Organotin in the Tagus estuary

The tri(n-butyl)tin (TBT) moiety has been shown to have complex ecotoxicological effects on estuarine populations. In the Tagus the massive die-off of the Portuguese oyster (Crassostrea angulata Lmk), has been attributed to the introduction and use of this contaminant by shipyards. This paper reviews previous work by others and reassesses our results obtained in water and sediments of the Tagus estuary, as a contribution to the understanding of tin geochemistry and organotin speciation in this estuary. Contrary to earlier results, the latest surveys show that in the open waters of the Tagus measurable concentrations of all the three butyltin species occur, exhibiting peak concentrations at two locations that indicate two previously undetected sources of TBT. TBT also presents a peak concentration in sediments near the Lisnave shipyards, as previously suggested. The latest surveys still detected methylated forms of tin, particularly monomethyltin (Me Sn³⁺), in Tagus sediments, with maximum concentrations in the vicinity of urban effluent discharges. The concentrations for TBT and its degradation products found in the Tagus are potentially harmful to the populations of gastropods and endemic bivalves.     

Association of vasoactive intestinal peptide with polymer-grafted liposomes: Structural aspects for pulmonary delivery

A polymer-grafted liposomal formulation that has the potential to be developed for aerosolic pulmonary delivery of vasoactive intestinal peptide (VIP), a potent vasodilatory neuropeptide, is described. As VIP is prone to rapid proteolytic degradation in the microenvironment of the lung a proper delivery system is required to increase the half-life and bioavailability of the peptide. Here we investigate structural parameters of unilamellar liposomes composed of palmitoyl-oleoyl-phosphatidylcholine, lyso-stearyl-phosphatidylglycerol and distearyl-phosphatidyl-ethanolamine covalently linked to polyethylene glycol 2000, and report on VIP-lipid interaction mechanisms. We found that the cationic VIP is efficiently entrapped by the negatively charged spherical liposomes and becomes converted to an amphipathic α-helix. By fluorescence spectroscopy using single Trp-modified VIP we could show that VIP is closely associated to the membrane. Our data suggest that the N-terminal random-coiled domain is embedded in the interfacial headgroup region of the phospholipid bilayer. By doing so, neither the bilayer thickness of the lipid membrane nor the mobility of the phospholipid acyl chains are affected as shown by small angle X-ray scattering and electron spin resonance spectroscopy. Finally, in an ex vivo lung arterial model system we found that liposomal-associated VIP is recognized by its receptors to induce vasodilatory effects with comparable high relaxation efficiency as free VIP but with a significantly retarded dilatation kinetics. In conclusion, we have designed and characterized a liposomal formulation that is qualified to entrap biologically active VIP and displays structural features to be considered for delivery of VIP to the lung.