Bis(thiophenolate)pyridine pincer ligands and trivalent zirconocene complexes relevant to early transition metal polymerization catalysts

Two major topics are covered: the first chapter is focused on the development of post-metallocene complexes for propylene polymerization. The second and third chapters investigate the consequences of diisobutylaluminum hydride (HAlⁱBu₂) additives in zirconocene based polymerization systems.

The synthesis, structure, and solution behavior of early metal complexes with a new tridentate LX₂ type ligand, bis(thiophenolate)pyridine ((SNS) = (2-C₆H₄S)₂-2,6-C₅H₃N) are investigated. SNS complexes of Ti, Zr, and Ta having dialkylamido coligands were synthesized and structurally characterized. The zirconium complex, (SNS)Zr(NMe₂)₂, displays C₂ symmetry in the solid state. Solid-state structures of tantalum complexes (SNS)Ta(NMe₂)₃ and (SNS)TaCl(NEt₂)₂ also display pronounced C₂ twisting of the SNS ligand. 1D and 2D NMR experiments show that (SNS)Ta(NMe₂)₃ is fluxional with rotation about the Ta N(amide) bonds occurring on the NMR timescale. The fluxional behavior of (SNS)TaCl(NEt₂)₂ in solution was also studied by variable temperature ¹H NMR. Observation of separate signals for the diastereotopic protons of the methylene unit of the diethylamide indicates that the complex remains locked on the NMR timescale in one diastereomeric conformation at temperatures below -50 °C.

Reduction of Zr(IV) metallocenium cations with sodium amalgam (NaHg) produces EPR signals assignable to Zr(III) metallocene complexes. Thus, chloro-bridged heterobinuclear ansa-zirconocenium cation [((SBI))Zr(μ-Cl)₂AlMe₂]⁺B(C₆F₅)_4¯ (SBI = rac-dimethylsilylbis(1-indenyl)), gives rise to an EPR signal assignable to the complex (SBI)Zr^III(μ-Cl)₂AlMe₂, while (SBI)Zr^III-Me and (SBI)Zr^III(-H)2AlⁱBu₂ are formed by reduction of [(SBI)Zr(μ-Me)₂AlMe₂]⁺B(C₆F₅)_4¯ and [(SBI)Zr(μ-H)₃(AlⁱBu₂)₂]⁺B(C₆F₅)4¯, respectively. These products are also formed, along with (SBI)Zr^III-ⁱBu and [(SBI)Zr^III]⁺ AlR4¯ when (SBI)ZrMe₂ reacts with HAlⁱBu₂, eliminating isobutane en route to the Zr(III) complex. Studies concerning the interconversion reactions between these and other (SBI)Zr(III) complexes and reaction mechanisms involved in their formation are also reported.

The addition of HAlⁱBu₂ to precatalyst [(SBI)Zr(µ-H)₃(AlⁱBu₂)₂]⁺ significantly slows the polymerization of propylene and changes the kinetics of polymerization from 1st to 2nd order with respect to propylene. This is likely due to competitive inhibition by HAlⁱBu₂. When the same reaction is investigated using [(ⁿBuCp)₂Zr(μ-H)₃(AlⁱBu₂)₂]⁺, hydroalumination between propylene and HAlⁱBu₂ is observed instead of propylene polymerization.

Paths Towards High Efficiency Silicon Photovoltaics

While photovoltaics hold much promise as a sustainable electricity source, continued cost reduction is necessary to continue the current growth in deployment. A promising path to continuing to reduce total system cost is by increasing device efficiency. This thesis explores several silicon-based photovoltaic technologies with the potential to reach high power conversion efficiencies. Silicon microwire arrays, formed by joining millions of micron diameter wires together, were developed as a low cost, low efficiency solar technology. The feasibility of transitioning this to a high efficiency technology was explored. In order to achieve high efficiency, high quality silicon material must be used. Lifetimes and diffusion lengths in these wires were measured and the action of various surface passivation treatments studied. While long lifetimes were not achieved, strong inversion at the silicon / hydrofluoric acid interface was measured, which is important for understanding a common measurement used in solar materials characterization.

Cryogenic deep reactive ion etching was then explored as a method for fabricating high quality wires and improved lifetimes were measured. As another way to reach high efficiency, growth of silicon-germanium alloy wires was explored as a substrate for a III-V on Si tandem device. Patterned arrays of wires with up to 12% germanium incorporation were grown. This alloy is more closely lattice matched to GaP than silicon and allows for improvements in III-V integration on silicon.

Heterojunctions of silicon are another promising path towards achieving high efficiency devices. The GaP/Si heterointerface and properties of GaP grown on silicon were studied. Additionally, a substrate removal process was developed which allows the formation of high quality free standing GaP films and has wide applications in the field of optics.

Finally, the effect of defects at the interface of the amorphous silicon heterojuction cell was studied. Excellent voltages, and thus efficiencies, are achievable with this system, but the voltage is very sensitive to growth conditions. We directly measured lateral transport lengths at the heterointerface on the order of tens to hundreds of microns, which allows carriers to travel towards any defects that are present and recombine. This measurement adds to the understanding of these types of high efficiency devices and may aid in future device design.

Spatial and seasonal relationships between Pacific harbor seals (Phoca vitulina richardii) and their prey, at multiple scales

Knowing where pinnipeds forage is vital to managing and protecting their populations, and for assessing potential interactions with fisheries. We assessed the spatial relationship between the seasonal distribution of Pacific harbor seals (Phoca vitulina richardii) outfitted with satellite transmitters and the seasonal distributions of potential harbor seal prey species in San Francisco Bay, California. Pearson’s correlation coefficients were calculated between the number of harbor seal locations in an area of the San Francisco Bay and the abundance of specific prey species in the same area. The influence of scale on the analyses was assessed by varying the scale of analysis from 1 to 10 km. There was consistency in the prey species targeted by harbor seals year-round, although there were seasonal differences between the most important prey species. The highest correlations between harbor seals and their prey were found for seasonally abundant benthic species, located within about 10 km of the primary haul-out site. Probable foraging habitat for harbor seals was identified, based on areas with high abundances of prey species that were strongly correlated with harbor seal distribution. With comparable local data inputs, this approach has potential application to pinniped management in other areas, and to decisions about the location of marine reserves designed to protect these species.

Revisão taxonômica das espécies brasileiras de Funariaceae Schwagr. (Bryophyta)

Funariaceae Schwägrichen é uma família de musgos cosmopolita que crescem em diversos habitats, por um ou raramente dois anos, mas algumas espécies podem ser perenes. Possuem como característica marcante o gametófito uniforme e uma ampla diversidade na arquitetura do esporófito. Este estudo realizou a revisão taxonômica da família Funariaceae no Brasil através da análise dos espécimes-tipos de coleções de herbários, nacionais e internacionais, e consulta a literatura específica sobre os táxons. É apresentada uma listagem revista e atualizada da família Funariaceae que ocorrem no Brasil, chaves de identificação para gêneros e espécies, descrições morfológicas, distribuição geográfica, status de conservação, ecologia, comentários, relação do material examinado e ilustrações. Para o Brasil eram citados 51 binômios agrupados em três gêneros: Entosthodon Schwagr. (11 binômios), Funaria Hedw. (20 binômios) e Physcomitrium (Brid.) Brid. (20 binômios). Os gêneros são taxonomicamente distintos pelo tipo de ornamentação dos esporos, forma da cápsula, forma das células do exotécio, presença ou ausência de peristômio, comprimento da seta, forma do ânulo e forma da caliptra. Após a revisão dos nomes foi estabelecida uma combinação nova a partir de Funaria ramulosa (Hampe) Paris: Entosthodon ramulosus (Hampe) M. S. Dias & D. F. Peralta. Foram estabelecidos 10 novos sinônimos: Funaria luteolimbata Broth. F. obtusa-apiculata Müll. Hal. e F. ramulosa (Hampe) Paris como sinônimos de Entosthodon ramulosus (Hampe) M. S. Dias & D. F. Peralta; Physcomitrium flavum (Müll. Hal.) Broth. como sinônimo de E. bonplandii (Hook.) Mitt.; Physcomitrium badium Broth. como sinônimo de P. umbonatum Mitt.; P. lindmanii Broth., P. sylvestre Müll. Hal. e P. convolutaceum Müll. Hal. como sinônimos de P. thieleanum Hampe. P. serrulatum Mitt., P. cupulare Müll Hal. e P. platyphylloides Paris como sinônimos de P. subsphaericum Schimp. Entosthodon puiggarii Geh. & Hampe é o nome legítimo do táxon Physcomitrium puiggarii Geh & Hampe e foi constatado que Funaria capillipes (Müll. Hal. ex Broth.) Broth., é uma combinação inválida. Seis táxons foram excluídos de Funariaceae por não possuírem os caracteres morfológicos diagnósticos da família e seis espécies não foram incluídas no tratamento taxonômico por falta de informação sobre as mesmas e foram consideradas como espécies duvidosas. Portanto, são reconhecidos para o Brasil 11 táxons em Funariaceae: quatro de Entosthodon (E. bonplandii (Hook.) Mitt., E. obtusifolius Hook. f. in Hooker, E. puiggarii Geh. & Hampe in Hampe & Geheeb. e E. ramulosus (Hampe) M. S. Dias & D. F. Peralta); dois de Funaria (F. calvescens Schwagr. e F. hygrometrica Hedw.) e cinco de Physcomitrium (P. capillipes Müll. Hal. ex Broth., P. falcifolium Müll. Hal. in Brotherus, P. umbonatum Mitt., P. subsphaericum Schimp. e P. thieleanum Hampe). Cinco táxons são endêmicos do Brasil: Entosthodon puiggarii, E. ramulosus, Physcomitrium capillipes, P. falcifolium, P. umbonatum e a espécie P. capillipes é conhecida apenas pelo tipo nomenclatural. A partir da análise de diversos materiais originais, é apresentada aqui uma nova reinterpretação da família Funariaceae do Brasil, com novas sinonimizações, reconhecimento de uma nova combinação, e lectótipos

Increasing Creel Interview Efficiency Through Early Survey Termination

Operational modifications based on recreational angler activity patterns can be successfully formulated to increase creel survey efficiency without a significant loss of information. This study was conducted to estimate the amount of Texas marine sport-boat angler interview and retained fish data (bay and Gulf) that would be missed both coastwide and within each bay system if surveys were terminated early when no angler interviews were conducted by a specified time. Using this method, <3 percent of the total interviews and retained fish would be missed coastwide by terminating surveys at 1400 hours on weekends and 1600 hours on weekdays throughout the survey year. This would result in the early termination of 14 percent of the weekend surveys and 23 percent of the weekday surveys, thus allowing an annual redirection of 440 work-hours and $6,063 in operating expenses.

O que nos une, o que nos separa: do encontro e da distância na fotografia

A pesquisa desenvolvida parte de um diálogo entre a minha produção artística e uma reflexão teórica sobre fotografia. Reflexão que não se esgota neste trabalho, mas, ao contrário, abre novas brechas para imagens e palavras que virão. O fio condutor da minha produção fotográfica reflete uma forma específica de pensar a fotografia para além da imagem, que eleva a ideia de instante a uma potência de momento fotográfico. A expectação é pensada aqui como uma interação onde surge uma nova relação entre fotógrafo-fotografado. O interesse pelos olhares que atravessam a câmera, além daqueles que, mais tarde, pousarão na superfície da imagem, aproxima esta pesquisa da filosofia de Georges Didi-Huberman, que propõe um diálogo incessante entre o visível e o invisível na imagem e descortina o jogo entre o perto e o distante no olhar. Como a fotografia percorre as distâncias fazendo desse caminho também um encontro? A fotografia é tomada como um elo e também como objeto. Diferentes materialidades da imagem definem diferentes temporalidades. O tempo que ronda o ato fotográfico se alarga e se estreita em função de seus meios de produção. Mauricio Lissovsky aponta a expectação como fator determinante das imagens fotográficas. Suely Rolnik, em suas direções cartográficas sentimentais, guia essa trama fluida, que também se compõe pelo afeto. Miwon Kwon, ao pensar a sensação de instabilidade e não pertencimento, sugere novas formas de relação com o lugar estrangeiro. Hal Foster considera a inserção da arte na vida social uma dimensão intrínseca à prática artística contemporânea. Nesse contexto, localizo a minha pesquisa. Alguns trabalhos de Nan Goldin, Sophie Calle, Rosângela Rennó e Alexandre Sequeira, entre outros artistas e pesquisadores, são trazidos à cena, para compor e perpetuar o delicado jogo de olhares, distâncias, imagens e encontros