Reaction of 2-methyl-1,4-naphthoquinone and its 3-substituted derivatives with active methylene group anions and with diazo compounds

The reaction of 2-chloro-3-methyl-1,4-naphthoquinone (3) with the anion of ethyl cyanoacetate led to a mixture of two epimeric fused-ring cyclopropane compounds, characterised as exo- and endo-1-cyano-1 -ethoxycarbonyl-1a-methyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (8) and (9). Various hydrolysis products of these were prepared and an X-ray crystallographic analysis was carried out on one of them, 1-carbamoyl-1 -carboxy-1a-methyl-1a,7a-dihydro-1H-cyclopropa[b]-naphthalene-2,7-dione (17). The reaction of 2-methyl-1,4-naphthoquinone (1) with ethyl diazoacetate gave a fused pyrazoline derivative, 3-ethoxycarbonyl-4-hydroxy-9a-methyl-1,9a-dihydro-benz[f]indazol-9-one (22), while reaction of 2-methyl-3-nitro-1,4-naphthoquinone (5) with diazomethane led to a fused Δ2-isoxazoline N-oxide, 3a-methyl-3,3a-dihydroisoxazolo[3,4-b]naphthalene-4,9-dione 1-oxide (26).

The impact of Group Intelligence software on enquiry-based learning

Despite the increasing use of groupware technologies in education, there is little evidence of their impact, especially within an enquiry-based learning (EBL) context. In this paper, we examine the use of a commercial standard Group Intelligence software called GroupSystems®ThinkTank. To date, ThinkTank has been adopted mainly in the USA and supports teams in generating ideas, categorising, prioritising, voting and multi-criteria decision-making and automatically generates a report at the end of each session. The software was used by students carrying out an EBL project, set by employers, for a full academic year. The criteria for assessing the impact of ThinkTank on student learning were those of creativity, participation, productivity, engagement and understanding. Data was collected throughout the year using a combination of interviews and questionnaires, and written feedback from employers. The overall findings show an increase in levels of productivity and creativity, evidence of a deeper understanding of their work but some variation in attitudes towards participation in the early stages of the project.

Approaches to the synthesis of novel photoactive side chain liquid crystalline polymers containing analogues of the cinnamate ester group

A series of chain liquid crystalline copolymers of 4-cyanophenyl 4′-(6-methacryloyloxyhexyloxy)benzoate and 2-methacryloyloxyethyl β-(1-naphthyl)-propenoate were prepared by free radical polymerization. The corresponding polyacrylates could not be prepared in the same way and an alternative method was used for their preparation involving the synthesis of copolymers of the mesogenic monomer and 2-hydroxyethyl acrylate followed by treatment of the resulting polymers with β-(1-naphthyl)propenoyl chloride. The materials are of interest as photoactive liquid crystalline polymers. The effect of introducing a bulky nonmesogenic group into a liquid crystalline copolymer generally lowers the clearing temperature and raises Tg but also gives rise to contrasting phase behaviour in these two series of polymers. Polymethacrylates which show mesomorphism have sharp transitions and continue to exhibit a highly ordered smectic phase over the bulk of their liquid crystal range. Polyacrylates, on the other hand, exhibit a weakening and broadening-out of their thermal transitions consistent with a lowering of order. These results emphasize the effect of the polymer backbone on phase behaviour.

Second Strike and you are (finally) out? The Quashing of the Prevention of Infiltration Law (Amendment no. 4)

The blog-post critically analyses the Israeli Supreme Court judgment (HCJ 8425/13 Anon v. Knesset et al) quashing the Prevention of Infiltration Law (Amendment no. 4), offering themes of comparative constitutional interest.

Time for review: supporting the work of an advisory group

This paper raises methodological issues about the challenges and dilemmas of inclusive research practices reflecting on the work of an advisory group carrying out research on using Information and Communication Technology (ICT) to enhance community participation. The interests of three parties can be identified – the commissioning agent, the researchers and the researched – and these interplayed throughout the course of the research determining the outcomes. Given the relationship between inclusive research and advocacy, there were particular gains in enabling the voice of the advisory group to shape the way in which the research was conducted and to disseminate the findings both within the organisation and beyond. However, the fragility of these new structures required organisational changes for the research to be truly empowering. The experience of the group suggests the need for their involvement at all stages of the research process

Paleomagnetism of the Santa Fe Group, central Brazil: Implications for the late Paleozoic apparent polar wander path for South America

Paleomagnetic and rockmagnetic data are reported for the Floresta Formation (Santa Fe Group) of the Sanfranciscana Basin, central Brazil. This formation represents the Permo-Carboniferous glacial record of the basin and comprises the Brocoto (diamictites and flow diamictites), Brejo do Arroz (red sandstones and shales with dropstones and invertebrate trails), and Lavado (red sandstones) members, which crop out near the cities of Santa Fe de Minas and Canabrava, Minas Gerais State. Both Brejo do Arroz and Lavado members were sampled in the vicinities of the two localities. Alternating field and thermal demagnetizations of 268 samples from 76 sites revealed reversed components of magnetization in all samples in accordance with the Permo-Carboniferous Reversed Superchron. The magnetic carriers are magnetite and hematite with both minerals exhibiting the same magnetization component, suggesting a primary origin for the remanence. We use the high-quality paleomagnetic pole for the Santa Fe Group (330.9 degrees E 65.7 degrees S; N = 60; alpha(95) = 4.1 degrees; k = 21) in a revised late Carboniferous to early Triassic apparent polar wander path for South America. On the basis of this result it is shown that an early Permian Pangea A-type fit is possible if better determined paleomagnetic poles become available.

Diagnostic reference levels for the most frequent radiological examinations carried out in Brazil

Objectives. A large-scale survey of doses to patients undergoing the most frequent radiological examinations was carried out in health services in Sao Paulo (347 radiological examinations per 1 000 inhabitants), the most populous Brazilian state. Methods. A postal dosimetric kit with thermoluminescence dosimeters was used to evaluate the entrance surface dose (ESD) to patients. A stratified sampling technique applied to the national health database furnished important data on the distribution of equipment and the annual number of examinations. Chest, head (skull and sinus), and spine (cervical, thoracic, and lumbar) examinations were included in the trial. A total of 83 rooms and 868 patients were included, and 1 415 values of ESD were measured. Results. The data show large coefficients of variation in tube charge, giving rise to large variations in ESD values. Also, a series of high ESD values associated with unnecessary localizing fluoroscopy were detected. Diagnostic reference levels were determined, based on the 75th percentile (third quartile) of the ESD distributions. For adult patients, the diagnostic reference levels achieved are very similar to those obtained in international surveys. However, the situation is different for pediatric patients: the ESD values found in this survey are twice as large as the international recommendations for chest radiographs of children. Conclusions. Despite the reduced number of ESD values and rooms for the pediatric patient group, it is recommended that practices in chest examinations be revised and that specific national reference doses and image quality be established after a broader survey is carried out.

Azo-group dihedral angle torsion dependence on temperature: A theorerical-experimental study

Quantum chemical calculations were carried out to explain the observed shifts in the absorption spectrum of different azo-aromatic compounds due to changes in the dihedral angle of the azo-group. Our results reveal that the pi-pi* transition presents a hypsochromic shift and an oscillator strength drop upon increase of the dihedral angle. Nevertheless, the pi-pi* transition exhibits the opposite behavior. This effect is attributed to the reduction in the pi-electron conjugation length of the molecule. Experimentally, we performed temperature dependence measurements of the linear absorption spectrum. Both the theoretical and experimental results demonstrate that small energy changes are mirrored in the electronic transitions of conjugated linear molecules. (C) 2010 Elsevier B.V. All rights reserved.

The effect of carbonyl group in the asymmetry Of (3,4)J(CH) coupling constants in norbornanones

A rationalization of the known difference between the (3,4)J(C4H1) and (3,4)J(C1H4) couplings transmitted mainly through the 7-bridge in norbornanone is presented in terms of the effects of hyperconjugative interactions involving the carbonyl group. Theoretical and experimental studies Of (3,4)J(CH) couplings were carried out in 3-endo- and 3-exo-X-2-norbornanone derivatives (X = Cl, Br) and in exo- and endo-2-noborneol compounds. Hyperconjugative interactions were studied with the natural bond orbital (NBO) method. Hyperconjugative interactions involving the carbonyl pi*c(2) =o and sigma*c(2) =o antibonding orbitals produce a decrease of three-bond contribution to both (3,4) J(C4H1) and (3,4)J(C1H4) couplings. However, the latter antibonding orbital also undergoes a strong sigma c(3)-c(4) ->sigma*c(2) =o interaction, which defines an additional coupling pathway for (3,4)J(C4H1) but not for (3,4)J(C1H4). This pathway is similar to that known for homoallylic couplings, the only difference being the nature of the intermediate antibonding orbital; i.e. for (3,4)J(C4H1) it is of sigma*-type, while in homoallylic couplings it is of pi*-type. Copyright (c) 2007 John Wiley & Sons, Ltd.

Chemostratigraphy of the Tamengo Formation (Corumba Group, Brazil) A contribution to the calibration of the Ediacaran carbon-isotope curve

The Corumba Group cropping out in the southern Paraguay Belt in Brazil is one of the most complete Ediacaran sedimentary archives of palaeogeographic climatic biogeochemical and biotic evolution in southwestern Gondwana The unit hosts a rich fossil record including acritarchs vendotaenids (Vendo taenia Eoholynia) soft-bodied metazoans (Corumbella) and skeletal fossils (Cloudina Titanotheca) The Tamengo Formation made up mainly of limestones and marls provides a rich bio- and chemostratigraphic record Several outcrops formerly assigned to the Cuiaba Group are here included in the Tamengo Formation on the basis of lithological and chemostratigraphical criteria High-resolution carbon isotopic analyses are reported for the Tamengo Formation showing (from base to top) (1) a positive delta(13)C excursion to +4 parts per thousand PDB above post-glacial negative values (2) a negative excursion to -3 5 parts per thousand associated with a marked regression and subsequent transgression (3) a positive excursion to +5 5 parts per thousand and (4) a plateau characterized by delta(13)C around +3 parts per thousand A U-Pb SHRIMP zircon age of an ash bed Interbedded in the upper part of the delta(13)C positive plateau yielded 543 +/- 3 Ma which is considered as the depositional age (Babinski et al 2008a) The positive plateau in the upper Tamengo Formation and the preceding positive excursion are ubiquitous features in several successions worldwide including the Nama Group (Namibia) the Dengying Formation (South China) and the Nafun and Ara groups (Oman) This plateau is constrained between 542 and 551 Ma thus consistent with the age of the upper Tamengo Formation The negative excursion of the lower Tamengo Formation may be correlated to the Shuram-Wonoka negative anomaly although delta(13)C values do not fall beyond -3 5 parts per thousand in the Brazilian sections Sedimentary breccias occur just beneath this negative excursion in the lower Tamengo Formation One possible interpretation of the origin of these breccias is a glacioeustatic sea-level fall but a tectonic interpretation cannot be completely ruled out Published by Elsevier B V

Tectono-sedimentary evolution of the Neoproterozoic BIF-bearing Jacadigo Group, SW-Brazil

The Jacadigo Group contains one of the largest sedimentary iron and associated manganese deposits of the Neoproterozoic. Despite its great relevance, no detailed sedimentological study concerning the unit has been carried out to date. Here we present detailed sedimentological data and interpretation on depositional systems, system tracts, external controls on basin evolution, basin configuration and regional tectonic setting of the Jacadigo Basin. Six depositional systems were recognized: (I) an alluvial fan system; (II) a siliciclastic lacustrine system; (III) a fan-delta system; (IV) a bedload-dominated river system; (V) an iron formation-dominated lacustrine or marine gulf system; and (VI) a rimmed carbonate platform system. The interpreted depositional systems are related to three tectonic system tracts. The first four depositional systems are mainly made of continental siliciclastics and refer to the rift initiation to early rift climax stage; the lake/gulf system corresponds to the mid to late rift climax stage and the carbonate platform represents the immediate to late post rift stage (Bocaina Formation deposits of the Ediacaran fossil-bearing Corumba Group). The spatial distribution of the depositional systems and associated paleocurrent patterns indicate a WNW-ESE orientation of the master fault zone related to the formation of the Jacadigo Basin. Thus, the iron formations of the Jacadigo Group were deposited in a starved waterbody related to maximum fault displacement and accommodation rates in a restricted continental rift basin. The Fe-Si-Mn source was probably related to hydrothermal plume activity that reached the basin through the fault system during maximum fault displacement phases. Our results also suggest a restricted tectono-sedimentary setting for the type section of the Puga Formation. The Jacadigo Group and the Puga Formation, usually interpreted as glacial deposits, are readdressed here as basin margin gravitational deposits with no necessary relation to glacial processes. (C) 2011 Elsevier B.V. All rights reserved.

Involutions and free pairs of bicyclic units in integral group rings

If * : G -> G is an involution on the finite group G, then * extends to an involution on the integral group ring Z[G] . In this paper, we consider whether bicyclic units u is an element of Z[G] exist with the property that the group < u, u*> generated by u and u* is free on the two generators. If this occurs, we say that (u, u*)is a free bicyclic pair. It turns out that the existence of u depends strongly upon the structure of G and on the nature of the involution. One positive result here is that if G is a nonabelian group with all Sylow subgroups abelian, then for any involution *, Z[G] contains a free bicyclic pair.

Opting out of oppositionality : toward an informed and engaged "third wave" feminism

I begin by citing a definition of "third wave" from the glossary in Turbo Chicks: Talking Young Feminisms at length because it communicates several key issues that I develop in this project. The definition introduces a tension within "third wave" feminism of building and differentiating itself from second wave feminism, the newness of the term "third wave," its association with "young" women, complexity of contemporary feminisms, and attention to multiple identities and oppressions. Uncovering explanations of "third wave" feminism that go beyond, like this one, generational associations, is not an easy task. Authors consistently group new feminist voices together by age under the label "third wave" feminists without questioning the accuracy of the designation. Most explorations of "third wave" feminism overlook the complexities and distinctions that abound among "young" feminists ; not all young feminists espouse similar ideas, tactics, and actions; and for various reasons, not all young feminists identify with a "third wave" of feminism. Less than a year after I began to learn about feminism I discovered Barbara Findlen's Listen Up: Voices From the Next Feminist Generation. Although the collection nor its contributors declare association with "third wave" feminism, consequent reviews and citations in articles identify it, along with Rebecca Walker's To Be Real: Telling the Truth and Changing the Voice of Feminism, as a major text of "third wave" feminism. Re-reading Listen Up since beginning to research "third wave" feminism, I now understand its fundamental influence on my research questions as a starting point for assessing persistent exclusion in contemporary feminism, rather than as a revolutionary text (as it is claimed to be in many reviews). Findlen begins the introduction with the bold claim, "My feminism wasn't shaped by antiwar or civil rights activism ..." (xi). Framing the collection with a disavowal of the influence women of color's organizational efforts negates, for me, the project's proclaimed commitment to multivocality. Though several contributions examine persistent exclusion within contemporary feminist movement, the larger project seems to rely on these essays to reflect this commitment, suggesting that Listen Up does not go beyond the "add and stir" approach to "diversity." Interestingly, this statement does not appear in the new edition of Listen Up published in 2001. And the content has changed with this new edition, including several more Latina contributors and other "corrective" additions.

The value of local partners in Brazil: the effects of ownership clusters and business group membership on firm value in emerging markets

Este estudo analisa como a classe de acionistas afeta o valor das empresas brasileiras listadas na bolsa de valores no ponto de vista da governança corporativa. O trabalho examina a interação entre o valor das empresas e cinco tipos de concentrações acionárias comumente presente em mercados emergentes: famílias, agentes públicos, investidores estrangeiros, executivos e investidores financeiros nacionais. A análise empírica demonstra que o mix e a concentração de participação acionária afeta significativamente o valor das empresas. Utilizando uma compilação única de dados em painel de 2004 a 2008, a presente pesquisa também desenvolve hipóteses sobre o efeito da participação em grupos econômicos para o valor das empresas. A investigação encontra evidências de que, apesar de sua importância para o desenvolvimento de empresas brasileiras, o capital familiar, instituições públicas, e investidores estrangeiros estão cedendo lugar a monitores mais especializados e menos concentrados, como executivos e instituições financeiras nacionais. Estes resultados indicam que a governança corporativa no Brasil pode estar alcançando níveis de maturidade mais elevados. Adicionalmente, apesar de não haver indicação da existência de correlação entre a participação em grupos econômicos e o valor das empresas, os resultados indicam que a presença de um tipo específico de acionista em uma empresa do grupo facilita investimentos futuros desta classe de acionista em outras empresas do mesmo grupo, sinalizando que os interesses acionários são provavelmente perpetuados dentro de uma mesma rede de empresas. Finalmente, a pesquisa demonstra que enquanto o capital familiar prefere investir em empresas com ativa mobilidade do capital, investidores internacionais e instituições públicas procuram investimentos em equity com menor mobilidade de capital, o que lhes garante mais transparência com relação ao uso dos recursos e fundos das empresas.

The influence of the supply chain agents on the new product development's performance: an analysis based on the multi-group moderation

Este estudo buscou verificar a influencia dos agentes da cadeia de suprimentos no desempenho do desenvolvimento de novos produtos quando os agentes são analisados em conjunto. A motivação desta pesquisa veio de estudos que alertaram para a consideração da integração da cadeia de suprimentos como um constructo multidimensional, englobando o envolvimento da manufatura, fornecedores e clientes no desenvolvimento de novos produtos; e devido à falta de informação sobre as influencias individuais destes agentes no desenvolvimento de novos produtos. Sob essas considerações, buscou-se construir um modelo analítico baseado na Teoria do Capital Social e Capacidade Absortiva, construir hipóteses a partir da revisão da literatura e conectar constructos como cooperação, envolvimento do fornecedor no desenvolvimento de novos produtos (DNP), envolvimento do cliente no DNP, envolvimento da manufatura no DNP, antecipação de novas tecnologias, melhoria contínua, desempenho operacional do DNP, desempenho de mercado do NPD e desempenho de negócio do DNP. Para testar as hipóteses foram consideradas três variáveis moderadoras, tais como turbulência ambiental (baixa, média e alta), indústria (eletrônicos, maquinários e equipamentos de transporte) e localização (América, Europa e Ásia). Para testar o modelo foram usados dados do projeto High Performance Manufacturing que contém 339 empresas das indústrias de eletrônicos, maquinários e equipamentos de transporte, localizadas em onze países. As hipóteses foram testadas por meio da Análise Fatorial Confirmatória (AFC) incluindo a moderação muti-grupo para as três variáveis moderadoras mencionadas anteriormente. Os principais resultados apontaram que as hipóteses relacionadas com cooperação foram confirmadas em ambientes de média turbulência, enquanto as hipóteses relacionadas ao desempenho no DNP foram confirmadas em ambientes de baixa turbulência ambiental e em países asiáticos. Adicionalmente, sob as mesmas condições, fornecedores, clientes e manufatura influenciam diferentemente no desempenho de novos produtos. Assim, o envolvimento de fornecedores influencia diretamente no desempenho operacional e indiretamente no desempenho de mercado e de negócio em baixos níveis de turbulência ambiental, na indústria de equipamentos de transporte em países da Americanos e Europeus. De igual forma, o envolvimento do cliente influenciou diretamente no desempenho operacional e indiretamente no desempenho de mercado e do negócio em médio nível de turbulência ambiental, na indústria de maquinários e em países Asiáticos. Fornecedores e clientes não influenciam diretamente no desempenho de mercado e do negócio e não influenciam indiretamente no desempenho operacional. O envolvimento da manufatura não influenciou nenhum tipo de desempenho do desenvolvimento de novos produtos em todos os cenários testados.