Spontaneous Charging and Crystallization of Water Droplets in Oil

We study the spontaneous charging and the crystallization of spherical micron-sized water-droplets dispersed in oil by numerically solving, within a Poisson-Boltzmann theory in the geometry of a spherical cell, for the density profiles of the cations and anions in the system. We take into account screening, ionic Born self-energy differences between oil and water, and partitioning of ions over the two media. We find that the surface charge density of the droplet as induced by the ion partitioning is significantly affected by the droplet curvature and by the finite density of the droplets. We also find that the salt concentration and the dielectric constant regime in which crystallization of the water droplets is predicted is enhanced substantially compared to results based on the planar oil-water interface, thereby improving quantitative agreement with recent experiments.Comment: 10 pages, 7 figures, submitted for publicatio

Ion association in low-polarity solvents: comparisons between theory, simulation, and experiment

The association of ions in electrolyte solutions at very low concentration and low temperature is studied using computer simulations and quasi-chemical ion-pairing theory. The specific case of the restricted primitive model (charged hard spheres) is considered. Specialised simulation techniques are employed that lead to efficient sampling of the arrangements and distributions of clusters and free ions, even at conditions corresponding to nanomolar solutions of simple salts in solvents with dielectric constants in the range 5-10, as used in recent experimental work on charged-colloid sus- pensions. A direct comparison is effected between theory and simulation using a variety of clustering criteria and theoretical approximations. It is shown that conventional distance-based cluster criteria can give erroneous results. A reliable set of theoretical and simulation estimators for the degree of association is proposed. The ion-pairing theory is then compared to experimental results for salt solutions in low-polarity solvents. The agreement is excellent, and on this basis some calculations are made for the screening lengths which will figure in the treatment of colloid-colloid interactions in such solutions. The accord with available experimental results is complete

Liquid-liquid interfacial tension of electrolyte solutions

It is theoretically shown that the excess liquid-liquid interfacial tension between two electrolyte solutions as a function of the ionic strength I behaves asymptotically as O(- I^0.5) for small I and as O(+- I) for large I. The former regime is dominated by the electrostatic potential due to an unequal partitioning of ions between the two liquids whereas the latter regime is related to a finite interfacial thickness. The crossover between the two asymptotic regimes depends sensitively on material parameters suggesting that, depending on the actual system under investigation, the experimentally accessible range of ionic strengths can correspond to either the small or the large ionic strength regime. In the limiting case of a liquid-gas surface where ion partitioning is absent, the image chage interaction can dominate the surface tension for small ionic strength I such that an Onsager-Samaras limiting law O(- I ln(I)) is expected. The proposed picture is consistent with more elaborate models and published measurements.Comment: Accepted for publication in Physical Review Letter

Stability of additive-free water-in-oil emulsions

We calculate ion distributions near a planar oil-water interface within non-linear Poisson-Boltzmann theory, taking into account the Born self-energy of the ions in the two media. For unequal self-energies of cations and anions, a spontaneous charge separation is found such that the water and oil phase become oppositely charged, in slabs with a typical thickness of the Debye screening length in the two media. From the analytical solutions, the corresponding interfacial charge density and the contribution to the interfacial tension is derived, together with an estimate for the Yukawa-potential between two spherical water droplets in oil. The parameter regime is explored where the plasma coupling parameter exceeds the crystallization threshold, i.e. where the droplets are expected to form crystalline structures due to a strong Yukawa repulsion, as recently observed experimentally. Extensions of the theory that we discuss briefly include numerical calculations on spherical water droplets in oil, and analytical calculations of the linear PB-equation for a finite oil-water interfacial width.Comment: 9 pages, 4 figures, accepted by JPCM for proceedings of LMC

Optimality in superselective surface binding by multivalent DNA nanostars

Weak multivalent interactions govern a large variety of biological processes like cell-cell adhesion and virus-host interactions. These systems distinguish sharply between surfaces based on receptor density, known as superselectivity. Earlier experimental and theoretical work provided insights into the control of selectivity: Weak interactions and a high number of ligands facilitate superselectivity. Present experimental studies typically involve tens or hundreds of interactions, resulting in a high entropic contribution leading to high selectivities. However, if, and if so how, systems with few ligands, such as multi-domain proteins and virus binding to a membrane, show superselective behavior is an open question. Here, we address this question with a multivalent experimental model system based on star shaped branched DNA nanostructures (DNA nanostars) with each branch featuring a single stranded overhang that binds to complementary receptors on a target surface. Each DNA nanostar possesses a fluorophore, to directly visualize DNA nanostar surface adsorption by total internal reflection fluorescence microscopy (TIRFM). We observe that DNA nanostars can bind superselectively to surfaces and bind optimally at a valency of three. We quantitatively explain this optimum by extending the current theory with interactions between DNA nanostar binding sites (ligands). Our results add to the understanding of multivalent interactions, by identifying microscopic mechanisms that lead to optimal selectivity, and providing quantitative values for the relevant parameters. These findings inspire additional design rules which improve future work on selective targeting in directed drug delivery.Comment: 14 pages, 4 figure

The sediment of mixtures of charged colloids: segregation and inhomogeneous electric fields

We theoretically study sedimentation-diffusion equilibrium of dilute binary, ternary, and polydisperse mixtures of colloidal particles with different buoyant masses and/or charges. We focus on the low-salt regime, where the entropy of the screening ions drives spontaneous charge separation and the formation of an inhomogeneous macroscopic electric field. The resulting electric force lifts the colloids against gravity, yielding highly nonbarometric and even nonmonotonic colloidal density profiles. The most profound effect is the phenomenon of segregation into layers of colloids with equal mass-per-charge, including the possibility that heavy colloidal species float onto lighter ones

Sedimentation of binary mixtures of like- and oppositely charged colloids: the primitive model or effective pair potentials?

We study sedimentation equilibrium of low-salt suspensions of binary mixtures of charged colloids, both by Monte Carlo simulations of an effective colloids-only system and by Poisson-Boltzmann theory of a colloid-ion mixture. We show that the theoretically predicted lifting and layering effect, which involves the entropy of the screening ions and a spontaneous macroscopic electric field [J. Zwanikken and R. van Roij, Europhys. Lett. {\bf 71}, 480 (2005)], can also be understood on the basis of an effective colloid-only system with pairwise screened-Coulomb interactions. We consider, by theory and by simulation, both repelling like-charged colloids and attracting oppositely charged colloids, and we find a re-entrant lifting and layering phenomenon when the charge ratio of the colloids varies from large positive through zero to large negative values

Dynamics of Binary Mixtures with Ions: Dynamic Structure Factor and Mesophase Formation

Dynamic equations are presented for polar binary mixtures containing ions in the presence of the preferential solvation. In one-phase states, we calculate the dynamic structure factor of the composition accounting for the ion motions. Microphase separation can take place for sufficiently large solvation asymmetry of the cations and the anions. We show two-dimensional simulation results of the mesophase formation with an antagonistic salt, where the cations are hydrophilic and the anions are hydrophobic. The structure factor S(q) in the resultant mesophase has a sharp peak at an intermediate wave number on the order of the Debye-Huckel wave number. As the quench depth is increased, the surface tension nearly vanishes in mesophases due to an electric double layer.Comment: 24 pages, 10 figures, to appear in Journal of Physics: Condensed Matte

Improving the implementation of health workforce policies through governance: a review of case studies

<p>Abstract</p> <p>Introduction</p> <p>Responsible governance is crucial to national development and a catalyst for achieving the Millennium Development Goals. To date, governance seems to have been a neglected issue in the field of human resources for health (HRH), which could be an important reason why HRH policy formulation and implementation is often poor. This article aims to describe how governance issues have influenced HRH policy development and to identify governance strategies that have been used, successfully or not, to improve HRH policy implementation in low- and middle-income countries (LMIC).</p> <p>Methods</p> <p>We performed a descriptive literature review of HRH case studies which describe or evaluate a governance-related intervention at country or district level in LMIC. In order to systematically address the term 'governance' a framework was developed and governance aspects were regrouped into four dimensions: 'performance', 'equity and equality', 'partnership and participation' and 'oversight'.</p> <p>Results and discussion</p> <p>In total 16 case studies were included in the review and most of the selected studies covered several governance dimensions. The dimension 'performance' covered several elements at the core of governance of HRH, decentralization being particularly prominent. Although improved equity and/or equality was, in a number of interventions, a goal, inclusiveness in policy development and fairness and transparency in policy implementation did often not seem adequate to guarantee the corresponding desirable health workforce scenario. Forms of partnership and participation described in the case studies are numerous and offer different lessons. Strikingly, in none of the articles was 'partnerships' a core focus. A common theme in the dimension of 'oversight' is local-level corruption, affecting, amongst other things, accountability and local-level trust in governance, and its cultural guises. Experiences with accountability mechanisms for HRH policy development and implementation were lacking.</p> <p>Conclusion</p> <p>This review shows that the term 'governance' is neither prominent nor frequent in recent HRH literature. It provides initial lessons regarding the influence of governance on HRH policy development and implementation. The review also shows that the evidence base needs to be improved in this field in order to better understand how governance influences HRH policy development and implementation. Tentative lessons are discussed, based on the case studies.</p