Soft effective interactions between weakly charged polyelectrolyte chains

We apply extensive Molecular Dynamics simulations and analytical considerations in order to study the conformations and the effective interactions between weakly charged, flexible polyelectrolyte chains in salt-free conditions. We focus on charging fractions lying below 20%, for which case there is no Manning condensation of counterions and the latter can be thus partitioned in two states: those that are trapped within the region of the flexible chain and the ones that are free in the solution. We examine the partition of counterions in these two states, the chain sizes and the monomer distributions for various chain lengths, finding that the monomer density follows a Gaussian shape. We calculate the effective interaction between the centers of mass of two interacting chains, under the assumption that the chains can be modeled as two overlapping Gaussian charge profiles. The analytical calculations are compared with measurements from Molecular Dynamics simulations. Good quantitative agreement is found for charging fractions below 10%, where the chains assume coil-like configurations, whereas deviations develop for charge fraction of 20%, in which case a conformational transition of the chain towards a rodlike configuration starts to take place.Comment: 38 pages, 12 figures, 2 tables. Revised version of the manuscript. Selected for publication in the V\irtual Journal of Biological Physics Research, issue of 1 september, 200

Influence of anti- and prooxidants on rhizogenesis from hypocotyls of Mesembryanthemum crystallinum L. cultured in vitro

The enrichment with antioxidants (glutathione or ascorbate) or prooxidants (alloxan, methylviologen, hydrogen peroxide) of root inducing medium significantly decreased rhizogenesis frequency (alloxan, hydrogen peroxide) or inhibited roots regeneration (ascorbate, methylviologen) during the in vitro culture of Mesembryanthemum crystallinum L. hypocotyls. The adventitious roots morphology, root hairs length and density, was also influenced. Changes in the rhizogenesis course were related to the differences in hydrogen peroxide concentration during following days of culture between explants exhibiting morphogenic potential and those without the ability to form adventitious roots. In explants with morphogenic potential, rhizogenesis induction was always accompanied by a high level of hydrogen peroxide followed by the decrease in H_{2}O_{2} content in following days. In contrast, in the explants without regeneration potential, the level of hydrogen peroxide was increasing during the culture period. Activity patterns of superoxide dismutase (SOD) and guaiacol peroxidase (POX) in the following days of culture were similar in the explants exhibiting regeneration potential cultured on different media. Total activity of SOD decreased during initial days of culture and then increased due to the activation of additional SOD isoform described as MnSODII. The activity of POX was low during the rhizogenesis induction, and then increased during following days of culture; the increase was correlated with the decrease in hydrogen peroxide content. In the explants without the ability to regenerate roots, the total activity of SOD was low throughout the whole culture period, whereas the POX activity was significantly higher than in hypocotyls with regeneration potential. It might be concluded that the increase in hydrogen peroxide during initial stages of rhizogenesis and the induction of MnSODII are prerequisites for adventitious roots formation from hypocotyls of M. crystallinum, independently in the presence of anti- or prooxidant in the culture medium

Semigroups of partial transformations with kernel and image restricted by an equivalence

For an arbitrary set X and an equivalence relation μ on X, denote by Pμ(X) the semigroup of partial transformations α on X such that xμ⊆x(ker(α)) for every x∈dom(α), and the image of α is a partial transversal of μ. Every transversal K of μ defines a subgroup G=GK of Pμ(X). We study subsemigroups ⟨G,U⟩ of Pμ(X) generated by G∪U, where U is any set of elements of Pμ(X) of rank less than |X/μ|. We show that each ⟨G,U⟩ is a regular semigroup, describe Green’s relations and ideals in ⟨G,U⟩, and determine when ⟨G,U⟩ is an inverse semigroup and when it is a completely regular semigroup. For a finite set X, the top J-class J of Pμ(X) is a right group. We find formulas for the ranks of the semigroups J, G∪I, J∪I, and I, where I is any proper ideal of Pμ(X).authorsversionpublishe

Fluid-fluid demixing transitions in colloid--polyelectrolyte star mixtures

We derive effective interaction potentials between hard, spherical colloidal particles and star-branched polyelectrolytes of various functionalities and smaller size than the colloids. The effective interactions are based on a Derjaguin-like approximation, which is based on previously derived potentials acting between polyelectrolyte stars and planar walls. On the basis of these interactions we subsequently calculate the demixing binodals of the binary colloid--polyelectrolyte star mixture, employing standard tools from liquid-state theory. We find that the mixture is indeed unstable at moderately high overall concentrations. The system becomes more unstable with respect to demixing as the star functionality and the size ratio grow.Comment: 24 pages, 9 figures, submitted to Journal of Physics: Condensed Matte

Triazolophostins: a library of novel and potent agonists of IP3 receptors.

IP3 receptors are channels that mediate the release of Ca(2+) from the intracellular stores of cells stimulated by hormones or neurotransmitters. Adenophostin A (AdA) is the most potent agonist of IP3 receptors, with the β-anomeric adenine contributing to the increased potency. The potency of AdA and its stability towards the enzymes that degrade IP3 have aroused interest in AdA analogs for biological studies. The complex structure of AdA poses problems that have necessitated optimization of synthetic conditions for each analog. Such lengthy one-at-a-time syntheses limit access to AdA analogs. We have addressed this problem by synthesizing a library of triazole-based AdA analogs, triazolophostins, by employing click chemistry. An advanced intermediate having all the necessary phosphates and a β-azide at the anomeric position was reacted with various alkynes under Cu(i) catalysis to yield triazoles, which upon deprotection gave triazolophostins. All eleven triazolophostins synthesized are more potent than IP3 and some are equipotent with AdA in functional analyses of IP3 receptors. We show that a triazole ring can replace adenine without compromising the potency of AdA and provide facile routes to novel AdA analogs.A. M. V. thanks the University Grants Commission (UGC) India for a Senior Research Fellowship (SRF) during this work. K. M. S. thanks the Department of Science and Technology (DST) India for Swarnajayanti Fellowship, Ramanujan Fellowship and for financial support. C. W. T. and V. K. were supported by the Wellcome Trust, Biotechnology and Biological Sciences Research Council, and the German Academic Exchange Service (V. K.).This is the final published version. It first appeared at http://dx.doi.org/10.1039/C5OB00440

Polyelectrolyte stars in planar confinement

We employ monomer-resolved Molecular Dynamics simulations and theoretical considerations to analyze the conformations of multiarm polyelectrolyte stars close to planar, uncharged walls. We identify three mechanisms that contribute to the emergence of a repulsive star-wall force, namely: the confinement of the counterions that are trapped in the star interior, the increase in electrostatic energy due to confinement as well as a novel mechanism arising from the compression of the stiff polyelectrolyte rods approaching the wall. The latter is not present in the case of interaction between two polyelectrolyte stars and is a direct consequence of the impenetrable character of the planar wall.Comment: 34 pages, 8 figures. Revised version of the manuscript. To appear in J. Chem. Phys. May, 200

Determining protein similarity by comparing hydrophobic core structure

Formal assessment of structural similarity is − next to protein structure prediction − arguably the most important unsolved problem in proteomics. In this paper we propose a similarity criterion based on commonalities between the proteins’ hydrophobic cores. The hydrophobic core emerges as a result of conformational changes through which each residue reaches its intended position in the protein body. A quantitative criterion based on this phenomenon has been proposed in the framework of the CASP challenge. The structure of the hydrophobic core − including the placement and scope of any deviations from the idealized model − may indirectly point to areas of importance from the point of view of the protein’s biological function. Our analysis focuses on an arbitrarily selected target from the CASP11 challenge. The proposed measure, while compliant with CASP criteria (70–80% correlation), involves certain adjustments which acknowledge the presence of factors other than simple spatial arrangement of solids

Sexual Dimorphism of Staminate- and Pistillate-Phase Flowers of Saponaria officinalis (Bouncing Bet) Affects Pollinator Behavior and Seed Set

The sequential separation of male and female function in flowers of dichogamous species allows for the evolution of differing morphologies that maximize fitness through seed siring and seed set. We examined staminate- and pistillate-phase flowers of protandrous Saponaria officinalis for dimorphism in floral traits and their effects on pollinator attraction and seed set. Pistillate-phase flowers have larger petals, greater mass, and are pinker in color, but due to a shape change, pistillate-phase flowers have smaller corolla diameters than staminate-phase flowers. There was no difference in nectar volume or sugar content one day after anthesis, and minimal evidence for UV nectar guide patterns in staminate- and pistillate-phase flowers. When presented with choice arrays, pollinators discriminated against pistillate-phase flowers based on their pink color. Finally, in an experimental garden, in 2012 there was a negative correlation between seed set of an open-pollinated, emasculated flower and pinkness (as measured by reflectance spectrometry) of a pistillate-phase flower on the same plant in plots covered with shade cloth. In 2013, clones of genotypes chosen from the 2012 plants that produced pinker flowers had lower seed set than those from genotypes with paler flowers. Lower seed set of pink genotypes was found in open-pollinated and hand-pollinated flowers, indicating the lower seed set might be due to other differences between pink and pale genotypes in addition to pollinator discrimination against pink flowers. In conclusion, staminate- and pistillate-phase flowers of S. officinalis are dimorphic in shape and color. Pollinators discriminate among flowers based on these differences, and individuals whose pistillate-phase flowers are most different in color from their staminate-phase flowers make fewer seeds. We suggest morphological studies of the two sex phases in dichogamous, hermaphroditic species can contribute to understanding the evolution of sexual dimorphism in plants without the confounding effects of genetic differences between separate male and female individuals

High speed electric motors based on high performance novel soft magnets

Novel Co-based soft magnetic materials are presented as a potential substitute for electrical steels in high speed motors for current industry applications. The low losses, high permeabilities, and good mechanical strength of these materials enable application in high rotational speed induction machines. Here, we present a finite element analysis of Parallel Path Magnetic Technology rotating motors constructed with both silicon steel and Co-based nanocomposite. The later achieved a 70% size reduction and an 83% reduction on NdFeB magnet volume with respect to a similar Si-steel design.Fil: Silveyra, Josefina María. Universidad de Buenos Aires. Facultad de Ingenieria. Departamento de Fisica. Laboratorio de Sólidos Amorfos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Tecnologías y Ciencias de la Ingeniería; Argentina; ArgentinaFil: Leary, A. M.. University Of Carnegie Mellon; Estados UnidosFil: DeGeorge, V.. University Of Carnegie Mellon; Estados UnidosFil: Simizu, S.. Advanced Materials Corporation; Estados UnidosFil: McHenry, M. E.. University Of Carnegie Mellon; Estados Unido