Organotitanium and niobium chemistry. I. Structure and reactivity of a titanium ethylene complex. II. Reactivity of decamethyl niobocene derivatives

The synthesis and X-ray diffraction study of bis(pentamethylcyclopentadienyl) ethylene titanium (I) are reported. This complex represents the first example of an isolable ethylene adduct of a group IV metal, a key intermediate in Ziegler-Natta olefin polymerization schemes. While treatment of I with ethylene leads to only traces of polymer after months, I participates in a wide range of stoichiometric and catalytic reactions. These include the catalytic conversion of ethylene specifically to butadiene and ethane and the catalytic isomerization of alkenes. Detailed studies have been carried out on the stoichiometric reactions of I with nitriles and alkynes. At low temperatures, nitriles react to form metallacycloimine species which more slowly undergo a formal 1,3-hydrogen shift to generate metallacycloeneamines. The lowest energy pathway for this rearrangement is an intramolecular hydrogen shift which is sensitive to the steric bulk of the R substituent. The reactions of I with alkynes yield metallacyclopentene complexes with high regioisomer selectivity. Carbonylation of the metallacyclopentene (η-C₅Me₅5)₂TiC(CH₃)=C(CH₃)CH₂ under relatively mild conditions cleanly produces the corresponding cyclopentenone and [C₅(CH₃)₅]₂Ti(CO)₂. Compounds derived from CO₂ and acetaldehyde have also been isolated.

The synthesis and characterization of bis-(η-pentamethylcyclopentadienyl) niobium(III) tetrahydroborate (II) are described and a study of its temperature-dependent proton NMR spectroscopic behavior is reported. The complex is observed to undergo a rapid intramolecular averaging process at elevated temperatures. The free energy of activation, ΔG^≠ = 16.4 ± 0.4 kcal/mol, is calculated. The reinvestigation of a related compound, bis(η-cyclopentadienyl)niobium(III) tetrahydroborate, established ΔG^≠ = 14.6 ± 0.2 kcal/mol for the hydrogen exchange process. The tetrahydroborate complex, II reacts with pyridine and dihydrogen to yield (η-C₅Me₅5)₂NbH₃ (III). The reactivity of III with CO and ethylene is reported.

Optimal guidance of low-thrust interplanetary space vehicles

The low-thrust guidance problem is defined as the minimum terminal variance (MTV) control of a space vehicle subjected to random perturbations of its trajectory. To accomplish this control task, only bounded thrust level and thrust angle deviations are allowed, and these must be calculated based solely on the information gained from noisy, partial observations of the state. In order to establish the validity of various approximations, the problem is first investigated under the idealized conditions of perfect state information and negligible dynamic errors. To check each approximate model, an algorithm is developed to facilitate the computation of the open loop trajectories for the nonlinear bang-bang system. Using the results of this phase in conjunction with the Ornstein-Uhlenbeck process as a model for the random inputs to the system, the MTV guidance problem is reformulated as a stochastic, bang-bang, optimal control problem. Since a complete analytic solution seems to be unattainable, asymptotic solutions are developed by numerical methods. However, it is shown analytically that a Kalman filter in cascade with an appropriate nonlinear MTV controller is an optimal configuration. The resulting system is simulated using the Monte Carlo technique and is compared to other guidance schemes of current interest.

On the local Tamagawa number conjecture for Tate motives

There is a wonderful conjecture of Bloch and Kato that generalizes both the analytic Class Number Formula and the Birch and Swinnerton-Dyer conjecture. The conjecture itself was generalized by Fukaya and Kato to an equivariant formulation. In this thesis, I provide a new proof for the equivariant local Tamagawa number conjecture in the case of Tate motives for unramified fields, using Iwasawa theory and (φ,Γ)-modules, and provide some work towards extending the proof to tamely ramified fields.

Fiber-optic integration and efficient detection schemes for optomechanical resonators

With the advent of the laser in the year 1960, the field of optics experienced a renaissance from what was considered to be a dull, solved subject to an active area of development, with applications and discoveries which are yet to be exhausted 55 years later. Light is now nearly ubiquitous not only in cutting-edge research in physics, chemistry, and biology, but also in modern technology and infrastructure. One quality of light, that of the imparted radiation pressure force upon reflection from an object, has attracted intense interest from researchers seeking to precisely monitor and control the motional degrees of freedom of an object using light. These optomechanical interactions have inspired myriad proposals, ranging from quantum memories and transducers in quantum information networks to precision metrology of classical forces. Alongside advances in micro- and nano-fabrication, the burgeoning field of optomechanics has yielded a class of highly engineered systems designed to produce strong interactions between light and motion.

Optomechanical crystals are one such system in which the patterning of periodic holes in thin dielectric films traps both light and sound waves to a micro-scale volume. These devices feature strong radiation pressure coupling between high-quality optical cavity modes and internal nanomechanical resonances. Whether for applications in the quantum or classical domain, the utility of optomechanical crystals hinges on the degree to which light radiating from the device, having interacted with mechanical motion, can be collected and detected in an experimental apparatus consisting of conventional optical components such as lenses and optical fibers. While several efficient methods of optical coupling exist to meet this task, most are unsuitable for the cryogenic or vacuum integration required for many applications. The first portion of this dissertation will detail the development of robust and efficient methods of optically coupling optomechanical resonators to optical fibers, with an emphasis on fabrication processes and optical characterization.

I will then proceed to describe a few experiments enabled by the fiber couplers. The first studies the performance of an optomechanical resonator as a precise sensor for continuous position measurement. The sensitivity of the measurement, limited by the detection efficiency of intracavity photons, is compared to the standard quantum limit imposed by the quantum properties of the laser probe light. The added noise of the measurement is seen to fall within a factor of 3 of the standard quantum limit, representing an order of magnitude improvement over previous experiments utilizing optomechanical crystals, and matching the performance of similar measurements in the microwave domain.

The next experiment uses single photon counting to detect individual phonon emission and absorption events within the nanomechanical oscillator. The scattering of laser light from mechanical motion produces correlated photon-phonon pairs, and detection of the emitted photon corresponds to an effective phonon counting scheme. In the process of scattering, the coherence properties of the mechanical oscillation are mapped onto the reflected light. Intensity interferometry of the reflected light then allows measurement of the temporal coherence of the acoustic field. These correlations are measured for a range of experimental conditions, including the optomechanical amplification of the mechanics to a self-oscillation regime, and comparisons are drawn to a laser system for phonons. Finally, prospects for using phonon counting and intensity interferometry to produce non-classical mechanical states are detailed following recent proposals in literature.

Studies of response to earthquake ground motion

A study is made of the accuracy of electronic digital computer calculations of ground displacement and response spectra from strong-motion earthquake accelerograms. This involves an investigation of methods of the preparatory reduction of accelerograms into a form useful for the digital computation and of the accuracy of subsequent digital calculations. Various checks are made for both the ground displacement and response spectra results, and it is concluded that the main errors are those involved in digitizing the original record. Differences resulting from various investigators digitizing the same experimental record may become as large as 100% of the maximum computed ground displacements. The spread of the results of ground displacement calculations is greater than that of the response spectra calculations. Standardized methods of adjustment and calculation are recommended, to minimize such errors.

Studies are made of the spread of response spectral values about their mean. The distribution is investigated experimentally by Monte Carlo techniques using an electric analog system with white noise excitation, and histograms are presented indicating the dependence of the distribution on the damping and period of the structure. Approximate distributions are obtained analytically by confirming and extending existing results with accurate digital computer calculations. A comparison of the experimental and analytical approaches indicates good agreement for low damping values where the approximations are valid. A family of distribution curves to be used in conjunction with existing average spectra is presented. The combination of analog and digital computations used with Monte Carlo techniques is a promising approach to the statistical problems of earthquake engineering.

Methods of analysis of very small earthquake ground motion records obtained simultaneously at different sites are discussed. The advantages of Fourier spectrum analysis for certain types of studies and methods of calculation of Fourier spectra are presented. The digitizing and analysis of several earthquake records is described and checks are made of the dependence of results on digitizing procedure, earthquake duration and integration step length. Possible dangers of a direct ratio comparison of Fourier spectra curves are pointed out and the necessity for some type of smoothing procedure before comparison is established. A standard method of analysis for the study of comparative ground motion at different sites is recommended.

On the set of eigenvalues of a class of equimodular matrices

The structure of the set ϐ(A) of all eigenvalues of all complex matrices (elementwise) equimodular with a given n x n non-negative matrix A is studied. The problem was suggested by O. Taussky and some aspects have been studied by R. S. Varga and B.W. Levinger.

If every matrix equimodular with A is non-singular, then A is called regular. A new proof of the P. Camion-A.J. Hoffman characterization of regular matrices is given.

The set ϐ(A) consists of m ≤ n closed annuli centered at the origin. Each gap, ɤ, in this set can be associated with a class of regular matrices with a (unique) permutation, π(ɤ). The association depends on both the combinatorial structure of A and the size of the a_ii. Let A be associated with the set of r permutations, π₁, π₂,…, π_r, where each gap in ϐ(A) is associated with one of the π_k. Then r ≤ n, even when the complement of ϐ(A) has n+1 components. Further, if π(ɤ) is the identity, the real boundary points of ɤ are eigenvalues of real matrices equimodular with A. In particular, if A is essentially diagonally dominant, every real boundary point of ϐ(A) is an eigenvalues of a real matrix equimodular with A.

Several conjectures based on these results are made which if verified would constitute an extension of the Perron-Frobenius Theorem, and an algebraic method is introduced which unites the study of regular matrices with that of ϐ(A).

Alveolar nitric oxide and its role in pediatric asthma control assessment

Resumen Background: Nitric oxide can be measured at multiple flow rates to determine proximal (maximum airway nitric oxide flux; Jaw(NO)) and distal inflammation (alveolar nitric oxide concentration; CA(NO)). The main aim was to study the association among symptoms, lung function, proximal (maximum airway nitric oxide flux) and distal (alveolar nitric oxide concentration) airway inflammation in asthmatic children treated and not treated with inhaled glucocorticoids. Methods: A cross-sectional study with prospective data collection was carried out in a consecutive sample of girls and boys aged between 6 and 16 years with a medical diagnosis of asthma. Maximum airway nitric oxide flux and alveolar nitric oxide concentration were calculated according to the two-compartment model. In asthmatic patients, the asthma control questionnaire (CAN) was completed and forced spirometry was performed. In controls, differences between the sexes in alveolar nitric oxide concentration and maximum airway nitric oxide flux and their correlation with height were studied. The correlation among the fraction of exhaled NO at 50 ml/s (FENO50), CA(NO), Jaw(NO), forced expiratory volume in 1 second (FEV1) and the CAN questionnaire was measured and the degree of agreement regarding asthma control assessment was studied using Cohen's kappa. Results: We studied 162 children; 49 healthy (group 1), 23 asthmatic participants without treatment (group 2) and 80 asthmatic patients treated with inhaled corticosteroids (group 3). CA(NO) (ppb) was 2.2 (0.1-4.5), 3 (0.2-9.2) and 2.45 (0.1-24), respectively. Jaw(NO) (pl/s) was 516 (98.3-1470), 2356.67 (120-6110) and 1426 (156-11805), respectively. There was a strong association (r = 0.97) between FENO50 and Jaw(NO) and the degree of agreement was very good in group 2 and was good in group 3. There was no agreement or only slight agreement between the measures used to monitor asthma control (FEV1, CAN questionnaire, CA(NO) and Jaw(NO)). Conclusions: The results for CA(NO) and Jaw(NO) in controls were similar to those found in other reports. There was no agreement or only slight agreement among the three measure instruments analyzed to assess asthma control. In our sample, no additional information was provided by CA(NO) and Jaw(NO).

Origem e função da fantasia na obra freudiana

O objetivo desse estudo foi investigar a origem e a função da fantasia na obra de Sigmund Freud, por meio do papel que desempenha na constituição do psiquismo humano e da sua importância em produzir um sentido para a vida. A pesquisa - de cunho bibliográfico - buscou esclarecer os diferentes usos e modificações do termo "fantasia" no decorrer das descobertas realizadas por Freud ao longo de sua vida e obra, desde o período denominado de pré-psicanalítico (1886/1899) até os últimos textos publicados no Esboço de Psicanálise (1940 [1938]). A análise da investigação revelou três grandes eixos descritivos, complexos, por vezes contraditórios e submetidos a constantes redefinições que caracterizam a fantasia como um sintoma, uma criação e um enigma da transmissão geracional. A conclusão corrobora o pressuposto de que a vida não tem sentido sem a capacidade de fantasiar. A fantasia ocupa um lugar de fundamental importância no pensamento freudiano, comparecendo como um elemento essencial na constituição do psiquismo e revelando horizontes, para que os estudiosos da psicanálise pudessem ampliar essa investigação tão reveladora da psiquê.

Ontogênse do sorriso no contexto da interação mãe-bebê

Esta tese teve como objetivos: (I) propor uma articulação teórica para o estudo do sorriso contemplando a dimensão histórica, sociocultural e evolutiva da espécie humana e seu aparato biológico; (II) realizar dois estudos empíricos, um longitudinal, da terceira semana ao sexto mês de vida de dois bebês e outro transversal, com bebês de um, dois e cinco meses de nascidos, com o propósito de: (II.1) investigar se há algum padrão de sorrisos em termos de freqüência, duração e características morfológicas, e se ocorrem transformações nesse padrão nos seis primeiros meses de vida; (II.2) analisar padrões de sorriso apresentados na presença de comportamentos afetivos da mãe, nesse período; e (II.3) verificar se os bebês respondem de modo contingente, com sorrisos, aos comportamentos afetivos da mãe, e se há padrões diferenciados por tipo de sorriso. Participaram do estudo longitudinal duas díades mãe-bebê, filmadas em suas residências, semanalmente. Do estudo transversal, para cada grupo de diferentes idades, participaram vinte díades mãe-bebê, também filmadas em suas residências. As categorias de observação, comuns aos dois estudos, foram codificadas em duas partes, sendo a referente aos sorrisos do bebê com comportamentos mutuamente exclusivos e exaustivos. Os índices de Kappa de Cohen e de concordância indicaram boa fidedignidade entre os observadores. Entre outras evidências, verificou-se tendência de trajetória de curva ascendente para os sorrisos dos bebês no período estudado, F(1,22) = 6,77, p<0,05, para um dos bebês do estudo longitudinal, e, F(1,23) = 7,85, p<0,05, para o outro. Os dois bebês revelaram uma tendência particular a exibir com mais freqüência um ou dois tipos de sorrisos. Os sorrisos da mãe, como demais comportamentos afetivos, mostraram-se potenciais eliciadores de sorrisos de tipos variados nos bebês. Correlações significativas foram encontradas, na pesquisa longitudinal, entre os tipos mais freqüentes de sorrisos dos bebês e os sorrisos de suas mães (r=0,77, p<0,0017, para um dos bebês, e r=0,62, p<0,0017, para o outro). Também no estudo transversal foi verificada correlação entre o sorriso simples e o sorriso da mãe (r=0,70, p<0,0007). Sorrisos de diferentes tipos foram exibidos pelos bebês, tanto no estudo longitudinal, quanto no transversal, como respostas contingentes aos comportamentos maternos observados. Esses e outros resultados indicam uma associação significativa entre os sorrisos dos bebês e comportamentos afetivos das mães. A relevância da temática desse trabalho contrasta com a carência de estudos brasileiros sobre o tema. Entende-se que essa lacuna precisa ser superada, e esta tese representou um movimento nessa direção.

A relação mãe e filha e a aposta libidinal da mulher

O presente trabalho tem como objetivo investigar, sob a luz da psicanálise, o vínculo existente entre mães e filhas e suas conseqüências para a vida sexual das mulheres. Para tanto, o recorte teórico feito contempla a teoria do feminino em psicanálise e, mais especificamente, a fase pré-edipiana em Freud e sua leitura lacaniana. O argumento norteador dessa dissertação parte do princípio de que, no momento da incidência da castração pela descoberta de uma falta articulada ao significante, uma mulher reedita seu vínculo pré-edipiano com o Outro materno e apela por um significante que a represente como mulher. Este apelo se reatualiza durante toda a sua vida e torna nebulosa a distância a ser construída e mantida entre demanda e desejo, o que problematiza a assunção do desejo como separado do desejo do Outro primordial. Lacan nomeia de devastação a persistência desse endereçamento de demanda infinita de amor. É no vínculo amoroso mantido e sempre reeditado entre a menina e sua mãe que se localiza a problemática de suas escolhas libidinais. Para as mulheres, amor e devastação possuem estreito parentesco porque ambos estão sob o registro do sem limite e da falta de significante no Outro. Diante desse gozo fora da lógica fálica e da falta de um significante que defina o que é uma mulher, a devastação se apresenta como resposta no relacionamento entre mãe e filha e nas parcerias amorosas.

Strengthening governance across scales in aquatic agricultural systems

Aquatic agricultural systems in developing countries face increasing competition from multiple stakeholders operating from local to national and regional scales over rights to access and use natural resources—land, water, wetlands, and fisheries-essential to rural livelihoods. A key implication is the need to strengthen governance to enable equitable decision-making amidst such competition, building capacities for resilience and transformations that reduce poverty. This paper provides a simple framework to analyze the governance context for aquatic agricultural system development focused on three dimensions: stakeholder representation, distribution of power, and mechanisms of accountability. Case studies from Cambodia, Bangladesh, Malawi/Mozambique, and Solomon Islands illustrate the application of these concepts to fisheries and aquaculture livelihoods in the broader context of intersectoral and cross-scale governance interacti

Modelos teóricos da deficiência no discurso acadêmico brasileiro: perspectivas integracionistas e o campo da saúde coletiva

Atualmente, a deficiência é pensada através de dois modelos principais: o modelo médico e o modelo social. Cada um deles adota paradigmas próprios para a definição da deficiência e a proposição de ações reparadoras. Os efeitos sociais da adoção destes modelos variam amplamente, indo da exclusão à inclusão social de pessoas com deficiência. Esta dissertação apresenta a contribuição de perspectivas críticas recentes - nomeadas aqui como perspectivas integracionistas - que congregam elementos dos modelos anteriores. Essas perspectivas apontam para os limites dos modelos tradicionais, e propõem uma abordagem integrada que possa dar conta da complexidade do fenômeno da deficiência, característica que as tornam particularmente interessantes para o campo da Saúde Coletiva. No Brasil a deficiência ainda é considerada uma temática específica de determinados nichos de conhecimento, mais ligados aos campos da saúde e da educação. O tema da deficiência permanece abordado de modo incipiente pelas ciências humanas e sociais no país. No entanto, o país atravessa um momento de transição de paradigmas a respeito da deficiência: ao mesmo tempo em que desenvolvemos dispositivos legais alinhados às diretrizes da Convenção sobre os Direitos das Pessoas com Deficiência (ONU), ainda há uma enorme diferença entre os discursos circulantes e as práticas efetivamente dirigidas às pessoas com deficiência. Por esta razão, este trabalho buscou traçar um panorama do discurso acadêmico brasileiro sobre a deficiência, visando avaliar como as diferentes perspectivas e modelos teóricos emergem nas narrativas acadêmicas sobre o tema. Para isso, foi realizada uma revisão bibliográfica em base de dados virtuais (SciELO Brazil). Foram selecionados para a amostra artigos cujos conteúdos se relacionavam à questão da deficiência no Brasil e trouxessem achados de pesquisas empíricas, relatos de experiência, pesquisas documentais ou estudos de caso no tema da deficiência. Procedimentos quantitativos e qualitativos foram usados para a análise da amostra. O trabalho se divide em duas partes: a primeira parte apresenta os principais modelos teóricos da deficiência e a contribuição crítica das perspectivas integracionistas. O propósito de tal discussão teórica é situar a deficiência em sua transversalidade e destacar as relações entre a adoção de um modelo e as práticas e discursos sobre a deficiência que dele se derivam. A segunda parte do trabalho apresenta e discute os dados da pesquisa, buscando levantar as especificidades do contexto brasileiro sobre o tema da deficiência, relacionando os achados com os debates internacionais do campo dos Estudos sobre Deficiência.

A nursery site of the Alaska skate (Bathyraja parmifera) in the eastern Bering Sea

A nursery site for the Alaska skate (Bathyraja parmifera) was sampled seasonally from June 2004 to July 2005. At the small nursery site (~2 km2), located in a highly productive area near the shelf-slope interface at the head of Bering Canyon in the eastern Bering Sea, reproductive males and females dominated the catch and neonate and juvenile skates were rare. Seasonal samples showed summertime (June and July) as the peak reproductive time in the nursery although some reproduction occurred throughout the year. Timeseries analysis of embryo length frequencies revealed that three cohorts were developing simultaneously and the period of embryonic development was estimated at 3.5 years and average embryo growth rate at 0.2 mm/day. Estimated egg case deposition occurred mainly during summertime and hatching occurred during winter months. Protracted hatching times may be common for oviparous elasmobranch species and may be directly correlated with ambient temperatures as evident from a meta-data analysis. Evidence indicates that the Alaska skate uses the eastern Bering Sea outer continental shelf region for reproduction and the middle and inner shelf regions as habitat for immature and subadults. Skate nurseries may be vulnerable to disturbances because they are located in highly productive areas and because embryos develop slowly.

Emerging patterns of species richness, diversity, population density, and distribution in the skates (Rajidae) of Alaska

Six years of bottom-trawl survey data, including over 6000 trawls covering over 200 km2 of bottom area throughout Alaska’s subarctic marine waters, were analyzed for patterns in species richness, diversity, density, and distribution of skates. The Bering Sea continental shelf and slope, Aleutian Islands, and Gulf of Alaska regions were stratified by geographic subregion and depth. Species richness and relative density of skates increased with depth to the shelf break in all regions. The Bering Sea shelf was dominated by the Alaska skate (Bathyraja parmifera), but species richness and diversity were low. On the Bering Sea slope, richness and diversity were higher in the shallow stratum, and relative density appeared higher in subregions dominated by canyons. In the Aleutian Islands and Gulf of Alaska, species richness and relative density were generally highest in the deepest depth strata. The data and distribution maps presented here are based on species-level data collected throughout the marine waters of Alaska, and this article represents the most comprehensive summary of the skate fauna of the region published to date.

Re-estimation of small-scale fishery catches for U.S. flag-associated island areas in the western Pacific: the last 50 years

Nearshore fisheries in the tropical Pacific play an important role, both culturally and as a reliable source of food security, but often remain under-reported in statistics, leading to undervaluation of their importance to communities. We re-estimated nonpelagic catches for Guam and the Commonwealth of the Northern Mariana Islands (CNMI), and summarize previous work for American Samoa for 1950−2002. For all islands combined, catches declined by 77%, contrasting with increasing trends indicated by reported data. For individual island entities, re-estima-tion suggested declines of 86%, 54%, and 79% for Guam, CNMI, and American Samoa, respectively. Except for Guam, reported data primarily represented commercial catches, and hence under-represented contributions by subsistence and recreational fisheries. Guam’s consistent use of creel surveys for data collection resulted in the most reliable reported catches for any of the islands considered. Our re-estimation makes the scale of under-reporting of total catches evident, and provides valuable baselines of likely historic patterns in fisheries catches.