112 research outputs found
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
- âŠ