Domains in Melts of Comb-Coil Diblock Copolymers: Superstrong Segregation Regime

Conditions for the crossover from the strong to the superstrong segregation regime are analyzed for the case of comb-coil diblock copolymers. It is shown that the critical interaction energy between the components required to induce the crossover to the superstrong segregation regime is inversely proportional to mb = 1 + n/m, where n is the degree of polymerization of the side chain and m is the distance between successive grafting points. As a result, the superstrong segregation regime, being rather rare in the case of ordinary block copolymers, has a much better chance to be realized in the case of diblock copolymers with combs grafted to one of the blocks.

Self-Assembly of Supramolecular Triblock Copolymer Complexes

Four different poly(tert-butoxystyrene)-b-polystyrene-b-poly(4-vinylpyridine) (PtBOS-b-PS-b-P4VP) linear triblock copolymers, with the P4VP weight fraction varying from 0.08 to 0.39, were synthesized via sequential anionic polymerization. The values of the unknown interaction parameters between styrene and tert-butoxystyrene and between tert-butoxystyrene and 4-vinylpyridine were determined from random copolymer blend miscibility studies and found to satisfy 0.031<χS,tBOS<0.034 and 0.39<χ4VP,tBOS<0.43, the latter being slightly larger than the known 0.30<χS,4VP≤0.35 value range. All triblock copolymers synthesized adopted a P4VP/PS core/shell cylindrical self-assembled morphology. From these four triblock copolymers supramolecular complexes were prepared by hydrogen bonding a stoichiometric amount of pentadecylphenol (PDP) to the P4VP blocks. Three of these complexes formed a triple lamellar ordered state with additional short length scale ordering inside the P4VP(PDP) layers. The self-assembled state of the supramolecular complex based on the triblock copolymer with the largest fraction of P4VP consisted of alternating layers of PtBOS and P4VP(PDP) layers with PS cylinders inside the latter layers. The difference in morphology between the triblock copolymers and the supramolecular complexes is due to two effects: (i) a change in effective composition and, (ii) a reduction in interfacial tension between the PS and P4VP containing domains. The small angle X-ray scattering patterns of the supramolecules systems are very temperature sensitive. A striking feature is the disappearance of the first order scattering peak of the triple lamellar state in certain temperature intervals, while the higher order peaks (including the third order) remain. This is argued to be due to the thermal sensitivity of the hydrogen bonding and thus directly related to the very nature of these systems.

Green areas around homes reduce atopic sensitization in children

Peer reviewe

Self-assembly in solution of a reversible comb-shaped supramolecular polymer

We report a single step synthesis of a polyisobutene with a bis-urea moiety in the middle of the chain. In low polarity solvents, this polymer self-assembles by hydrogen bonding to form a combshaped polymer with a central hydrogen bonded backbone and polyisobutene arms. The comb backbone can be reversibly broken, and consequently, its length can be tuned by changing the solvent, the concentration or the temperature. Moreover, we have proved that the bulkiness of the side-chains have a strong influence on both the self-assembly pattern and the length of the backbone. Finally, the density of arms can be reduced, by simply mixing with a low molar mass bis-urea

A compositional turnover zone of biogeographical magnitude within lowland Amazonia

Aim To assess the relative roles of geologically defined terrain types ( environmental heterogeneity) and a major river ( physical dispersal barrier) as predictors of ecological structuring and biogeographical differentiation within Amazonian forests.Location Western Brazilian Amazonia, where the Jurua river and its terraces cross a 1000-km-long boundary between two geological formations ( the Solimoes and Ica Formations).Methods We sampled a 500-km stretch of the Jurua with 71 transects ( 5 m by 500 m) that spanned both the river and the geological boundary. All transects were inventoried for pteridophytes ( ferns and lycophytes) and Melastomataceae, and a subset of 39 transects also for palms and Zingiberales. Three surface soil samples were collected from each transect. The data were analysed using ordinations, regression trees, indicator species analyses and Mantel tests.Results All plant groups showed congruent species turnover between geologically defined terrain types, but little evidence of isolation by the river or geographical distance. Soil cation concentration differed between the Solimoes Formation and other terrain types and emerged as the main explanatory factor for species turnover. A large proportion of the plant species were significant indicators for specific parts of the soil cation concentration gradient, and these edaphic associations were congruent with those found in other parts of Amazonia. Pteridophytes had a larger proportion of species in the cation-rich soils than the other plant groups did, and palms had a higher proportion of generalists.Main conclusions The geological boundary between the Solimoes and Ica formations is confirmed as significant floristic turnover zone. As it runs in a north-south orientation for more than 1000 km, the edaphic differences associated with this boundary have wide-ranging implications for speciation and biogeographical patterns in Amazonia

Testing main Amazonian rivers as barriers across time and space within widespread taxa

AimPresent Amazonian diversity patterns can result from many different mechanisms and, consequently, the factors contributing to divergence across regions and/or taxa may differ. Nevertheless, the riverâ barrier hypothesis is still widely invoked as a causal process in divergence of Amazonian species. Here we use modelâ based phylogeographic analyses to test the extent to which major Amazonian rivers act similarly as barriers across time and space in two broadly distributed Amazonian taxa.LocalAmazon rain forest.TaxonThe lizard Gonatodes humeralis (Sphaerodactylidae) and the tree frog Dendropsophus leucophyllatus (Hylidae).MethodsWe obtained RADseq data for samples distributed across main river barriers, representing main Areas of Endemism previously proposed for the region. We conduct modelâ based phylogeographic and genetic differentiation analyses across each population pair.ResultsMeasures of genetic differentiation (based on FST calculated from genomic data) show that all rivers are associated with significant genetic differentiation. Parameters estimated under investigated divergence models showed that divergence times for populations separated by each of the 11 bordering rivers were all fairly recent. The degree of differentiation consistently varied between taxa and among rivers, which is not an artifact of any corresponding difference in the genetic diversities of the respective taxa, or to amounts of migration based on analyses of the siteâ frequency spectrum.Main conclusionsTaken together, our results support a dispersal (rather than vicariance) history, without strong evidence of congruence between these species and rivers. However, once a species crossed a river, populations separated by each and every river have remained isolatedâ in this sense, rivers act similarly as barriers to any further gene flow. This result suggests differing degrees of persistence and gives rise to the seeming contradiction that the divergence process indeed varies across time, space and species, even though major Amazonian rivers have acted as secondary barriers to gene flow in the focal taxa.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/152608/1/jbi13676_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/152608/2/jbi13676.pd

Evolution within a language: environmental differences contribute to divergence of dialect groups

Background: The processes leading to the diversity of over 7000 present-day languages have been the subject of scholarly interest for centuries. Several factors have been suggested to contribute to the spatial segregation of speaker populations and the subsequent linguistic divergence. However, their formal testing and the quantification of their relative roles is still missing. We focussed here on the early stages of the linguistic divergence process, that is, the divergence of dialects, with a special focus on the ecological settings of the speaker populations. We adopted conceptual and statistical approaches from biological microevolution and parallelled intra-lingual variation with genetic variation within a species. We modelled the roles of geographical distance, differences in environmental and cultural conditions and in administrative history on linguistic divergence at two different levels: between municipal dialects (cf. in biology, between individuals) and between dialect groups (cf. in biology, between populations).Results: We found that geographical distance and administrative history were important in separating municipal dialects. However, environmental and cultural differences contributed markedly to the divergence of dialect groups. In biology, increase in genetic differences between populations together with environmental differences may suggest genetic differentiation of populations through adaptation to the local environment. However, our interpretation of this result is not that language itself adapts to the environment Instead, it is based on Homo sapiens being affected by its environment, and its capability to adapt culturally to various environmental conditions. The differences in cultural adaptations arising from environmental heterogeneity could have acted as nonphysical barriers and limited the contacts and communication between groups. As a result, linguistic differentiation may emerge over time in those speaker populations which are, at least partially, separated.Conclusions: Given that the dialects of isolated speaker populations may eventually evolve into different languages, our result suggests that cultural adaptation to local environment and the associated isolation of speaker populations have contributed to the emergence of the global patterns of linguistic diversity

Using digital soil maps to infer edaphic affinities of plant species in Amazonia: Problems and prospects

Amazonia combines semi-continental size with difficult access, so both current ranges of species and their ability to cope with environmental change have to be inferred from sparse field data. Although efficient techniques for modeling species distributions on the basis of a small number of species occurrences exist, their success depends on the availability of relevant environmental data layers. Soil data are important in this context, because soil properties have been found to determine plant occurrence patterns in Amazonian lowlands at all spatial scales. Here we evaluate the potential for this purpose of three digital soil maps that are freely available online: SOTERLAC, HWSD, and SoilGrids. We first tested how well they reflect local soil cation concentration as documented with 1,500 widely distributed soil samples. We found that measured soil cation concentration differed by up to two orders of magnitude between sites mapped into the same soil class. The best map-based predictor of local soil cation concentration was obtained with a regression model combining soil classes from HWSD with cation exchange capacity (CEC) from SoilGrids. Next, we evaluated to what degree the known edaphic affinities of thirteen plant species (as documented with field data from 1,200 of the soil sample sites) can be inferred from the soil maps. The species segregated clearly along the soil cation concentration gradient in the field, but only partially along the model-estimated cation concentration gradient, and hardly at all along the mapped CEC gradient. The main problems reducing the predictive ability of the soil maps were insufficient spatial resolution and/or georeferencing errors combined with thematic inaccuracy and absence of the most relevant edaphic variables. Addressing these problems would provide better models of the edaphic environment for ecological studies in Amazonia