Continuous-Flow Laboratory SAXS for In Situ Determination of the Impact of Hydrophilic Block Length on Spherical Nano-Object Formation during Polymerization-Induced Self-Assembly

In situ small-angle X-ray scattering (SAXS) is a powerful technique for characterizing block-copolymer nano-object formation during polymerization-induced self-assembly. To work effectively in situ, it requires high intensity X-rays which enable the short acquisition times required for real-time measurements. However, routine access to synchrotron X-ray sources is expensive and highly competitive. Flow reactors provide an opportunity to obtain temporal resolution by operating at a consistent flow rate. Here, we equip a flow-reactor with an X-ray transparent flow-cell at the outlet which facilitates the use of a low-flux laboratory SAXS instrument for in situ monitoring. The formation and morphological evolution of spherical block copolymer nano-objects was characterized during reversible addition fragmentation chain transfer polymerization of diacetone acrylamide in the presence of a series of poly(dimethylacrylamide) (PDMAm) macromolecular chain transfer agents with varying degrees of polymerization. SAXS analysis indicated that during the polymerization, highly solvated, loosely defined aggregates form after approximately 100 s, followed by expulsion of solvent to form well-defined spherical particles with PDAAm cores and PDMAm stabilizer chains, which then grow as the polymerization proceeds. Analysis also indicates that the aggregation number (Nagg) increases during the reaction, likely due to collisions between swollen, growing nanoparticles. In situ SAXS conducted on PISA syntheses using different PDMAm DPs indicated a varying conformation of the chains in the particle cores, from collapsed chains for PDMAm47 to extended chains for PDMAm143. At high conversion, the final Nagg decreased as a function of increasing PDMAm DP, indicating increased steric stabilization afforded by the longer chains which is reflected by a decrease in both core diameter (from SAXS) and hydrodynamic diameter (from DLS) for a constant core DP of 400

Life path analysis: scaling indicates priming effects of social and habitat factors on dispersal distances

1. Movements of many animals along a life-path can be separated into repetitive ones within home ranges and transitions between home ranges. We sought relationships of social and environmental factors with initiation and distance of transition movements in 114 buzzards Buteo buteo that were marked as nestlings with long-life radio tags. 2. Ex-natal dispersal movements of 51 buzzards in autumn were longer than for 30 later in their first year and than 35 extra-natal movements between home ranges after leaving nest areas. In the second and third springs, distances moved from winter focal points by birds that paired were the same or less than for unpaired birds. No post-nuptial movement exceeded 2 km. 3. Initiation of early ex-natal dispersal was enhanced by presence of many sibs, but also by lack of worm-rich loam soils. Distances travelled were greatest for birds from small broods and with relatively little short grass-feeding habitat near the nest. Later movements were generally enhanced by the absence of loam soils and short grassland, especially with abundance of other buzzards and probable poor feeding habitats (heathland, long grass). 4. Buzzards tended to persist in their first autumn where arable land was abundant, but subsequently showed a strong tendency to move from this habitat. 5. Factors that acted most strongly in ½-km buffers round nests, or round subsequent focal points, usually promoted movement compared with factors acting at a larger scale. Strong relationships between movement distances and environmental characteristics in ½-km buffers, especially during early ex-natal dispersal, suggested that buzzards became primed by these factors to travel far. 6. Movements were also farthest for buzzards that had already moved far from their natal nests, perhaps reflecting genetic predisposition, long-term priming or poor habitat beyond the study area

Land change dynamics: insights from Intensity Analysis applied to an African emerging city

Land change in Kigali, Rwanda, is examined using Intensity Analysis, which measures the temporal stationarity of changes among categories. Maps for 1981, 2002 and 2014 were produced that show the land categories Built, Vegetated and Other, which is composed mainly of croplands and bare surfaces. Land change accelerated from the first time interval (1981–2002) to the second time interval (2002–2014), as increased human and economic activities drove land transformation. During the first interval, Vegetated showed net loss whereas Built showed net gain, in spite of a small transition directly from Vegetated to Built. During the second interval, Vegetated showed net gain whereas Built showed nearly equal amounts of gross loss and gross gain. The gain of Built targeted Other during both time intervals. A substantial portion of overall change during both time intervals consisted of simultaneous transitions from Vegetated to Other in some locations and from Other to Vegetated in other locations