Espécies polinucleares de cobre e ferro com catalisadores de oxidação e modelos de sítios ativos

Diferentes complexos de cobre(II), contendo ligantes do tipo base de Schiff e um grupamento imidazólico, com interesse bioinorgânico, catalítico e como novos materiais, foram preparados na forma de sais perclorato, nitrato ou cloreto e caracterizados através de diferentes técnicas espectroscópicas (UV/Vis, IR, EPR, Raman) e espectrometria de massa Tandem (ESI-MS/MS), além de análise elementar, condutividade molar e medidas de propriedades magnéticas. Alguns destes compostos, obtidos como cristais adequados, tiveram suas estruturas determinadas por cristalografia de raios-X. As espécies di- e polinucleares contendo pontes cloreto, mostraram desdobramentos das hiperfinas nos espectros de EPR, relacionados à presença do equilíbrio com a respectiva espécie mononuclear, devido à labilidade dos íons cloretos, dependendo do contra-íon e do tipo de solvente utilizado. Adicionalmente, em solução alcalina, estes compostos estão em equilíbrio com as correspondentes espécies polinucleares, onde os centros de cobre estão ligados através de um ligante imidazolato. Em meio alcalino, estes compostos polinucleares contendo ponte imidazolato foram também isolados e caracterizados por diferentes técnicas espectroscópicas e magnéticas. Através da variação estrutural e também do ligante-ponte foi possível modular o fenômeno da interação magnética entre os íons de cobre em estruturas correlatas di- e polinucleares. Os respectivos parâmetros magnéticos foram obtidos com ajuste das curvas experimentais de XM vs T, correlacionando-se muito bem com a geometria, ângulos e distâncias de ligação entre os íons, quando comparado com outros complexos similares descritos na literatura. Posteriormente, estudaram-se os fatores relacionados com a reatividade de todas essas espécies como catalisadores na oxidação de substratos de interesse (fenóis e aminas), através da variação do tamanho da cavidade nas estruturas cíclicas ou de variações no ligante coordenado ao redor do íon metálico. Vários deles se mostraram bons miméticos de tirosinases e catecol oxidases. Um novo complexo-modelo da citocromo c oxidase (CcO), utilizando a protoporfirina IX condensada ao quelato N,N,-bis[2-(1,2-metilbenzimidazolil)etil]amino e ao resíduo de glicil-L-histidina, foi sintetizado e caracterizado através de diferentes técnicas espectroscópicas, especialmente EPR. A adição de H2O2 ao sistema completamente oxidado, FeIII/CuII, a -55°C, ou o borbulhamento de oxigênio molecular a uma solução do complexo na sua forma reduzida, FeII/CuI, saturada de CO, resultou na formação de adutos com O2, de baixo spin, estáveis a baixas temperaturas.

Moi et temps chez Leibniz: ou l’unité de la notio completa et de la vis primitiva

La fusion entre la logique et la dynamique déclenche chez G. W. Leibniz une réforme de la notion de substance qui altère profondément le rapport entre le Je et le temps. Prototype de la substantialité, miroir de Dieu et expression du Tout créé, le Je dirait beaucoup, notamment Être, Un, Même: la persistance d’un « sujet » logique, d’un « je ne sais quoi » de métaphysique et d’un « personnage » moral. Sous l’angle de la temporalité, le Je véhicule tous les temps possibles et réels, passés et futurs. Il est question donc d’une communauté poly- et pan-chronique qui propose une sorte de synchronie de la diversité temporelle dans la notion complète et dans la force primitive qui semblent ainsi s’incliner vers ou se déplier de l’Eternel.

Inflation and Unemployment In EMU and the United States. ACES Working Papers No. 10, 2008

The original purpose of this paper was to see why the Phillips Curve numbers seem to be so much worse for the EMU countries than the United States since EMU was began operation in 1990. The problem is that there is no evidence of a Phillips curve relationship in EMU or in the United States during this seventeen year period. As can be seen in Figures 1 and 2, it just is not there. In about half the years unemployment and inflation moved in the opposite direction, as Phillips would predict, but in other half of the years they moved in the same direction. This may be a matter of time lags, with unemployment lagging inflation, but it seems clear that the Phillips curve is a poor tool for explaining these year to year outcomes in Europe or the United States.

Labor Market Policy Decentralization in Germany, the United Kingdom and Italy - Dynamics and Reasons. ACES Working Papers No. 5, 2008

This article argues that welfare-to-work or activation policies, which have been adopted across a range of OECD countries during the last two decades, do not only have led to changes in the substance of the welfare state but also to transformations in its institutional configuration. This institutional transformation includes the spatial reconfiguration of the welfare state, which has given new roles to the supra-national, national, and sub-national levels of government as well as private actors in the management and creation of labor market policies. By bringing institutions into these debates, this article seeks to expand the literature on welfare-to-work and activation as to date authors working on this topic have said very little about the degree, types, and reasons for the spatial re-configuration of welfare-to-work policies across different states. To fill a gap in the literatures on changes in the welfare state and its territorial configuration in particular, we compare trends in the re-configuration of welfare-to-work policies in Italy, Germany and the United Kingdom. We find that there is a cross-national trend, when it comes to the institutional effects of the implementation of activation. These trends bear a tension between decentralization and centralization, as both central and sub-national levels of government have acquired new responsibilities to implement the activation paradigm.

US bilateral regional agreements: The negative welfare effects of multiplicity in country of origin rules - A new methodology. ACES Working Papers No. 2, 2008

The intent of this paper is to present a formal methodology for estimating rules of origin requirements. Section II of the paper presents the concept of the ROO. Earlier attempts to capture the costs of ROO are presented in Section III. Our suggested methodology relying on the tariff equivalents literature is presented in Section IV.

Is the "Dubai model" a new paradigm for growth and investment strategies for oil-based economies? Case study: Eurasia. ACES Working Papers No. 8, 2008

The first part of the paper addresses the theoretical background of economic growth and competitive advantage models. Although there is a whole set of research on a relationship between foreign direct investments and economic growth, little has been said on foreign direct investments and national competitive advantage with respect to economic growth of oil and gas abundant countries of Middle East and Central Asia. The second part of our paper introduces the framework of the so-called "Dubai Model" in detail and outlines the key components necessary to develop sustainable comparative advantage for the oil-rich economies. The third part proceeds with the methodology employed to measure the success of the "Dubai Model" in the UAE and in application to other regions. The last part brings the results and investigates the degree to which other oil and gas countries in the region (i.e. Saudi Arabia, Kuwait, Qatar, Iran) have adopted the so-called "Dubai Model". It also examines if the Dubai Model is being employed in the Eurasian (Central Asian) oil and gas regions of Kazakhstan, Azerbaijan, Turkmenistan and Uzbekistan. The objective is to gauge if the Eurasian economies are employing the traditional growth strategies of oil-rich non-OECD countries in managing their natural resources or are they adopting the newer non-traditional model of economic growth, such as the "Dubai Model."

Society's level of literacy: A cross cultural study. ACES Working Papers No. 4, 2008

In this study, the relationship between the country's level of literacy and its national culture will be explored. Cultural differences effect the way that people think and react. Culture is "the value shared amongst distinctive social groups and classes" (Soley and Pandya 2003, 206). House, et al. (2004, 57) define culture as "shared motives, values, beliefs, identities, and interpretations or meanings of significant events that result from common experiences of members of collectives and are transmitted across age generations." Dutch anthropologist Geert Hofstede (1991) considers culture to be "the collective programming of the mind. Culture is a stem of collectively held values" (Hofstede 1981, p. 240).

EU's response to Burma/Myanmar. ACES Working Papers (student research grant), August 2009

This paper so far includes documentation on the timeline of relations between the EU and Burma/Myanmar.

Strategic knowledge serendipity and arbitrage & intellectual venture capitalists: An emerging breed of knowledge entrepreneurs; and Part II: Global and Local (GloCal) knowledge logistics for innovation and competitiveness. ACES Working Papers, August 2009

Strategic Knowledge: While entrepreneurship may occur as a natural result of personal drive, it occurs most often, most robustly and is most sustainable in an environment designed to encourage it. Potential entrepreneurs become active entrepreneurs when the conditions are most supportive of their commercial opportunities and their business thus helping channel the two key qualities they exhibit as individuals obsessed maniacs and clairvoyant oracles (Carayannis, GWU Lectures, 2000-2005) and (Carayannis et at, 2003a) towards the generation of sustainable wealth. So far, entrepreneurial scholars who turn into intellectual venture capitalists by founding knowledge-driven companies remain one of the least explored specie in the territory of entrepreneurship. GloCal: The increasing engagement of firms within global knowledge and production networks and their ability to source knowledge globally as well as locally (GloCally), for the development of innovation capacities will shape the future of UK's knowledge resources and its role in the global economy. Practices such as off-shoring R&D activities are widely adopted, creating challenging, and not very well understood, issues related to cross-country and inter-firm knowledge and technology flows. We seek to address the internationalisation and networking of research and innovation activities, including the roles and strategies of enterprises, universities, research centres, governments in a cross-country and inter-sectoral way, to assess the impact and the implications for sustaining and enhancing the competitiveness of UK firms and other British knowledge producers and users.

Assessing US and EU Foreign Targeting Arab Youth: Lessons from Morocco. ACES Working Papers (progress report), August 2009

As stated in the opening sentence of the proposal submitted for the ACES grant in 2009, the research that this seed grant is supporting is ambitious and large in scale. The primary goal is to produce a book-length study that assesses the priorities and impact of European and American foreign aid targeting youth in the Middle East and North Africa (MENA). To date, the research undertaken with the support of the grant has helped in providing some preliminary data for a) testing few hypotheses, b) fine-tuning the research design; and c) pointing to the direction where more conceptual and ethnographic research should be undertaken.

Sustaining international competitive advantage through capability renewal: the case of CEMEX. ACES Working Papers, August 2009

In this paper we do not enter in the dispute of whether a new theory is needed to explain the factors that make it possible for EMNEs to give their initial steps beyond their home markets. Rather, we are interested in finding out how some of these firms have been able to sustain their international competitive edge for decades allowing them to become major players in their industry at the global level.

Market clusters for international franchising. ACES Working Papers, August 2009

While many studies of franchising have examined the organizational antecedents of internationalization, few have examined how differences among markets lead to this internationalization. Studies linking environmental factors to the companies' decision to internationalize showed that various political, social and economic factors either attract or repel international franchising investment. We build on these studies' selected variables to understand the similarities and differences among international franchising markets. Using these variables, our results show that countries divide into eight clusters with similar international franchising market characteristics. A discussion of each cluster follows with implications for franchising research.

Global and local (GloCal) knowledge logistics for innovation and competitiveness. ACES Working Papers, August 2010

The increasing engagement of firms within global knowledge and production networks and their ability to source knowledge globally as well as locally (GloCally), for the development of innovation capacities will shape the future of UK's knowledge resources and its role in the global economy. Practices such as off-shoring R&D activities are widely adopted, creating challenging, and not very well understood, issues related to cross-country and inter-firm knowledge and technology flows. We seek to address the internationalisation and networking of research and innovation activities, including the roles and strategies of enterprises, universities, research centres, governments in a cross-country and inter-sectoral way, to assess the impact and the implications for sustaining and enhancing the competitiveness of UK firms and other British knowledge producers and users.

Reverse Offshoring of Services: The New Wave of Emerging Offshorers. ACES Working Papers, August 2010

Offshore outsourcing of services accelerated at the end of 1990s in developed countries. In recent years, developing countries have also offshored services, not only to developed countries but also to other developing countries. Yet, to date little attention has been paid to the emergence of this reverse offshoring. The focus of this research is on the determinants of reverse offshoring of services; as such we will investigate what drives these firms from developing countries to offshore services.

Growing global brands in foreign markets: A brand equity perspective. Impact of national culture on trademark registrations in emerging economy: Evidence from Russia. ACES Working Papers, August 2010

In this study we explore how firms deploy intellectual property assets (trademarks) in international context and the impact of cultural characteristics on such activities. Trademarks capture important elements of firm's brand-building efforts. Using growth model, a special case of hierarchical linear model, we demonstrate that that stock of trademarks in foreign market increase future trademark activity. Also, we explore the moderating roles of two cultural dimensions, individualism and masculinity, on such relationships. The findings indicated that firms from countries closer to host market (Russia) on individualism dimension tend to register more trademarks in host market. The opposite result is observed for masculinity dimension.