderate levels of formal education and high levels of fishing dependence which limited their employment opportunities outside the fishery. Most of the vessels were small (20 ft) and outfitted with a single outboard engine (80 hp). Hook and line and SCUBA were dominant gears because of their versatility and cost effectiveness. Fishermen suggested that their opposition to the regulations would continue unless they were afforded greater regulatory flexibility and provided with a larger role in the decision-making process. Fishermen were adamant about the need to reconsider the income reporting requirements to secure a fishing license because of the potential for losing public assistance benefits. They also objected to increasing the minimum size of many deepwater snapper (Lutjanidae) and grouper (Serranidae) species because it forced them to discard dead fish, a practice they consider wasteful since these species do not survive the ascent to the surface once hooked.

A Biogeographic assessment off North/Central California: In support of the National Marine Sanctuaries of Cordell Bank, Gulf of the Farallones and Monterey Bay. Phase II - Environmental setting and update to marine birds and animals

NOAA’s National Centers for Coastal Ocean Science (NCCOS) conducts and supports research, monitoring, assessments, and technical assistance to meet NOAA’s coastal stewardship and management responsibilities. In 2001 the Biogeography Branch of NCCOS partnered with NOAA’s National Marine Sanctuary Program (NMSP) to conduct biogeographic assessments to support the management plan updates for the sanctuaries. The first biogeographic assessment conducted in this partnership focused on three sanctuaries off north/ central California: Cordell Bank, Gulf of the Farallones and Monterey Bay. Phase I of this assessment was conducted from 2001 to 2004, with the primary goal to identify and gather the best available data and information to characterize and identify important biological areas and time periods within the study area. The study area encompasses the three sanctuaries and extends along the coastal ocean off California from Pt. Arena to Pt. Sal (35°-39°N). This partnership project was lead by the NCCOS Biogeography Branch, but included over 90 contributors and 25 collaborating institutions. Phase I results include: 1) a report on the overall assessment that includes hundreds of maps, tables and analyses; 2) an ecological linkage report on the marine and estuarine ecosystems along the coast of north/central California, and 3) related geographic information system (GIS) data and other summary data files, which are available for viewing and download in several formats at the following website: http://ccma.nos.noaa.gov/products/biogeography/canms_cd/welcome.html Phase II (this report) was initiated in the Fall of 2004 to complete the analyses of marine mammals and update the marine bird colony information. Phase II resulted in significant updates to the bird and mammal chapters, as well as adding an environmental settings chapter, which contains new and existing data and maps on the study area. Specifically, the following Phase II topics and items were either revised or developed new for Phase II: •environmental, ecological settings – new maps on marine physiographic features, sea surface temperature and fronts, chlorophyll and productivity •all bird colony or roost maps, including a summary of marine bird colonies •updated at-sea data CDAS data set (1980-2003) •all mammal maps and descriptions •new overall density maps for eight mammal species •new summary pinniped rookery/haulout map •new maps on at-sea richness for cetaceans and pinnipeds •most text in the mammal chapter •new summary tables for mammals on population status and spatial and temporal patterns