结构精修研究合成温度对LiFePO_4结构的影响

固相法合成具有橄榄石型结构的LiFePO_4晶体,合成温度分别为670、700、730℃.采用XRD结构精修对合成LiFePO_4的结构进行了研究.研究发现随着合成温度的变化,晶胞参数a、b和c发生变化,晶胞参数的变化是等比例的增加或减少.由于合成温度的变化,Fe-O八面体中Fe-O键长发生变化,Fe-O键长的变化将会使得Fe的3 d轨道能量发生变化.相对于合成温度670、730℃,在700℃合成的LiFePO_4晶体具有最大的锂离子扩散有效面积.

The stability of traveling wave solutions of parabolic equations

A method for determining by inspection the stability or instability of any solution u(t,x) = ɸ(x-ct) of any smooth equation of the form u_t = f(u_(xx),u_x,u where ∂/∂a f(a,b,c) > 0 for all arguments a,b,c, is developed. The connection between the mean wavespeed of solutions u(t,x) and their initial conditions u(0,x) is also explored. The mean wavespeed results and some of the stability results are then extended to include equations which contain integrals and also to include some special systems of equations. The results are applied to several physical examples.

Sobre los procesos de (re)organización institucional cívica en Hispania

Estíbaliz Ortiz de Urbina (ed.)

Salvaging the freshwater ecosystems in Nigeria: great threat to sustainable fisheries and aquaculture development

Nigeria, the country of many rivers is also rich in lakes, and wetlands, sustainable and wise use of these inland aquatic ecosystem and water resources has become a matter of widespread and intense concern. Unhealthy freshwater ecosystems and seriously diminishing and unequal availability of quality freshwater call for high quality limnological research and expertise to underpin the enhancement of sustainable fisheries and aquaculture development.In every regard of national health, agriculture and economics, the continued over exploitation and misuse of finite freshwater resources is directly causal to the progressively deteriorating fish production and general standard of living.The integration of basic understanding of inland ecosystems with applied problems and their solutions should be of fundamental concern to all stakeholders in our freshwater resource. This is a basic element in creating an attractive and security ensured economic for investment in fisheries development, including aquaculture. This is the focus of this paper

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(C<sub>6F₅)_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(C<sub>6F₅)_4¯ and [(SBI)Zr(μ-H)₃(AlⁱBu₂)₂]⁺B(C<sub>6F₅)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.

Zirconocenes as models for homogeneous Ziegler-Natta olefin polymerization catalysts

Using density functional theory, we studied the fundamental steps of olefin polymerization for zwitterionic and cationic Group IV ansa-zirconocenes and a neutral ansa- yttrocene. Complexes [H₂E(C₅H₄)₂ZrMe]ⁿ (n = 0: E = BH₂ (1), BF₂ (2), AlH₂(3); n = +: E = CH₂(4), SiH₂(5)) and H₂Si(C₅H₄)₂YMe were used as computational models. The largest differences among these three classes of compounds were the strength of olefin binding and the stability of the β-agostic alkyl intermediate towards β-hydrogen elimination. We investigated the effect of solvent on the reaction energetics for land 5. We found that in benzene the energetics became very similar except that a higher olefin insertion barrier was calculated for 1. The calculated anion affinity of [CH₃BF₃]^- was weaker towards 1 than 5. The calculated olefin binding depended primarily on the charge of the ansa linker, and the olefin insertion barrier was found to decrease steadily in the following order: [H<sub>2b>C(C5H4)2ZrMe]⁺ > [F2B(C₅H₄)₂ZrMe] ≈ [H₂B(C<sub>5H₄)₂ZrMe] > [H₂Si(C₅H₄)₂ZrMe]⁺ > [H₂Al(C₅H₄)₂ZrMe].

We prepared ansa-zirconocene dicarbonyl complexes Me₂ECp₂Zr(CO)₂ (E = Si, C), and t-butyl substituted complexes (t-BuCp)₂Zr(CO)₂, Me₂E(t-BuCp)₂Zr(CO)₂ (E = Si, C), (Me₂Si)₂(t-BuCp)₂Zr(CO)₂ as well as analogous zirconocene complexes. Both the reduction potentials and carbonyl stretching frequencies follow the same order: Me₂SiCp₂ZrCl₂> Me<sub>2b>CCp2ZrCl2> Cp2ZrCl2> (Me2Si)2b>Cp2ZrCl2. This ordering is a result of both the donating abilities of the cyclopentadienyl substituents and the orientation of the cyclopentadiene rings. Additionally, we prepared a series of analogous cationic zirconocene complexes [LZrOCMe3][MeB(C_{6F5)3] (L = CP2, Me2SiCp2, Me2b>CCP2, (Me2Si)2b>Cp2) and studied the kinetics of anion dissociation. We found that the enthalpy of anion dissociation increased from 10.3 kcal•mol^-1 to 17.6 kcal•mol^-1 as exposure of the zirconium center increased.}

We also prepared series of zirconocene complexes bearing 2,2-dimethyl-2-sila-4-pentenyl substituents (and methyl-substituted olefin variants). Methide abstraction with B(C<sub>6F₅) results in reversible coordination of the tethered olefin to the cationic zirconium center. The kinetics of olefin dissociation have been examined using NMR methods, and the effects of ligand variation for unlinked, singly [SiMe₂]-linked and doubly [SiMe₂]-linked bis(cyclopentadienyl) arrangements has been compared (ΔG‡ for olefin dissociation varies from 12.8 to 15.6 kcal•mol^-1). Methide abstraction from 1,2-(SiMe₂)₂(η⁵-C₅H₃)₂Zr(CH₃)-(CH_{2b>CMe2b>CH2b>CH = CH2) results in rapid β-allyl elimination with loss of isobutene yielding the allyl cation [{1,2-(SiMe2)2(η⁵-C5H3)2Zr(η³-CH2b>CH=CH2)]⁺.}

Polymerization of functionalized olefins with neutral group ten catalysts

This thesis describes the preparation, characterization, and application of welldefined single-component group ten salicylaldimine complexes for the polymerization of ethylene to high molecular weight materials as well as the copolymerization of ethylene and functionalized olefins. After an initial introduction to the field, Chapter 2 describes the preparation of PPh₃ complexes that contain a series of modified salicylaldimine and naphthaldimine ligands. Such complexes were activated for polymerization by the addition of cocatalysts such as Ni(COD)₂ or B(C<sub>6F₅)₃. As the steric demand of the ligand set increased-the molecular weight, polymerization activity, and lifetime of the catalyst was observed to increase. In fact, complexes containing "bulky" ligands, such as the [^Anthr,HSal] ligand (2.5), were found to be highly-active single component complexes for the polymerization of ethylene. Model hydrido compound were prepared-allowing for a better understanding of both the mechanism of polymerization and one mode of decomposition.

Chapter 3 describes the effect which additives play on neutral Ni^II polymerization catalysts such as 2.5. The addition of excess ethers, esters, ketones, anhydrides, alcohols, and water do not deactivate the catalysts for polymerization. However, the addition of excess acid, thiols, and phosphines was observed to shut-down catalysis. Since excess phosphine was found to inhibit catalysis, "phosphine-free" complexes, such as the acetonittile complex (3.26), were prepared. The acetonitrile complex was found to be the most active neutral polymerization catalyst prepared to date.

Chapter 4 outlines the use of catalyst 2.5 and 3.26 for the preparation of linear functionalized copolymers containing alcohols, esters, anhydrides, and ethers. Copolymers can be prepared with γ-functionalized-α-olefins, functionalized norbornenes, and functionalized tricyclononenes, with up to 30 mol% comonomer incorporation.

Chapter 5 outlines the preparation of a series of Pt^II alkyl/olefin salicylaldimine complexes which serve as models for the active species in the Ni^II-catalyzed polymerization process. Understanding the nature of the M-olefin interaction as a the electronic and steric properties of the salicylaldimine ligand is varied has allowed for a number of predictions about the design of future polymerization systems.

Geomorphology of a Portion of the Easternmost Ventura Basin

The Humphreys Quadrangle is a portion of the easternmost Ventura Basin underlain by a thick series of Tertiary sedimentary rocks. On these rocks a great variety of geomorphic forms have been molded by the processes of running water typical of a semi-arid climate and by several types of mass movement. Among the different categories of mass movement present, a new type, the siltflow, was observed.

The geomorphic forms of special interest present in the quadrangle are rock cones, open canyonheads, asymmetric canyons, and stream terraces and straths. The author urges the adoption of the definition of strath as that part of an old dissected valley floor, including the floors of tributary valleys, which was not part of the floodplain of the main valley stream.

An old erosion surface, the Puckett Mesa Surface, is present in the Humphreys Quadrangle which is correlative with certain of the older stream terraces. By correlating the variation of gradient and of fill of the stream terraces with post –Wisconsin climatic fluctuations the age of the Puckett Mesa Surface is set at approximately 6000 B.C. This correlation sets the probable age of the older Rancho La Brea deposits at 6000 to 8000 B. C. and the probable age of the Carpenteria brea deposits at 1000 to 1 B. C.

A Comparison of the SNP Variation in the Calcification PMCA Gene of Lottia gigantea between a Santa Barbara Population and a More Acidic Monterey Bay Population

As the atmospheric levels of CO2 rise from human activity, the carbonic acid levels of the ocean increase, causing ocean acidification. This increase in acidity breaks down the calcified bodies that many marine organisms depend upon. Upwelling regions such as Monterey Bay in California have pH levels that are not expected to reach the open ocean for a few decades. This study reviews one of the common intertidal animals of the California coast, the Owl Limpet Lottia gigantea, and its genetic variation of the plasma membrane Ca2+ ATPase (PMCA) in relation to the acidity of its environment. The PMCA protein functions in the calcification process of many organisms. Specifically in limpets, this gene functions to form its protective shell. Single-nucleotide polymorphisms (SNPs) were found among five sections of the gene to determine variation between the acidic environment population in Monterey, California and the non-acidic environment population in Santa Barbara, California. While some variation was determined, the Monterey Bay and Santa Barbara Lottia gigantea populations are not significantly distinct at the PMCA gene. Sections B, C, and D were found to be linked. Only one location in Section B was found to have an amino acid change within an exon. Section A has the strongest connection to the sampling location. Monterey individuals were seen to be more genetically recognizable, while Santa Barbara individuals showed slightly more variation. Understanding the trends of ocean acidification, upwelling region activities, and population genetics will assist in determining how the ocean environment will behave in the future.

Geoquímica orgânica aplicada à formação Irati, área de Herval, Rio Grande do Sul (RS), bacia do Paraná

Esta dissertação tem por objetivo o estudo geoquímico detalhado em poço da Bacia do Paraná, mais especificamente na cidade de Herval (RS), visando preencher algumas das lacunas existentes em termos de geoquímica orgânica da Formação Irati. Com base nos dados de carbono orgânico total, enxofre total, resíduo insolúvel, raios-gama, isótopos de carbono da matéria orgânica, pirólise Rock-Eval e biomarcadores individualizaram-se dez unidades quimioestratigráficas. Biomarcadores foram usados na caracterização dos ambientes deposicionais, na discriminação da origem da matéria orgânica e da influência da litologia. O ambiente deposicional das unidades A, B, C é óxico com salinidade normal. O topo da unidade B representa a superfície de inundação máxima, onde os valores de COT aumentam. Com base nos biomarcadores caracterizou-se um paleoambiente deposicional com alguma tendência anóxica. Nas unidades D e G ocorrem os folhelhos intercalados com carbonatos. Nestas, a concentração de COT é acima de 1%, porém, somente na unidade G há bom potencial gerador para gás e condensado. As unidades E e I apresentam elevados teores de carbono orgânico total, chegando a 16%. Os dados de pirólise Rock-Eval indicam um bom a excelente potencial gerador para óleo e gás. Os dados isotópicos possibilitaram a divisão da Formação Irati, no poço em estudo, em três ciclos. O primeiro, da base para o topo, corresponde ao Membro Taquaral, os outros dois correspondem ao Membro Assistência. No Membro Assistência o δ13C varia de acordo com a salinidade, aumento da produtividade primária e da preservação da matéria orgânica (anoxia).

四川地区出土古玻璃的质子激发X荧光分析

abstract {Proton induced X-ray emission (PIXE) technique is an effective method for the chemical composition analysis of ancient glass samples without destruction. Chemical composition of the ancient glass samples dated from the Warring States Period (770-476 B.C.) to the Six Dynasties Period (220-589 A.D.), which were unearthed in Sichuan area, was quantitatively determined by the PIXE technique. The results show that the glass Bi (disc) and the glass eye beads of the Warring States Period all belong to the PbO-BaO-SiO₂ system. According to the composition and shape, we infer that these glass Bi and eye beads were made in China. Whereas, the chemical compositions of the glass ear pendants and beads of the Six Dynasties Period are varied, including K₂O-CaO-SiO₂, K₂O-SiO₂ and other glass systems. Based on the obtained results and those from literatures, some questions related to the technical propagation of the ancient Chinese glass are discussed.}

Calculations of bond dissociation energies and dipole moments in energetic materials using density-functional methods

We compare the effectiveness of six exchange/correlation functional combinations (Becke/Lee, Yang and Parr; Becke-3/Lee, Yang and Parr; Becke/Perdew-Wang 91; Becke-3/Perdew-Wang 91; Becke/Perdew 86; Becke-3/Perdew 86) for computing C-N, O-O and N-NO2 dissociation energies and dipole moments of five compounds. The studied compounds are hexabydro-1,3,5-trinitro-1,3,5-triazine (RDX), dimethylnitramine, cyanogen, nitromethane and ozone. The Becke-3/Perdew 86 in conjunction with 6-31G

γ-LiAlO_2上a面ZnO薄膜的光谱特性研究

利用激光脉冲沉积(PLD)技术在(302)γ-LiAlO2衬底上成功生长了非极性的a面(1120)ZnO薄膜,光致发光谱(PL)带边发射峰半峰宽仅为115meV.研究了非极性ZnO薄膜光谱特性的面内各向异性,发现随着入射光偏振方向改变,在偏振透射光谱上,吸收边移动了20meV,这与A、B激子和C激子的能量差一致;而在拉曼光谱上,激发光偏振方向的改变导致E2模式的强度发生明显改变.

A Comunicação Alternativa favorecendo a aprendizagem de crianças com autismo, Asperger e Angelman: formação continuada de profissionais de Educação e Saúde

A formação continuada de profissionais de Educação e Saúde se constitui como objeto desta dissertação. Na presente pesquisa pretendi planejar, implementar e avaliar os efeitos de um programa de formação continuada de profissionais de Educação e Saúde, oferecendo instruções e orientações de uso dos recursos da Comunicação Alternativa e Ampliada (CAA), para favorecer a comunicação e aprendizagem de crianças com autismo, Asperger e Angelman. Os estudos foram realizados em uma escola regular e em uma instituição especializada, com abordagem clínica-terapêutica-educacional. O universo da pesquisa abrangeu oito profissionais: duas professoras de classes regulares de ensino, uma professora especialista (Atendimento Educacional Especializado), duas estagiárias (estudantes de Pedagogia), exercendo a função de mediadora do aluno com autismo incluído, uma professora da instituição especializada, um auxiliar da professora e uma psicóloga. Também nove crianças fizeram parte desse universo: uma criança com autismo, incluída em classe regular e oito crianças que frequentavam a instituição especializada, sendo duas com Asperger, quatro com autismo e duas com Angelman. Para responder à pergunta principal do estudo: A Comunicação Alternativa e Ampliada pode favorecer a comunicação e a aprendizagem de crianças com autismo, Asperger e Angelman?, foi necessário conhecer os profissionais, as instituições e as respectivas gestoras, bem como o corpo docente, a equipe técnica e as crianças assistidas pelos profissionais, para verificar as suas necessidades, potencialidades, interesses e limitações. Outro elemento fundamental na proposta de formação dos profissionais foram os procedimentos do ensino e da consultoria colaborativa. A pesquisa foi desenvolvida em três estudos, durante o período de julho de 2010 a abril de 2012. Foi utilizado o delineamento intrasujeitos do tipo A-B (estudo I) e A-B-C (estudos II e III) e análise qualitativa dos resultados. Os procedimentos iniciais adotados foram: aplicação de questionários para os profissionais e os responsáveis pelas crianças, entrevistas semiestruturadas com as gestoras das instituições, observações in loco, filmagens das atividades pedagógicas e anotações de campo. Com base nos questionários, entrevistas, observações e anotações foram levantadas as principais dificuldades e necessidades dos profissionais e das crianças e construídos protocolos de observação dos comportamentos destes sujeitos. Durante o desenvolvimento dos estudos foram realizadas filmagens das atividades pedagógicas e anotações de campo, bem como reuniões com os profissionais, para orientações e planejamento das atividades pedagógicas adaptadas a serem desenvolvidas com as crianças, bem como materiais e recursos da CAA. Os resultados apontaram à presença de algumas modificações nos comportamentos dos profissionais e nos comportamentos das crianças. Revelaram ainda, que este trabalho proporcionou aos profissionais a oportunidade de reverem as suas atuações e as suas crenças, com relação à inclusão de crianças com autismo, Asperger e Angelman em ambientes não protegidos. Foi possível verificar as contribuições dos procedimentos e dos recursos da CAA, para favorecer a comunicação, a autorregulação e a aprendizagem dessas crianças e o quanto os procedimentos do ensino e da consultoria colaborativa se apresentam como promissores para o desenvolvimento dos profissionais.

Prisioneros de los piratas: política y propaganda en la captura de Julio César y Clodio

Este artículo se inscribe dentro del programa de perfeccionamiento postdoctoral en el extranjero del Departamento de Educación, Universidades e Investigación del Gobierno Vasco. Forma parte, asimismo, del proyecto HAR2010-21893: «El discurso sobre el imperio en la República romana: Estrategias de dominación en la oratoria diplomática»