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.

Oscillatory Shear Flow-Induced Alignment of Lamellar Melts of Hydrogen-Bonded Comb Copolymer Supramolecules

In this work we present the orientational behavior of comb copolymer-like supramolecules P4VP(PDP)1.0, obtained by hydrogen bonding between poly(4-vinylpyridine) and pentadecylphenol, during large-amplitude oscillatory shear flow experiments over a broad range of frequencies (0.001-10 Hz). The alignment diagram, presenting the macroscopic alignment in T/TODT vs ω/ωc, contains three regions of parallel alignment separated by a region of perpendicular alignment. For our material, the order-disorder temperature TODT = 67 °C and ωc, the frequency above which the distortion of the chain conformation dominates the materials’ viscoelasticity, is around 0.1 Hz at 61 °C. For the first time flipping from a pure transverse alignment via biaxial transverse/perpendicular alignment to a perpendicular alignment as a function of the strain amplitude was found.

Green areas around homes reduce atopic sensitization in children

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Nanosheet formation by an anionic surfactant-like peptide and modulation of self-assembly through ionic complexation

The surfactant-like peptide (Ala)6-(Asp) (A6D) is shown to self-assemble into ultrathin (3 nm thick) nanosheets in aqueous solution above a critical aggregation concentration. A combination of circular dichroism and FTIR spectroscopy and X-ray diffraction shows that the nanosheets comprise interdigitated bilayers of the peptide with β-sheet conformation. The self-assembly can be modulated by addition of hexamethylenediamine which is expected to interact with the anionic C terminus (and C-terminal D residue) of the peptide. Multiple ordered nanostructures can be accessed depending on the amount of added diamine. Nanosheet and bicontinuous network structures were observed using cryogenic-TEM and small-angle X-ray scattering. Addition of hexamethylenediamine at a sufficiently large molar ratio leads to disruption of the ordered nanostructure and the formation of a solution of A6D–diamine molecular complexes with highly charged end groups. The multiple acid-functionalized nanostructures that are accessible in this system are expected to have many applications in the fabrication of new nanomaterials

Self-assembly of the toll-like receptor agonist macrophage-activating lipopeptide MALP-2 and of its constituent peptide

The self-assembly of the macrophage-activating lipopeptide MALP-2 in aqueous solution has been investigated and is compared to that of the constituent peptide GNNDESNISFKEK. MALP-2 is a toll-like receptor agonist lipopeptide with diverse potential biomedical applications and its self-assembly has not previously been examined. It is found to self-assemble, above a critical aggregation concentration (cac), into remarkable “fibre raft” structures, based on lateral aggregation of β-sheet based bilayer tapes. Peptide GNNDESNISFKEK also forms β-sheet structures above a cac, although the morphology is distinct, comprising highly extended and twisted tape structures. A detailed insight into the molecular packing within the MALP-2 raft and GNNDESNISFKEK nanotape structures is obtained through X-ray diffraction and small-angle X-ray scattering. These results point to the significant influence of the attached lipid chains on the self-assembly motif, which lead to the raft structure for the lipopeptide assemblies

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

Self-assembly of telechelic tyrosine end-capped PEO and poly(alanine) polymers in aqueous solution

The self-assembly in aqueous solution of three novel telechelic conjugates comprising a central hydrophilic polymer and short (trimeric or pentameric) tyrosine end-caps has been investigated. Two of the conjugates have a central poly(oxyethylene) (polyethylene oxide, PEO) central block with different molar masses. The other conjugate has a central poly(l-alanine) (PAla) sequence in a purely amino-acid based conjugate. All three conjugates self-assemble into β-sheet based fibrillar structures, although the fibrillar morphology revealed by cryogenic-TEM is distinct for the three polymers—in particular the Tyr5-PEO6k-Tyr5 forms a population of short straight fibrils in contrast to the more diffuse fibril aggregates observed for Tyr5-PEO2k-Tyr5 and Tyr3-PAla-Tyr3. Hydrogel formation was not observed for these samples (in contrast to prior work on related systems) up to quite high concentrations, showing that it is possible to prepare solutions of peptide–polymer-peptide conjugates with hydrophobic end-caps without conformational constraints associated with hydrogelation. The Tyr5-PEO6k-Tyr5 shows significant PEO crystallization upon drying in contrast to the Tyr5-PEO2k-Tyr5 conjugate. Our findings point to the remarkable ability of short hydrophobic peptide end groups to modulate the self-assembly properties of polymers in solution in model peptide-capped “associative polymers”. Retention of fluidity at high conjugate concentration may be valuable in potential future applications of these conjugates as bioresponsive or biocompatible materials, for example exploiting the enzyme-responsiveness of the tyrosine end-group

Effects of phenotypic variation on consumer coexistence and prey community structure

A popular idea in ecology is that trait variation among individuals from the same species may promote the coexistence of competing species. However, theoretical and empirical tests of this idea have yielded inconsistent findings. We manipulated intraspecific trait diversity in a ciliate competing with a nematode for bacterial prey in experimental microcosms. We found that intraspecific trait variation inverted the original competitive hierarchy to favour the consumer with variable traits, ultimately resulting in competitive exclusion. This competitive outcome was driven by foraging traits (size, speed and directionality) that increased the ciliate's fitness ratio and niche overlap with the nematode. The interplay between consumer trait variation and competition resulted in non-additive cascading effects-mediated through prey defence traits-on prey community assembly. Our results suggest that predicting consumer competitive population dynamics and the assembly of prey communities will require understanding the complexities of trait variation within consumer species.Peer reviewe

Ethnobotanical knowledge is vastly under-documented in northwestern South America

A main objective of ethnobotany is to document traditional knowledge about plants before it disappears. However, little is known about the coverage of past ethnobotanical studies and thus about how well the existing literature covers the overall traditional knowledge of different human groups. To bridge this gap, we investigated ethnobotanical data-collecting efforts across four countries (Colombia, Ecuador, Peru, Bolivia), three ecoregions (Amazon, Andes, Chocó), and several human groups (including Amerindians, mestizos, and Afro-Americans). We used palms (Arecaceae) as our model group because of their usefulness and pervasiveness in the ethnobotanical literature. We carried out a large number of field interviews (n = 2201) to determine the coverage and quality of palm ethnobotanical data in the existing ethnobotanical literature (n = 255) published over the past 60 years. In our fieldwork in 68 communities, we collected 87,886 use reports and documented 2262 different palm uses and 140 useful palm species. We demonstrate that traditional knowledge on palm uses is vastly under-documented across ecoregions, countries, and human groups. We suggest that the use of standardized data-collecting protocols in wide-ranging ethnobotanical fieldwork is a promising approach for filling critical information gaps. Our work contributes to the Aichi Biodiversity Targets and emphasizes the need for signatory nations to the Convention on Biological Diversity to respond to these information gaps. Given our findings, we hope to stimulate the formulation of clear plans to systematically document ethnobotanical knowledge in northwestern South America and elsewhere before it vanishesThis study was funded by the European Union, 7th Framework Programme (contract no. 212631), the Russel E. Train Education for Nature Program of the WWF (to NPZ), the Anne S. Chatham fellowship of the Garden Club of America (to NPZ), and the Universidad Autónoma de Madrid travel grants programme (to RCL

First record of promops davisoni (Thomas, 1921) (chiroptera, molossidae) from Chile and a description of its echolocation calls

[Primer registro de promops davisoni (Thomas, 1921) (chiroptera, molossidae) en Chile, y des-cripción de sus llamadas de ecolocación]Few studies have been conducted on the bat fauna of the Arica and Parinacota region, northern Chile. The genus Promops (Gervais, 1855) is a poorly known group of molossid bats, with three species widely distributed in Central and South America. We report for the first time the species Promops davisoni in Chile. Identification was based on echolocation calls obtained at the Azapa and Lluta valleys and compared to reference calls from Tacna, Peru. We report the species as far as 127 km south of the previous published southernmost record in Pampa Alta, Peru. In addition we obtained an individual found at the Anzota caves, near the city of Arica. The species is found on the coast and in the fluvial valleys of Northern Chile, with altitudes ranging from sea level to 822 m a.s.l. We propose that the distribution of P. davisoni may extend further south, to the locality of Tana in the Tarapacá region, based on the capacity of the species to cross distances of over 100 km over large desert areas. With this species, we increase the known bat fauna of Chile to 14 species, and the bat fauna of the Arica and Parinacota region to nine species. © SAREM, 2018.Peer reviewe