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.

Aqueous Self-Assembly of a Protein-Mimetic Ampholytic Block Copolypeptide

This report describes the aggregation behavior of an ABC-type ampholytic block copolypeptide, poly(ethylene oxide)-block-poly(l-lysine)-block-poly(l-glutamate), in aqueous media in dependence of pH. Polypeptide secondary structures and self-assemblies are investigated by circular dichroism (CD), Fourier transform infrared (FT-IR) and NMR spectroscopy, zeta potential measurements, analytical ultracentrifugation (AUC), dynamic/static light scattering (DLS/SLS), and cryogenic transmission electron microscopy (cryo-TEM). The polymer chains tend to form vesicles when the hydrophobic polypeptide helix is located at the chain end (acidic pH) and are existing as single chains when it is located in the center and flanked by the two hydrophilic segments (basic pH). Precipitation occurs in the intermediate pH range due to polyion complexation of the charged polypeptide segments

Large scale interaction analysis predicts that the Gerbera hybrida floral E function is provided both by general and specialized proteins

BACKGROUND:The ornamental plant Gerbera hybrida bears complex inflorescences with morphologically distinct floral morphs that are specific to the sunflower family Asteraceae. We have previously characterized several MADS box genes that regulate floral development in Gerbera. To study further their behavior in higher order complex formation according to the quartet model, we performed yeast two- and three-hybrid analysis with fourteen Gerbera MADS domain proteins to analyze their protein-protein interaction potential.RESULTS:The exhaustive pairwise interaction analysis showed significant differences in the interaction capacity of different Gerbera MADS domain proteins compared to other model plants. Of particular interest in these assays was the behavior of SEP-like proteins, known as GRCDs in Gerbera. The previously described GRCD1 and GRCD2 proteins, which are specific regulators involved in stamen and carpel development, respectively, showed very limited pairwise interactions, whereas the related GRCD4 and GRCD5 factors displayed hub-like positions in the interaction map. We propose GRCD4 and GRCD5 to provide a redundant and general E function in Gerbera, comparable to the SEP proteins in Arabidopsis. Based on the pairwise interaction data, combinations of MADS domain proteins were further subjected to yeast three-hybrid assays. Gerbera B function proteins showed active behavior in ternary complexes. All Gerbera SEP-like proteins with the exception of GRCD1 were excellent partners for B function proteins, further implicating the unique role of GRCD1 as a whorl- and flower-type specific C function partner.CONCLUSIONS:Gerbera MADS domain proteins exhibit both conserved and derived behavior in higher order protein complex formation. This protein-protein interaction data can be used to classify and compare Gerbera MADS domain proteins to those of Arabidopsis and Petunia. Combined with our reverse genetic studies of Gerbera, these results reinforce the roles of different genes in the floral development of Gerbera. Building up the elaborate capitulum of Gerbera calls for modifications and added complexity in MADS domain protein behavior compared to the more simple flowers of, e.g., Arabidopsis.Peer reviewe

Differences in topographic and soil habitat specialization between trees and two understorey plant groups in a Costa Rican lowland rain forest

Two core questions in plant community ecology are to what extent the distributions of species are structured by local environmental conditions, and whether taxa differ in this regard. We compared the distributions of trees, Melastomataceae and ferns on soil and topographic gradients in a Costa Rican lowland rain forest (trees and ferns 983 plots, Melastomataceae 277 plots). To test whether these plant groups differed in the prevalence or type of habitat specialization, we calculated species' environmental optima and tolerances on each gradient. Habitat specialization was defined as a significantly biased optimum, or a narrow tolerance, relative to values obtained under spatially restricted randomizations of species occurrences. Within plant groups, we also asked whether the dispersion of species optima differed from random expectation on each gradient. Fern optima were over-dispersed on multiple gradients, implying considerable interspecific habitat partitioning, and tree optima were over-dispersed in relation to topographic position. Habitat specialization was more prevalent in the two predominantly understorey groups than in trees (75% of Melastomataceae species, 81-87% of ferns, 57-58% of trees). Species optima of Melastomataceae and ferns also tended towards lower landscape positions than did those of trees, perhaps reflecting a higher proportion of drought-sensitive species in these two groups

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.

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.

Restructuring of lipid membranes by an arginine-capped peptide bolaamphiphile

We study the self-assembly of arginine-capped bolaamphiphile peptide RA3R (A: alanine, R: arginine) together with its binding to model membranes and its cytotoxicity and antimicrobial activity. Anionic 2-oleoyl-1-palmitoyl-sn-glycero-3-phospho-rac-(1-glycerol) sodium salt/2-oleoyl-1-palmitoyl-sn-glycero-3-phosphoethanolamine (POPG/POPE) vesicles and zwitterionic 1,2-dioleoyl-sn-glycero-3-phosphocholine/2-oleoyl-1-palmitoyl-sn-glycero-3-phosphocholine (POPC/DOPC) vesicles are used as model membranes to mimic bacterial and mammalian cell membranes, respectively. We show that RA3R adopts a polyproline-II collagen-like conformation in water. Binding of RA3R to POPG/POPE vesicles induces a strong correlation between the lipid bilayers, driven by RA3R/POPG attractive electrostatic interaction together with a shift of the intramolecular POPE zwitterionic interaction toward an attractive electrostatic interaction with the RA3R. Populations of RA3R/POPG/POPE vesicles comprise different bilayer spacings, dA and dB, controlled by the conformation of the lipid chains corresponding to the Lβ (gel-like) and Lα (liquid-crystal) phases, respectively. Cryo-TEM images reveal the presence of vesicles with no internal structure, compartmentalized thin-wall vesicles, or multilayer vesicles with uncorrelated layers and compartmentalization depending on the RA3R/POPG/POPE composition. In contrast, the interaction of RA3R with multilamellar POPC/DOPC vesicles leads to the decorrelation of the lipid bilayers. RA3R was tolerated by skin fibroblast cells for a concentration up to 0.01 wt %, while 0.25 wt % RA3R proved to be an efficient antibacterial agent against Gram-positive bacteria L. monocytogenes. Our results highlight the ability of RA3R to distinguish between bacterial and mammalian cells and establish this peptide as a candidate to reduce the proliferation of L. monocytogenes bacteria

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

Weight concerns as a predictor of smoking cessation according to nicotine dependence : A population-based study

Background: Nicotine-dependent smokers find it difficult to quit smoking. Additionally, smoking-specific weight concerns may affect smoking cessation although the evidence is controversial. We investigated whether smoking-specific weight concerns predict the probability of cessation and, if so, whether the effect varies according to the level of nicotine dependence. Methods: The study was conducted with a population-based sample of 355 adult daily smokers who participated in the baseline examination in 2007 and in the 2014 follow-up. Baseline nicotine dependence was classified as low or high (Fagerstrom Test for Nicotine Dependence; 0-3 vs. 4-10 points). Within these groups, we examined whether baseline weight concerns predict smoking status (daily, occasional, ex-smoker) at follow-up by using multinomial logistic regression with adjustment for multiple covariates. Results: Among low-dependent participants at baseline, 28.5% had quit smoking, while among highly dependent participants 26.1% had quit smoking. The interaction between weight concerns and nicotine dependence on follow-up smoking status was significant. Among participants with low nicotine dependence per the fully adjusted model, greater weight concerns predicted a lower likelihood of both smoking cessation (relative risk ratio 0.93 [95% CI 0.87-1.00]) and smoking reduction to occasional occurrence (0.89 [95% CI 0.81-0.98]). Weight concerns were not associated with follow-up smoking status among participants with high nicotine dependence. Conclusions: Weight concerns are associated with a smaller likelihood of quitting among smokers with low nicotine dependence. Weight concerns should be addressed in smoking cessation interventions, especially with smokers who have low nicotine dependence.Peer reviewe