Organometallic derivatives of diphosphazanes. 2. Seven-coordinated Group 6 metal tricarbonyl complexes of diphosphazane ligands. X-ray crystal structure of [WI2(CO)3{P(OPh)2}2NPh]

The reactions of the complexes [MI2(CO)3-(NCMe)2] (M = Mo, W) with the diphosphazane ligands RN{P(OPh)2}2 (R = Me, Ph) in CH2Cl2 at room temperature afford new seven-coordinated complexes of the type [MI2(CO)3{P(OPh)2}2NR]. The molybdenum complexes are sensitive to air oxidation even in the solid state, whereas the tungsten complexes are more stable in the solid state and in solution. The structure of the tungsten complex [WI2(CO)3{P(OPh)2}2NPh] has been determined by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system with the space group Pna 2(1), a = 19.372 (2) angstrom, b = 11.511 (1) angstrom, c = 15.581 (1) angstrom, and Z = 4. Full-matrix least-squares refinement with 3548 reflections (I > 2.5-sigma-(I)) led to final R and R(w) values of 0.036 and 0.034, respectively. The complex adopts a slightly distorted pentagonal-bypyramidal geometry rarely observed for such a type of complexes; two phosphorus atoms of the diphosphazane ligand, two iodine atoms, and a carbonyl group occupy the equatorial plane, and the other two carbonyl groups, the apical positions.

NH3 adsorption on PtM (Fe, Co, Ni) surfaces: Cooperating effects of charge transfer, magnetic ordering and lattice strain

Adsorption of a molecule or group with an atom which is less electronegative than oxygen (0) and directly interacting with the surface is very relevant to development of PtM (M = 3d-transition metal) catalysts with high activity. Here, we present theoretical analysis of the adsorption of NH3 molecule (N being less electronegative than 0) on (111) surfaces of PtM (Fe, Co, Ni) alloys using the first principles density functional approach. We find that, while NH3-Pt interaction is stronger than that of NH3 with the elemental M-surfaces, it is weaker than the strength of interaction of NH3 with M-site on the surface of PtM alloy. (C) 2016 Published by Elsevier B.V.

Review of selected organisational IDs and development of use cases for the Jisc CASRAI-UK Organisational Identifiers Working Group

This project aimed to investigate and review candidates for providing an authoritative, widely used unique identifier for organisations involved in research in the UK. Specifically, we undertook to: ● clarify a representative but not comprehensive set of use cases for the UK research community to use organisational identifiers (orgIDs); ● survey and interview a small number of well-informed people in the field in order to create and prioritise a list of desirable features for the provision of orgIDs and potential services built around them; ● check the use cases and these required features against four possible candidate orgIDs and their providers; ● inform the Working Group of our conclusions and, if appropriate, make recommendations for adoption by the UK research community.

The role of agricultural co-operatives in the development of fisheries in Nigeria

Problems faced by the fishery sector in Nigeria are examined and the role that agricultural cooperatives play in fishery development considered. The importance of improving the marketing and distribution system through fishermen cooperatives is stressed. It is concluded that for the successful implementation of fishery products, there is need for regular communication, cooperation and collaboration among relative agencies

Carbon-carbon bond forming reactions from bis(carbene)-platinum(II) complexes and olefin polymerization and oligomerization using group 4 post-metallocene complexes

A long-standing challenge in transition metal catalysis is selective C–C bond coupling of simple feedstocks, such as carbon monoxide, ethylene or propylene, to yield value-added products. This work describes efforts toward selective C–C bond formation using early- and late-transition metals, which may have important implications for the production of fuels and plastics, as well as many other commodity chemicals.

The industrial Fischer-Tropsch (F-T) process converts synthesis gas (syngas, a mixture of CO + H₂) into a complex mixture of hydrocarbons and oxygenates. Well-defined homogeneous catalysts for F-T may provide greater product selectivity for fuel-range liquid hydrocarbons compared to traditional heterogeneous catalysts. The first part of this work involved the preparation of late-transition metal complexes for use in syngas conversion. We investigated C–C bond forming reactions via carbene coupling using bis(carbene)platinum(II) compounds, which are models for putative metal–carbene intermediates in F-T chemistry. It was found that C–C bond formation could be induced by either (1) chemical reduction of or (2) exogenous phosphine coordination to the platinum(II) starting complexes. These two mild methods afforded different products, constitutional isomers, suggesting that at least two different mechanisms are possible for C–C bond formation from carbene intermediates. These results are encouraging for the development of a multicomponent homogeneous catalysis system for the generation of higher hydrocarbons.

A second avenue of research focused on the design and synthesis of post-metallocene catalysts for olefin polymerization. The polymerization chemistry of a new class of group 4 complexes supported by asymmetric anilide(pyridine)phenolate (NNO) pincer ligands was explored. Unlike typical early transition metal polymerization catalysts, NNO-ligated catalysts produce nearly regiorandom polypropylene, with as many as 30-40 mol % of insertions being 2,1-inserted (versus 1,2-inserted), compared to <1 mol % in most metallocene systems. A survey of model Ti polymerization catalysts suggests that catalyst modification pathways that could affect regioselectivity, such as C–H activation of the anilide ring, cleavage of the amine R-group, or monomer insertion into metal–ligand bonds are unlikely. A parallel investigation of a Ti–amido(pyridine)phenolate polymerization catalyst, which features a five- rather than a six-membered Ti–N chelate ring, but maintained a dianionic NNO motif, revealed that simply maintaining this motif was not enough to produce regioirregular polypropylene; in fact, these experiments seem to indicate that only an intact anilide(pyridine)phenolate ligated-complex will lead to regioirregular polypropylene. As yet, the underlying causes for the unique regioselectivity of anilide(pyridine)phenolate polymerization catalysts remains unknown. Further exploration of NNO-ligated polymerization catalysts could lead to the controlled synthesis of new types of polymer architectures.

Finally, we investigated the reactivity of a known Ti–phenoxy(imine) (Ti-FI) catalyst that has been shown to be very active for ethylene homotrimerization in an effort to upgrade simple feedstocks to liquid hydrocarbon fuels through co-oligomerization of heavy and light olefins. We demonstrated that the Ti-FI catalyst can homo-oligomerize 1-hexene to C₁₂ and C₁₈ alkenes through olefin dimerization and trimerization, respectively. Future work will include kinetic studies to determine monomer selectivity by investigating the relative rates of insertion of light olefins (e.g., ethylene) vs. higher α-olefins, as well as a more detailed mechanistic study of olefin trimerization. Our ultimate goal is to exploit this catalyst in a multi-catalyst system for conversion of simple alkenes into hydrocarbon fuels.

Methodology of the Lake Victoria Fisheries Research Project's Co-management survey

In this book section, the theoretical background to the methodology is outlined, questionnaire development described, sample selection outlined and biases and shortcomings to the survey noted.

Creche Odetinha: um estudo de caso

Esta Pesquisa, de natureza qualitativa, teve por objetivo, descrever e analisar o processo de formação (2009) de um grupo de educadores os Agentes Auxiliares de Creche1 (AAC)-, recém concursados, através de um Estudo de Caso. Para tanto, fez parte das análises as recentes mudanças nas políticas de educação infantil do município do Rio de Janeiro (1997-2010) e o percurso de constituição da unidade de educação infantil -Creche Municipal Odetinha Vidal de Oliveira, através do relato de alguns de seus líderes comunitários. No município do Rio de Janeiro, as creches públicas resultaram da transferência das instituições que pertenciam à antiga Secretaria de Desenvolvimento Social (SMDS), atual Secretaria Municipal de Assistência Social (SMAS), para a Secretaria Municipal de Educação (SME). Atualmente, a rede municipal de ensino totaliza 255 creches municipais, com 33.348 alunos, em horário integral (7h -17h). No ano de 2005, o poder executivo do município do Rio de Janeiro, através da Lei 3985 de 08 de abril, criou a categoria funcional de Agente Auxiliar de Creche, que passou a integrar o Quadro de Pessoal de Apoio à Educação. O ingresso ao cargo deu-se através de concurso público, realizado em 2007, constituído de provas e provas de títulos, sendo exigida, a formação mínima em nível fundamental (o que fere a LDBEN 9394/96) e carga horária de 40 horas semanais. A seleção ocorreu regionalmente, isto é, por CRE. Em junho de 2008, o quadro de pessoal das creches públicas do município do Rio de Janeiro passou a contar em sua estrutura, com os novos profissionais egressos do concurso, marcando uma nova trajetória na história dessas instituições. A partir da análise do perfil destes educadores, meu objetivo foi refletir sobre a formação em serviço necessária para atender às especificidades de trabalho com criança de zero a três anos. Estaremos assim, co-participando na implementação de políticas públicas de Educação Infantil da prefeitura quanto à formação em serviço dos agentes auxiliares de creche. Para tanto, propomos três temas comuns e complementares de pesquisa: Inserção das crianças e famílias à creche; Brincar/Brincadeira; Arranjo espacial. Os instrumentos utilizados na pesquisa foram: observação participativa, questionários, e entrevistas. Foram também desenvolvidas, com os educadores, atividades de formação e sessões reflexivas que proporcionem o pleno desenvolvimento profissional desses sujeitos.

Larval development and identification of the genus Triglops (Scorpaeniformes: Cottidae)

Prior to Pietsch’s (1993) revision of the genus Triglops, identification of their larvae was difficult; six species co-occur in the eastern North Pacific Ocean and Bering Sea and three co-occur in the western North Atlantic Ocean. We examined larvae from collections of the Alaska Fisheries Science Center and Atlantic Reference Centre and used updated meristic data, pigment patterns, and morphological characters to identify larvae of Triglops forficatus, T. macellus, T. murrayi, T. nybelini, T. pingeli, and T. scepticus; larvae of T. metopias, T. dorothy, T. jordani, and T. xenostethus have yet to be identified and are thus not included in this paper. Larval Triglops are characterized by a high myomere count (42–54), heavy dorsolateral pigmentation on the gut, and a pointed snout. Among species co-occurring in the eastern North Pacific Ocean, T. forficatus, T. macellus, and T. pingeli larvae are distinguished from each other by meristic counts and presence or absence of a series of postanal ventral melanophores. Triglops scepticus is differentiated from other eastern North Pacific Ocean larvae by having 0–3 postanal ventral melanophores, a large eye, and a large body depth. Among species co-occurring in the western North Atlantic Ocean, T. murrayi and T. pingeli larvae are distinguished from each other by meristic counts (vertebrae, dorsal-fin rays, and anal-fin rays once formed), number of postanal ventral melanophores, and first appearance and size of head spines. Triglops nybelini is distinguished from T. murrayi and T. pingeli by a large eye, pigment on the lateral line and dorsal midline in flexion larvae, and a greater number of dorsal-fin rays and pectoral-fin rays once formed.

Co-expression of CD173 (H2) and CD174 (Lewis Y) with CD44 suggests that fucosylated histo-blood group antigens are markers of breast cancer-initiating cells

Histo-blood group antigens CD173 (H2) and CD174 (Lewis Y) are known to be developmentally regulated carbohydrate antigens which are expressed to a varying degree on many human carcinomas. We hypothesized that they might represent markers of cancer-initiating cells (or cancer stem cells, CSC). In order to test this hypothesis, we examined the co-expression of CD173 and CD174 with stem cell markers CD44 and CD133 by flow cytometry analysis, immunocytochemistry, and immunohistochemistry on cell lines and tissue sections from breast cancer. In three breast cancer cell lines, the percentage of CD173(+)/CD44(+) cells ranged from 17% to > 60% and of CD174(+)/CD44(+) from 21% to 57%. In breast cancer tissue sections from 15 patients, up to 50% of tumor cells simultaneously expressed CD173, CD174, and CD44 antigens. Co-expression of CD173 and CD174 with CD133 was also observed, but to a lesser percentage. Co-immunoprecipitation and sandwich ELISA experiments on breast cancer cell lines suggested that CD173 and CD174 are carried on the CD44 molecule. The results show that in these tissues CD173 (H2) and CD174 (LeY) are associated with CD44 expression, suggesting that these carbohydrate antigens are markers of cancer-initiating cells or of early progenitors of breast carcinomas.

Co-management approach on fisher group: a case study on Ramsar site, Tanguar haor in Bangladesh

In Bangladesh, wetlands are managed through leasing system traditionally from time immemorial. Recently the Government accepted co-management approach for wetland fisheries management and this approach is being practiced in few wetlands for maximize revenue income. A study was carried out to evaluate trend and impact of co-management in Tanguar haor (a Ramsar site wetland) on fisheries resources and livelihood of resident people in the immediate vicinity of the wetland. In Tanguar haor, conflict between leaseholders and the local community was a common phenomenon in the past. Since 2003 the district administration of Sunamganj has been managing the vast wetland resources, however, local people participation was ignored in haor management system. Average monthly fish catch of fishermen increased by 17% after introduction of co-management system and 7 fish species reappeared after introduction of co-management. Average monthly volume of fish catch has increased from 70 kg to 87 kg. A well-defined management structure has been developed for integration of all people of Tanguar haor which would enable them to raise voice jointly and influence policy in their favour.