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.

Brf1 post-transcriptionally regulates pluripotency and differentiation responses downstream of Erk MAP Kinase

FGF/Erk MAP Kinase Signaling is a central regulator of mouse embryonic stem cell (mESC) self-renewal, pluripotency and differentiation. However, the mechanistic connection between this signaling pathway activity and the gene circuits stabilizing mESCs in vitro remain unclear. Here we show that FGF signaling post-transcriptionally regulates the mESC transcription factor network by controlling the expression of Brf1 (zfp36l1), an AU-rich element mRNA binding protein. Changes in Brf1 level disrupts the expression of core pluripotency-associated genes and attenuates mESC self-renewal without inducing differentiation. These regulatory effects are mediated by rapid and direct destabilization of Brf1 targets, such as Nanog mRNA. Interestingly, enhancing Brf1 expression does not compromise mESC pluripotency, but does preferentially regulate differentiation to mesendoderm by accelerating the expression of primitive streak markers. Together, these studies demonstrate that FGF signals utilize targeted mRNA degradation by Brf1 to enable rapid post-transcriptional control of gene expression.

An assessment of post-plague reintroduced native white-clawed crayfish, a Ustropotamobius pallipes, in the Sherston Avon and Tetbury Avon, Wiltshire

This article reports on the success of reintroducing native crayfish (Austropotamobius pallipes) in the Sherston and Tetbury Avon, following extinction of the population from crayfish plague. The authors describe and review the survey methods that were used and identify a survey technique that was found to be the most rapid and robust for monitoring crayfish populations. Such a survey technique could be adopted as a standard method.

A photographic record of a pre- and post-lake creation event from World War II at Valley, Isle of Anglesey, UK

The article compares a recent aerial photograph of the lowlands of the Isle of Anglesey area with a German surveillance photograph from 1941. The authors aim to infer the environmental changes made to this sand dune and lake system as a direct consequence of constructing the airfield. Part of Tywyn Trewan, the extensive sand dune system, was completely destroyed in order to create runways and the technical and domestic accommodation to house a strategic airfield. As part of the dredging, six new water bodies with a combined surface area of approximately 6 ha were created.

Long-term natural acidification of upland sites in Cumbria: Evidence from post-glacial lake sediments

Studies by the Freshwater Biological Association over the last 25 years have supplied data relevant to the levels of acidity in local soils and water before the onset of industrial pollution and current interest in acid rain. This article reviews published analysis from cores of lake sediments, in or near the catchment of the River Duddon. Electron spin resonance spectra of humic acids and iodine values confirm evidence from pollen analysis for a history of progressive acidification of the source material of lake sediments since before 5000 radiocarbon years, in upland catchments of the Lake District. Processes involved included: removal of basic ions from soils by rainfall, the effects of which were intensified by removal by man of deciduous forest; acidification of soils and waters by decomposition products of Calluna and further acidification of waters by Sphagnum species which colonized habitats where drainage became impeded by paludification processes.

Evolución geodinámica del Macizo Ibérico meridional (Zona de Ossa-Morena y Zona Centro Ibérica). XXV Reunión de la Comisión de Tectónica de la SGE (Sociedad Geológica de España)

La evolución geodinámica de zonas poliorogénicas es tanto más difícil cuanto más fragmentarios son los datos cartográficos que impiden correlacionar segmentos diferentes. Un buen ejemplo de ello son los numerosos modelos evolutivos y reconstrucciones paleogeográficas propuestos para la cadena hercínica. En el Macizo Ibérico la correlación entre áreas se ha intentado resolver con subdivisiones en zonas similares a las propuestas para otros macizos variscos. En las zonas más complejas se optó por una subdivisión en “Dominios”, a los que se llegó a equiparar con “terrenos” independientes, con evoluciones geodinámicas poco o nada relacionables. Un buen ejemplo de ello son las diversas propuestas de subdivisión de la Zona de Ossa-Morena, reflejo de las deficiencias cartográficas y de la dificultad de correlacionar cartografías anejas, delineándose mapas de difícil interpretación y leyendas muy complicadas con centenares de términos. Durante los últimos 10 años un equipo de la Universidad de Extremadura y la Universidad del País Vasco ha revisado sistemáticamente la cartografía geológica de Extremadura, obteniéndose un mapa continuo con una leyenda única, en la que todos los materiales están debidamente diferenciados, correlacionados y muchos de ellos datados. Este trabajo ha supuesto la culminación de más de 35 años dedicados de forma ininterrumpida a la investigación y cartografía geológica del Macizo Ibérico meridional. Ello ha permitido proponer una subdivisión mucho más sencilla y poner de manifiesto la falta de significado de la subdivisiones en Dominios y Unidades existentes en distintos trabajos.

Cultura de consumo y ciudadanía activa en la sociedad contemporánea: discursos y prácticas convencionales y post-convencionales en la generación del baby-boom

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River Tawd post stocking survey 1998

The River Tawd is a tributary of the River Douglas catchment. The Tawd is approximately 8km in length from its source, to the south of Skelmersdale, to its confluence with the River Douglas at Snipe Hall farm. The aim of this study was to determine whether the water quality of the River Tawd had improved sufficiently to allow a mixed coarse fish population to establish itself on the river after the stocking of juvenile Roach (Rutilus rutilus), Dace (Leucisus leucisus) and Chub (Leucisus cephalus) in 1997. This report will consider the survival of the stocked fish. If the stocking was successful, other potential stocking sites will be recommended for future stocking with a view to developing the River Tawd fishery.

A working guide to the assessment, implementation and post project monitoring of fisheries habitat improvement schemes in South Cumbria

Due to changes in land use over the last century, the physical nature of many streams and rivers in the British Isles has probably changed. In some cases this change may be large for example as a result of flood defence schemes and is easily observed, whilst in other cases altered land use, farming, forestry or urbanization may have resulted in more subtle changes to river features. This working guide draws together a way of assessing habitat in any stream or river and determine sites or reaches on the assessed watercourse that may benefit from habitat improvement schemes. It will determine a method of measuring existing habitat in a broad sense, whilst referring to R and D studies currently being undertaken in this area. A method of prioritising any proposed habitat restoration work will be suggested. The limitations of fisheries improvement schemes in terms of cross functional acceptance (flood defence and conservation) will be examined along with suggested proposals for some example watercourses. The need for pre and post enhancement monitoring will be discussed as will the requirement for maintenance programs on schemes. Finally methods for determining the cost benefits of small schemes will be examined, compared to other currently used enhancement strategies. This will allow small scale revenue schemes to be used to back up pre project cost benefit analysis as required in future capital submissions.

Influence of different post-treatments on the structure and optical properties of zinc oxide thin films

Zinc oxide (ZnO) films with c-oriented were grown on fused quartz glass substrates at room temperature using dc reactive magnetron sputtering. The as-grown films were annealed at 700 degrees C in air and bombarded by ion beam, respectively. The effects of post-treatments on the structural and optical properties of the ZnO films were investigated by X-ray diffraction (XRD), photoluminescence (PL), optical transmittance and absorption measurements. The XRD spectra indicate that the crystal quality of ZnO films has been improved by both the post-treatments. Compared with the as-grown sample, both annealed and bombarded samples exhibited blueshift in the UV emission peaks, and a strong green emission was found in the annealed ZnO film. In both optical transmittance and absorption spectra, a blueshift of the band-gap edge was observed in the bombarded film, while a redshift was observed in the annealed film. (c) 2004 Elsevier B.V. All rights reserved.

Flavio Josefo e o paradigma de circularidade cultural entre as comunidades judaicas e a sociedade romana na Urbs do século I d.C

O paradigma de circularidade cultural entre a comunidade judaica e a sociedade romana foi construído pela historiografia através da análise do contato sociocultural e embates entre romanos e judeus que, ao longo da história, ocuparam o mesmo espaço em diversas regiões anexadas ao Império Romano. As relações de poder estabelecidas entre Roma e Jerusalém, após a ocupação da Judéia, apontam para uma hierarquização nas relações sociais, culturais e políticas entre romanos e judeus. O conceito de circularidade cultural de Carlo Ginzburg nos permite, a partir da trajetória de Flávio Josefo, identificar a dualidade no mundo social de Josefo, na qual, de um lado estavam as culturas dominantes (sociedade romana) e, do outro, as culturas subalternas (comunidades judaicas) que, apesar da marcação das diferenças, se influenciavam reciprocamente.