Synthesis and Coordination Chemistry of a New N-4-Polydentate Class of Pyridyl-Functionalized Scorpionate Ligands: Complexes of Fe-II, Zn-II, V-IV, Pd-II and Use for Heterobimetallic Systems

The new potentially N-4-multidentate pyridyl-functionalized scorpionates 4-((tris-2,2,2-(pyrazol-1-ypethoxy)methyl)pyridine (TpmPy, (1)) and 4-((tris-2,2,2-(3-phenylpyrazol-1-yl)ethoxy)methyl)pyridine (TpmPy(Ph), (2)) have been synthesized and their coordination behavior toward Fe-II, Ni-II, Zn-II, Cu-II, Pd-II, and V-III centers has been studied. Reaction of (1) with Fe(BF4)(2)center dot 6H(2)O yields [Fe(TpmPy)(2)](BF4)(2) (3), that, in the solid state, shows the sandwich structure with trihapto ligand coordination via the pyrazolyl arms, and is completely low spin (LS) until 400 K. Reactions of 2 equiv of (1) or (2) with Zn-II or Ni-II chlorides give the corresponding metal complexes with general formula [MCl2(TpmPy*)(2)] (M = Zn, Ni; TpmPy* = TpmPy, TpmPy(Ph)) (4-7) where the ligand is able to coordinate through either the pyrazolyl rings (in case of [Ni(TpmPy)(2)Cl-2 (5)) or the pyridyl-side (for [ZnCl2(TpmPy)(2)] (4), [ZnCl2(TpmPy(Ph))(2)] (6) and [NiCl2(TpmPy(Ph))(2)] (7)). The reaction of (1) with VCl3 gives [VOCl2(TpmPy)] (8) that shows the N-3-pyrazolyl coordination-mode. Moreover, (1) and react with cis-[PdCl2(CH3CN)(2)] to give the disubstituted complexes [PdCl2(TprnPy)(2)] (9) and [PdCl2(TpmPy(Ph))(2)] (10), respectively, bearing the scorpionate coordinated via the pyridyl group. Compounds (9) and (10) react with Fe(BF4)(2) to give the heterobimetallic Pd/Fe systems [PdCl2(mu-TpmPy)(2)-Fe](BF4)(2) (11) and [PdCl2(mu-TpmPy(Ph))(2)Fe-2(H2O)(6)]BF4)(4) (13), respectively. Compound (11) can also be formed from reaction of (3) with cis-[PdCl2(CH3CN)(2)], while reaction of (3) with Cu(NO3)(2).2.5H(2)O generates [Fe(mu-TpmPy)(2)-Cu(NO3)(2)](BF4)(2) (12), confirming the multidentate ability of the new chelating ligands. The X-ray diffraction analyses of compounds (1), (3), (4), (5), and (9) are also reported.

Construção de uma base de dados espectral (IV) de toners de impressoras laser para identificação forense de documentos

Esta dissertação surgiu com o objectivo de se criar uma base de dados de Toners para impressoras e fotocopiadoras e um método fiável de comparação de espectros para estudos forenses e de investigação criminal. Para viabilizar o estudo, efectuou-se à priori a recolha de várias amostras de Toners, de diferentes marcas, de cartuchos originais e remanufacturados aplicando de seguida dois métodos de análise distintos: a Espectroscopia de infravermelho com transformada de Fourier (FT-IR) e a Espectroscopia de Absorção-Reflexão (ATR - Reflectância total atenuada). A espectroscopia FT-IR permitiu obter a base de dados de espectros em suporte KBr e usando o software OPUS, das várias amostras de Toners dos cartuchos originais e remanufacturados recolhidas. Para se criar o método de comparação entre espectros, realizou-se o mesmo procedimento mas agora para amostras obtidas por raspagem de um papel impresso /quadrados 2x2), bem como para o papel de impressão para se poder descontar este da amostra. Dado que o interesse desta análise se remetia ao estudo de textos escritos, efectuou-se a análise de um texto padrão por Espectroscopia FT-IR. O método foi utilizado à posteriori como método de comparação e uma alternativa (não destrutiva) ao método de FT-IR para se aplicar a casos reais. Os espectros foram obtidos num microscópio usando o silício como acessório ATR e o software OMNIC. Finalizado o estudo pode-se concluir, quanto à espectroscopia FT-IR, que as amostras da marca HP e Minolta apresentaram espectros muito semelhantes, quando se faz uma análise global dos mesmos. No entanto, as restantes marcas são também muito parecidas entre si, mas ainda é possível encontrar algumas distinções quando se efectua a comparação visual principalmente abaixo da zona de impressão digital (<6000 cm-1). Relativamente aos Toners remanufacturados, constata-se que são muito semelhantes e que diferem da marca original apenas pelo elevado grau de humidade que possuem. No que diz respeito ao método ATR, verificou-se que apesar de ser um método não destrutivo da amostra revela-se bastante limitado, devido ao uso do cristal de Silício como acessório que só atinge comprimentos de onda entre 4000-1500cm-1.

Happiness, hope and affection as predictors of quality of life and functionality of individuals with heart failure at 3 month follow up

Introduction: Meeting the actual role of positive psychology, begins to be recognized the contribution of positive variables in health outcomes. Objective: To know the contribution of happiness, hope and affection individually and as a whole in the quality of life and functionality of individuals with heart failure. Population and Methodology: 128 individuals with heart failure, 98 men and 30 women, 61.9±12,1 years of age, 6,6±3,9 years of school and 74,2% retired because of this disease. 56,3% were in Class III of New York Heart Association, with poor left ventricular ejection fraction (25,3±6,2%). The clinical history was of 9,4±8,5 years for this heart disease and had at least one hospitalization due to heart failure with 51,6% having ischemic heart disease.

Syntheses, Molecular Structures, Electrochemical Behavior, Theoretical Study, and Antitumor Activities of Organotin(IV) Complexes Containing 1-(4-Chlorophenyl)-1-cyclopentanecarboxylato Ligands

The organotin(IV) compounds [Me2Sn(L)(2)] (1), [Et(2)sn(L)(2)] (2), [(Bu2Sn)-Bu-n(L)(2)] (3), [(n)Oct(2)Sn(L)(2)] (4), [Ph2Sn(L)(2)] (5), and [PhOSnL](6) (6) have been synthesized from the reactions of 1-(4-chlorophenyl)-1-cyclopentanecarboxylic acid (HL) with the corresponding diorganotin(IV) oxide or dichloride. They were characterized by IR and multinuclear NMR spectroscopies, elemental analysis, cyclic voltammetry, and, for 2, 3, 4 and 6, single crystal X-ray diffraction analysis. While 1-5 are mononuclear diorganotin (IV) compounds, the X-ray diffraction of 6 discloses a hexameric drumlike structure with a prismatic Sn6O6 core. All these complexes undergo irreversible reductions and were screened for their in vitro antitumor activities toward HL-60, BGC-823, Bel-7402, and KB human cancer cell lines. Within the mononuclear compounds, the most active ones (3, 5) are easiest to reduce (least cathodic reduction potentials), while the least active ones (1, 4) are the most difficult to reduce. Structural rearrangements (i.e., Sn-O bond cleavages and trans-to-cis isomerization) induced by reduction, which eventually can favor the bioactivity, are disclosed by theoretical/electrochemical studies.

A Hexanuclear Mixed-Valence Oxovanadium(IV,V) Complex as a Highly Efficient Alkane Oxidation Catalyst

The new hexanuclear mixed-valence vanadium complex [V3O3(OEt)(ashz)(2)(mu-OEt)](2) (1) with an N,O-donor ligand is reported. It acts as a highly efficient catalyst toward alkane oxidations by aqueous H2O2. Remarkably, high turnover numbers up to 25000 with product yields of up to 27% (based on alkane) stand for one of the most active systems for such reactions.

Pyrazole or tris(pyrazolyl)ethanol oxo-vanadium(IV) complexes as homogeneous or supported catalysts for oxidation of cyclohexane under mild conditions

The oxovanadium(IV) complexes [VO(acac)(2)(Hpz)].HC(pz)(3) 1.HC(pz)(3) (acac= acetylacetonate, Hpz = pyrazole, pz = pyrazoly1) and [VOCl2{HOCH2C(pz)(3)}] 2 were obtained from reaction of [VO(acac)(2)] with hydrotris(1-pyrazolyl)methane or of VCl(3)with 2,2,2-tris(1-pyrazolyl)ethanol. The compounds were characterized by elemental analysis, IR, Far-IR and EPR spectroscopies, FAB or ESI mass-spectrometry and, for 1, by single crystal X-ray diffraction analysis. 1 and 2 exhibit catalytic activity for the oxidation of cyclohexane to the cyclohexanol and cyclohexanone mixture in homogeneous system (TONS up to 1100) under mild conditions (NCMe, 24h, room temperature) using benzoyl peroxide (BPO), tert-butyl hydroperoxide (TBHP), m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide or the urea-hydrogen peroxide adduct (UHP) as oxidants. 1 and 2 were also immobilized on a polydimethylsiloxane membrane (1-PDMS or 2-PDMS) and the systems acted as supported catalysts for the cyclohexane oxidation using the above oxidants (TONs up to 620). The best results were obtained with mCPBA or BP0 as oxidant. The effects of various parameters, such as the amount of catalyst, nitric acid, reaction time, type of oxidant and oxidant-to-catalyst molar ratio, were investigated, for both homogeneous and supported systems. (C) 2012 Elsevier B.V. All rights reserved.

Beyond methodological nationalism: The contribution of Robert E. Park to the history of intercultural communication

The legacy of nineteenth century social theory followed a “nationalist” model of society, assuming that analysis of social realities depends upon national boundaries, taking the nation-state as the primary unit of analysis, and developing the concept of methodological nationalism. This perspective regarded the nation-state as the natural - and even necessary - form of society in modernity. Thus, the constitution of large cities, at the end of the 19th century, through the intense flows of immigrants coming from diverse political and linguistic communities posed an enormous challenge to all social research. One of the most significant studies responding to this set of issues was The Immigrant Press and its Control, by Robert E. Park, one of the most prominent American sociologists of the first half of the 20th century. The Immigrant Press and its Control was part of a larger project entitled Americanization Studies: The Acculturation of Immigrant Group into American Society, funded by the Carnagie Corporation following World War I, taking as its goal to study the so-called “Americanization methods” during the 1920s. This paper revisits that particular work by Park to reveal how his detailed analysis of the role of the immigrant press overcame the limitations of methodological nationalism. By granting importance to language as a tool uniting each community and by showing how the strength of foreign languages expressed itself through the immigrant press, Park demonstrated that the latter produces a more ambivalent phenomenon than simply the assimilation of immigrants. On the one hand, the immigrant press served as a connecting force, driven by the desire to preserve the mother tongue and culture while at the same time awakening national sentiments that had, until then, remained diffuse. Yet, on the other hand, it facilitated the adjustment of immigrants to the American context. As a result, Park’s work contributes to our understanding of a particular liminal moment inherent within many intercultural contexts, the space between emigrant identity (emphasizing the country of origin) and immigrant identity (emphasizing the newly adopted country). His focus on the role played by media in the socialization of immigrant groups presaged later work on this subject by communication scholars. Focusing attention on Park’s research leads to other studies of the immigrant experience from the same period (e.g., Thomas & Znaniecki, The Polish Peasant in Europe and America), and also to insights on multi-presence and interculturality as significant but often overlooked phenomena in the study of immigrant socialization.

Redox-active cytotoxic diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes: Reduction behaviour and theoretical interpretation

Two series of new diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl), formulated as the mononuclear [R2Sn(HL)(2)] (1:2) (a, R=Bu-n and Ph) and the polymeric [R2SnL](n) (1:1) (b, R=Bu-n) compounds, were prepared and fully characterized. Single crystal X-ray diffraction for [(Bu2Sn)-Bu-n{C5H9C(O)NHO}(2)] (3a) discloses the cis geometry and strong intermolecular NH center dot center dot center dot O interactions. The in vitro cytotoxic activities of the complexes were evaluated against HL-60, Bel-7402, BGC-823 and KB human tumour cell lines, the greater activity concerning [(Bu2Sn)-Bu-n(HL)(2)] [HL=C3H5C(O)NHO (1a), C6H11C(O)NHO (4a)] towards BGC-823. The complexes undergo, by cyclic voltammetry and controlled-potential electrolysis, one irreversible overall two-electron cathodic process at a reduction potential that does not appear to correlate with the antitumour activity. The electrochemical behaviour of [R2Sn(C5H9C(O)NHO)(2)] [R=Bu-n (3a), Ph (7a)] was also investigated using density functional theory (DFT) methods, showing that the ultimate complex structure and the mechanism of its formation are R dependent: for the aromatic (R = Ph) complex, the initial reduction step is centred on the phenyl ligands and at the metal, being followed by a second reduction with Sn-O and Sn-C ruptures, whereas for the alkyl (R=Bu-n) complex the first reduction step is centred on one of the hydroxamate ligands and is followed by a second reduction with Sn-O bond cleavages and preservation of the alkyl ligands. In both cases, the final complexes are highly coordinative unsaturated Sn-II species with the cis geometry, features that can be of biological significance.

A teaching-learning sequence of colour informed by history and philosophy of science

In this work, we present a teaching-learning sequence on colour intended to a pre-service elementary teacher programme informed by History and Philosophy of Science. Working in a socio-constructivist framework, we made an excursion on the history of colour. Our excursion through history of colour, as well as the reported misconception on colour helps us to inform the constructions of the teaching-learning sequence. We apply a questionnaire both before and after each of the two cycles of action-research in order to assess students’ knowledge evolution on colour and to evaluate our teaching-learning sequence. Finally, we present a discussion on the persistence of deep-rooted alternative conceptions.

A didactic sequence of elementary geometric optics Informed by history and philosophy of science

The concepts and instruments required for the teaching and learning of geometric optics are introduced in the didactic processwithout a proper didactic transposition. This claim is secured by the ample evidence of both wide- and deep-rooted alternative concepts on the topic. Didactic transposition is a theory that comes from a reflection on the teaching and learning process in mathematics but has been used in other disciplinary fields. It will be used in this work in order to clear up the main obstacles in the teachinglearning process of geometric optics. We proceed to argue that since Newton’s approach to optics, in his Book I of Opticks, is independent of the corpuscular or undulatory nature of light, it is the most suitable for a constructivist learning environment. However, Newton’s theory must be subject to a proper didactic transposition to help overcome the referred alternative concepts. Then is described our didactic transposition in order to create knowledge to be taught using a dialogical process between students’ previous knowledge, history of optics and the desired outcomes on geometrical optics in an elementary pre-service teacher training course. Finally, we use the scheme-facet structure of knowledge both to analyse and discuss our results as well as to illuminate shortcomings that must be addressed in our next stage of the inquiry.