894 resultados para Nucleophilic addition to carbonyl


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Although many optical fibre applications are based on their capacity to transmit optical signals with low losses, it can also be desirable for the optical fibre to be strongly affected by a certain physical parameter in the environment. In this way, it can be used as a sensor for this parameter. There are many strong arguments for the use of POFs as sensors. In addition to being easy to handle and low cost, they demonstrate advantages common to all multimode optical fibres. These specifically include flexibility, small size, good electromagnetic compatibility behaviour, and in general, the possibility of measuring any phenomenon without physically interacting with it. In this paper, a sensor based on POF is designed and analysed with the aim of measuring the volume and turbidity of a low viscosity fluid, in this case water, as it passes through a pipe. A comparative study with a commercial sensor is provided to validate the proven flow measurement. Likewise, turbidity is measured using different colour dyes. Finally, this paper will present the most significant results and conclusions from all the tests which are carried out.

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Phosphorus removal by wetlands and basins in Lake Tahoe may be improved through designing these systems to filter storm water through media having higher phosphorus removal capabilities than local parent material. Substrates rich in iron, aluminum and calcium oftentimes have enhanced phosphorus removal. These substrates can be naturally occurring, byproducts of industrial or water treatment processes, or engineered. Phosphorus removal fundamentally occurs through chemical adsorption and/or precipitation and much of the phosphorus can be irreversibly bound. In addition to these standard media, other engineered substrates are available to enhance P removal. One such substrate is locally available in Reno and uses lanthanum coated diatomaceous earth for arsenate removal. This material, which has a high positive surface charge, can also irreversibly remove phosphorus. Physical factors also affect P removal. Specifically, specific surface area and particle shape affect filtration capacity, contact area between water and the surface area, and likelihood of clogging and blinding. A number of substrates have been shown to effectively remove P in case studies. Based upon these studies, promising substrates include WTRs, blast furnace slag, steel furnace slag, OPC, calcite, marble Utelite and other LWAs, zeolite and shale. However, other nonperformance factors such as environmental considerations, application logistics, costs, and potential for cementification narrow the list of possible media for application at Tahoe. Industrial byproducts such as slags risk possible leaching of heavy metals and this potential cannot be easily predicted. Fly ash and other fine particle substrates would be more difficult to apply because they would need to be blended, making them less desirable and more costly to apply than larger diameter media. High transportation costs rule out non-local products. Finally, amorphous calcium products will eventually cementify reducing their effectiveness in filtration systems. Based upon these considerations, bauxite, LWAs and expanded shales/clays, iron-rich sands, activated alumina, marble and dolomite, and natural and lanthanum activated diatomaceous earth are the products most likely to be tested for application at Tahoe. These materials are typically iron, calcium or aluminum based; many have a high specific surface area; and all have low transportation costs. (PDF contains 21 pages)

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The organometallic chemistry of the hexagonally close-packed Ru(001) surface has been studied using electron energy loss spectroscopy and thermal desorption mass spectrometry. The molecules that have been studied are acetylene, formamide and ammonia. The chemistry of acetylene and formamide has also been investigated in the presence of coadsorbed hydrogen and oxygen adatoms.

Acetylene is adsorbed molecularly on Ru(001) below approximately 230 K, with rehybridization of the molecule to nearly sp^3 occurring. The principal decomposition products at higher temperatures are ethylidyne (CCH_3) and acetylide (CCH) between 230 and 350 K, and methylidyne (CH) and surface carbon at higher temperatures. Some methylidyne is stable to approximately 700 K. The preadsorption of hydrogen does not alter the decomposition products of acetylene, but reduces the saturation coverage and also leads to the formation of a small amount of ethylene (via an η^2-CHCH_2 species) which desorbs molecularly near 175 K. Preadsorbed oxygen also reduces the saturation coverage of acetylene but has virtually no effect on the nature of the molecularly chemisorbed acetylene. It does, however, lead to the formation of an sp^2-hybridized vinylidene (CCH_2) species in the decomposition of acetylene, in addition to the decomposition products that are formed on the clean surface. There is no molecular desorption of chemisorbed acetylene from clean Ru(001), hydrogen-presaturated Ru(001), or oxygen-presaturated Ru(001).

The adsorption and decomposition of formamide has been studied on clean Ru(001), hydrogen-presaturated Ru(001), and Ru(001)-p(1x2)-O (oxygen adatom coverage = 0.5). On clean Ru(001), the adsorption of low coverages of formamide at 80 K results in CH bond cleavage and rehybridization of the carbonyl double bond to produce an η^2 (C,O)-NH_2CO species. This species is stable to approximately 250 K at which point it decomposes to yield a mixture of coadsorbed carbon monoxide, ammonia, an NH species and hydrogen adatoms. The decomposition of NH to hydrogen and nitrogen adatoms occurs between 350 and 400 K, and the thermal desorption products are NH_3 (-315 K), H_2 (-420 K), CO (-480 K) and N_2 (-770 K). At higher formamide coverages, some formamide is adsorbed molecularly at 80 K, leading both to molecular desorption and to the formation of a new surface intermediate between 300 and 375 K that is identified tentatively as η^1(N)-NCHO. On Ru(001)- p(1x2)-O and hydrogen-presaturated Ru(001), formamide adsorbs molecularly at 80 K in an η^1(O)- NH_2CHO configuration. On the oxygen-precovered surface, the molecularly adsorbed formamide undergoes competing desorption and decomposition, resulting in the formation of an η^2(N,O)-NHCHO species (analogous to a bidentate formate) at approximately 265 K. This species decomposes near 420 K with the evolution of CO and H_2 into the gas phase. On the hydrogen precovered surface, the Η^1(O)-NH_2CHO converts below 200 K to η^2(C,O)-NH_2CHO and η^2(C,O)-NH^2CO, with some molecular desorption occurring also at high coverage. The η^2(C,O)-bonded species decompose in a manner similar to the decomposition of η^2(C,O)-NH_2CO on the clean surface, although the formation of ammonia is not detected.

Ammonia adsorbs reversibly on Ru(001) at 80 K, with negligible dissociation occurring as the surface is annealed The EEL spectra of ammonia on Ru(001) are very similar to those of ammonia on other metal surfaces. Off-specular EEL spectra of chemisorbed ammonia allow the v(Ru-NH_3) and ρ(NH_3) vibrational loss features to be resolved near 340 and 625 cm^(-1), respectively. The intense δ_g (NH_3) loss feature shifts downward in frequency with increasing ammonia coverage, from approximately 1160 cm^(-1) in the low coverage limit to 1070 cm^(-1) at saturation. In coordination compounds of ammonia, the frequency of this mode shifts downward with decreasing charge on the metal atom, and its downshift on Ru(001) can be correlated with the large work function decrease that the surface has previously been shown to undergo when ammonia is adsorbed. The EELS data are consistent with ammonia adsorption in on-top sites. Second-layer and multilayer ammonia on Ru(001) have also been characterized vibrationally, and the results are similar to those obtained for other metal surfaces.

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Progress towards the synthesis of the spermine-conjugated Dynemicin analog 4 is described. The synthetic route starts with the Michael addition of menthyl acetoacetate to trans-ethyl crotonate followed by a Dieckman condensation to form the cyclohexanedione 14 which, through a series of chemical reactions, is transformed into the quinone imine 6. Key features in the route include the Suzuki coupling reaction of the aryl boronic acid 11 and the enol triflate 12, thermal deprotection/internal amidation of the biaryl 19, cis addition of the (Z)-enediyne 33 to the quinoline 25, intramolecular acetylide addition to a carbonyl within the ketone 29, and an addition/elimination of the cyanophthalide to the quinone imine 6 to form the anthraquinone 36 utilizing the Kraus and Sugimoto methodology.

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The 1,3-dipolar cycloadditions of trimethylsilyl diazomethane with camphorsultam-derived acrylates are reported as a means for the efficient synthesis of optically active pyrazolines. Trimethylsilyl diazomethane is a safe, commercially available diazoalkane which provides Δ1-pyrazolines 1n good yield and diastereoselectivity when camphorsultam-derived acrylates are used as the reaction dipolarophiles . These initial cycloadducts are subsequently converted to stable, characterizable Δ2-pyrazolines upon desilylation.

A manifold of reactions that can be applied to these Δ2-pyrazolines has been developed which includes pyrazoline reduction, N-N bond reduction, addition to the pyrazoline C=N by mild carbon nucleophiles, and both solvolytic and reductive chiral auxiliary removal. Additionally, it has been demonstrated that the pyrazoline reduction products can take part in peptide coupling reactions that allow for the pyrazolidines to serve as proline-like molecules. The development of this methodology is a general solution to the problem of highly substituted, functionalized pyrazoline synthesis. Importantly, the pyrazolines thus provided have been demonstrated to be amenable to reactions that add to their value as synthetic intermediates.

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Não há duvidas sobre a grandeza e intensidade que pode existir no relacionamento entre mãe e filho, porém, quando esse recém nascido é um bebê prematuro e/ou necessita de hospitalização em uma Unidade de Terapia Intensivo Neonatal (UTIN) pode haver um pode haver um choque, uma grande decepção, pois essa mãe não poderá interagir de forma plena com seu filho, não poderá amamentar e nem cuidar dele da forma habitual que se espera. Neste sentido, esse estudo propõe uma reflexão sobre a atuação do enfermeiro quanto à relação mãe/recém-nascido na UTIN. Assim sendo, tem-se como objeto A vivência do enfermeiro na construção/desenvolvimento da relação mãe/recém-nascido na UTIN. E como objetivo Compreender o significado da ação do enfermeiro na aproximação mãe/recém-nascido. Para o embasamento teórico foi necessário pensar sobre a prática do enfermeiro na UTIN, no que diz respeito a sua assistência, o processo de humanização neste ambiente e na inserção da família nos cuidados. Outro conceito fundamental discutido foi a interação, destacando o pensamento fenomenológico de Alfred Schutz. Estudo do tipo descritivo, desenvolvido com abordagem qualitativa e o referencial teórico-metodológico da fenomenologia. O cenário para sua realização foi a UTIN de um grande hospital da rede pública, localizado no subúrbio da cidade do Rio de Janeiro e foram sujeitos 16 enfermeiros lotados nesta unidade. A entrevista fenomenológica foi a técnica utilizada para captar as vivências profissionais e em seguida realizou-se a análise compreensiva tendo em vista a categorização. Como resultado chegou-se a 3 categorias do vivido; (1) ambientar as mães na UTIN: o começo da relação,(2) aproximar através do toque: usando os sentidos para se relacionar e (3) melhorar a relação entre mãe/recém-nascido: pensando no futuro. Além dessas categorias foi possível a apreensão do contexto vivencial das experiências dos enfermeiros no relacionamento com as mães de recém-nascidos na UTIN. Conclui-se que os enfermeiros que trabalham em UTIN têm a percepção de quão fundamental é promover a aproximação entre mãe e filho nesse ambiente. Contudo, essa ação ainda acontece de forma intuitiva, sem nenhum embasamento, e ainda muitas vezes é desprestigiada em detrimento da grande carga de trabalho deste setor, ou a gravidade do recém-nascido. É preciso que haja um maior engajamento por parte dos enfermeiros, em aprimorar as estratégias de aproximação entre mãe e recém-nascido, visando sempre um relacionamento mais saudável e harmonioso no futuro. Deste modo, o estudo contribui para enriquecer esta temática e despertar nos enfermeiros neonatologistas um olhar que compreenda não só os aspectos biológicos, mas também os psicossocias e torne, assim, a assistência ao recém nascido e sua família mais plena.

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Decarboxylation and decarbonylation are important reactions in synthetic organic chemistry, transforming readily available carboxylic acids and their derivatives into various products through loss of carbon dioxide or carbon monoxide. In the past few decades, palladium-catalyzed decarboxylative and decarbonylative reactions experienced tremendous growth due to the excellent catalytic activity of palladium. Development of new reactions in this category for fine and commodity chemical synthesis continues to draw attention from the chemistry community.

The Stoltz laboratory has established a palladium-catalyzed enantioselective decarboxylative allylic alkylation of β-keto esters for the synthesis of α-quaternary ketones since 2005. Recently, we extended this chemistry to lactams due to the ubiquity and importance of nitrogen-containing heterocycles. A wide variety of α-quaternary and tetrasubstituted α-tertiary lactams were obtained in excellent yields and exceptional enantioselectivities using our palladium-catalyzed decarboxylative allylic alkylation chemistry. Enantioenriched α-quaternary carbonyl compounds are versatile building blocks that can be further elaborated to intercept synthetic intermediates en route to many classical natural products. Thus our chemistry enables catalytic asymmetric formal synthesis of these complex molecules.

In addition to fine chemicals, we became interested in commodity chemical synthesis using renewable feedstocks. In collaboration with the Grubbs group, we developed a palladium-catalyzed decarbonylative dehydration reaction that converts abundant and inexpensive fatty acids into value-added linear alpha olefins. The chemistry proceeds under relatively mild conditions, requires very low catalyst loading, tolerates a variety of functional groups, and is easily performed on a large scale. An additional advantage of this chemistry is that it provides access to expensive odd-numbered alpha olefins.

Finally, combining features of both projects, we applied a small-scale decarbonylative dehydration reaction to the synthesis of α-vinyl carbonyl compounds. Direct α-vinylation is challenging, and asymmetric vinylations are rare. Taking advantage of our decarbonylative dehydration chemistry, we were able to transform enantioenriched δ-oxocarboxylic acids into quaternary α-vinyl carbonyl compounds in good yields with complete retention of stereochemistry. Our explorations culminated in the catalytic enantioselective total synthesis of (–)-aspewentin B, a terpenoid natural product featuring a quaternary α-vinyl ketone. Both decarboxylative and decarbonylative chemistries found application in the late stage of the total synthesis.

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A Hipóxia-Isquêmica (HI) pré-natal é caracterizada por uma redução no aporte de oxigênio e nutrientes para o feto durante o período gestacional, que pode acarretar, a longo prazo, em dificuldade de concentração e aprendizagem, hiperatividade e déficit de memória. Esses prejuízos podem persistir ou se agravar até a idade adulta, levando ainda ao aparecimento de doenças como epilepsia e paralisia cerebral (PC). A privação de oxigênio e nutrientes, assim como o estresse materno, anemia, eclâmpsia e uso de drogas durante a gestação, podem causar estresse oxidativo durante os períodos críticos do desenvolvimento, e pode ser a principal razão para as mudanças que levam a programação fetal. O objetivo deste estudo foi relacionar a geração de espécies reativas e a consequente formação de estresse oxidativo nos animais adultos, com as alterações da biodisponibilidade do óxido nítrico de forma sistêmica, além de mudanças nos comportamentos motor e de ansiedade, manutenção da memória e aprendizado. Para a hipóxia, foi utilizado o modelo de clampeamento das artérias uterinas das ratas no 18 dia gestacional por 45 min, analisando os filhotes após 90 dias de nascidos. Foram utilizados os testes Open Field e labirinto em cruz elevada para a análise comportamental, e análises das enzimas glutationa peroxidase (GPx), superóxido desmutase (SOD) e catalase, além de quantificação de nitritos, TBARs e carbonilação de proteínas para avaliação de mecanismos oxidantes e antioxidantes. Os resultados demonstraram que o insulto durante a gestação pode acarretar em redução na formação da enzima GPx, além de maior concentração de nitritos analisados nos soros dos animais hipoxiados quando comparados aos controles, contribuindo para o dano oxidativo. Também foi observada redução na memória de habituação e comportamento motor, além de elevado comportamento ansioso em animais hipoxiados, diferentemente de controles. Concluímos assim que a hipóxia isquêmica pré-natal pode alterar permanentemente o estado oxidativo dos animais, além de atuar na formação do comportamento motor, memória de habituação e ansiedade. As descobertas aqui apresentadas contribuem para ampliar o entendimento acerca do evento de hipóxia isquêmica pré-natal, além de prover ferramentas para o desenvolvimento de mecanismos protetores e preventivos aos possíveis danos por ela causados.

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Sediments are an essential component of rivers and of their biological functioning. In addition to their influence on river geomorphology (maintenance of river forms and habitats such as pools and sand bars), sediments also include nutrients, detritus and organic debris of various sizes which interact with the river’s different life forms, including fish. The interaction between sediments and aquatic organisms, directly or indirectly through the effects of sediments on physical habitats, unquestionably influences the biodiversity and productivity of a river. The current report reviews the interactions between sediments and fish in tropical rivers and in the Mekong, and focuses more specifically on a reduction of sediment loads following dam const

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The potential for changes to onboard handling practices in order to improve the fate of juvenile school prawns (Metapenaeus macleayi) discarded during trawling were investigated in two Australian rivers (Clarence and Hunter) by comparing a purpose-built, water-filled sorting tray against a conventional dry tray across various conditions, including the range of typical delays before the start of sorting the catch (2 min vs. 15 min). Juvenile school prawns (n= 5760), caught during 32 and 16 deployments in each river, were caged and sacrificed at four times: immediately (T0), and at 24 (T24), 72 (T72), and 120 (T12 0) hours after having been discarded. In both rivers, most mortalities occurred between T0 and T24 and, after adjusting for control deaths (<12%), were greatest for the 15-min conventional treatment (up to 41% at T120). Mixed-effects logistic models revealed that in addition to the sampling time, method of sorting, and delay in sorting, the weight of the catch, salinity, and percentage cloud cover were significant predictors of mortality. Although trawling caused some mortalities and comparable stress (measured as L -lactate) in all school prawns, use of the water tray lessened the negative impacts of some of the above factors across both the 2-min and 15-min delays in sorting so that the overall discard mortality was reduced by more than a third. When used in conjunction with selective trawls, widespread application of the water tray should help to improve the sustainability of trawling for school prawns.

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Rather than using more or less ideal conditions for setting experimental controls, the use of conditions similar to those likely to be encountered by farmers should produce research results which are realistically achievable on the farm. ICLARM has developed an approach to farmer-led experimentation which utilizes a spreadsheet to collate and analyze data collected from participating farmers. The simulation of actual management practices utilized by farmers produced results in replicated on-station trials which were within 11% of net yields on-farm. In addition to giving researchers a tool for comparing farm and station management practices, giving farmers a realistic indication of what yields will be if a technology is adopted should help overcome the problems of disillusionment often encountered when farm results fall below those expected by researchers on the basis of experiment station studies.

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Ciguatoxins (CTX) are polyether neurotoxins that target voltage-gated sodium channels and are responsible for ciguatera, the most common fish-borne food poisoning in humans. This study characterizes the global transcriptional response of mouse liver to a symptomatic dose (0.26 ng/g) of the highly potent Pacific ciguatoxin-1 (P-CTX-1). At 1 h post-exposure 2.4% of features on a 44K whole genome array were differentially expressed (p ≤ 0.0001), increasing to 5.2% at 4 h and decreasing to 1.4% by 24 h post-CTX exposure. Data were filtered (|fold change| ≥ 1.5 and p ≤ 0.0001 in at least one time point) and a trend set of 1550 genes were used for further analysis. Early gene expression was likely influenced prominently by an acute 4°C decline in core body temperature by 1 h, which resolved by 8 h following exposure. An initial downregulation of 32 different solute carriers, many involved in sodium transport, was observed. Differential gene expression in pathways involving eicosanoid biosynthesis and cholesterol homeostasis was also noted. Cytochrome P450s (Cyps) were of particular interest due to their role in xenobiotic metabolism. Twenty-seven genes, mostly members of Cyp2 and Cyp4 families, showed significant changes in expression. Many Cyps underwent an initial downregulation at 1 h but were quickly and strongly upregulated at 4 and 24 h post-exposure. In addition to Cyps, increases in several glutathione S-transferases were observed, an indication that both phase I and phase II metabolic reactions are involved in the hepatic response to CTX in mice.

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A total of 45 ponds used for fish polyculture were investigated in three zones of Bangladesh to identify the differences among the zones in respect to aqua-ecology, culture practices, fish productivity and health management. Four hundred and fifty fish from three zones were clinically examined by naked eye and histopathology. Out of total number of fish examined, 45 fish from Dhaka zones were examined for parasites and bacteria in addition to histopathology. Faded and haemorrhagic gill, skin, fin, scale loss and lesions were observed during fish examination. Aeromonas spp. Pseudomonas spp. and Streptococcus spp. were isolated respectively from 56%, 46% and 39% affected fish. Among the five water quality parameters analyzed, the highest average hardness and alkalinity respectively were recorded in Rajshahi (156 ppm and 142 ppm) followed by Dhaka (146 ppm and 132 ppm) and Chittagong (81 ppm and 90 ppm). The highest average pH was recorded in Mymensingh (7.52) followed by Rajshahi (7.13) and Chittagong (7.05). Water holding capacity of soil in Rajshahi zone was poor compared to other zones and farmers were found to be reluctant to fish farming.

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RFID technology can be used to its fullest potential only with software to supplement the hardware with powerful capabilities for data capture, filtering, counting and storage. The EPCglobal Network architecture encourages minimizing the amount of business logic embedded in the tags, readers and middleware. This creates the need for a Business Logic Layer above the event filtering layer that enhances basic observation events with business context - i.e. in addition to the (what, when, where) information about an observation, it adds context information about why the object was there. The purpose of this project is to develop an implementation of the Business Logic Layer. This application accepts observation event data (e.g. from the Application Level Events (ALE) standard interface), enriches them with business context and provides these enriched events to a repository of business-level events (e.g. via the EPC Information Services (EPCIS) capture interface). The strength of the application lies in the automatic addition of business context. It is quick and easy to adapt any business process to the framework suggested and equally easy to reconfigure it if the business process is changed. A sample application has been developed for a business scenario in the retail sector.

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As interest increases in fish production, fish farming is on the rise as more fish is produced in ponds, cages and tanks. However not all fish can be sold out and consumed at the same time, in addition to this, different consumers show different preference. Some individua Is tend to prefer smoked fish to fresh and fried fish. Apart from satisfying the different consumer preferences, fish smoking is important because it in creases the self life of fish, there by reducing post harvest losses. It also adds value to the fish and in this way the farmer can fetch more money from farmed products. Although the technology has been around for several years amongst the fishing communities, it is not well known amongst fish farmers. There is need to bring fish fanners on board to know how to construct the smoking kiln through the stapes out lined below.