Complexes of copper(II) with 3-(ortho-substituted phenylhydrazo)pentane-2,4-diones: syntheses,properties and catalytic activity for cyclohexane oxidation

Reactions of copper(II) with 3-phenylhydrazopentane-2,4-diones X-2-C6H4-NHN = C{C(= O)CH3}(2) bearing a substituent in the ortho-position [X = OH (H2L1) 1, AsO3H2 (H3L2) 2, Cl (HL3) 3, SO3H (H2L4) 4, COOCH3 (HL5) 5, COOH (H2L6) 6, NO2 (HL7) 7 or H (HL8) 8] lead to a variety of complexes including the monomeric [CuL4(H2O)(2)]center dot H2O 10, [CuL4(H2O)(2)] 11 and [Cu(HL4)(2)(H2O)(4)] 12, the dimeric [Cu-2(H2O)(2)(mu-HL2)(2)] 9 and the polymeric [Cu(mu-L-6)](n)] 13 ones, often bearing two fused six-membered metallacycles. Complexes 10-12 can interconvert, depending on pH and temperature, whereas the Cu(II) reactions with 4 in the presence of cyanoguanidine or imidazole (im) afford the monomeric compound [Cu(H2O)(4){NCNC(NH2)(2)}(2)](HL4)(2)center dot 6H(2)O 14 and the heteroligand polymer [Cu(mu-L-4)(im)](n) 15, respectively. The compounds were characterized by single crystal X-ray diffraction (complexes), electrochemical and thermogravimetric studies, as well as elemental analysis, IR, H-1 and C-13 NMR spectroscopies (diones) and ESI-MS. The effects of the substituents in 1-8 on the HOMO-LUMO gap and the relative stability of the model compounds [Cu(OH)(L-8)(H2O)]center dot H2O, [Cu(L-1)(H2O)(2)]center dot H2O and [Cu(L-4)(H2O)(2)]center dot H2O are discussed on the basis of DFT calculations that show the stabilization follows the order: two fused 6-membered > two fused 6-membered/5-membered > one 6-membered metallacycles. Complexes 9, 10, 12 and 13 act as catalyst precursors for the peroxidative oxidation (with H2O2) of cyclohexane to cyclohexanol and cyclohexanone, in MeCN/H2O (total yields of ca. 20% with TONs up to 566), under mild conditions.

The tricks of the trade (un)exposed

One of the filmic trends which has been neglected by the Academy Awards is the metacinema, which for practical purposes I will consider to be a cross between the complexities of the self-reflexive cinema (highly connoted with modernism) and the Hollywood Film (the classical films about the urge to ‘make it’ in Hollywood). Indeed, these films have always existed and some, as Sunset Boulevard (Billy Wilder, 1950, USA) and Mulholland Dr. (David Lynch, 2001, FRA/USA), have even made it to the ceremony, but were, predictably, defeated in the main categories, by other more ‘serious’ or less self-reflexive products. The United States has always insisted on not revealing the tricks of the trade while, ironically, generating films that deal with this theme, in order to cater to the curiosity of the metacinema-inclined spectator. For this reason such films are usually about the universe of cinema but not its medium, at least not in a way that discloses the operations of the technical apparatus. Why are these films not viewed as serious enough and artistic enough to be awarded Oscars by the Academy in the categories of Best Picture, Best Director, Best Screenplay, and Best Cinematography? Are they being discarded for the same reasons that comedy and musicals usually are? Or are they being punished for being too unveiling? Or is the industry going for commercial products that can easily be pushed on a global scale and make a profit?

Da formação inicial à inserção na profissão

Dissertação apresentada à Escola Superior de Educação de Lisboa Para a obtenção do Grau de Mestre em Ciências da Educação - Especialidade Supervisão em Educação

Riders in the storm: the professions and healthcare governance

The public sector is facing turbulent times and this also challenges the health professions who are expected to serve both the interests of the citizens and the cost-containment and austerity policies of governments. This article seeks to explore the changing role of the health professions. I introduce an approach on ‘citizen professionals’ as active players in the policy process and mediators between the state/policymakers and the citizens/patients. The aim is to highlight a transformative potential of professionalism and the connectedness with other sets of governance, like management. Empirical material from a German case study and a comparative European study serve to illustrate the arguments, drawing on policy analysis and secondary sources. The results bring the complexity of transformations and new emergent forms of professionalism into view that cannot be understood in traditional categories of conflict, exclusion and jurisdiction. Exploring the potential of the health professions to creatively respond to new challenges may reveal new opportunities for innovating healthcare policy beyond market and management.

Novas perspetivas sobre as identidades de classe

Há mais de uma década começou a formar-se um movimento de reconversão nos estudos sobre as classes sociais, orientado pela ideia de que é preciso dar mais relevo aos processos culturais, à formação de identidades, ao gosto e à expressão de modos de vida e proceder ao exame direto da maneira como as posições de classe são vividas. Nesta perspetiva, as culturas de classe deixam de designar apenas tipos de comportamento próprios de grupos de desigualdade e passam a ser vistas também como modos de diferenciação, em que as categorias de classe operam através de distinções individualizadas e comparações relacionais com membros de outras classes. O que o conceito de identidade de classe quer agora indicar é um sentido das distâncias sociais dentro das hierarquias, que recorre às diferenças culturais para se exprimir. Este texto recenseia os desenvolvimentos teóricos e as bases empíricas desta linha de trabalho, emergente na sociologia britânica a partir do final da década de 90, com as propostas de autores como Savage, Skeggs, Reay, ou Bottero, entre outros.

Plano de marketing para a empresa: Salss - Importação e Comércio Lda

Trabalho de projeto apresentado à Escola Superior de Comunicação Social como parte dos requisitos para obtenção de grau de mestre em Publicidade e Marketing.

Detect and pointing algorithm's performance for a planar smart antenna array: a review

An adaptive antenna array combines the signal of each element, using some constraints to produce the radiation pattern of the antenna, while maximizing the performance of the system. Direction of arrival (DOA) algorithms are applied to determine the directions of impinging signals, whereas beamforming techniques are employed to determine the appropriate weights for the array elements, to create the desired pattern. In this paper, a detailed analysis of both categories of algorithms is made, when a planar antenna array is used. Several simulation results show that it is possible to point an antenna array in a desired direction based on the DOA estimation and on the beamforming algorithms. A comparison of the performance in terms of runtime and accuracy of the used algorithms is made. These characteristics are dependent on the SNR of the incoming signal.

Escrever para aprender estudo do meio

Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Didáticas Integradas em Língua Portuguesa, Matemática, Ciências Naturais e Sociais