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Inocencio, S, Cordeiro T, Matos I, Danede F, Sotomayor JC, Fonseca IM, Correia NT, Corvo MC, Dionisio M.  2021.  Ibuprofen incorporated into unmodified and modified mesoporous silica: From matrix synthesis to drug release, {JAN}. MICROPOROUS AND MESOPOROUS MATERIALS. 310:110541. AbstractWebsite

{Aiming to rationalize the release profile of an incorporated pharmaceutical drug in terms of its mobility, driven by guest-host interactions, the poorly water-soluble ibuprofen drug was loaded in a mesoporous inorganic silica matrix with unmodified (MCM-41) and modified surface (MCM-41sil) by post-synthesis silylation, both having pore sizes similar to 3 nm. The single calorimetric detection of a broad glass transition step for both ibuprofen com-posites indicates full drug amorphization, confirmed by the only appearance of an amorphous halo in the powder XRD patterns. Moreover, a gradient profile is disclosed by the heat flux derivative plot in the glass transition, in coherence with the thermogravimetric profile that shows a multi-step decomposition trace for confined ibuprofen in these matrixes. While identical guest dynamics, as probed by dielectric relaxation spectroscopy, were found in both dehydrated composites, a significant molecular population with faster relaxation exists in the hydrated state for the drug inside the unmodified matrix. This was rationalized as the concurrence of true confinement effects, which manifest under nanometer dimensions, and greater water affinity of the unmodified matrix, forcing the drug molecules to be placed mostly in the pore core. Finite size effects are also felt in both dehydrated composites, however guest-host interactions give origin to a dominant population with slowed down mobility that governs the overall guest dynamics. In spite of an inferior number of active sites for drug adsorption in the silylated matrix, a faster ibuprofen delivery in phosphate buffer (pH = 6.8) was observed when the drug is released from unmodified MCM-41 in the hydrated state. Therefore, our results suggest that a relevant role is played by water molecules, which impair a strong guest adsorption in the host surface more efficiently than the limited surface modification, influence the higher ratio of a faster population in the pore core and facilitate the diffusion of the aqueous releasing media inside pores.}

Azevedo, G, Domingues B, Abreu H, Sousa-Pinto I, Feio G, Hilliou L.  2015.  Impact of cultivation of Mastocarpus stellatus in IMTA on the seaweeds chemistry and hybrid carrageenan properties. Carbohydr Polym. 116:140-8. AbstractWebsite

The biomass yield potential of Mastocarpus stellatus, a commercially attractive carrageenophyte for foods and pharmaceutics, was investigated by cultivating the seaweeds in the nutrient-rich outflow of a commercial fish farm. Results from two consecutive 4 weeks experiments indicate that the cultivation of this seaweed produces a mean biomass of 21 to 40.6 gDW m(-2) day(-1) depending on the time of the experiment. DRIFT and CP-MAS NMR analyses of seaweeds indicate that cultivation during May affected quantitatively the seaweeds chemistry, and thus the chemical and gelling properties of native extracts of kappa/iota-hybrid carrageenan (KI). Overall, algal growth leads to the production of more sulphated KI, the percentage increase varying between 27% and 44% for the two experiments. However, alkali treatment of seaweeds before extraction reduces the variations in gelling properties of KI induced by the algal growth. This study demonstrates the capacity of growing M. stellatus in an integrated multi-trophic aquaculture system for the sustainable production of high value polysaccharides.

Mouquinho, A, Corvo MC, Almeida PL, Feio GM, Sotomayor J.  2020.  Influence of chain length of prepolymers in permanent memory effect of PDLC assessed by solid-state NMR. Liquid Crystals. 47:522–530., Number 4: Taylor & Francis AbstractWebsite

The relationship between linear chain (ethylene oxide units) length of polymerisable monomers with morphology, electro-optical properties and 13C nuclear magnetic resonance (NMR) spectroscopy of the corresponding polymer-dispersed liquid crystal (PDLC) films was investigated. The preferred liquid crystal molecule alignment and permanent memory effect of PDLC were greatly influenced by the length of the molecular chain of prepolymers to be incorporated as a polymer matrix. By increasing the number of ethylene oxide in prepolymer chain and maintaining the number of functionalities (polymerisable groups in each monomer molecule), the permanent memory effect of PDLC increased, as proved by solid-state 13C NMR spectroscopy.