Total Synthesis of the Potent HIF-1 Inhibitory Antitumor Natural Product, (8R)-Mycothiazole, via Baldwin–Lee CsF/CuI sp3–sp2-Stille Cross-Coupling. Confirmation of the Crews Reassignment

A convenient asymmetric total synthesis of the potent HIF-1 inhibitory antitumor natural product, (−)- or (+)-(8R)-mycothiazole (1), is described. Not only does our synthesis confirm the 2006 structural reassignment made by Crews (Crews, P., et al. J. Nat. Prod. 2006, 69, 145), it revises the [α]_D data previously reported for this molecule in MeOH from −13.7° to +42.3°. The newly developed route to (8R)-1 sets the C(8)–OH stereocenter via Sharpless AE/2,3-epoxy alcohol reductive ring opening and utilizes two Baldwin–Lee CsF/cat. CuI Stille cross-coupling reactions with vinylstannanes 8 and 3 to efficiently elaborate the C(1)–C(4) and C(14)–C(18) sectors.

Electron dynamics and frequency coupling in a radio-frequency capacitively biased planar coil inductively coupled plasma system

The electron dynamics in a planar coil inductively coupled plasma (ICP) system with a capacitively biased electrode is investigated using space and phase resolved optical emission spectroscopy. The two power source frequencies are exact multiple of each other and phase-locked. In this configuration, the system is investigated when the coil is operated in both E-mode and H-mode. The results show that in a phase synchronized RF biased ICP, the electrode bias power couples with the capacitive contribution of the coil, in both E-mode and H-modes, similar to dual-frequency capacitively coupled plasmas (2f-CCPs). It is also demonstrated that in H-mode, the phase between the electrode bias frequency and the ICP coil frequency influences the electron heating, similar to the electrical asymmetry effect in 2f-CCPs.

Investigation of tanpura string vibrations using a two-dimensional time-domain model incorporating coupling and bridge friction

Tanpura string vibrations have been investigated previously using numerical models based on energy conserving schemes derived from a Hamiltonian description in one-dimensional form. Such time-domain models have the property that, for the lossless case, the numerical Hamiltonian (representing total energy of the system) can be proven to be constant from one time step
to the next, irrespective of any of the system parameters; in practice the Hamiltonian can be shown to be conserved within machine precision. Models of this kind can reproduce a jvari effect, which results from the bridge-string interaction. However the one-dimensional formulation has recently been shown to fail to replicate the jvaris strong dependence on the thread placement. As a first step towards simulations which accurately emulate this sensitivity to the thread placement, a twodimensional model is proposed, incorporating coupling of controllable level between the two string polarisations at the string termination opposite from the barrier. In addition, a friction force acting when the string slides across the bridge in horizontal direction is introduced, thus effecting a further damping mechanism. In this preliminary study, the string is terminated at the position of the thread. As in the one-dimensional model, an implicit scheme has to be used to solve the system, employing Newton's method to calculate the updated positions and momentums of each string segment. The two-dimensional model is proven to be energy conserving when the loss parameters are set to zero, irrespective of the coupling constant. Both frequency-dependent and independent losses are then added to the string, so that the model can be compared to analogous instruments. The influence of coupling and the bridge friction are investigated.

Intermediate-coupling R -matrix calculations of electron-impact excitation of Fe 5+

For applications to laboratory and astrophysical plasmas, there is a great need for accurate electron-impact excitation data between individual levels in the lower charge-state ions of iron. Recently, we have reported on the first intermediate-coupling R -matrix calculation of electron-impact excitation in Fe 4+ , in which the close-coupling expansion of the target included levels from both ground and excited configurations (Ballance et al 2007 J. Phys. B: At. Mol. Opt. Phys. [/0953-4075/40/23/f01] 40 F327 , 2008 Europhys. News 39 14). In this paper, we present the results of two large intermediate-coupling Dirac R -matrix calculations of electron-impact excitation of Fe 5+ . The results from the two calculations, which differ only in the configuration–interaction expansions of the target, are compared. These comparisons provide some indication of the accuracy of the calculations and the resulting data should be useful in modelling plasmas containing iron.

Electron-impact excitation of Fe2: a comparison of intermediate coupling frame transformation, Breit-Pauli and Dirac R-matrix calculations

Modeling the spectral emission of low-charge iron group ions enables the diagnostic determination of the local physical conditions of many cool plasma environments such as those found in H II regions, planetary nebulae, active galactic nuclei etc. Electron-impact excitation drives the population of the emitting levels and, hence, their emissivities. By carrying-out Breit-Pauli and intermediate coupling frame transformation (ICFT) R-matrix calculations for the electron-impact excitation of Fe$^{2+}$ which both use the exact same atomic structure and the same close-coupling expansion, we demonstrate the validity of the application of the powerful ICFT method to low-charge iron group ions. This is in contradiction to the finding of Bautista et al. [Ap.J.Lett, 718, L189, (2010)] who carried-out ICFT and Dirac R-matrix calculations for the same ion. We discuss possible reasons.

Electron-impact excitation of Fe 4+ : an intermediate-coupling R -matrix calculation

For a number of years, there has been a major effort to calculate electron-impact excitation data for every ion stage of iron embodied by the ongoing efforts of the IRON project by Hummer et al (1993 Astron. Astrophys. 279 298). Due to the complexity of the targets, calculations for the lower stages of ionization have been limited to either intermediate-coupling calculations within the ground configurations or LS -coupling calculations of the ground and excited configurations. However, accurate excitation data between individual levels within both the ground and excited configurations of the low charge-state ions are urgently required for applications to both astrophysical and laboratory plasmas. Here we report on the results of the first intermediate-coupling R -matrix calculation of electron-impact excitation for Fe 4+ for which the close-coupling (CC) expansion includes not only those levels of the 3d 4 ground configuration, but also the levels of the 3d 3 4s, 3d 3 4p, 3d 3 4d and 3d 2 4s 2 excited configurations. With 359 levels in the CC expansion and over 2400 scattering channels for many of the J Π partial waves, this represents the largest electron–ion scattering calculation to date and it was performed on massively parallel computers using a recently developed set of relativistic parallel R -matrix programs.

The time-dependent close-coupling method for atomic and molecular collision processes

We review the development of the time-dependent close-coupling method to study atomic and molecular few body dynamics. Applications include electron and photon collisions with atoms, molecules, and their ions.

Studies on magnetocaloric and magnetic coupling effects

O presente trabalho apresenta novas metodologias desenvolvidas para a análise das propriedades magnéticas e magnetocalóricas de materiais, sustentadas em considerações teóricas a partir de modelos, nomeadamente a teoria de transições de fase de Landau, o modelo de campo médio molecular e a teoria de fenómeno crítico. São propostos novos métodos de escala, permitindo a interpretação de dados de magnetização de materiais numa perspectiva de campo médio molecular ou teoria de fenómeno crítico. É apresentado um método de estimar a magnetização espontânea de um material ferromagnético a partir de relações entropia/magnetização estabelecidas pelo modelo de campo médio molecular. A termodinâmica das transições de fase magnéticas de primeira ordem é estudada usando a teoria de Landau e de campo médio molecular (modelo de Bean-Rodbell), avaliando os efeitos de fenómenos fora de equilíbrio e de condições de mistura de fase em estimativas do efeito magnetocalórico a partir de medidas magnéticas. Efeitos de desordem, interpretados como uma distribuição na interacção magnética entre iões, estabelecem os efeitos de distribuições químicas/estruturais nas propriedades magnéticas e magnetocalóricas de materiais com transições de fase de segunda e de primeira ordem. O uso das metodologias apresentadas na interpretação das propriedades magnéticas de variados materiais ferromagnéticos permitiu obter: 1) uma análise quantitativa da variação de spin por ião Gadolínio devido à transição estrutural do composto Gd5Si2Ge2, 2) a descrição da configuração de cluster magnético de iões Mn na fase ferromagnética em manganites da família La-Sr e La-Ca, 3) a determinação dos expoentes críticos β e δ do Níquel por métodos de escala, 4) a descrição do efeito da pressão nas propriedades magnéticas e magnetocalóricas do composto LaFe11.5Si1.5 através do modelo de Bean-Rodbell, 5) uma estimativa da desordem em manganites ferromagnéticas com transições de segunda e primeira ordem, 6) uma descrição de campo médio das propriedades magnéticas da liga Fe23Cu77, 7) o estudo de efeitos de separação de fase na família de compostos La0.70-xErxSr0.30MnO3 e 8) a determinação realista da variação de entropia magnética na família de compostos de efeito magnetocalórico colossal Mn1-x-yFexCryAs.

Microphytobenthos vs Hydrobia: trophic coupling in estuarine environment

Os estuários são ambientes complexos, biologicamente diversos e muito importantes no que respeita à produtividade primária. As zonas intertidais destes ecossistemas são ocupadas por organismos que possuem uma elevada capacidade de sobrevivência e adaptação face às variadas e rápidas alterações nos factores ambientais (tais como temperatura, salinidade, conteúdo hídrico, etc.). As cadeias tróficas com origem no ecossistema estuarino bentónico são essencialmente herbívoras, regulando o fluxo de energia desde o fundo sedimentar e através do ecossistema. Nas áreas estuarinas intertidais a produção primária é essencialmente suportada pelo microfitobentos (MPB). Estas comunidades de microalgas bênticas constituem uma importante fonte de matéria orgânica e são por si só a principal fonte alimentar para as populações de Hydrobia. Neste contexto, a interacção MPB - Hydrobia é um modelo-chave na investigação da cadeia trófica estuarina de origem bentónica, actuando como um importante canal de transporte de energia para os níveis tróficos superiores, especialmente se considerarmos que Hydrobia é uma importante presa para peixes, aves e caranguejos. O presente estudo tem por objectivos gerais: i) a investigação do controlo ambiental (particularmente da luz e do teor em água do sedimento) e endógeno na migração vertical do MPB e ii) a identificação e potencial utilização de marcadores tróficos (pigmentos e ácidos gordos) úteis à investigação da interacção MPB – Hydrobia em laboratório e em condições naturais, considerando a existência de uma elevada plasticidade trófica por parte da Hydrobia e a elevada densidade populacional que estes organismos podem apresentar. A primeira fase de investigação resultou na comparação do papel dos estímulos ambientais e do controlo endógeno nos padrões de comportamento migratório vertical do microfitobentos, demonstrando a existência de um controlo essencialmente endógeno na formação e desintegração do biofilme superficial. A regulação e manutenção da biomassa à superfície do sedimento são claramente controladas pela variação dos factores ambientais, em especial da luz, cuja presença é essencial à formação total do biofilme microalgal à superfície do sedimento intertidal. Foi proposta uma nova abordagem metodológica com vista à estimativa nãodestrutiva do teor de água de sedimentos intertidais vasosos , possibilitando o estudo da influência da acção do vento no conteúdo hídrico dos sedimentos e o consequente impacto da dessecação na comunidade microfitobêntica. Observou-se que a dessecação provoca efeitos limitantes não só na biomassa superficial mas também na actividade fotossintética dos biofilmes microfitobênticos, conduzindo à diminuição da produtividade primária. No que respeita à dinâmica trófica da interacção MPB - Hydrobia foi estabelecido o uso do pigmento feoforbide a, quantificado nas partículas fecais da fauna, como marcador trófico que permite estimar a quantidade de biomassa de microalgas (clorofila a) incorporada pelos organismos animais.Para tal foi investigada e comprovada a existência de uma relação significativa entre a concentração de feopigmentos excretados e a concentração de clorofila a ingerida. Estes estudos foram desenvolvidos numa primeira fase à escala diária, considerando os efeitos dos ciclos sazonais, dia-noite e maré, e depois com a validação em condições naturais, numa escala mensal. A taxa de ingestão média de indivíduos de H. ulvae varia ao longo do dia, com o máximo em torno dos períodos diurnos de maré baixa, o que pode estar relacionado com a disponibilidade de MPB. As taxas de ingestão (TI) de H. ulvae variam ainda em função da estação do ano (TI verão > TI primavera) e em função da densidade de indivíduos (> densidade, < ingestão). Verificou-se um efeito negativo na concentração de clorofila disponível após herbívoria independentemente da densidade de indivíduos. Finalmente, a comparação dos perfis de ácidos gordos de H. ulvae provenientes de diferentes habitats com os perfis de potenciais fontes alimentares permitiu demonstrar que os ácidos gordos são ferramentas úteis na identificação do habitat ocupado por estes organismos. No entanto, apesar da ocupação de diferentes habitats e da integração de múltiplas fontes de produção primária na sua dieta foram sempre observados significativos níveis de ácidos gordos específicos de microalgas (em particular diatomáceas), reforçando o papel importante das comunidades de microalgas bênticas na dieta das populações de H. ulvae.

Coupling anchovy eggs and hydrodynamic model as an assessement tool for estuarine ecohydrological management

Nitrate and urban waste water directives have raised the need for a better understanding of coastal systems in European Union. The incorrect application of these directives can lead to important ecological or social penalties. In the paper this problem is addressed to Ria Formosa Coastal Lagoon. Ria Formosa hosts a Natural Park, important ports of the southern Portuguese coast and significant bivalve aquaculture activity. Four major urban waste water treatment plants discharging in the lagoon are considered in this study. Its treatment level must be selected, based on detailed information from a monitoring program and on a good knowledge of the processes determining the fate of the material discharged in the lagoon. In this paper the results of a monitoring program and simulations using a coupled hydrodynamic and water quality / ecological model, MOHID, are used to characterise the system and to understand the processes in Ria Formosa. It is shown that the water residence time in most of the lagoon is quite low, of the order of days, but it can be larger in the upper parts of the channels where land generated water is discharged. The main supply of nutrients to the lagoon comes from the open sea rather than from the urban discharges. For this reason the characteristics and behaviour of the general lagoon contrasts with the behaviour of the upper reaches of the channels where the influence of the waste water treatment plants are high. In this system the bottom mineralization was found to be an important mechanism, and the inclusion of that process in the model was essential to obtain good results.

Ultra compact pseudo-elliptic inline waveguide bandpass filters using bypass coupling

This paper presents an ultra compact waveguide bandpass filter that exhibits a pseudo-elliptic response. The transmission zero created in the upper stopband to form a rapid roll off is produced through a bypass coupling with higher order modes. A 3rd order filter is designed at the centre frequency of 9.4 GHz with a 5.3% fractional bandwidth. The proposed structure's size is 38% smaller than one of a 3rd order E-plane extracted pole filter with comparable response. Additionally, this configuration allows larger span of different bandwidths. The filter has been fabricated and tested using E-plane waveguide technology, which has benefits of being inexpensive and having mass producible capabilities. Measurements of such a fabricated filter validate the simulated results.

Wind resource modelling in complex terrain using different mesoscale–microscale coupling techniques

Wind resource evaluation in two sites located in Portugal was performed using the mesoscale modelling system Weather Research and Forecasting (WRF) and the wind resource analysis tool commonly used within the wind power industry, the Wind Atlas Analysis and Application Program (WAsP) microscale model. Wind measurement campaigns were conducted in the selected sites, allowing for a comparison between in situ measurements and simulated wind, in terms of flow characteristics and energy yields estimates. Three different methodologies were tested, aiming to provide an overview of the benefits and limitations of these methodologies for wind resource estimation. In the first methodology the mesoscale model acts like “virtual” wind measuring stations, where wind data was computed by WRF for both sites and inserted directly as input in WAsP. In the second approach, the same procedure was followed but here the terrain influences induced by the mesoscale model low resolution terrain data were removed from the simulated wind data. In the third methodology, the simulated wind data is extracted at the top of the planetary boundary layer height for both sites, aiming to assess if the use of geostrophic winds (which, by definition, are not influenced by the local terrain) can bring any improvement in the models performance. The obtained results for the abovementioned methodologies were compared with those resulting from in situ measurements, in terms of mean wind speed, Weibull probability density function parameters and production estimates, considering the installation of one wind turbine in each site. Results showed that the second tested approach is the one that produces values closest to the measured ones, and fairly acceptable deviations were found using this coupling technique in terms of estimated annual production. However, mesoscale output should not be used directly in wind farm sitting projects, mainly due to the mesoscale model terrain data poor resolution. Instead, the use of mesoscale output in microscale models should be seen as a valid alternative to in situ data mainly for preliminary wind resource assessments, although the application of mesoscale and microscale coupling in areas with complex topography should be done with extreme caution.

Hydrogeomechanics for rock engineering: coupling subsurface hydrogeomechanical assessement and hydrogeotechnical mapping on fracturated rock masses

The present work aims to achieve and further develop a hydrogeomechanical approach in Caldas da Cavaca hydromineral system rock mass (Aguiar da Beira, NW Portugal), and contribute to a better understanding of the hydrogeological conceptual site model. A collection of several data, namely geology, hydrogeology, rock and soil geotechnics, borehole hydraulics and hydrogeomechanics, was retrieved from three rock slopes (Lagoa, Amores and Cancela). To accomplish a comprehensive analysis and rock engineering conceptualisation of the site, a multi‐technical approach were used, such as, field and laboratory techniques, hydrogeotechnical mapping, hydrogeomechanical zoning and hydrogeomechanical scheme classifications and indexes. In addition, a hydrogeomechanical data analysis and assessment, such as Hydro‐Potential (HP)‐Value technique, JW Joint Water Reduction index, Hydraulic Classification (HC) System were applied on rock slopes. The hydrogeomechanical zone HGMZ 1 of Lagoa slope achieved higher hydraulic conductivities with poorer rock mass quality results, followed by the hydrogeomechanical zone HGMZ 2 of Lagoa slope, with poor to fair rock mass quality and lower hydraulic parameters. In addition, Amores slope had a fair to good rock mass quality and the lowest hydraulic conductivity. The hydrogeomechanical zone HGMZ 3 of Lagoa slope, and the hydrogeomechanical zones HGMZ 1 and HGMZ 2 of Cancela slope had a fair to poor rock mass quality but were completely dry. Geographical Information Systems (GIS) mapping technologies was used in overall hydrogeological and hydrogeomechanical data integration in order to improve the hydrogeological conceptual site model.

Coupling electrokinetics and iron nanoparticles for the remediation of contaminated soils

Fundação para a Ciência e a Tecnologia - PTDC/AGR-­AAM/101643/2008 NanoDC ; SFRH/BD/76070/2011 ; FP7-­PEOPLE-­IRSES-­2010-­269289-­ ELECTROACROSS

Phospha-adamantanes as ligands for palladium-catalyzed cross-coupling reactions

New and robust methodologies have been designed for palladium-catalyzed crosscoupling reactions involving·a novel·class oftertiary phosphine ligand incorporating a phospha-adamantane framework. It has been realized that bulky, electron-rich phosphines, when used as ligands for palladium, allow for cross-coupling reactions involving even the less reactive aryl halide substrates with a variety of coupling partners. In an effort to design new ligands suitable for carrying out cross-coupling transformations, the secondary phosphine, 1,3,5,7-tetramethyl-2,4,8-trioxa-6phosphaadamantane was converted into a number of tertiary phosphine derivatives. The ability of these tertiary phosphaadamantanes to act as effective ligands in the palladiumcatalyzed Suzuki cross-coupling was examined. 1,3,5,7-Tetramethyl-6-phenyl-2,4,8trioxa- 6-phosphaadamantane (PA-Ph) used in combination with Pdz(dba)3permitted the reaction of an array of aryl iodides, bromides and chlorides with a variety arylboronic acids to give biaryls in good to excellent yields. Subsequently, palladium complexes of PA-Ph were prepared and isolated in high yields as air stable palladium bisphosphine complexes. Two different kinds of crystals were isolated and upon characterization revealed two complexes, Pd(PA-Ph)z.dba and Pd(PA-Ph)zOz. Preliminary screening for their catalytic activity indicated that the former is more reactive than the latter. Pd(PAPh) z.dba was applied as the catalyst for Sonogashira cross-coupling reactions of aryl iodides and bromides and in the reactions of aryl bromides and chlorides with ketones to give a-arylated ketones at mild temperatures in high yields.