Cyclopentadienyl-functionalised N-heterocyclic carbenes: synthesis, coordination to Mo, Ru, Rh

Dissertation presented to obtain the Ph.D degree in Chemistry

How does gender affect visiting a world heritage site?

To date few studies have been undertaken in Portugal dealing with the attitudes, motivations, and profile of tourists who visit World Heritage Sites. Also, few studies have dealt with destination image (e.g., Agapito, Mendes & Valle, 2010; Lopes, 2011). As far as it is known, none have approached the issue of gender differences in the choice of a Portuguese heritage destination. Since cultural tourism destinations need to differentiate themselves from each other, appropriate market segmentation must be based on a deep understanding of the customers’ motivations and preferences. Keeping in mind results from empirical literature (e.g., Silberberg, 1995; Beerli & Martin, 2004; Richards, 2004; Pérez, 2009; Sheng, Shen, & Chen, 2008), gender seems to be a possible approach to market segmentation, whether for Guimarães or for other cultural tourism destinations around the world. Located in the north-western region of Portugal, Guimarães is a city of strong symbolic and cultural significance, and the nomination of its historical centre as a World Heritage Site in 2001 enhanced its tourism potential. This study analyses the possible relation between gender and attitudes and motivations towards a World Heritage Site, such as Guimarães. Additionally, the empirical approach used in the study tries to capture differences in the perceived attributes of the city. Commonalities and distinctions within and between groups of tourists, by focusing on the specific characteristic of gender, were analysed. The study addressed two main questions: first, whether males and females have similar or different preferences in choosing the city as their destination; and, second, whether there are gender differences in the perception of the attributes of Guimarães. A better understanding of the gendered nature of the destination is a valuable cue for shaping products and services according to visitors’ preferences.

Qual é o efeito da globalização na exploração da mão de obra no setor sucroalcooleiro no Brasil?

Dissertação apresentada para cumprimento dos requisitos necessários à obtenção do grau de Mestre em Globalização e Ambiente

Activity-Dependent Neurorehabilitation Beyond Physical Trainings: "Mental Exercise" Through Mirror Neuron Activation

The activity dependent brain repair mechanism has been widely adopted in many types of neurorehabilitation. The activity leads to target specific and non-specific beneficial effects in different brain regions, such as the releasing of neurotrophic factors, modulation of the cytokines and generation of new neurons in adult hood. However physical exercise program clinically are limited to some of the patients with preserved motor functions; while many patients suffered from paralysis cannot make such efforts. Here the authors proposed the employment of mirror neurons system in promoting brain rehabilitation by "observation based stimulation". Mirror neuron system has been considered as an important basis for action understanding and learning by mimicking others. During the action observation, mirror neuron system mediated the direct activation of the same group of motor neurons that are responsible for the observed action. The effect is clear, direct, specific and evolutionarily conserved. Moreover, recent evidences hinted for the beneficial effects on stroke patients after mirror neuron system activation therapy. Finally some music-relevant therapies were proposed to be related with mirror neuron system.

Strange Dynamics in a Fractional Derivative of Complex-Order Network of Chaotic Oscillators

We study the peculiar dynamical features of a fractional derivative of complex-order network. The network is composed of two unidirectional rings of cells, coupled through a "buffer" cell. The network has a Z3 × Z5 cyclic symmetry group. The complex derivative Dα±jβ, with α, β ∈ R+ is a generalization of the concept of integer order derivative, where α = 1, β = 0. Each cell is modeled by the Chen oscillator. Numerical simulations of the coupled cell system associated with the network expose patterns such as equilibria, periodic orbits, relaxation oscillations, quasiperiodic motion, and chaos, in one or in two rings of cells. In addition, fixing β = 0.8, we perceive differences in the qualitative behavior of the system, as the parameter c ∈ [13, 24] of the Chen oscillator and/or the real part of the fractional derivative, α ∈ {0.5, 0.6, 0.7, 0.8, 0.9, 1.0}, are varied. Some patterns produced by the coupled system are constrained by the network architecture, but other features are only understood in the light of the internal dynamics of each cell, in this case, the Chen oscillator. What is more important, architecture and/or internal dynamics?

Reabilitação Funcional da Mão

A autora neste trabalho foca a complexidade anatómica e funcional da mão e procede há caracterização da etiologia das diferentes patologias que a afectam, destacando as de carácter traumático. Salienta a importância do exame objectivo no diagnóstico e da intervenção multidisciplinar no tratamento dessas patologias e das suas eventuais complicações. O tratamento de reabilitação deve ser iniciado precocemente e estabelecido em função da etiologia, idade e repercussão funcional. Destaca as particularidades da reabilitação da mão na criança e no adulto e os riscos que a incorrecta orientação terapêutica pode ter no desenvolvimento da criança. Referencia as diferentes modalidades terapêuticas utilizadas pela Medicina Física e de Reabilitação, nomeadamente as técnicas cinesiológicas e a utilização de ortoteses seus objectivos e indicações e os riscos da imobilização prolongada. Na reabilitação da mão salienta ainda a importância da terapia ocupacional nomeadamente na área da reeducação sensitiva.

Infecções da Mão e do Pé na Criança

As particularidades anatómicas e fisiopatológicas da Mao e do Pé levam a que as infecções localizadas adquiram aspectos especificos. Foram revistos 77 doentes internados e/ou seguidos em consulta externa do Hospital de Dona Estefânia com Infcções da Mão (25) e do Pé (52), no periodo de Janeiro de 1991 a Janeiro de 1994. Foram tratados em ambulatório os doentes com paroníquia (7 da mao e 42 do pe), um doente com polpite da mão e um com celulite do dorso da mao. Os restantes 16 com infecções da mão (64%) e 15 com infecções do pé (29%), foram internados tendo sido tratados com imobilização, elevação da zona afectada e antibioticoterapia endovenosa. Em todos os casos de abcesso foi efectuada drenagem cirurgica, 16 da mão e 22 do pé. Nas infecções da mão nao houve sequelas. Nas infecções do péhouve uma osteite do primeiro metatarso e umaa fistula cutânea.

Acidentes com Fogo de Artifício: Lesões da Mão na Criança

Análise da experiência e resultados da Instituição no trammento e reabilitação de lesões da mão provocadas pela explosão de artefactos de fogo de artifício. Casuística do HDE entre Janeiro de 1990 e Janeiro de 1997 constituída por 8 doentes estudados por um protocolo uniforme de avaliação. Na presente série todos os doentes são do meio rural. Verificou-se uma predominância do sexo masculino com 87%. A idade mais atingida foi a dos 10 anos. As lesões foram unilaterais em 87%. Registou-se uma prevalência da mão esquerda em 55%. O primeiro dedo foi o mais atingido com 25,5%. Nas lesões residuais, a amputação foi a mais frequente com 75%, seguida da brida com 62,2% e da alteração da sensibilidade táctil em 50% dos casos. O tratamento cirúrgico e de reabilitação precoce é importante para o prognóstico funcional do doente, mas é na prevenção destes acidentes que está a melhor solução para estes casos.

TUBERCULOSIS INFECTION MIGHT INCREASE THE RISK OF INVASIVE CANDIDIASIS IN AN IMMUNOCOMPETENT PATIENT

Deep Candida infections commonly occur in immunosuppressed patients. A rare case of a multiple deep organ infection with Candida albicansand spinal tuberculosis was reported in a healthy young man. The 19-year-old man complained of month-long fever and lower back pain. He also had a history of scalded mouth syndrome. Coinfection with Mycobacterium tuberculosis and Candida albicans was diagnosed using the culture of aspirates from different regions. Symptoms improved considerably after antifungal and antituberculous therapy. This case illustrates that infection with tuberculosis might impair the host's immune system and increase the risk of invasive candidiasis in an immunocompetent patient.

A Novel Autosomal Recessive GJA1 Missense Mutation Linked to Craniometaphyseal Dysplasia

Craniometaphyseal dysplasia (CMD) is a rare sclerosing skeletal disorder with progressive hyperostosis of craniofacial bones. CMD can be inherited in an autosomal dominant (AD) trait or occur after de novo mutations in the pyrophosphate transporter ANKH. Although the autosomal recessive (AR)form of CMD had been mapped to 6q21-22 the mutation has been elusive. In this study, we performed whole-exome sequencing for one subject with AR CMD and identified a novel missense mutation (c.716G>A, p.Arg239Gln) in the C-terminus of the gap junction protein alpha-1 (GJA1) coding for connexin 43 (Cx43). We confirmed this mutation in 6 individuals from 3 additional families. The homozygous mutation cosegregated only with affected family members. Connexin 43 is a major component of gap junctions in osteoblasts, osteocytes, osteoclasts and chondrocytes. Gap junctions are responsible for the diffusion of low molecular weight molecules between cells. Mutations in Cx43 cause several dominant and recessive disorders involving developmental abnormalities of bone such as dominant and recessive oculodentodigital dysplasia (ODDD; MIM #164200, 257850) and isolated syndactyly type III (MIM #186100), the characteristic digital anomaly in ODDD. However, characteristic ocular and dental features of ODDD as well as syndactyly are absent in patients with the recessive Arg239Gln Cx43 mutation. Bone remodeling mechanisms disrupted by this novel Cx43 mutation remain to be elucidated.

Kinetic, Structural, and EPR Studies Reveal That Aldehyde Oxidoreductase from Desulfovibrio gigas Does Not Need a Sulfido Ligand for Catalysis and Give Evidence for a Direct Mo-C Interaction in a Biological System

J. Am. Chem. Soc., 2009, 131 (23), pp 7990–7998 DOI: 10.1021/ja809448r

Molybdenum Induces the expression of a protein containing a new heterometallic Mo-Fe cluster in desulfoVibrio alaskensis

Biochemistry. 2009 Feb 10;48(5):873-82. doi: 10.1021/bi801773t.

Mo and W bis-MGD enzymes: nitrate reductases and formate dehydrogenases

J Biol Inorg Chem (2004) 9: 791–799 DOI 10.1007/s00775-004-0573-9

Activation of N2O reduction by the fully reduced micro4-sulfide bridged tetranuclear Cu Z cluster in nitrous oxide reductase

J. Am. Chem. Soc., 2003, 125 (51), pp 15708–15709 DOI: 10.1021/ja038344n