Frederico Sanches

O carcinoma ductal écrino é uma neoplasia cutânea rara com curso clínico agressivo. O seu diagnóstico implica a exclusão dum adenocarcinoma primário noutra localização com metastização cutânea, já que os dados histológicos e imunohistoquímicos por si sós não o permitem. Reporta-se o caso clínico de um homem de 75 anos com um tumor de 3cm localizado na hemiface direita, o qual foi excisado e cujo exame histológico e imunohistoquímico apontavam para o diagnóstico de um carcinoma ductal écrino. A investigação complementar mostrou múltiplos nódulos pulmonares e pleurais, bem como envolvimento neoplásico da coluna vertebral dorsal e lombar. O exame histológico e imunohistoquímico destes achados, complementado com a ausência de achados imagiológicos sugestivos de uma neoplasia primária noutro local, permitiram o diagnóstico de um carcinoma ductal écrino metastizado. O doente morreu 6 meses após a primeira observação.

The observation of photocatalytic water splitting on the surface of anatase TiO2 crystals has stimulated many investigations of the underlying processes. Nevertheless, a molecular level understanding of the reaction is not available. Therefore, the work carried out here is focused on improving the understanding of the water splitting mechanism by studying anatase TiO2 surfaces with hybrid-exchange density functional theory calculations. Initially, a simple and systematic methodology for the simulation of constant current scanning tunnelling microscopy (STM) images is developed in order to study TiO2 surfaces. The methodology has to overcome a significant limitation of local basis set calculations: the poor description of the charge density in the vacuum region above the surface. The methodology is tested on various surfaces and the simulated STM images are found to accurately reproduce experimental data. The next step was to re-establish the atomistic structures of the (101), (001) and (100) surfaces. The relative stability of these surfaces is interpreted in terms of the coordination of the surface ions and the geometry surrounding them. Furthermore, the electronic properties are studied. Based on relative positions of the conduction and valence bands of the low-index surfaces studied the (101) and (001) surfaces were identified as the most likely destinations for photo-generated electrons and holes, respectively. The atomistic structure of two surfaces vicinal to the (101) surface – the (514) and (516) surfaces – was established. The surface formation energy of these surfaces is low and the (516) surface contributes significantly (27%) to the surface area of an equilibrium crystallite, which could suggest that this surface is exposed in nanoparticles. The conduction band edge of this surface was computed to be more negative than that of the (101) surface. Thus, if the (516) surface is exposed in nanostructures, it would replace the (101) surface as the most likely destination for photo-generated electrons. Under-coordinated ions at the steps of these vicinal surfaces were identified as preferential adsorption sites and water adsorption was studied at these sites. In general, it was found that water preferentially adsorbs in the molecular adsorption mode on all sites tested, with the exception of the Ti4c on the (514) surface, where the dissociative mode is preferred. Nevertheless, at the (516) step the binding energy of the dissociative adsorption mode is comparable to that of the molecular case. Therefore, if it were possible to preferentially expose the Ti5c-O2c-Ti5c motif from the (516) surface, or even the Ti4c of the (514) surface the reactivity for water photolysis could be enhanced.

Ductal eccrine carcinoma is a rare and aggressive skin cancer. Its diagnosis implies the exclusion of a primary adenocarcinoma located elsewhere with cutaneous metastization, as the histological and immunohistochemical analysis are not sufficient by themselves. We report the clinical case of a 75-year-old male with a 3 cm width tumor located on the right hemiface, which was excised and whose histology and immunohistochemistry pointed towards an eccrine ductal carcinoma. The complementary investigation showed multiple pleural and pulmonary nodules, as well as neoplastic involvement of the dorsal and lumbar vertebral column. Their histological and immnunohistochemical examination, supplement with the absence of imagiologic findings suggesting a primary tumor in another location, allowed the diagnosis of a metastatic eccrine ductal carcinoma. The patient died 6 months after the initial consultation.