Approaches to alpha-amino acids via rearrangement to electron-deficient nitrogen: Beckmann and Hofmann rearrangements of appropriate carboxyl-protected substrates

The titled approaches were effected with various 2-substituted benzoylacetic acid oximes 3 (Beckmann) and 2-substituted malonamic acids 9 (Hofmann), their carboxyl groups being masked as a 2,4,10-trioxaadamantane unit (an orthoacetate). The oxime mesylates have been rearranged with basic Al2O3 in refluxing CHCl3, and the malonamic acids with phenyliodoso acetate and KOH/MeOH. Both routes are characterized by excellent overall yields. Structure confirmation of final products was conducted with X-ray diffraction in selected cases. The final N-benzoyl and N-(methoxycarbonyl) products are alpha-amino acids with both carboxyl and amino protection; hence, they are of great interest in peptide synthesis.

Electrophile-Induced C-C Bond Activation of Vinylcyclopropanes for the Synthesis of Z-Alkylidenetetrahydrofurans

We present a detailed study on the behavior of vinylcyclopropanes as masked donor acceptor system toward the stereoselective synthesis of Z-alkylidenetetrahydrofurans. Results of bromenium catalyzed indirect activation of C-C bond of vinylcyclopropanes and concomitant cyclization to alkylidenetetrahydrofuran and other heterocycles have been discussed. The stereoselective formation of the Z-isomer is strongly controlled by the extent of destabilization of one of the gauche conformers of the vinylcyclopropane. The ring-opening/cyclization step was found to be stereospecific as in the case of DA cyclopropanes. The activation of the C-C bond leads to a tight-carbocation intermediate, which is evident from the complete retention of the stereochemistry. The retention of configuration has been established by a necessary control experiment that rules out the possibility of a double inversion pathway. The present results serve as direct stereochemical evidence in support of a tight ion-pair intermediate versus the controversial S(N)2 pathway. A 2D potential energy scan has been carried out at B3LYP/6-31G(d) level theory to obtain the relative energies of the conformers. The Z-selectivity observed has been explained on the basis of the relative population of the conformers and modeling the intermediate and transition state involved in the reaction at M06-2x/6-31+G(d) level. Energy profile for the cyclization step was modeled considering various possible pathways through which cyclization can happen. The methodology has been successfully demonstrated on vinylcyclobutanes as well.

Characterization and Performance Study of Packaged Micropump for Drug Delivery

In this work, we present the characterization and performance studies of self-priming peristaltic pump for drug delivery application. Conventional materials and methods have been used to fabricate single cam mechanism based peristaltic micropump. To control the fluid flow precisely in micro liter range, a single cam mechanism has been used instead of conventional roller mechanism. The fabricated pump is suitable for liquid, gas and foam. Using water as a fluid medium, a flow rate of 12.5 mu l/rpm is achieved using a flexible silicone tube of inner diameter 1.5 mm and outer diameter 2.5 mm. Other than water, higher viscosity fluids showed a decrease in the flow rate. The designed micropump exhibits a linear dependence of flow rate in the voltage range of 2.5V to 5V. Drug delivery using micropump demands that the micropump has to pump against the blood pressure (maximum of 25kPa) with constant flow rate. Here the designed pump is able to pump the liquid with a constant flow rate of 500 mu l/min (water) up to a backpressure of 40kPa. It was observed that, by increasing the backpressure above 40kPa, flow rate of the pump gradually decreased to 125 mu l/min at 120kPa. In addition, Micropump based drug delivery demands that the micropump should be normally in closed condition in all the positions to avoid drug leakage and bleeding. Hence, micropump has been characterized for normally closed condition in all positions (0 degrees to 360 degrees). However, a minute leak of 0.14 % was found for an inlet pressure of 140kPa. Also, the normally closed region with no leak is observed up to 60kPa of pressure in all positions (0 degrees to 360 degrees).

Levels of Alpha-Toxin Correlate with Distinct Phenotypic Response Profiles of Blood Mononuclear Cells and with agr Background of Community-Associated Staphylococcus aureus Isolates

Epidemiological studies of Staphylococcus aureus have shown a relation between certain clones and the presence of specific virulence genes, but how this translates into virulence-associated functional responses is not fully elucidated. Here we addressed this issue by analyses of community-acquired S. aureus strains characterized with respect to antibiotic resistance, ST types, agr types, and virulence gene profiles. Supernatants containing exotoxins were prepared from overnight bacterial cultures, and tested in proliferation assays using human peripheral blood mononuclear cells (PBMC). The strains displayed stable phenotypic response profiles, defined by either a proliferative or cytotoxic response. Although, virtually all strains elicited superantigen-mediated proliferative responses, the strains with a cytotoxic profile induced proliferation only in cultures with the most diluted supernatants. This indicated that the superantigen-response was masked by a cytotoxic effect which was also confirmed by flow cytometry analysis. The cytotoxic supernatants contained significantly higher levels of alpha-toxin than did the proliferative supernatants. Addition of alpha-toxin to supernatants characterized as proliferative switched the response into cytotoxic profiles. In contrast, no effect of Panton Valentine Leukocidin, delta-toxin or phenol soluble modulin alpha-3 was noted in the proliferative assay. Furthermore, a significant association between agr type and phenotypic profile was found, where agrII and agrIII strains had predominantly a proliferative profile whereas agrI and IV strains had a predominantly cytotoxic profile. The differential response profiles associated with specific S. aureus strains with varying toxin production could possibly have an impact on disease manifestations, and as such may reflect specific pathotypes.

Netzmaterial und Selektivität in der Ostseedorschfischerei

Since some time fishing gear scientists express their concern over an observed tendency of the commercial fishery to proceed from codend netting yarns of 3 to 4 mm to higher values or to switch to the use of double instead of single yarn. A recent large EU-financed project collected statistical evidence on the detrimental effect of such behaviour on the selectivity of the codends. In this context data on cod are very scarce. German-Polish experiments in the Baltic from 1999 to 2001 aimed at filling this gap. The investigations prove a clear evidence of a negativ ecorrelation between netting yarn diameter and selectivity factor and/or L50. In addition they demonstrate a clear negative effect on selectivity when switching from single to double yarn The effects are of an order of magnitude that counteracting effects as catch size are masked and support the decision of the IBSFC to define maximum yarn diameters both for single and double yarn netting. A measuring instrument for the enforcement of these new regulations was introduced right in time.

Successful handstripping of hatchery bred and reared male African catfish, Clarias gariepinus (Burchell, 1822)

A total of 45 Male and 5 female Clarias gariepinus bred and reared in the hatchery in sunning for one year were obtained for this experiment. The fish were then housed separately according to their sexes and maintained on trout diet at 10% body weight for two days before they were subjected to induction. These were then induced using both human chorionic gonadotropin (hCG - 500iu) and carp pituitary suspension (CPS -3mg kg super(-1) suspended in 0.9% saline) either as priming or resolving doses. The milt produced was used to fertilize eggs tripped from females. The results indicated high milt production, motility and fertility in most males

Experiments in Neutrino Mass and Mixing: Part I - New Limits on Heavy Neutrino Emission in Nuclear Beta Decay. Part II - Fast Neutron Backgrounds for the San Onofre Neutrino Detector

In Part I of this thesis, a new magnetic spectrometer experiment which measured the β spectrum of ^(35)S is described. New limits on heavy neutrino emission in nuclear β decay were set, for a heavy neutrino mass range between 12 and 22 keV. In particular, this measurement rejects the hypothesis that a 17 keV neutrino is emitted, with sin^2 θ = 0.0085, at the 6δ statistical level. In addition, an auxiliary experiment was performed, in which an artificial kink was induced in the β spectrum by means of an absorber foil which masked a fraction of the source area. In this measurement, the sensitivity of the magnetic spectrometer to the spectral features of heavy neutrino emission was demonstrated.

In Part II, a measurement of the neutron spallation yield and multiplicity by the Cosmic-ray Underground Background Experiment is described. The production of fast neutrons by muons was investigated at an underground depth of 20 meters water equivalent, with a 200 liter detector filled with 0.09% Gd-loaded liquid scintillator. We measured a neutron production yield of (3.4 ± 0.7) x 10^(-5) neutrons per muon-g/cm^2, in agreement with other experiments. A single-to-double neutron multiplicity ratio of 4:1 was observed. In addition, stopped π^+ decays to µ^+ and then e^+ were observed as was the associated production of pions and neutrons, by the muon spallation interaction. It was seen that practically all of the π^+ produced by muons were also accompanied by at least one neutron. These measurements serve as the basis for neutron background estimates for the San Onofre neutrino detector.

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).

A emergência da competência oral como sistema dinâmico, adaptativo e complexo no ensino-aprendizagem de inglês como língua adicional para iniciantes

No âmbito do ensino-aprendizagem de línguas adicionais, pesquisas acerca do desenvolvimento da oralidade têm demonstrado que se trata de um fenômeno multidimensional. Nakatani (2010) mostrou que o domínio de estratégias comunicacionais são indicadores de desempenho linguístico e se relacionam com a proficiência do aprendiz; Kang, Rubin e Pickering (2010) observaram que os traços fonológicos afetam a percepção sobre inteligibilidade e proficiência; Hewitt e Stephenson (2011), e Ahmadian (2012) indicaram que as condições psicológicas individuais interferem na qualidade da produção oral. Escribano (2004) sugeriu que a referência contextual é essencial na construção de sentido; Gao (2011) apontou os benefícios do ensino baseado na construção do sentido, a partir de metáforas conceptuais (LAKOFF e JOHNSON, 1980), codificação dupla (CLARK e PAIVIO, 1991) e esquemas imagéticos (LAKOFF, 1987); e Ellis e Ferreira-Junior (2009) demonstraram que as construções exibem efeitos de recência e priming, afetando o uso da linguagem dos parceiros interacionais. Tais estudos apontam para a natureza complexa da aquisição de L2, mas o fazem dentro do paradigma experimental da psicolinguística. Já Larsen-Freeman (2006), demonstra que a fluência, a precisão e a complexidade desenvolvem-se com o tempo, com alto grau de variabilidade, dentro do paradigma da Teoria da Complexidade. Em viés semelhante, Paiva (2011) observa que os sistemas de Aquisição de Segunda Língua (ASL) são auto-organizáveis. Esses trabalhos, no entanto, não abordaram aprendizes de L2 com proficiência inicial, como pretendo fazer aqui. Tendo como referenciais teóricos a Teoria da Complexidade e a Linguística Cognitiva, o presente trabalho apresenta um estudo de caso, qualitativo-interpretativista, com nuances quantitativos, que discute os processos de adaptação que emergiram na expressão oral de um grupo de aprendizes iniciantes de inglês como língua adicional no contexto vocacional. Parte do entendimento de que na sala de aula vários (sub)sistemas complexos coocorrem, covariando e coadaptando-se em diferentes níveis. A investigação contou com dados transcritos de três avaliações coletados ao longo de 28 horas de aula, no domínio ENTREVISTA DE EMPREGO. Após observar a produção oral das aprendizes, criei uma taxonomia para categorizar as adaptações que ocorreram na sintaxe, semântica, fonologia e pragmática da língua-alvo. Posteriormente organizei as categorias em níveis de prototipicidade (ROSCH et al, 1976) de acordo com as adaptações mais frequentes. Finalmente, avaliei a inteligibilidade de cada elocução, classificando-as em três níveis. A partir desses dados, descrevi como a prática oral dessas participantes emergiu e se desenvolveu ao longo das 28 horas. Os achados comprovam uma das premissas da Linguística Cognitiva ao mostrarem que os níveis de descrição linguística funcionam conjuntamente em prol do sucesso comunicacional. Além disso, demonstram que a função do professor, como discutem LARSEN-FREEMAN e CAMERON (2008), não é gerar uniformidade, mas sim oportunizar vivências que estabeleçam continuidade entre o mundo, o corpo e a mente

Qualidade da imagem nas pacientes com suspeita de Endometriose infiltrada profunda : comparação entre a ultrassonografia transvaginal antes e após a realização do preparo retal

Comparar a qualidade da imagem entre a ultrassonografia transvaginal sem preparo intestinal e após preparo intestinal nas pacientes com suspeita de endometriose infiltrativa profunda do compartimento posterior e avaliar do grau de desconforto das pacientes em relação ao preparo intestinal. Estudo transversal com dados coletados prospectivamente, incluindo 39 pacientes com suspeita clínica de endometriose do compartimento posterior do ambulatório de Endometriose do Hospital Universitário Pedro Ernesto (HUPE) da Universidade do Estado do Rio de Janeiro (UERJ), no Rio de Janeiro. As pacientes foram submetidas à ultrassonografia transvaginal (USTVG) sem preparo intestinal prévio, seguido de nova USTVG uma hora após realização do enema retal. Os vídeos dos exames gravados foram editados, com ênfase na avaliação do compartimento posterior, com interesse na identificação do nódulo retrocervical e do retossigmóide. Foram graduados conforme a qualidade da imagem pelo examinador e por um radiologista (ambos mascarados), que marcaram uma nota de 0 a 10, usando a escala analógica visual. Restaram apenas 26 pacientes. Em relação ao desconforto devido a realização do enema retal, todas pacientes (100%) relataram apenas um desconforto discreto. Conforme a opção escolhida pelos avaliadores em relação ao melhor método, eles concordaram em 13 (50%) pacientes que a ultrassonografia transvaginal com preparo retal é melhor. Foi usado o teste não-paramétrico de Wilcoxon para amostras dependentes. O p-valor obtido foi de 0.042, considerado significativo (abaixo de 0.05). Isto significa que a realização do enema retal antes da realização da ultrassonografia transvaginal proporcionou uma qualidade melhor na avaliação dos nódulos. A diferença entre as avaliações com e sem preparo retal é maior nos nódulos menores que 2cm, porque encontramos a diferença de 1,1 entre os valores das medianas dos dois tipos de exames. Nos nódulos maiores que 2cm, a diferença encontrada foi de apenas 0,65. A realização do enema retal previamente à realização da ultrassonografia transvaginal no diagnóstico do nódulo endometriótico mostra uma melhora discretamente significativa na qualidade da imagem, comparativamente a não realização de preparo intestinal prévio. Somente nos casos onde o nódulo era menor que 2 cm, foram encontrados valores estatisticamente significativos com o preparo retal. O enema retal causa discreto desconforto, porém isto não parece ser um fator limitante na realização da ultrassonografia com preparo intestinal.

Efeitos da proteção e do envigoramento na germinação e estabelecimento de plântulas de duas espécies arbóreas visando a semeadura direta

A importância das florestas na mitigação do clima é reconhecida e a necessidade da conservação e restauração se tornou mais evidente. Diversas técnicas tem sido estudadas para facilitar a restauração. Nesse sentido, a semeadura direta se apresenta como uma alternativa de baixo custo para a restauração, entretanto o sucesso dessa técnica depende da criação de condições favoráveis para a germinação e estabelecimento de plântulas. O objetivo desse estudo foi avaliar os efeitos de técnicas que podem ser associadas à semeadura direta, aumentando a chance de sucesso. Dois diferentes tipos de protetores (gaiolas metálicas e bambus) foram utilizadas para avaliar a germinação e estabelecimento de Euterpe edulis Mart., uma espécie de sementes recalcitrante. Além disso, outros fatores foram considerados, como o tamanho da semente, presença dos envoltórios do fruto e posição de semeadura. A porcentagem de persistência de sementes ou frutos, germinação (%), emergência de plântulas (%), altura e diâmetro do colo das plântulas e recrutamento foram avaliados no primeiro experimento e germinação (%), emergência de plântulas (%), altura e recrutamento foram avaliados no segundo experimento. A exclusão da redação nãofoi o fator mais importante no sucesso do uso da semente, mas sim a mudança microclimática provocada pela proteção de tubos de bambu. Para a outra espécie estudada, Simira cf. glaziovii (Standl) Steyerm, uma espécie de sementes não recalcitrantes, técnicas de condicionamento foram utilizadas para avaliar a viabilidade e manutenção da qualidade fisiológica após três meses de armazenamento. Os tratamentos consistiram em hidrocondicionamento e osmocondicionamento e estes, seguidos por secagem e armazenamento. O controle também foi armazenado para comparação entre os tratamentos. Os resultados foram favoráveis tanto para condicionamento quanto para o armazenamento após condicionamento. Este estudo mostrou que a semeadura direta pode ser uma alternativa para ambas espécies quando associadas a práticas que favorecem a germinação e estabelecimento. O sucesso no uso das sementes recalcitrantes depende da criação de condições climáticas favoráveis, que podem ser conseguidas com o uso de protetores de tubos de bambu. Para espécies não recalcitrantes, a manutenção da viabilidade das sementes durante o armazenamento permite o uso em períodos mais favoráveis à germinação.

Early response to nanoparticles in the Arabidopsis transcriptome compromises plant defence and root-hair development through salicylic acid signalling

Background: The impact of nano-scaled materials on photosynthetic organisms needs to be evaluated. Plants represent the largest interface between the environment and biosphere, so understanding how nanoparticles affect them is especially relevant for environmental assessments. Nanotoxicology studies in plants allude to quantum size effects and other properties specific of the nano-stage to explain increased toxicity respect to bulk compounds. However, gene expression profiles after exposure to nanoparticles and other sources of environmental stress have not been compared and the impact on plant defence has not been analysed. Results: Arabidopsis plants were exposed to TiO2-nanoparticles, Ag-nanoparticles, and multi-walled carbon nanotubes as well as different sources of biotic (microbial pathogens) or abiotic (saline, drought, or wounding) stresses. Changes in gene expression profiles and plant phenotypic responses were evaluated. Transcriptome analysis shows similarity of expression patterns for all plants exposed to nanoparticles and a low impact on gene expression compared to other stress inducers. Nanoparticle exposure repressed transcriptional responses to microbial pathogens, resulting in increased bacterial colonization during an experimental infection. Inhibition of root hair development and transcriptional patterns characteristic of phosphate starvation response were also observed. The exogenous addition of salicylic acid prevented some nano-specific transcriptional and phenotypic effects, including the reduction in root hair formation and the colonization of distal leaves by bacteria. Conclusions: This study integrates the effect of nanoparticles on gene expression with plant responses to major sources of environmental stress and paves the way to remediate the impact of these potentially damaging compounds through hormonal priming.

News from Academy Bay

Darwin Station Director's report. Release of captive-bred land iguanas. Land iguanas breed on Venecia. The age of the giant tortoise. Visitors and events at the Charles Darwin Research Station (January - April 1982). Photo of Masked Booby and Swallow-tailed Gull.

Inter-decadal climate variability in the Southern Hemisphere: evidence from Tasmanian tree rings over the past three millennia

EXTRACT (SEE PDF FOR FULL ABSTRACT): The characterization of inter-decadal climate variability in the Southern Hemisphere is severely constrained by the shortness of the instrumental climate records. To help relieve this constraint, we have developed and analyzed a reconstruction of warm-season (November-April) temperatures from Tasmanian tree rings that now extends back to 800 BC. A detailed analysis of this reconstruction in the time and frequency domains indicates that much of the inter-decadal variability is principally confined to four frequency bands with mean periods of 31, 57, 77, and 200 years. ... In so doing, we show how a future greenhouse warming signal over Tasmania could be masked by these natural oscillations unless they are taken into account.

土壤有机物添加对温带半干旱草地地下生物过程的影响

大气CO2 浓度和降水量增加有可能大幅提高中国北方部分草地生态系统净初级生产力，进而导致向土壤中输送的有机物相应增加。本研究以位于内蒙古自治区东乌珠穆沁旗内的半干旱草地生态系统为研究对象，通过向10−20 cm 土层添加不同质量和数量的植物凋枯物碎屑模拟有机物输入增加和喷灌模拟降水量提升，同时测定土壤微生物群落动态和植物生长指标，探讨在增加有机物输入和土壤水分的情况下土壤生物过程的变化及其对土壤碳排放和贮存的反馈作用。 研究结果表明，有机物添加可促进植物地上部分及根系的生长，并显著提高土壤中可溶性有机碳（能量）和氮（养分）的含量。土壤能量和养分水平的提高促进了土壤微生物的生长：在底物可利用性水平较高时，r−对策微生物（指具有生长迅速、C/N 值较低的微生物群组）在群落中占优势地位；随着底物水平的降低，土壤中K-对策微生物（指具有生长缓慢、C/N 值较高的微生物群组）在群落中逐渐占据优势地位。土壤微生物群落组成的改变进一步导致了微生物功能群代谢活性和特征的变化，具体表现为提高了有机物添加处理中土壤细菌群落的代谢潜能，并使细菌在群落水平上的生理剖面特征明显区别于未添加有机物的处理。 研究样地内土壤微生物主要受到底物中的能量（碳）限制，土壤活性有机质库作为可利用性较高的能量和养分的重要来源，对土壤微生物活性和土壤碳周转起着比水分因子更加重要的作用。土壤水分主要影响植物生长和根系活性，并增加了土壤微生物对底物响应的复杂性，但它对地下生物过程的作用程度以底物中能量和养分水平为前提。 利用稳定性13C 同位素示踪技术测量后发现，添加C4-植物凋枯物会加速C3 底物中碳的分解速度。结合有机物添加后土壤有机质库的变化，可以推测植物凋枯物（即能量物质）输入增加会导致土壤原生有机碳的正向激发效应。在此过程中，土壤微生物群落组成及功能群代谢活性的变化起着至关重要的作用。 不同光合途径（C3 和C4）的植物和同一植物不同器官组织（地上部分和根系）的凋枯物添加对地下生物过程，特别是土壤微生物群落代谢功能的影响是不同的。在添加C3-草本凋枯物的处理中，土壤细菌群落主要利用的碳源为氨基酸类化合物；而在添加C4-植物凋枯物的处理中，土壤细菌群落主要利用的碳源为羧酸类化合物。 本研究在野外自然条件下证明了在能量缺乏的中国北方草地生态系统中，土壤有机物输入增加不但不会提高土壤有机碳库的大小，而且可能导致土壤原生有机碳的激发效应。在利用土壤呼吸与环境因子（如温度）的关系进行模拟预测土壤碳排放时，需要考虑不同生态系统底物中的能量和养分水平，以及土壤微生物和植物根系等地下生物过程对底物水平的适应性。