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Application of an Indenyl Molybdenum Dicarbonyl Complex in the Isomerisation of α-Pinene Oxide to Campholenic Aldehyde

Publication . Bruno, S.; Gomes, A. C.; Gamelas ou Carla A. Gamelas, Carla; Abrantes, M.; Oliveira, M. C.; Valente, A.; Almeida-Paz, Filipe; Pillinger, M.; Romão, C.; Gonçalves, I.

The complex [{(Z5-Ind)Mo(CO)2(m-Cl)}2] (1) has been tested for the industrially relevant catalytic isomerisation of a-pinene oxide (PinOx) to campholenic aldehyde (CPA) in the liquid phase. PinOx conversion and CPA selectivity are strongly influenced by the solvent employed. Complete conversion of PinOx was achieved within 1 min at 55 1C or 30 min at 35 1C using 1,2-dichloroethane as solvent, giving CPA in 68% yield. Other products included trans-carveol, iso-pinocamphone and trans-pinocarveol. The stability of 1 under the reaction conditions used was investigated by using FT-IR spectroscopy and electrospray ionisation mass spectrometry (ESI-MS) to characterise recovered solids. In the presence of air/moisture 1 undergoes oxidative decarbonylation upon dissolution to give oxomolybdenum species that are proposed to include a tetranuclear oxomolybdenum(V) complex. Conversely, ESI-MS studies of 1 dissolved in dry acetonitrile show mononuclear species of the type [IndMo(CO)2(CH3CN)n]+. The crystal structure of the ring-slipped dicarbonyl complex [(Z3-Ind)Mo(CO)2Cl(CH3CN)2] (2) (obtained after dissolution of 1 in acetonitrile) is reported.

2013Journal article

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Use of organomolybdenum compounds for promoted hydrolysis of phosphoester bonds in aqueous media

Publication . Gomes, A.; Gamelas ou Carla A. Gamelas, Carla; Fernandes, J.; Almeida-Paz, F.; Nunes, P.; Pillinger, M.; Gonçalves, I.; Romão, C.; Abrantes, M.

The dissolution of the indenyl (Ind) complex [{(η5‐Ind)Mo(CO)2(μ‐Cl)}2] (1) in N,N′‐dimethylformamide (DMF) gives the ring‐slipped complex [(η3‐Ind)Mo(CO)2Cl(DMF)2] (2). The aerial oxidation of 2 leads to the formation of the dinuclear oxomolybdenum(V) chloride [Mo2O2(DMF)4(μ‐O)2Cl2] (3). The structures of 2 and 3·DMF have been determined by single‐crystal X‐ray diffraction. Compounds 1 and 3 were examined as promoters of phosphoester bond hydrolysis in para‐nitrophenylphosphate (pNPP), which was used as a model substrate. The reactions were performed in aqueous solution at 55 °C and followed by 1H NMR spectroscopy. For assays performed with 30–100 mol‐% of 1 or 3 relative to pNPP, both compounds promote the production of para‐nitrophenol (pNPh) from pNPP. Compound 3 is especially active in promoting the hydrolytic cleavage of the phosphoester bond (t1/2 < 80 min).

2014Journal article

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Use of organomolybdenum compounds for promoted hydrolysis of phosphoester bonds in aqueous media

Publication . Gamelas ou Carla A. Gamelas, Carla; Gomes, Ana C.; Fernandes, José A.; Paz, Filipe A. Almeida; Nunes, Patrique; Pillinger, Martyn; Gonçalves, Isabel S.; Romão, Carlos C.; Abrantes, Marta

2016-09Conference object

Open access

Controlled drug release from hydrogels for contact lenses: drug partitioning and diffusion

Publication . Pimenta, A.F.R.; Ascenso, J.; Fernandes, J.C.S.; Colaço, R.; Serro, A.P.; Saramago, B.

Optimization of drug delivery from drug loaded contact lenses assumes understanding the drug transport mechanisms through hydrogels which relies on the knowledge of drug partition and diffusion coefficients. We chose, as model systems, two materials used in contact lens, a poly-hydroxyethylmethacrylate (pHEMA) based hydrogel and a silicone based hydrogel, and three drugs with different sizes and charges: chlorhexidine, levofloxacin and diclofenac. Equilibrium partition coefficients were determined at different ionic strength and pH, using water (pH 5.6) and PBS (pH 7.4). The measured partition coefficients were related with the polymer volume fraction in the hydrogel, through the introduction of an enhancement factor following the approach developed by the group of C. J. Radke (Kotsmar et al., 2012; Liu et al., 2013). This factor may be decomposed in the product of three other factors EHS, Eel and Ead which account for, respectively, hard-sphere size exclusion, electrostatic interactions, and specific solute adsorption. While EHS and Eel are close to 1, Ead > > 1 in all cases suggesting strong specific interactions between the drugs and the hydrogels. Adsorption was maximal for chlorhexidine on the silicone based hydrogel, in water, due to strong hydrogen bonding. The effective diffusion coefficients, De, were determined from the drug release profiles. Estimations of diffusion coefficients of the non-adsorbed solutes D = De × Ead allowed comparison with theories for solute diffusion in the absence of specific interaction with the polymeric membrane.

2016-12Journal article

Open access

The effect of albumin and cholesterol on the biotribological behavior of hydrogels for contact lenses

Publication . Silva, D.; Fernandes, A. C.; Nunes, T. G.; Colaço, R.; Serro, A. P.

The irritation/discomfort associated with the use of contact lenses (CLs) is often related to the eyelid-lens friction. Although the use of such devices is widespread, the information about the influence of the lacrimal fluid biomolecules on the tribological behavior of the CLs hydrogels is scarce. In this work, we investigated the effect of the presence of albumin and cholesterol in the lubricant medium, on the frictional response of two model hydrogels for CLs: a hydroxyethylmethacrylate based hydrogel, HEMA/PVP, and a silicone based one, TRIS/NVP/HEMA. Tribological experiments were done in a nanotribometer, in water and in the presence of solutions of those biomolecules. It was observed a significant increase of the friction coefficient (μ) for HEMA/PVP when the lubricant contains cholesterol, and for TRIS/NVP/HEMA when it contains albumin. Solid-state NMR and DSC analysis revealed that HEMA/PVP hydrated in cholesterol solution has a lower amount of free and loosely bound water than the hydrogel hydrated in water. Therefore, a smaller amount of water shall be released into the contact region during the friction tests with cholesterol solution, leading to a thinner film in the contact zone, and consequently to a higher μ. Concerning TRIS/NVP/HEMA, QCM-D studies showed that this hydrogel adsorbs less albumin than HEMA/PVP and that the formed film is more rigid, which can explain the increase of μ. The obtained results contribute to understand the influence of lacrimal fluid composition on the tribological behavior of CLs materials, being relevant for the selection and optimization of these devices.

2015-10Journal article

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