Sulfonated Schiff base copper(ii) complexes as efficient and selective catalysts in alcohol oxidation: syntheses and crystal structures

The reaction between 2-aminobenzenesulfonic acid and 2-hydroxy-3-methoxybenzaldehyde produces the acyclic Schiff base 2-[(2-hydroxy-3-methoxyphenyl) methylideneamino] benzenesulfonic acid (H2L center dot 3H(2)O) (1). In situ reactions of this compound with Cu(II) salts and, eventually, in the presence of pyridine (py) or 2,2'-bipyridine (2,2'-bipy) lead to the formation of the mononuclear complexes [CuL(H2O)(2)] (2) and [CuL(2,2'-bipy)]center dot DMF center dot H2O (3) and the diphenoxo-bridged dicopper compounds [CuL(py)](2) (4) and [CuL(EtOH)](2)center dot 2H(2)O (5). In 2-5 the L-2-ligand acts as a tridentate chelating species by means of one of the O-sulfonate atoms, the O-phenoxo and the N-atoms. The remaining coordination sites are then occupied by H2O (in 2), 2,2'-bipyridine (in 3), pyridine (in 4) or EtOH (in 5). Hydrogen bond interactions resulted in R-2(2) (14) and in R-4(4)(12) graph sets leading to dimeric species (in 2 and 3, respectively), 1D chain associations (in 2 and 5) or a 2D network (1). Complexes 2-5 are applied as selective catalysts for the homogeneous peroxidative (with tert-butylhydroperoxide, TBHP) oxidation of primary and secondary alcohols, under solvent-and additive-free conditions and under low power microwave (MW) irradiation. A quantitative yield of acetophenone was obtained by oxidation of 1-phenylethanol with compound 4 [TOFs up to 7.6 x 10(3) h(-1)] after 20 min of MW irradiation, whereas the oxidation of benzyl alcohol to benzaldehyde is less effective (TOF 992 h(-1)). The selectivity of 4 to oxidize the alcohol relative to the ene function is demonstrated when using cinnamyl alcohol as substrate.

Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols

A one-pot template reaction of sodium 2-(2-(dicyanomethylene) hydrazinyl) benzenesulfonate (NaHL1) with water and manganese(II) acetate tetrahydrate led to the mononuclear complex [Mn(H2O)(6)](HL1a)(2)center dot 4H(2)O (1), where (HL1a) -= 2-(SO3-)C6H4(NH)=N=C(C N) (CONH2) is the carboxamide species derived from nucleophilic attack of water on a cyano group of (HL1) . The copper tetramer [Cu-4(H2O)(10)(-) (1 kappa N: kappa O-2: kappa O, 2 kappa N: k(O)-L-2)(2)]center dot 2H(2)O (2) was obtained from reaction of Cu(NO3)(2)center dot 2.5H(2)O with sodium 5-(2( 4,4-dimethyl-2,6-dioxocyclohexylidene) hydrazinyl)-4-hydroxybenzene-1,3-disulfonate (Na2H2L2). Both complexes were characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray diffraction. They exhibit a high catalytic activity for the solvent-and additive-free microwave (MW) assisted oxidation of primary and secondary alcohols with tert-butylhydroperoxide, leading to yields of the oxidized products up to 85.5% and TOFs up to 1.90 x 103 h(-1) after 1 h under low power (5-10 W) MW irradiation. Moreover, the heterogeneous catalysts are easily recovered and reused, at least for three consecutive cycles, maintaining 89% of the initial activity and a high selectivity.

Derek Jarman’s allegories of spectacle: inter-artistic embodiment

ABSTRACT - Derek Jarman was a multifaceted artist whose intermedial versatility reinforces a strong authorial discourse. He constructs an immersive allegorical world of hybrid art where different layers of cinematic, theatrical and painterly materials come together to convey a lyrical form and express a powerful ideological message. In Caravaggio (1986) and Edward II (1991), Jarman approaches two european historical figures from two different but concomitant perspectives. In Caravaggio, through the use of tableaux of abstract meaning and by focusing on the detailing of the models’ poses, Jarman re-enacts the allegorical spirit of Caravaggio’s paintings through entirely cinematic resources. Edward II was a king, and as a statesman he possessed a certain dose of showmanship. In this film Jarman reconstructs the theatrical basis of Christopher Marlowe’s Elizabethan play bringing it up to date in a successfully abstract approach to the musical stage. In this article, I intend to conjoin the practice of allegory in film with certain notions of existential phenomenology as advocated by Vivian Sobchack and Laura U. Marks, in order to address the relationship between the corporeality of the film and the lived bodies of the spectators. In this context, the allegory is a means to convey intradiegetically the sense-ability at play in the cinematic experience, reinforcing the textural and sensual nature of both film and viewer, which, in turn, is also materially enhanced in the film proper, touching the spectator in a supplementary fashion. The two corporealities favour an inter-artistic immersion achieved through coenaesthesia.

Electron driven reactions in complexes embedded in superfluid helium droplets

A thesis submitted to the University of Innsbruck for the doctor degree in Natural Sciences, Physics and New University of Lisbon for the doctor degree in Physics, Atomic and Molecular Physics

Um mundo, um governo: a importância e desafios das relações entre a união europeia e o mercosul no cenário das associações inter-regionais

Dissertação apresentada para cumprimento dos requisitos necessários à obtenção do grau de Mestre em Ciência Política e Relações Internacionais

Giardia duodenalis: INTER-STRAIN VARIABILITY OF PROTEINS, ANTIGENS, PROTEASES, ISOENZYMES AND NUCLEIC ACIDS

Giardia duodenalis isolates from asymptomatic or symptomatic patients and from animals present similarities and differences in the protein composition, antigenic profile, pattern of proteases and isoenzymes, as well as in nucleic acids analysis. In the present overview, these differences and similarities are reviewed with emphasis in the host-parasite interplay and possible mechanisms of virulence of the protozoon.

Oxo-molybdenum(VI) complexes containing chiral ligands: catalytic applications in selective epoxidations

Dissertation presented to obtain the Ph.D. degree in Chemistry

Bacterial inter-species communication mediated by the autoinducer-2 signal

Dissertation presented to obtain the Ph.D degree in Biology by Universidade Nova de Lisboa, Instituto de Tecnologia Química e Biológica, Instituto Gulbenkian de Ciência.

NMR studies of transiente protein complexes

Dissertação apresentada para obtenção do Grau de Doutor em Bioquímica,especialidade Bioquímica Física,pela Universidade Nova de Lisboa,Faculdade de Ciências e Tecnologia

Characterization of a clone from an adult worm cDNA library selected with anti-Schistosoma mansoni human antibodies dissociated from immune complexes: a preliminary report

Considering the scarcity of defined antigens, actually useful and reliable for use in the field studies, we propose an alternative method for selection of cDNA clones with potential use in the diagnosis of schistosomiasis. Human antibodies specific to a protein fraction of 31/32 kDa (Sm31/32), dissociated from immune complexes, are used for screening of clones from an adult worm cDNA library. Partial sequencing of five clones, selected through this strategy, showed to be related to Schistosoma mansoni: two were identified as homologous to heat shock protein 70, one to glutathione S-transferase, one to homeodomain protein, and one to a previously described EST (expressed sequence tag) of S. mansoni. This last clone was the most consistently reactive during the screening process with the anti-Sm31/32 antibodies dissociated from the immune complexes. The complete sequence of this clone was obtained and the translation data yielded only one ORF (open reading frame) that code for a protein with 57 amino acids. Based on this amino acid sequence two peptides were chemically synthesized and evaluated separately against a pool of serum samples from schistosomiasis patients and non-schistosomiasis individuals. Both peptides showed strong reactivity only against the positive pool, suggesting that these peptides may be useful as antigens for the diagnosis of schistosomiasis mansoni.

Interculturality in the Primary EFL Classroom: Increasing Tolerance through (Inter) Cultural Awareness

Dissertação apresentada para cumprimento dos requisitos necessários à obtenção do grau de Mestre em Didáctica do Inglês,

Nós dizemos que eles são como nós precisamos que eles sejam para nos podermos ver como nos vemos. Vicissitudes identitárias nas relações inter-étnicas

Como Calhoun (1996) e Mennell (1996) referem, apesar da atenção acrescida dada às construções, estratégias e políticas da identidade, permanece uma evidente dificuldade de articulação entre diferentes corpora e, nomeadamente, daqueles que derivam da utilização de um nível micro de observação e análise e de um nível de macro-focalização. (í^om base num estudo de caso, tentaremos evidenciar que (a) os processos identitários articulam as duas dimensões de análise e que (b) o nível micro- familiar constitui o referente e o mediador simbôlico-identitário adequado da articulação entre as micro e as macro-perspectivas,^ (c) a partir do qual emerge toda uma gama de idiomas simbólicos (familialistas, instrumentais e morais). O papel desempenhado pela experiência arcaica familiar tem a ver com o facto de que é nesse nível que se cruzam os gêneros e as gerações, se negoceia e gere a dimensão identitária da sexualidade, a moral e a construção diferenciada de identidades categoriais, e são organizadas as primeiras fronteiras entre «nós» e «eles»^, ao mesmo tempo que se vai diferenciando a identidade pessoal, sob a forma da construção do «indivíduo» que será progressivamente confrontado com a transposição projectiva do(s) poder(es) intra-familiar(es) para o nível macro do poder transcendental e dos poderes de Estado.

Das inter-etnicidades em processos de inserção social diferenciadas às dinâmicas do sistema-mundo: uma abordagem estrutural-dinâmica

Em pesquisas anteriores, procurámos mostrar que (i) as representações identitárias possuem uma estrutura multidimensional, cujos níveis (pessoal, bio-cultural, sócio-histórico / político, ideal, «moral», etc.) estão inter-relacionados, e formam um sistema identitário pessoal, se bem que partilhado, em proporções variáveis, com os outros emissores identitários inseridos na mesma categoria sócio-histórica; (ii) sistema identitário esse detentor de potencialidades estratégicas (Kastersztein, 1990) - ideológicas, simbólicas e fantasmáticas -, derivadas da articulação inconsciente entre os diferentes níveis mobilizados. Tentámos evidenciar ainda, no nível mais abrangente das representações identitárias dos grupos sócio-históricos, (iii) como o grau de sobreposição e convergência das atribuições identitárias, tanto ao grupo.de identificação como aos grupos de comparação interactiva, é parcial, indiciando estratégias de maior ou menor distanciação / aproximação identitária inter-nacional ou inter-étnica; (iv) e como, no seu conjunto, as representações identitárias apresentam uma lógica e uma economia retórica, tendenciosa e performativa (pro domo sua), criando para os sujeitos, no interior dos seus grupos, e para os seus grupos identitários, na comparação com os outros, uma imagem de primo inter pares, na medida em que constroiem como «real» o «real identitariamente conveniente» e não aquele que «objectivamente » é «objectivado» (em termos de poder tecnológico, econômico ou militar).

Prisão com fronteiras: relações inter-étnicas em meio prisional. Estudo de caso no estabelecimento prisional de Carregueira

Dissertação apresentada para cumprimento dos requisitos necessários à obtenção do grau de Mestre em Migrações, Inter-etnicidades e Transnacionalismo

Multipath inter-domain policy routing

Dissertação submetida para a obtenção do grau de Doutor em Engenharia Electrotécnica e de Computadores