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The protein corona, which forms on the nanoparticle's surface in most biological media, determines the nanoparticle's physicochemical characteristics. The formation of the protein corona has a significant impact on the biodistribution and clearance of nanoparticles in vivo. Therefore, the ability to influence the formation of the protein corona is essential to most biomedical applications, including drug delivery and imaging. In this study, we investigate the protein adsorption on nanoparticles with a hydrodynamic radius of 30 nm and a coating of thermoresponsive poly(2-isopropyl-2-oxazoline) in serum. Using multiangle dynamic light scattering (DLS) we demonstrate that heating of the nanoparticles above their phase separation temperature induces the formation of agglomerates, with a hydrodynamic radius of 1 mu m. In serum, noticeably stronger agglomeration occurs at lower temperatures compared to serum-free conditions. Cryogenic transmission electron microscopy (cryo-TEM) revealed a high packing density of agglomerates when serum was not present. In contrast, in the presence of serum, agglomerated nanoparticles were loosely packed, indicating that proteins are intercalated between them. Moreover, an increase in protein content is observed upon heating, confirming that protein adsorption is induced by the alteration of the surface during phase separation. After cooling and switching the surface back, most of the agglomerates were dissolved and the main fraction returned to the original size of approximately 30 nm as shown by asymmetrical flow-field flow fractionation (AF-FFF) and DLS. Furthermore, the amounts of adsorbed proteins are similar before and after heating the nanoparticles to above their phase-separation temperature. Overall, our results demonstrate that the thermoresponsivity of the polymer coating enables turning the corona formation on nanoparticles on and off in situ. As the local heating of body areas can be easily done in vivo, the thermoresponsive coating could potentially be used to induce the agglomeration of nanopartides and proteins and the accumulation of nanoparticles in a targeted body region.
Due to the adsorption of biomolecules, the control of the biodistribution of nanoparticles is still one of the major challenges of nanomedicine. Poly(2-ethyl-2-oxazoline) (PEtOx) for surface modification of nanoparticles is applied and both protein adsorption and cellular uptake of PEtOxylated nanoparticles versus nanoparticles coated with poly(ethylene glycol) (PEG) and non-coated positively and negatively charged nanoparticles are compared. Therefore, fluorescent poly(organosiloxane) nanoparticles of 15 nm radius are synthesized, which are used as a scaffold for surface modification in a grafting onto approach. With multi-angle dynamic light scattering, asymmetrical flow field-flow fractionation, gel electrophoresis, and liquid chromatography-mass spectrometry, it is demonstrated that protein adsorption on PEtOxylated nanoparticles is extremely low, similar as on PEGylated nanoparticles. Moreover, quantitative microscopy reveals that PEtOxylation significantly reduces the non-specific cellular uptake, particularly by macrophage-like cells. Collectively, studies demonstrate that PEtOx is a very effective alternative to PEG for stealth modification of the surface of nanoparticles.
Spatial analysis of the impacts of the Chaiten volcano eruption (Chile) in three fluvial systems
(2016)
The eruption of the Chaiten volcano in May 2008 generated morphological and ecological disturbances in adjacent river basins, and the magnitude of these disturbances depended on the type of dominant volcanic process affecting each of them. The aim of this study is to analyse the morphological changes in different periods in river segments of the Blanco, El Amarillo and Rayas river basins located near the Chaiten volcano. These basins suffered disturbances of different intensity and spatial distribution caused by tephra fall, dome collapses and pyroclastic density currents that damaged hillslope forests, widened channels and destroyed island and floodplain vegetation. Changes continued to occur in the fluvial systems in the years following the eruption, as a consequence of the geomorphic processes indirectly induced by the eruption. Channel changes were analyzed by comparing remote images of pre and post eruption conditions. Two periods were considered: the first from 2008 to 2009-2010 associated with the explosive and effusive phases of the eruption and the second that correspond to the post-eruption stage from 2009-2010 to 2013. Following the first phases channel segments widened 91% (38 m/yr), 6% (7 m/yr) and 7% (22 m/yr) for Blanco, Rayas and El Amarillo Rivers, respectively, compared to pre-eruption condition. In the second period, channel segments additionally widened 42% (8 m/yr), 2% (2 m/yr) and 5% (4 m/yr) for Blanco, Rayas and El Amarillo Rivers, respectively. In the Blanco River 62 and 82% of the islands disappeared in the first and second period, respectively, which is 6-8 times higher than in the El Amarillo approximately twice the Rayas. Sinuosity increased after the eruption only in the Blanco River but the three study channels showed a high braiding intensity mainly during the first post-eruption period. The major disturbances occurred during the eruptive and effusive phases of Chaiten volcano, and the intensity of these disturbances reflects the magnitude of the dominant volcanic processes affecting each basin. Inputs of sediment from dome collapses and pyroclastic density currents and not ash fall seem to explain morphologic channel change magnitudes in the study segments. The resulting knowledge can facilitate land use planning and design of river restoration projects in areas affected by volcanic eruptions disturbances. (C) 2016 Elsevier Ltd. All rights reserved.
Large earthquakes can increase the amount of water feeding stream flows, raise groundwater levels, and thus grant plant roots more access to water in water-limited environments. We examine growth and photosynthetic responses of Pine plantations to the Maule M-w 8.8 earthquake in headwater catchments of Chile's Coastal Range. We combine high-resolution wood anatomic (lumen area) and biogeochemical (delta 13C of wood cellulose) proxies of daily to weekly tree growth sampled from trees on floodplains and close to ridge lines. We find that, immediately after the earthquake, at least two out of six tree trees on valley floors had increased lumen area and decreased delta 13C, while trees on hillslopes had a reverse trend. Our results indicate a control of soil water on this response, largely consistent with models that predict how enhanced postseismic vertical soil permeability causes groundwater levels to rise on valley floors, but fall along the ridges. Statistical analysis with boosted regression trees indicates that streamflow discharge gained predictive importance for photosynthetic activity on the ridges, but lost importance on the valley floor after the earthquake. We infer that earthquakes may stimulate ecohydrological conditions favoring tree growth over days to weeks by triggering stomatal opening. The weak and short-lived signals that we identified, however, show that such responses are only valid under water-limited, rather than energy-limited tree, growth. Hence, dendrochronological studies targeted at annual resolution may overlook some earthquake effects on tree vitality.