436 research outputs found

    Solvent fluctuations around solvophobic, solvophilic and patchy nanostructures and the accompanying solvent mediated interactions

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    Using classical density functional theory (DFT) we calculate the density profile ρ(r)\rho({\mathbf r}) and local compressibility χ(r)\chi({\mathbf r}) of a simple liquid solvent in which a pair of blocks with (microscopic) rectangular cross-section are immersed. We consider blocks that are solvophobic, solvophilic and also ones that have both solvophobic and solvophilic patches. Large values of χ(r)\chi({\mathbf r}) correspond to regions in space where the liquid density is fluctuating most strongly. We seek to elucidate how enhanced density fluctuations correlate with the solvent mediated force between the blocks, as the distance between the blocks and the chemical potential of the liquid reservoir vary. For sufficiently solvophobic blocks, at small block separations and small deviations from bulk gas-liquid coexistence, we observe a strongly attractive (near constant) force, stemming from capillary evaporation to form a low density gas-like intrusion between the blocks. The accompanying χ(r)\chi({\mathbf r}) exhibits structure which reflects the incipient gas-liquid interfaces that develop. We argue that our model system provides a means to understanding the basic physics of solvent mediated interactions between nanostructures, and between objects such as proteins in water, that possess hydrophobic and hydrophilic patches.Comment: 19 pages, 21 figure

    The standard mean-field treatment of inter-particle attraction in classical DFT is better than one might expect

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    In classical density functional theory (DFT) the part of the Helmholtz free energy functional arising from attractive inter-particle interactions is often treated in a mean-field or van der Waals approximation. On the face of it, this is a somewhat crude treatment as the resulting functional generates the simple random phase approximation (RPA) for the bulk fluid pair direct correlation function. We explain why using standard mean-field DFT to describe inhomogeneous fluid structure and thermodynamics is more accurate than one might expect based on this observation. By considering the pair correlation function g(x)g(x) and structure factor S(k)S(k) of a one-dimensional model fluid, for which exact results are available, we show that the mean-field DFT, employed within the test-particle procedure, yields results much superior to those from the RPA closure of the bulk Ornstein-Zernike equation. We argue that one should not judge the quality of a DFT based solely on the approximation it generates for the bulk pair direct correlation function.Comment: 9 pages, 3 figure

    Solvent mediated interactions between model colloids and interfaces: A microscopic approach

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    We determine the solvent mediated contribution to the effective potentials for model colloidal or nano- particles dispersed in a binary solvent that exhibits fluid-fluid phase separation. Using a simple density functional theory we calculate the density profiles of both solvent species in the presence of the `colloids', which are treated as external potentials, and determine the solvent mediated (SM) potentials. Specifically, we calculate SM potentials between (i) two colloids, (ii) a colloid and a planar fluid-fluid interface, and (iii) a colloid and a planar wall with an adsorbed wetting film. We consider three different types of colloidal particles: colloid A which prefers the bulk solvent phase rich in species 2, colloid C which prefers the solvent phase rich in species 1, and `neutral' colloid B which has no strong preference for either phase, i.e. the free energies to insert the colloid into either of the coexisting bulk phases are almost equal. When a colloid which has a preference for one of the two solvent phases is inserted into the disfavored phase at statepoints close to coexistence a thick adsorbed `wetting' film of the preferred phase may form around the colloids. The presence of the adsorbed film has a profound influence on the form of the SM potentials.Comment: 17 Pages, 13 Figures. Accepted for publication in Journal of Chemical Physic

    Child Custody Evaluations: Ethical, Scientific, and Practice Considerations

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    Child custody evaluations are among the most difficult of forensic evaluations. The current paper examines differences between custody evaluations and other types of psychological and forensic evaluations. We also discuss important ethical issues regarding these evaluations and review the typical components of a custody evaluation, with particular attention on psychological testing as a component of custody evaluations. We then discuss the role ofresearch in informing the interpretation of the evaluation data and provide a complete sample custody evaluation report to illustrate several points from the manuscript

    Phylogeny of Celastraceae (spindle-tree family) subfamilies Hippocrateoideae and Salacioideae inferred from chloroplast and nuclear genes

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    The phylogeny of Celastraceae (the spindle-tree family) subfamilies Hippocrateoideae and Salacioideae, which include about 360 species of shrubs, trees, and vines in 25 genera, was inferred using plastid (matK, trnL-F) and nuclear (ITS and 26S rDNA) genes. Together, subfamilies Hippocrateoideae and Salacioideae contain all members of the former Hippocrateaceae, which are now recognized as a derived group within Celastraceae sensu stricto. Based on our results, Brassiantha, a monotypic genus endemic to New Guinea, is more closely related to the clade of Dicarpellum (New Caledonia) and Hypsophila (Queensland, Australia) than it is to the former Hippocrateaceae, in contrast to previous studies. This well supported resolution indicates that having a nectary disk positioned outside the stamens has been convergently derived in these two separate lineages. The clade of Kokoona and Lophopetalum was resolved as sister to the clade of Hippocrateoideae, Sarawakodendron, and Salacioideae. This resolution of Kokoona and Lophopetalum supports previous assertions that they are a "transitional link" between Celastraceae sensu stricto and the former Hippocrateaceae. Sarawakodendron, a monotypic genus endemic to Borneo, was resolved as sister to the clade of Salacioideae, which supports earlier assertions that Sarawakodendron is "transitional" between Kokoona, Lophopetalum, and Salacioideae. Based on our inferred phylogeny, arils as mucilaginous pulp are derived within Salacioideae and winged arils may be primitive within the former Hippocrateaceae as a whole. Finally, the former Hippocrateaceae had an Old World, rather than a New World, origin.College Honors

    Interfacial and wetting properties of a binary point Yukawa fluid

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    We investigate the interfacial phase behavior of a binary fluid mixture composed of repulsive point Yukawa particles. Using a simple approximation for the Helmholtz free energy functional, which yields the random phase approximation (RPA) for the pair direct correlation functions, we calculate the equilibrium fluid density profiles of the two species of particles adsorbed at a planar wall. We show that for a particular choice (repulsive exponential) of the wall potentials and the fluid pair-potential parameters, the Euler-Lagrange equations for the equilibrium fluid density profiles may be transformed into a single ordinary differential equation and the profiles obtained by a simple quadrature. For certain other choices of the fluid pair-potential parameters fluid-fluid phase separation of the bulk fluid is observed. We find that when such a mixture is exposed to a planar hard-wall, the fluid exhibits complete wetting on the species 2 poor side of the binodal, i.e. we observe a thick film of fluid rich in species 2 adsorbed at the hard-wall. The thickness of the wetting film grows logarithmically with the concentration difference between the fluid state-point and the binodal and is proportional to the bulk correlation length of the intruding (wetting) fluid phase. However, for state points on the binodal that are further from the critical point, we find there is no thick wetting film. We determine the accompanying line of first-order (pre-wetting) surface phase transitions which separate a thin and thick adsorbed film. We show that for some other choices of repulsive wall potentials the pre-wetting line is still present, but its location and extent in the phase diagram is strongly dependent on the wall-fluid interaction parameters.Comment: 11 pages, 7 figures. Accepted for publication in Journal of Chemical Physic

    Phylogeny of the celastraceae inferred from phytochrome B gene sequence and morphology

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    Phylogenetic relationships within Celastraceae were inferred using a simultaneous analysis of 61 morphological characters and 1123 base pairs of phytochrome B exon 1 from the nuclear genome. No gaps were interred, and the gene tree topology suggests that the primers were specific to a single locus that did not duplicate among the lineages sampled. This region of phytochrome B was most useful for examining relationships among closely related genera. Fifty-one species from 38 genera of Celastraceae were sampled. The Celastraceae sensu lato (including Hippocrateaceae) were resolved as a monophyletic group. Loesener\u27s subfamilies and tribes of Celastraceae were not supported. The Hippocrateaceae were resolved as a monophyletic group nested within a paraphyletic Celastraceae sensu stricto. Goupia was resolved as more closely related to Euphorbiaceae, Corynocarpaceae, and Linaceae than to Celastraceae. Plagiopteron (Flacourtiaceae) was resolved as the sister group of Hippocrateoideae. Brexia (Brexiaceae) was resolved as closely related to Elaeodendron and Pleurostylia. Canotia was resolved as the sister group of Acanthothamus within Celastraceae. Perrottetia and Mortonia were resolved as the sister group of the rest of the Celastraceae. Siphonodon was resolved as a derived member of Celastraceae. Maytenus was resolved as three disparate groups, suggesting that this large genus needs to be recircumscribed
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