N-aminopyrroledione-hydrazonoketene-pyrazolium oxide-pyrazolone rearrangements and pyrazolone tautomerism

Flash vacuum thermolysis (FVT) of 1-(dimethylamino)pyrrole-2,3-diones 5 causes extrusion of CO with formation of transient hydrazonoketenes 7. The transient ketenes 7 are observable in the form of weak bands at 2130 (7a) or 2115 cm(-1) (7b) in the Ar matrix IR spectra resulting from either FVT or photolysis of either 5 or 1,1- dimethylpyrazolium-5- oxides 8, and these absorptions are in excellent agreement with B3LYP/6-31G* frequency calculations. Under FVT conditions the ketenes 7 cyclize to pyrazolium oxides 8, which undergo 1,4-migration of a methyl group to yield 1,4-dimethyl-3-phenylpyrazole-5(4H)-one 9a and 1,4,4-trimethyl-3-phenylpyrazole-5(4H)-one 9b. All three tautomers of 9a have been characterized, viz. the CH form 9a (most stable form in the gas phase, the solid state and solvents of low polarity), the OH form 9a' (metastable solid at room temperature) and the NH form 9a (stable in aprotic dipolar solvents). The isomeric 1,4-dimethyl-5-phenylpyrazole-3(2H)-one 12 tautomerizes to the 3-hydroxypyrazole 12'. The crystal structure of the hydrochloride 14 of 9a'/9a is reported, representing the first structurally characterised example of a protonated 5-hydroxypyrazole.

An approach to verifying and debugging simulation models governed by ordinary differential equations: Part 2. Residuals analysis and a case study

In Part 1 of this paper a methodology for back-to-back testing of simulation software was described. Residuals with error-dependent geometric properties were generated. A set of potential coding errors was enumerated, along with a corresponding set of feature matrices, which describe the geometric properties imposed on the residuals by each of the errors. In this part of the paper, an algorithm is developed to isolate the coding errors present by analysing the residuals. A set of errors is isolated when the subspace spanned by their combined feature matrices corresponds to that of the residuals. Individual feature matrices are compared to the residuals and classified as 'definite', 'possible' or 'impossible'. The status of 'possible' errors is resolved using a dynamic subset testing algorithm. To demonstrate and validate the testing methodology presented in Part 1 and the isolation algorithm presented in Part 2, a case study is presented using a model for biological wastewater treatment. Both single and simultaneous errors that are deliberately introduced into the simulation code are correctly detected and isolated. Copyright (C) 2003 John Wiley Sons, Ltd.

Diálogos sobre a alfabetização, a leitura e a escrita no Programa Provinha Brasil

Esta pesquisa documental analisa as concepções de alfabetização, leitura e escrita subjacentes à Provinha Brasil no período 2008-2012 e o panorama em que esse programa de avaliação é produzido. Parte do referencial bakhtiniano e do conceito de alfabetização de Gontijo (2008, 2013). Ao tomar a Provinha como gênero do discurso, discute os elos precedentes dentro do contexto de produção dessa avaliação, a autoria do Programa e seus principais destinatários. Constata que a Provinha é criada como resposta às demandas de avaliação da alfabetização provenientes de organismos internacionais como o Banco Mundial e a Organização das Nações Unidas para a Educação (Unesco). A avaliação é elaborada pelo Instituto Nacional de Estudos e Pesquisas Educacionais Anísio Teixeira (Inep) como órgão que coordena as avaliações no País, em colaboração com pesquisadores de universidades e de organizações da sociedade civil, para demonstrar confiabilidade científica aliada à participação democrática no processo de produção. Seus principais destinatários são gestores de Secretarias de Educação e professores. Aos primeiros, cabe aderir ao programa de avaliação e tomar medidas administrativas para sua operacionalização nas redes. Os docentes têm o papel central de seguir as orientações do material e reorganizar sua prática em função de melhorias nos desempenhos das crianças no teste. Estas, por sua vez, são desconsideradas como sujeitos de dizeres e é legitimado um discurso homogeneizador sobre seu desenvolvimento. A partir dos testes aplicados e das matrizes de referência e seus eixos, a pesquisa analisa como a diferenciação teórica entre alfabetização e letramento se concretiza na organização das provas. A alfabetização, entendida como apropriação do sistema de escrita, é avaliada no primeiro eixo do teste principalmente como identificação de unidades menores da língua, como letras, sílabas e fonemas. As habilidades de leitura, ligadas ao letramento como concebido nos pressupostos do programa, são aferidas ora como decodificação de palavras e frases descontextualizadas, ora como apreensão de significado predeterminado do texto. A escrita somente é avaliada no ano de 2008 e por meio de itens que solicitavam codificação de palavras e frases ditadas pelo aplicador. Desse modo, a Provinha Brasil contribui para a subtração das potencialidades políticas e transformadoras do aprendizado da língua materna no País.

Estudo da evolução da paisagem da área do município de Linhares (ES) nos anos de 1985 e de 2013/2014, por meio das métricas

Trata a presente pesquisa sobre o estudo da evolução da área da paisagem que compõe o município de Linhares (ES), nos anos de 1985 e 2013/2014, que constitui o maior município do Estado do Espírito Santo. Foi realizada, por meio de processamento digital de imagens de satélites LANDSAT 5 e 8, a classificação de uso e ocupação da terra da área em estudo. Além disso usou-se as imagens do satélite RapdEye para acurácia da classificação digital das imagens. A partir dos resultados levantados de uso e ocupação foram definidas as matrizes da paisagem para 1985 e 2013/2014, bem como avaliadas as manchas que compõem a matriz. Foram aplicadas as métricas da paisagem utilizando a ferramenta de estatística Fragstats, possibilitando o cálculo dos Índices de Paisagem afim de avaliar a evolução qualitativa e quantitativa da paisagem do município de Linhares.

Avaliação da adsorção do herbicida 2,4-D em carvão ativado em pó utilizando água com diferentes qualidades

O 2,4-diclorofenoxiacético (2,4-D) é um dos herbicidas mais consumidos no Brasil e é preferencialmente usado devido a sua boa seletividade e baixo custo. Possui alta toxidade e baixa biodegradabilidade, oferecendo risco à saúde humana e ao meio ambiente, podendo ser encontrado em solos, águas superficiais e subterrâneas. Estudos mostram que o tratamento convencional da água possui baixa eficácia na remoção de microcontaminantes, com isso várias técnicas têm sido utilizadas na remoção de compostos em água, como a adsorção por carvão ativado. Apresenta-se a adsorção em carvão ativado tem se demonstrado como tecnologia eficiente na remoção de diversos contaminantes, dentre eles os agrotóxicos. Assim, o presente trabalho objetivou avaliar a adsorção do 2,4-D por três carvões ativados em pó (CAP) em água ultrapura e em água bruta do Rio Santa Maria da Vitória. A quantificação do herbicida foi analisada por cromatografia líquida de alta eficiência, após concentração da amostra pelo método de extração em fase sólida. Os ensaios de adsorção foram realizados com carvões ativados derivados da casca de coco (CAP-01), pinus (CAP-02) e palha de café (CAP-03), que foram caracterizados e avaliados na sua capacidade de remoção do 2,4-D nas duas matrizes de água. Dois modelos de isoterma de adsorção, Langmuir e Freundlich, foram aplicados para descrever os dados de adsorção, que indicaram o CAP-02 como o carvão que apresentou a melhor capacidade de adsorção do 2,4-D entre os carvões estudados, tanto em água ultrapura quanto em água bruta. Nos ensaios realizados em água bruta, houve redução da adsorção do 2,4-D para as três amostras de CAP, quando comparado com os ensaios realizados em água ultrapura, indicando interferência de compostos, como a matéria orgânica, no processo de adsorção.

Type checking cryptography implementations

Cryptographic software development is a challenging eld: high performance must be achieved, while ensuring correctness and com- pliance with low-level security policies. CAO is a domain speci c language designed to assist development of cryptographic software. An important feature of this language is the design of a novel type system introducing native types such as prede ned sized vectors, matrices and bit strings, residue classes modulo an integer, nite elds and nite eld extensions, allowing for extensive static validation of source code. We present the formalisation, validation and implementation of this type system

Eigenvalue computations in the context of data-sparse approximations of integral operators

In this work, we consider the numerical solution of a large eigenvalue problem resulting from a finite rank discretization of an integral operator. We are interested in computing a few eigenpairs, with an iterative method, so a matrix representation that allows for fast matrix-vector products is required. Hierarchical matrices are appropriate for this setting, and also provide cheap LU decompositions required in the spectral transformation technique. We illustrate the use of freely available software tools to address the problem, in particular SLEPc for the eigensolvers and HLib for the construction of H-matrices. The numerical tests are performed using an astrophysics application. Results show the benefits of the data-sparse representation compared to standard storage schemes, in terms of computational cost as well as memory requirements.

Error bounds for low-rank approximations of the first exponential integral kernel

A hierarchical matrix is an efficient data-sparse representation of a matrix, especially useful for large dimensional problems. It consists of low-rank subblocks leading to low memory requirements as well as inexpensive computational costs. In this work, we discuss the use of the hierarchical matrix technique in the numerical solution of a large scale eigenvalue problem arising from a finite rank discretization of an integral operator. The operator is of convolution type, it is defined through the first exponential-integral function and, hence, it is weakly singular. We develop analytical expressions for the approximate degenerate kernels and deduce error upper bounds for these approximations. Some computational results illustrating the efficiency and robustness of the approach are presented.

Templated synthesis of carbon materials mediated by porous clay heterostructures

Mesoporous carbon materials were prepared through template method approach using porous clay heterostructures (PCHs) as matrix and furfuryl alcohol as carbon precursor. Three PCHs prepared using amines with 8, 10 and 12 carbon atoms were used. The effect of several impregnation-polymerization cycles of the carbon precursor, the carbonization temperature and the need of a previous surface alumination were evaluated. The presence of two porosity domains was identified in all the carbon materials. These two domains comprise pores resulting from the carbonization of the polymer film formed in the inner structure of the PCH (domain I) and larger pores created by the clay particles aggregation (domain II). The predominance of the porosity associated to domain I or II can be achieved by choosing a specific amine to prepare the PCH matrix. Carbonization at 700 C led to the highest development of pores of domain I. In general, the second impregnation-polymerization cycle of furfuryl alcohol resulted in a small decrease of both types of porosity domains. Furthermore the previous acidification of the surface to create acidic sites proved to be unnecessary. The results showed the potential of PCHs as matrices to tailor the textural properties of carbons prepared by template mediated synthesis.

A two-Higgs doublet model with remarkable CP properties

We analyze generalized CP symmetries of two-Higgs doublet models, extending them from the scalar to the fermion sector of the theory. We show that, other than the usual CP transformation, there is only one of those symmetries which does not imply massless charged fermions. That single model which accommodates a fermionic mass spectrum compatible with experimental data possesses a remarkable feature. Through a soft breaking of the symmetry it displays a new type of spontaneous CP violation, which does not occur in the scalar sector responsible for the symmetry breaking mechanism but, rather, in the fermion sector.

Renormalization-group constraints on Yukawa alignment in multi-Higgs-doublet models

We write down the renormalization-group equations for the Yukawa-coupling matrices in a general multi-Higgs-doublet model. We then assume that the matrices of the Yukawa couplings of the various Higgs doublets to right-handed fermions of fixed quantum numbers are all proportional to each other. We demonstrate that, in the case of the two-Higgs-doublet model, this proportionality is preserved by the renormalization-group running only in the cases of the standard type-I, II, X, and Y models. We furthermore show that a similar result holds even when there are more than two Higgs doublets: the Yukawa-coupling matrices to fermions of a given electric charge remain proportional under the renormalization-group running if and only if there is a basis for the Higgs doublets in which all the fermions of a given electric charge couple to only one Higgs doublet.

Seasonal variation of total particulate matter and children respiratory diseases at Lisbon primary schools using passive methods

In this work, 14 primary schools of Lisbon city, Portugal, followed a questionnaire of the ISAAC - International Study of Asthma and Allergies in Childhood Program, in 2009/2010. The questionnaire contained questions to identify children with respiratory diseases (wheeze, asthma and rhinitis). Total particulate matter (TPM) was passively collected inside two classrooms of each of 14 primary schools. Two types of filter matrices were used to collect TPM: Millipore (IsoporeTM) polycarbonate and quartz. Three campaigns were selected for the measurement of TPM: Spring, Autumn and Winter. The highest difference between the two types of filters is that the mass of collected particles was higher in quartz filters than in polycarbonate filters, even if their correlation is excellent. The highest TPM depositions occurred between October 2009 and March 2010, when related with rhinitis proportion. Rhinitis was found to be related to TPM when the data were grouped seasonally and averaged for all the schools. For the data of 2006/2007, the seasonal variation was found to be related to outdoor particle deposition (below 10 μm).

Constraints on leptogenesis from a symmetry viewpoint

It is shown that type I seesaw models based on the standard model Lagrangian extended with three heavy Majorana right-handed fields do not have leptogenesis in leading order, if the symmetries of mass matrices are also the residual symmetry of the Lagrangian. In particular, flavor models that lead to a mass-independent leptonic mixing have a vanishing leptogenesis CP asymmetry. Based on symmetry arguments, we prove that in these models the Dirac-neutrino Yukawa coupling combinations relevant for leptogenesis are diagonal in the physical basis where the charged leptons and heavy Majorana neutrinos are diagonal.

Leptonic CP violation

Several topics on CP violation in the lepton sector are reviewed. A few theoretical aspects concerning neutrino masses, leptonic mixing, and CP violation will be covered, with special emphasis on seesaw models. A discussion is provided on observable effects which are manifest in the presence of CP violation, particularly, in neutrino oscillations and neutrinoless double beta decay processes, and their possible implications in collider experiments such as the LHC. The role that leptonic CP violation may have played in the generation of the baryon asymmetry of the Universe through the mechanism of leptogenesis is also discussed.

Abelian symmetries in the two-Higgs-doublet model with fermions

We classify all possible implementations of an Abelian symmetry in the two-Higgs-doublet model with fermions. We identify those symmetries which are consistent with nonvanishing quark masses and a Cabibbo-Kobayashi-Maskawa quark-mixing matrix (CKM), which is not block-diagonal. Our analysis takes us from a plethora of possibilities down to 246 relevant cases, requiring only 34 distinct matrix forms. We show that applying Z(n) with n >= 4 to the scalar sector leads to a continuous U(1) symmetry in the whole Lagrangian. Finally, we address the possibilities of spontaneous CP violation and of natural suppression of the flavor-changing neutral currents. We explain why our work is relevant even for non-Abelian symmetries.