Photoluminescence study of new lanthanide complexes with benzeneseleninic acids

New lanthanide complexes with benzeneseleninic (ABSe) and 4-chloro-benzeneseleninic (ABSeCl) acids have been synthesized and characterized by elemental analysis, infrared and UV-visible spectroscopies. The emission spectra of the trivalent europium complexes presented the typical electronic (5)D(0) -> (7)F(j) transitions of the ion (J = 0-4). The ground-state geometries of the europium complexes have been calculated by using the Sparkle/AM1 model. From these results, the 4f-4f intensity parameters and energies of the ligand singlet and triplet excited states have been obtained. The lower emission quantum yield for the [Eu(ABSe)(3)(H(2)O)(2)](H(2)O)(2) compound, as compared to the [Eu(Al(3)SeCl)(3)(H(2)O)(2)] one, can be associated to the higher numbers of water molecules, in the first and second coordination spheres, that contribute to the luminescence quenching. The [Eu(Al(3)Se)(3)(H(2)O)(2)](H(2)O)(2) complex presents an intermediate state whose energy difference with respect to the first excited singlet state is resonant with three phonons from the water molecules, favouring a multiphonon relaxation process from the singlet state followed by a fast internal conversion process; this effect is less pronounced in the complex with the ABSeCl ligand. The luminescence decay curves of the gadolinium complexes indicate that the level responsible for the intramolecular energy transfer process has a triplet character for both compounds. The nephelauxetic effect in these compounds was investigated under the light of a recently proposed covalency scale based on the concept of overlap polarizability of the chemical bond. (C) 2009 Elsevier B.V. All rights reserved.

Formation of out of plane oxime metallacycles in [Cu(2)] and [Cu(4)] complexes

The reaction Of Cu(ClO(4))(2)center dot 6H(2)O with dimethylglyoxime (H(2)dmg) in a 1:1 mole ratio in aqueous methanol at room temperature affords the dinuclear complex [Cu(2)(mu-Hdmg)(4)] (1). Reaction of 1 with [Cu(bpy)(H(2)O)(2)](ClO(4))(2) (bpy = 2,2`-bipyridine) in a 1:1 mole ratio in aqueous methanol at room temperature yields the tetranuclear complex [Cu(2)(mu-HdMg)(2)(mu-dMg)(2)(bpy)(2)(H(2)O)(2)](ClO(4))(2) (2). The direct reaction of Cu(ClO(4))(2)center dot 6H(2)O with H(2)dmg and bpy in a 2:21 mole ratio in aqueous methanol at room temperature also yields 2 quantitatively. The complexes 1 and 2 were structurally characterized by X-ray crystallography. Unlike the binding in Ni/Co-dmg, two different types of N-O bridging modes during the oxime based metallacycle formation and stacking of square planar units have been identified in these complexes. The neutral dinuclear complex 1 has CuN(4)O coordination spheres and complex 2 consists of a dicationic [Cu(2)(mu-HdMg)(2)(mu-dMg)(2)(bpy)(2)(H(2)O)(2)](2+) unit and two uncoordinated ClO(4)(-) anions having CuN(4)O and CuN(2)O(3) coordination spheres. The two copper(II) ions are at a distance of 3.846(8) angstrom in 1 for the trans out of plane link and at 3.419(10) and 3.684(10) angstrom in 2 for the trans out of plane and cis in plane arrangements, respectively. The average Cu-N(oxime) distances are 1.953 and 1.935 angstrom, respectively. The average basal and apical Cu-N(oxime) distances are 1.945, 2.295 and 2.429 angstrom. The UV-Vis spectra of 2 is similar to the spectrum of the reaction mixture of 1 and [Cu(bpy)(H(2)O)(2)](2+). Variable temperature magnetic properties measurement shows that the interaction between the paramagnetic copper centers in complex I is antiferromagnetic in nature. The EPR spectra of frozen solution of the complexes at 77 K consist of axially symmetric fine-structure transitions (Delta M(S) = 1) and half-field signals (Delta M(S) = 2) at ca. 1600 G, suggesting the presence of appreciable Cu-Cu interactions. (C) 2009 Elsevier Ltd. All rights reserved.

Using Polycarbonate Membranes as Templates for the Preparation of Au Nanostructures for Surface-Enhanced Raman Scattering

Polycarbonate membranes (PCM) of various pores sizes (400, 200, 100 and 50 nm) were used as templates for gold deposition. The electrodeposition from gold ions resulted in the formation of gold nanotubes when large pores size PCMs (400 and 200 nm) were used. On the other hand, gold nanowires were predominant for the PCMs with smaller pores size (100 and 50 nm). Surface-enhanced Raman scattering (SERS) from the probe molecule 4-mercaptopyridine (4-MPy) was obtained from all these nanostructures. The SERS efficiency of the substrates produced using the PC M templates were compared to two commonly used SERS platforms: a roughened gold electrode and gold nanostructures electrodeposited through organized polystyrene spheres (PSS). The SERS signal of the probe molecule increased as the pore diameter of the PCM template decreased. Moreover, the SERS efficiency from the nanostructures produced using 50 nm PCM templates was four and two times better than the signal from the roughened gold electrode and the PSS template, respectively. The SERS substrates prepared using PCM templates were more homogenous over a larger area (ca. 1 cm(2)), presented better spatial and sample to sample reproducibility than the other substrates. These results show that SERS substrates prepared using PCM templates are promising for the fabrication of planar SERS platforms for analytical/bioanalytical applications.

Oxorhenium(V) Complexes with 2,3-Dihydroxynaphthalene

2,3-Dihydroxynaphthalene (H(2)dhn) reacts with [ReOCl(3)-(PPh(3))(2)] or [ReOBr(3)(PPh(3))(2)] in a 1:1 molar ratio with formation of the isostructural complexes [ReOCl(2)(PPh(3))(2)(Hdhn)] (4) and [ReOBr(2)-(PPh(3))(2)(Hdhn)] (5). They have distorted octahedral coordination spheres with the halide and the triphenylphosphine ligands arranged in equatorial trans positions to each other. The Hdhn-ligand coordinates monodentately in trans position to the oxo ligand. Intramolecular hydrogen bonds between the Hdhn and the halogeno ligands stabilize this coordination mode. The products represent the first examples of oxorhenium(V) complexes with monodentate catecholate-type ligands.

Cationic and neutral phenylmercury(II) complexes with heterocyclic thione ligands. X-ray structures of [HgPh(dmpymtH)][BF(4)] center dot H(2)O and [{HgPh}(2)(mu-dtu)]

The neutral complex [HgPh(dmpymt)] 1 (dmpymtH = 4,6-dimethylpyrimidine-2(1H)-thione) reacts with HBF(4) to give the cationic complex [HgPh(dmpymtH)][BF(4)] 2. The X-ray molecular structure of the later revealed a [2+1] coordination sphere about the mercury(II) atom (C-Hg-S and Hg center dot center dot center dot N). In the dinuclear complex [(HgPh)(2)(mu-dtu)] 3 [dtuH(2) = 2,4(1H,3H)-pyrimidinedithione or dithiouracil] the coordination spheres are also [2+1] although dissimilar regarding the Hg center dot center dot center dot N secondary bonds. NMR spectroscopy ((1)H, (13)C and (199)Hg) studies were undertaken in solution and the results discussed in the light of the X-ray structures. (C) 2008 Elsevier B. V. All rights reserved.

A new Home, far from Home : The assimilation process of women involved in intercultural marriages based on Internet meeting

The internet has revolutionized the way we socialize, and as a consequence the way to love. The new communication technologies have facilitated intercultural relationships. Nowadays family relations are one of the major factors in immigration to European countries. Family relations means persons who arrive as family dependents and in accordance with laws regulating family reunification. This thesis aims to apply the classical assimilation theory stated by Milton Gordon (1964), which formulates a series of assimilation stages through which an individual must pass in order to be completely assimilated. In accordance with this theory, marriage is the final phase for a newcomer to fully incorporate into the host society. Thus, based on this presumption and other contemporary theories, the present study has analysed how women who get involved in intercultural marriages based on internet meeting experience these assimilation stages and evaluated the resources used by respondents to incorporate themselves into Swedish society.The main goal of the study was to determine if jumping to the last stage of assimilation does assure the incorporation in the social or/and labour spheres and the findings demonstrate that even though husbands are a valuable resource for assimilation, several cultural issues in Swedish society make it difficult to assure success for the newcomers.On the other hand, Sweden is a country with a strong national sentiment and the assimilation of immigrants still is an important issue to deal with. The Swedish Integration Board has disappeared and major projects for integration have been left in the hands of the municipalities or the Migration Board, institutions that still do not know how to deal with this dilemma.

Att leva och sälja sin dröm : Livsstilsföretagaren mellan familjeliv, marknadoch politisk retorik

Living and selling a dream: Lifestyle entrepreneurship in the intersection between family, market and political rhetoric The article focuses on lifestyle entrepreneurship, characterised by a balancing work between personal lifestyle motives and economic motives. It builds on a qualitative study of business owners who have realized a life dream of starting a countryside business in the tourism and hospitality industry in Sweden. Through the notion of ”balancing work”, the analysis focuses on the tension between a personal life sphere and a market. In particular, the analysis highlights how the notion of ”the life dream” emerges as a narrative practice of self-realization, simultaneously as it is offered as an experience product. The analysis demonstrates how the entrepreneurs balance between personal stories of togetherness and marketing practices, between images of right and wrong commodification, and between constraining working conditions and a popular image of the successful entrepreneur, reinforced by a political discourse on rural entrepreneurship. It is concluded that balancing work between personal identities and economic practices is a practice of valuation, offering new insights into working conditions and markets situated in the intersection between markets and personal life spheres.

« Moi d’ici, moi de là-bas » : La géographie imaginaire du roman Le Ventre de l’Atlantique de Fatou Diome

L’objectif de la présente étude est d’explorer la « géographie imaginaire » du roman Le Ventre de l’Atlantique, écrit par Fatou Diome. Le concept de la « géographie imaginaire » décrit les rapports de domination spatiale et la construction d’un « Autre », entièrement différent de « nous » (Saïd, 1980). Les deux pays du roman, la France et le Sénégal, sont analysés comme deux sphères inconciliables, associées aux oppositions comme nous – l’Autre, individualisme – collectivisme, rationalité - superstition. Deux images spatiales sont discutées dans ce mémoire: l’île Niodior au Sénégal et l‘océan Atlantique. L’isolation de l’île Niodior renforce la séparation en deux espaces opposés, alors que l’Atlantique constitue un élément parfois chargé de forces magiques, lié à la vie et à la mort. Evoquant l’idée d’hybridité, le roman montre également des espaces et des identités alternatifs, qui transgressent la structure coloniale.

Towards a post-patriarchal gender order : Confronting the universality and the particularity of violence against women

The issues of gender equality and women’s human rights have become major spheres of academic debate, policy and activism in virtually every corner of the globe. Violence against women, a relative latecomer to the international gender agenda, has provided a particularly critical entry point in challenging long standing gender ideologies and taboos as well as the gender biased mainstream human rights framework that kept, until recently, the gender specific abuses women experience outside of public scrutiny.

Fanfiction : la anonimicidad, el texto y el armario

This essay looks at slash, a genre within fanfiction, from the perspective of Sedgwick’s theory of the closet, which reflects on the concealing mechanisms associated with homosexuality. While the real author stays in the closet, disguised behind a pseudonym, slash texts present homosexual themes in a very explicit way, often relying on humor or subversive elements. Between these two spheres, the real author and the text, we can find what we call the author’s voice, conscious about the existing homophobic structures, a voice that uses different strategies to shield itself against them. Internet, with the possibility to stay anonymous, serves as a social closet where the masked authors create texts that subvert heteronormativity.

Organizações não-governamentais na (Re)construção da sociedade civil no Brasil: (dinâmicas, sujeitos e vinculações entre público e privado nos anos 90)

One of the main features of Brazilian civil society in the nineties is the widespread presence of nongovernamental organizations, religious and secular associations, and the emergence of private foundations as a social mediator midway state and market institutions. This research is a bibliographical discussion of the Social Sciences literature about these organizations, pertinent with their quantitative and qualitative profiles and scope of actions, identities and future role in the construction of the active citizenship in Brasil.

Valores, atitudes e comportamentos gerenciais requeridos pelo processo de globalização e as diretrizes para as ações de desenvolvimento de recursos humanos

O processo de globalização hoje uma realidade, alterando as relações entre nações, sociedades organizações. movimento de globalização da economia modifica radicalmente as relações do homem com meio produtivo social, levantando questões fundamentais quanto essência das transformações em curso, que justifiquem fenômenos tendências aparentemente inexplicáveis. Mudanças fortes velozes, exigindo dos indivíduos das organizações habilidade em se adaptarem em graus nunca antes requeridos, tornam-se as únicas certezas da atualidade, propiciando aparecimento simultâneo de várias tendências administrativas de mudança organizacional no contexto empresarial brasileiro. Este trabalho pretende proporcionar uma reflexão sobre os efeitos que as mudanças em curso tem produzido no quadro de valores, atitudes comportamentos gerenciais requeridos pelas organizações, bem como sobre novo papel ser desempenhado pela área de Desenvolvimento de Recursos Humanos.

A superação da pobreza através da distribuição justa das riquezas sociais: uma análise da consistência teórica do Programa Bolsa Família e das perspectivas dos beneficiários de saída autosustentada do programa

Bolsa Família is the major brazilian conditional cash transfer program. It provides money to poor families contingent on investments in human capital, such as sending children to school or bringing them to health centers. This work aims to investigate if this program, in its normative structure, can be considered an appropriate policy of income redistribution and if it is able, appliances of the Welfare State model in the brazilian society and to approach the program in two different ways: as an alternative to more traditional social assistance programs and as a demand-side complement to the supply of other social needs. We will work on the thesis that the program by itself can not provide vulnerable populations with enough means to overcome poverty and to participate effectively on the market. According to this assumption, this paper is going to consider the reasons why tackling income necessary, along with the program, that the Government - in both federal and local spheres shall place major investments in critical areas like education and health.

Política de recursos humanos na administração pública do Estado do Paraná: análise comparativa entre o discurso e a prática

The aim of this dissertation is to demonstrate what happens to the public administration in the state of Paraná through a case study, more specifically, in two organization: one, called in specific legal regime, 'direct administration' and the other, 'indirect administration', by means of structured interviews searching the distance between the discourse and practice which concerns to what was developed in the training area inside a human resource policy of the state. Since two decades, the training function in public administration of the state is changing and suffering some internal (re)structures. These changes are due to the pressure generated by either the natural requirement of changing in the same area or in the ways and aims from governmental spheres (state and federal). On one hand, this study analyzes the performance of training function during from 1987 to 1994, in order to verify the outcome factors of the not structured area and the coherency between programmed and accomplished actions. On the other hand, compare the discourse and practice based on a human resource policy implemented and adopted by the government. The results of field research with bibliographic examination allow to conclude that although the official and formal documents delineate a human resource policy to the state, there were evident contradictions between the proposal and what the state really fulfilled. The qualitative data analysis concluded that the majority of the actions are implemented casuisticaly. During the case study period, the human resource area specifically, training and development, suffered constant (re) tructures. The consequence was ¿ the both institutions, responsible for the training area, lost time and financial resources. Legal changes, internal dispute for institutional space, lack of tune and synchrony resulted once more in a discontinued action in the area. However it is perceptible that the government is worried about the development and evaluation of its civil services although it goes on behaving without a structured and integrated planning related to any human resource system. The study, therefore, confirms that the formulation and implementation of effective human resource policy, either through an analytic model or not, must be centralized in integrated action interrelated to all the subsystems of the human resource area, neither in a disguised way nor linked to the discourse of a law or government projects.

Federalismo fiscal: uma análise das relações intergovernamentais quanto ao atendimento das demandas sociais - o caso brasileiro

Este trabalho tem por objetivo analisar as relações entre as esferas de governo no Brasil, quanto ao provimento das demandas sociais. O foco do estudo reside nas relações que resultam em externalidades negativas, significando perdas para o bem-estar coletivo, que vai de encontro às pretensões da nova Carta Constitucional, promulgada em 1988. O exame das relações intergovernamentais é realizado sob a perspectiva de internalização das instituições ao modelo de análise, promovendo uma maior compreensão quanto aos comportamentos adotados pelas unidades federativas e, por conseguinte, seus resultados nos cenários político, econômico e social, em função do jogo federativo que se faz presente.