Norbornenyl- and nortricyclyl free radicals

The number, symmetry, and product-forming capabilities of the intermediates in the photoinitiated reductions of endo- and exo-5- bromonorbornene and 2-bromonortricyclene with tri-n-butyltin hydride at temperatures between -10° and 22° were investigated.

Three mechanisms were evaluated:

1. The 5-norbornenyl- and 2-nortricyclyl radicals isomerize reversibly with the former producing nortricyclene by abstraction of hydrogen from tri-n-butyltin hydride.

2. The 5-norbornenyl- and 2-nortricyclyl radicals isomerize reversibly, but some norbornene can be formed from the 2-nortricyclyl radical or some nortricyclene can be formed from the 5-norbornenyl radical by abstraction of hydrogen.

3. There is intervention of a "bridged" radical which may be for med reversibly or irreversibly from the 5-norbornenyl- and 2-nortricyclyl radicals.

Within small error limits, the ratios of norbornene to nortricyclene as a function of the concentration of tri-n-butyltin hydride are consistent with the first mechanism.

In the reductions with tri-n-butyltin deuteride, primary deuterium isotope effects of 2. 3 and 2. 1 for the abstraction of deuterium by the 2-nortricyclyl- and 5-norbornenyl radicals, respectively, were found. The primary deuterium isotope effects were invariant with the concentration of tri-n-butyltin deuteride, although the ratios of norbornene to nortricyclene changed appreciably over this range. This is consistent with the first mechanism, and can accommodate the formation of either product from more than one intermediate only if the primary kinetic deuterium isotope effects are nearly equal for all reactions leading to the single product.

The reduction of endo-5-bromonorbornene-5, 6, 6-d₃ with tri-n-butyltin hydride or tri-n-butyltin deuteride leads to both unrearranged and rearranged norbornenes. The ratios of unrearranged to rearranged norbornene require that the 5-norbornenyl-5, 6, 6-d₃ radical isomerize to an intermediate with the symmetry expected of a nortricyclyl free radical. The results are consistent with mechanism 1, but imply a surprising normal secondary kinetic deuterium isotope effect of about 1.25 for the abstraction of hydrogen by the 5-norbornenyl- 5, 6, 6-d₃ radical.

Approximate calculations show that there does not appear to be any substantial difference in the stabilities of the 5-norbornenyl and 2-nortricyclyl radicals.

Although the results can not exclude a small contribution by a mechanism other than mechanism 1, no such contribution is required to adequately explain the results.

Ratio of natural isotopes of nitrogen. I. Primary results: soils of Dombes [Translation from: Revue d'Ecologie et de Biologie du Sol 14, 279-287, 1977]

Utilization of the heavy isotope of nitrogen as a tracer has found numerous applications in soil biology. It allows better definition of different stages of the nitrogen cycle, in particular the immobilization-mineralization cycle. In this work, the authors report the results of calculations of natural isotope ratios of nitrogen in samples of water, soil and vegetation prevailing in Dombes and discuss the possibilities of errors and coefficients of fractionation.

Field and Laboratory Studies of Atmospheric Organic Aerosol

This thesis is the culmination of field and laboratory studies aimed at assessing processes that affect the composition and distribution of atmospheric organic aerosol. An emphasis is placed on measurements conducted using compact and high-resolution Aerodyne Aerosol Mass Spectrometers (AMS). The first three chapters summarize results from aircraft campaigns designed to evaluate anthropogenic and biogenic impacts on marine aerosol and clouds off the coast of California. Subsequent chapters describe laboratory studies intended to evaluate gas and particle-phase mechanisms of organic aerosol oxidation.

The 2013 Nucleation in California Experiment (NiCE) was a campaign designed to study environments impacted by nucleated and/or freshly formed aerosol particles. Terrestrial biogenic aerosol with > 85% organic mass was observed to reside in the free troposphere above marine stratocumulus. This biogenic organic aerosol (BOA) originated from the Northwestern United States and was transported to the marine atmosphere during periodic cloud-clearing events. Spectra recorded by a cloud condensation nuclei counter demonstrated that BOA is CCN active. BOA enhancements at latitudes north of San Francisco, CA coincided with enhanced cloud water concentrations of organic species such as acetate and formate.

Airborne measurements conducted during the 2011 Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE) were aimed at evaluating the contribution of ship emissions to the properties of marine aerosol and clouds off the coast of central California. In one study, analysis of organic aerosol mass spectra during periods of enhanced shipping activity yielded unique tracers indicative of cloud-processed ship emissions (m/z 42 and 99). The variation of their organic fraction (f₄₂ and f₉₉) was found to coincide with periods of heavy (f₄₂ > 0.15; f₉₉ > 0.04), moderate (0.05 < f₄₂ < 0.15; 0.01 < f₉₉ < 0.04), and negligible (f₄₂ < 0.05; f₉₉ < 0.01) ship influence. Application of these conditions to all measurements conducted during E-PEACE demonstrated that a large fraction of cloud droplet (72%) and dry aerosol mass (12%) sampled in the California coastal study region was heavily or moderately influenced by ship emissions. Another study investigated the chemical and physical evolution of a controlled organic plume emitted from the R/V Point Sur. Under sunny conditions, nucleated particles composed of oxidized organic compounds contributed nearly an order of magnitude more cloud condensation nuclei (CCN) than less oxidized particles formed under cloudy conditions. The processing time necessary for particles to become CCN active was short ( < 1 hr) compared to the time needed for particles to become hygroscopic at sub-saturated humidity ( > 4 hr).

Laboratory chamber experiments were also conducted to evaluate particle-phase processes influencing aerosol phase and composition. In one study, ammonium sulfate seed was coated with a layer of secondary organic aerosol (SOA) from toluene oxidation followed by a layer of SOA from α-pinene oxidation. The system exhibited different evaporative properties than ammonium sulfate seed initially coated with α-pinene SOA followed by a layer of toluene SOA. This behavior is consistent with a shell-and-core model and suggests limited mixing among different SOA types. Another study investigated the reactive uptake of isoprene epoxy diols (IEPOX) onto non-acidified aerosol. It was demonstrated that particle acidity has limited influence on organic aerosol formation onto ammonium sulfate seed, and that the chemical system is limited by the availability of nucleophiles such as sulfate.

Flow tube experiments were conducted to examine the role of iron in the reactive uptake and chemical oxidation of glycolaldehyde. Aerosol particles doped with iron and hydrogen peroxide were mixed with gas-phase glycolaldehyde and photochemically aged in a custom-built flow reactor. Compared to particles free of iron, iron-doped aerosols significantly enhanced the oxygen to carbon (O/C) ratio of accumulated organic mass. The primary oxidation mechanism is suggested to be a combination of Fenton and photo-Fenton reactions which enhance particle-phase OH radical concentrations.

A contribution to the algal flora of the Kola Peninsula [Translation from: Trudy Institut Botaniki Trudy Institut Botaniki Kharkivskii. Univ Vol. 4, pp. 53-76, 1941]

During recent years in connection with the industrialisation of the Kola Peninsula, the study of this district in the botanical respect, in particular the study of the microflora of various bodies of water, began to advance markedly. This article describes the algal flora of the Kola Peninsula. Morphological descriptions are given for three Tetraspora: Tetraspora simplex, Tetraspora tenera, Tetraspora imperfecta. Chlorophysema aduata is also described, and short descriptions of further algae found in the Kola Peninsula are given.

Photochemical electron transfer at fixed distance : a synthetic model of the photosynthetic primary process

A series of meso-phenyloctamethylporphyrins covalently bonded at the 4'phenyl position to quinones via rigid bicyclo[2.2.2]octane spacers were synthesized for the study of the dependence of electron transfer reaction rate on solvent, distance, temperature, and energy gap. A general and convergent synthesis was developed based on the condensation of ac-biladienes with masked quinonespacer-benzaldehydes. From picosecond fluorescence spectroscopy emission lifetimes were measured in seven solvents of varying polarity. Rate constants were determined to vary from 5.0x10⁹sec^-1 in N,N-dimethylformamide to 1.15x10¹⁰ Sec^-1 in benzene, and were observed to rise at most by about a factor of three with decreasing solvent polarity. Experiments at low temperature in 2-MTHF glass (77K) revealed fast, nearly temperature-independent electron transfer characterized by non-exponential fluorescence decays, in contrast to monophasic behavior in fluid solution at 298K. This example evidently represents the first photosynthetic model system not based on proteins to display nearly temperature-independent electron transfer at high temperatures (nuclear tunneling). Low temperatures appear to freeze out the rotational motion of the chromophores, and the observed nonexponential fluorescence decays may be explained as a result of electron transfer from an ensemble of rotational conformations. The nonexponentiality demonstrates the sensitivity of the electron transfer rate to the precise magnitude of the electronic matrix element, which supports the expectation that electron transfer is nonadiabatic in this system. The addition of a second bicyclooctane moiety (15 Å vs. 18 Å edge-to-edge between porphyrin and quinone) reduces the transfer rate by at least a factor of 500-1500. Porphyrinquinones with variously substituted quinones allowed an examination of the dependence of the electron transfer rate constant κ_ET on reaction driving force. The classical trend of increasing rate versus increasing exothermicity occurs from 0.7 eV≤ |ΔG^0'(R)| ≤ 1.0 eV until a maximum is reached (κ_ET = 3 x 10⁸ sec^-1 rising to 1.15 x 10¹⁰ sec^-1 in acetonitrile). The rate remains insensitive to ΔG⁰ for ~ 300 mV from 1.0 eV≤ |ΔG^0’(R)| ≤ 1.3 eV, and then slightly decreases in the most exothermic case studied (cyanoquinone, κ_ET = 5 x 10⁹ sec^-1).

Analysing the contribution of ATM/ATR pathway activation in establishing the premature senescence of E2F1/E2F2-/- bone-marrow-derived macrophages

E2F1 and E2F2 transcription factors have an important role during the regulation of cell cycle. In experiments done with E2F1/E2F2 knockout mice, it has been described that bone-marrow-derived macrophages (BMDM) undergo an early rapid proliferation event related to DNA hyper-replication. As a consequence, DNA damage response (DDR) pathway is triggered and E2F1/E2F2 knockout macrophages enter premature senescence related to G2/M phase arrest. The exact mechanism trough which DNA hyper-replication leads to DDR in absence of E2F1 and E2F2 remains undiscovered. To determine whether the ATR/ATM pathway, the master regulator of G2/M checkpoint, might be the surveillance mechanism in order to regulate uncontrolled proliferation in the DKO model, we monitored and analysis biochemical properties of BMDM cultures in the presence of caffeine, a potent inhibitor of ATM/ATR activity. Our results show that the addition of caffeine abolishes premature senescence in DKO BMDM, stimulates γ-H2AX accumulation and decreases Mcm2 expression.

Primary and secondary threshold intensities of ultraviolet-laser-induced domain nucleation in nearly stoichiometric LiTaO3

The primary and secondary threshold intensities of ultraviolet-laser-induced preferential domain nucleation in nearly stoichiometric LiTaO3 is observed. The primary threshold is the minimum intensity to achieve the instantaneous preferential domain nucleation within the focus by the combined action of irradiation and electric fields. The secondary threshold is the minimum intensity to achieve the memory effect without any irradiation within the original focus. The space charge field created by the photoionization carriers is thought to be responsible for the instantaneous effect. The explanation based on the formation and transformation of extrinsic defect is presented for the memory effect. (c) 2008 American Institute of Physics.

CONTRIBUTION TO THE DEVELOPMENT OF INTELLIGENT CONVERSATIONAL ASSISTANTS IN AUTOMOTIVE ENVIRONMENTS

Esta tesis presenta el diseño y desarrollo del Asistente Conversacional del Automóvil, Voice User Help en inglés, un sistema conversacional basado en el paradigma pregunta-respuesta y diseñado para consultar documentación del vehículo duartne la conducción. Este trabajo recoge investigaciones realizadas en los campos de la documentación técnica, recuperación de información, procesamineto de lenguaje natural, diseñode interfaces de usuario para vehículos, experiencia del usuario y computación afectiva con el fin de crear un asistente adaptativo y dinámico que modifica su comportamiento conversacional dependiendo del estado emocional del usuario.

Desempenho de tanques vegetados em um ecossistema engenheirado para tratamento descentralizado de esgotos domiciliares na Ilha Grande, RJ

A falta de infraestrutura adequada para a coleta e o tratamento de esgotos atinge várias comunidades costeiras e de sistemas insulares do Estado do Rio de Janeiro, que vivem em condições de insalubridade. O objetivo do presente estudo foi avaliar o desempenho de um ecossistema engenheirado para tratamento descentralizado de esgoto domiciliar implantado no Centro de Estudos Ambientais e Desenvolvimento Sustentável (CEADS) da UERJ, na Vila Dois Rios, Ilha Grande - RJ, com ênfase na contribuição de macrófitas e algas em tanques vegetados como tratamento terciário para a melhoria geral da qualidade do efluente e em especial, para remoção de nutrientes. O sistema é composto por caixa controladora de vazão, caixa de gordura, fossa séptica, filtro aerado submerso, decantador secundário e o conjunto de tanques vegetados contendo as macrófitas aquáticas Eichhornia crassipes, Schoenoplectus sp., Panicum cf. racemosum + Cyperus ligularis, além de um tanque de algas entre as 2 primeiras macrófitas. Os principais parâmetros monitorados em amostras quinzenais obtidas durante o período de 09/2009 a 07/2010 em 10 pontos de coleta equivalentes à saída do efluente de cada unidade de tratamento foram: OD, pH, Cond. Elétrica, Temperatura, DBO5, DQO, SST, SDT, Nitrogênio amoniacal, Nitrito, Nitrato e Fósforo total. A vazão média do sistema foi 52 L/h. A produção primária de biomassa das macrófitas e o metabolismo no tanque com algas também foram estimados. A eficiência média do ecossistema engenheirado foi de 93% de redução dos SST, 93% de DBO, 90% da DQO, 30% de N amoniacal e, 38% de Fósforo. O conjunto de tanques vegetados promoveu um aumento médio de oxigênio dissolvido (OD) em 182% comparados ao valor de saída do decantador. Pode-se concluir que esse sistema contribuiu para uma melhoria geral da qualidade do efluente final com relação a praticamente todos os parâmetros, ainda que em alguns casos, apenas de forma incremental. Houve maior produção média de biomassa (peso seco.dia-1) e retenção média de água na espécie E. crassipes (aguapé) em comparação com as espécies Schoenoplectus sp, P. cf. racemosum e C. ligularis. A baixa produção primária no tanque de algas em relação à respiração, pelo menos no período monitorado, indica condições desfavoráveis à remoção de nutrientes (N e P) nesse tanque através da incorporação na biomassa. Uma investigação mais detalhada acerca dos parâmetros de projeto que inclua um eventual redimensionamento do decantador e do tanque de algas é sugerida.

Efficacy and safety of autologous platelet rich plasma for the treatment of vascular ulcers in primary care: Phase III study

Background: Vascular ulcers are commonly seen in daily practice at all levels of care and have great impact at personal, professional and social levels with a high cost in terms of human and material resources. Given that the application of autologous platelet rich plasma has been shown to decrease healing times in various different studies in the hospital setting, we considered that it would be interesting to assess the efficacy and feasibility of this treatment in primary care. The objectives of this study are to assess the potential efficacy and safety of autologous platelet rich plasma for the treatment of venous ulcers compared to the conventional treatment (moist wound care) in primary care patients with chronic venous insufficiency (C, clinical class, E, aetiology, A, anatomy and P, pathophysiology classification C6). Design: We will conduct a phase III, open-label, parallel-group, multicentre, randomized study. The subjects will be 150 patients aged between 40 and 100 years of age with an at least 2-month history of a vascular venous ulcer assigned to ten primary care centres. For the treatment with autologous platelet rich plasma, all the following tasks will be performed in the primary care setting: blood collection, centrifugation, separation of platelet rich plasma, activation of coagulation adding calcium chloride and application of the PRP topically after gelification. The control group will receive standard moist wound care. The outcome variables to be measured at baseline, and at weeks 5 and 9 later include: reduction in the ulcer area, Chronic Venous Insufficiency Quality of Life Questionnaire score, and percentage of patients who require wound care only once a week. Discussion: The results of this study will be useful to improve the protocol for using platelet rich plasma in chronic vascular ulcers and to favour wider use of this treatment in primary care.

Osteometric analysis of the scapula and humerus of Rangifer tarandus and Cervus elaphus : A contribution to the discrimination of Late Pleistocene cervids

Fossil remains of reindeer (Rangifer tarandus) occurring outside their present range are an important indicator of formerly cold climatic conditions, but are easily confused with those of the red deer (Cervus elaphus). The locality of Kiputz IX has yielded one of the best-preserved Late Pleistocene reindeer populations of the southern Pyrenees, occurring in association with Bison priscus and the much more abundant Cervus elaphus. Fossil remains from this site are mostly complete and not affected by human intervention, thus creating the perfect conditions for reliable osteometric analyses. Here, we quantify diagnostic morphological features of the scapula and the humerus of Cervus elaphus and Rangifer tarandus to establish the potential of these bones to aid in interspecific discrimination. In the case of the scapula, the best species discriminator is the ratio of the minimum anteroposterior diameter of the scapular neck and the development of the articular process, while the breadth of the trochlea is the best discriminator in the case of the humerus.

O despertar do budismo no ocidente no século XXI: contrbuição ao debate

Esta tese apresenta como um dos seus aspectos fundamentais a compreensão de outra cultura, outra versão, outro conjunto de valores: o pensamento indiano, berço da Ahamkãra a consciência individual, o eu e das práticas ascéticas de origem pré-ariana e autóctone. No interior dessa tradição, foram escolhidos os ensinamentos do Buddha Shãkyamuni, por sua absoluta originalidade na concepção da individualidade, transformando radicalmente as concepções de subjetividade existentes em sua época. O intuito, ao buscar uma tradição em tudo diferente da nossa, é, por dirigir o foco para o mais contrastante, iluminar nossa própria tradição, enriquecer o campo de discussão das novas matrizes de subjetivação em nossa sociedade ocidental pós-moderna e globalizada. Com essa abordagem objetiva-se contribuir para o debate em torno do despertar do budismo ocidental, no séc. XXI, lançando algumas linhas de reflexão que auxiliem, por um lado, a contextualizar esse acontecimento, e, por outro, a ampliar o debate sobre as questões relativas à noção de sujeito, utilizada pelos teóricos da psicanálise, através da apresentação de uma outra versão, a do eu budista. A comparação entre uma forma de individualidade oriunda de uma sociedade tradicional e holista e a forma da individualidade contemporânea, oriunda de uma sociedade secularizada e individualista, é possível através do que Harpham denomina imperativo ascético, uma força estruturante primária e transcultural. Nesse sentido visualiza-se uma relação entre as práticas ascéticas e a construção do eu. Segundo Mauss, o eu também é uma categoria universal, presente em todas as culturas. Assim como se encontram variações sobre o repertório das práticas ascéticas disponíveis em diferentes culturas, encontram-se variações na forma da subjetividade, de acordo com o seu solo cultural e sua paisagem mental. Fizemos uma conexão entre as práticas ascéticas indianas e o que denominamos de identificação mística, a partir da qual foi possível inferir essa imbricação entre ascetismo, construção e sacralização do eu nos primórdios da civilização indiana. Com o budismo ocorre uma espécie de descentramento, a sacralização é estendida a todo o cosmo, as práticas de meditação sintonizam com todos os seres, com todos os animais, para eliminar as causas do sofrimento. O budismo nasce com uma vocação universalista e leva para fora das fronteiras da Índia esse eu construído a partir dos conceitos da Ãhimsa, a não-violência, e da noção de ausência de existência inerente, inscritos no pensamento budista há dois mil e quinhentos anos, despertando o interesse do ocidente após um longo período de obscurecimento.

Distribuição espacial do pico e ultraplâncton na plataforma continental e talude entre Cabo Frio (RJ) e Ubatuba (SP) e sua relação com a hidrodinâmica local: inverno de 2010

O picoplâncton (0,2 - 2,0 m) e ultraplâncton (> 2,0 - 5,0 m) despertam interesse por utilizarem ativamente a matéria orgânica dissolvida, estabelecendo a alça microbiana. Responsáveis por 50-80% da produção primária em águas oligotróficas, essas frações apresentam elevadas eficiência luminosa e razão superfície/volume que as permitem alcançar alto desenvolvimento mesmo sob baixas luminosidade e disponibilidade de nutrientes. Buscando relacionar a distribuição espacial e composição da comunidade pico e ultraplanctônica aos controles bottom-up na plataforma continental e talude ao largo dos Estados do Rio de Janeiro e São Paulo (22S a 26S), foram coletadas amostras de água em 39 estações oceanográficas e utilizadas as imagens dos sensores MODIS Terra e Aqua, bem como dados de hidrografia, para a descrição dos fenômenos oceanográficos de mesoescala. A abundância total de ambas as frações de tamanho, assim como a dominância do picoplâncton, reduziu em função do distanciamento da costa. Os organismos autotróficos foram em média (102 cél.mL-1 a 104 cél.mL-1 ) majoritariamente uma ordem de grandeza inferiores aos heterotróficos (103 cél.mL-1 a 105 cél.mL-1). A Água Central do Atlântico Sul (ACAS) e as plumas das baías de Guanabara e Sepetiba (RJ) permaneceram na plataforma interna favorecendo o aumento na concentração dos macronutrientes e refletindo na mudança da estrutura da comunidade através do aumento da contribuição de autótrofos no centro da plataforma, principalmente do ultraplâncton à superfície (cerca de 21%) e na profundidade do máximo de clorofila (44%). O transporte de águas costeiras carreadas por uma corrente de origem sul gerou o vórtice de plataforma identificado nas imagens de satélite para a região da plataforma interna de Ubatuba (SP), onde concentrações mais elevadas de amônio (0,28 M) e fosfato (9,64 M) a partir dos 50 m sustentaram maior densidade do ultra autótrofo (2,89 x 103 cél.mL-1) que superou a densidade de heterótrofos (2,50 x 103 cél.mL-1) no máximo de clorofila. Os resultados destacaram um forte gradiente nerítico-oceânico na distribuição dos organismos. Sugerem ainda a predominância do metabolismo heterotrófico na maior parte das águas oligotróficas da plataforma e talude entre o Rio de Janeiro e São Paulo, bem como a presença de caráter autotrófico naquelas regiões influenciadas por feições de mesoescala, como plumas estuarinas e vórtices de plataforma.