Overcharging: The Crucial Role of Excluded Volume

In this Letter we investigate the mechanism for overcharging of a single spherical colloid in the presence of aqueous salts within the framework of the primitive model by molecular dynamics (MD) simulations as well as integral-equation theory. We find that the occurrence and strength of overcharging strongly depends on the salt-ion size, and the available volume in the fluid. To understand the role of the excluded volume of the microions, we first consider an uncharged system. For a fixed bulk concentration we find that upon increasing the fluid particle size one strongly increases the local concentration nearby the colloidal surface and that the particles become laterally ordered. For a charged system the first surface layer is built up predominantly by strongly correlated counterions. We argue that this a key mechanism to produce overcharging with a low electrostatic coupling, and as a more practical consequence, to account for charge inversion with monovalent aqueous salt ions.Comment: 7 pages, 3 figs (4 EPS files). To appear in Europhysics Letter

The electrical double layer for a fully asymmetric electrolyte around a spherical colloid: an integral equation study

The hypernetted chain/mean spherical approximation (HNC/MSA) integral equation is obtained and solved numerically for a totally asymmetric primitive model electrolyte around a spherical macroparticle. The ensuing radial distribution functions show a very good agreement when compared to our Monte Carlo and molecular dynamics simulations for spherical geometry and with respect to previous anisotropic reference HNC calculations in the planar limit. We report an analysis of the potential vs charge relationship, radial distribution functions, mean electrostatic potential and cumulative reduced charge for representative cases of 1:1 and 2:2 salts with a size asymmetry ratio of 2. Our results are collated with those of the Modified Gouy-Chapman (MGC) and unequal radius Modified Gouy-Chapman (URMGC) theories and with those of HNC/MSA in the restricted primitive model (RPM) to assess the importance of size asymmetry effects. One of the most striking characteristics found is that,\textit{contrary to the general belief}, away from the point of zero charge the properties of an asymmetric electrical double layer (EDL) are not those corresponding to a symmetric electrolyte with the size and charge of the counterion, i.e. \textit{counterions do not always dominate}. This behavior suggests the existence of a new phenomenology in the EDL that genuinely belongs to a more realistic size-asymmetric model where steric correlations are taken into account consistently. Such novel features can not be described by traditional mean field theories like MGC, URMGC or even by enhanced formalisms, like HNC/MSA, if they are based on the RPM.Comment: 29 pages, 13 figure

Electrophoresis of a rod macroion under polyelectrolyte salt: Is mobility reversed for DNA?

By molecular dynamics simulation, we study the charge inversion phenomenon of a rod macroion in the presence of polyelectrolyte counterions. We simulate electrophoresis of the macroion under an applied electric field. When both counterions and coions are polyelectrolytes, charge inversion occurs if the line charge density of the counterions is larger than that of the coions. For the macroion of surface charge density equal to that of the DNA, the reversed mobility is realized either with adsorption of the multivalent counterion polyelectrolyte or the combination of electrostatics and other mechanisms including the short-range attraction potential or the mechanical twining of polyelectrolyte around the rod axis.Comment: 8 pages, 5 figures, Applied Statistical Physics of Molecular Engineering (Mexico, 2003). Journal of Physics: Condensed Matters, in press (2004). Journal of Physics: Condensed Matters, in press (2004

Laser-driven plasma waves in capillary tubes

The excitation of plasma waves over a length of up to 8 centimeters is, for the first time, demon- strated using laser guiding of intense laser pulses through hydrogen filled glass capillary tubes. The plasma waves are diagnosed by spectral analysis of the transmitted laser radiation. The dependence of the spectral redshift, measured as a function of filling pressure, capillary tube length and incident laser energy, is in excellent agreement with simulation results. The longitudinal accelerating field inferred from the simulations is in the range 1 -10 GV/m

Modification of the Sandia National Laboratories/California advanced coordinate measuring machine for high speed scanning

The Moore M48V high accuracy coordinate measuring machine (CMM), while mechanically capable of exact measurement of physical artifacts, is not, in its original configuration, well suited for rapid gathering of high density dimensional information. This report describes hardware and software modifications to the original control and data acquisition system that allow relatively high speed scanning of cylindrical features. We also estimate the accuracy of the individual point data on artifacts measured with this system and provide detailed descriptions of the hardware and software apparatus as an aid to others who may wish to apply the system to cylindrical or other simple geometries. 6 refs., 18 figs., 1 tab

DNA condensation and redissolution: Interaction between overcharged DNA molecules

The effective DNA-DNA interaction force is calculated by computer simulations with explicit tetravalent counterions and monovalent salt. For overcharged DNA molecules, the interaction force shows a double-minimum structure. The positions and depths of these minima are regulated by the counterion density in the bulk. Using two-dimensional lattice sum and free energy perturbation theories, the coexisting phases for DNA bundles are calculated. A DNA-condensation and redissolution transition and a stable mesocrystal with an intermediate lattice constant for high counterion concentration are obtained.Comment: 26 pages, 10 figure

Spectral analysis and zeta determinant on the deformed spheres

We consider a class of singular Riemannian manifolds, the deformed spheres $S^N_k$, defined as the classical spheres with a one parameter family $g[k]$ of singular Riemannian structures, that reduces for $k=1$ to the classical metric. After giving explicit formulas for the eigenvalues and eigenfunctions of the metric Laplacian $\Delta_{S^N_k}$, we study the associated zeta functions $\zeta(s,\Delta_{S^N_k})$. We introduce a general method to deal with some classes of simple and double abstract zeta functions, generalizing the ones appearing in $\zeta(s,\Delta_{S^N_k})$. An application of this method allows to obtain the main zeta invariants for these zeta functions in all dimensions, and in particular $\zeta(0,\Delta_{S^N_k})$ and $\zeta'(0,\Delta_{S^N_k})$. We give explicit formulas for the zeta regularized determinant in the low dimensional cases, $N=2,3$, thus generalizing a result of Dowker \cite{Dow1}, and we compute the first coefficients in the expansion of these determinants in powers of the deformation parameter $k$.Comment: 1 figur

Charge Fluctuation Forces Between Stiff Polyelectrolytes in Salt Solution: Pairwise Summability Re-examined

We formulate low-frequency charge-fluctuation forces between charged cylinders - parallel or skewed - in salt solution: forces from dipolar van der Waals fluctuations and those from the correlated monopolar fluctuations of mobile ions. At high salt concentrations forces are exponentially screened. In low-salt solutions dipolar energies go as $R^{-5}$ or $R^{-4}$; monopolar energies vary as $R^{-1}$ or $\ln{R}$, where $R$ is the minimal separation between cylinders. However, pairwise summability of rod-rod forces is easily violated in low-salt conditions. Perhaps the most important result is not the derivation of pair potentials but rather the demonstration that some of these expressions may not be used for the very problems that originally motivated their derivation.Comment: 8 pages and 1 fig in ps forma

Epidemio-clinical study of the first iterative cesarean in the gynecology-obstetric service at the teaching hospital of Cocody

Background: The iterative caesarean section, is a caesarean section that is performed on a uterus already healed, therefore for fear of maternal and perinatal risks, is recognized as one of the main causes of the inflation of caesarean section in the world. One in three caesarean sections is performed because of a scar uterus. Objective of this study was to analyse the epidemiological and clinical factors of iterative caesarean sections in the gynecology-obstetrics department at the Teaching Hospital of Cocody (Abidjan).Methods: This was a retrospective and descriptive study conducted from June 1st, 2018 to May 31st, 2019, including 349 iterative caesarean section cases.Results: The first iterative C-section accounted for 16.1% of the C-section indications during the study period. The average age of the patients was 30 years. Nearly half of the patients practiced in the informal sector 47.9%, were uneducated in 38.1% of cases and lived with a partner in 73.1% of cases. The majority of patients in this series 75.1% performed at least 4 ANCs. Patients were followed by prenatal visits in 61% of cases by midwives and in 8.6% of cases had an inter-reproductive space of less than 18 months. This study patients were evacuated in 46.4% of cases. Acute fetal distress was the first indication of first iterative caesarean section with 20.3% of cases. Emergency caesarean sections accounted for 84.4% of the cases in this series. Authors found maternal death 0.3% and 6.7% perinatal mortality.Conclusions: The iterative caesarean section is a caesarean section likely to cause difficulties and complications per- operative. Although in constant improvement the prognosis of the mother-child couple still remains a problem in this context, prenatal monitoring should be the prerogative of obstetrician gynecologists

Population inversion of a NAHS mixture adsorbed into a cylindrical pore

A cylindrical nanopore immersed in a non-additive hard sphere binary fluid is studied by means of integral equation theories and Monte Carlo simulations. It is found that at low and intermediate values of the bulk total number density the more concentrated bulk species is preferentially absorbed by the pore, as expected. However, further increments of the bulk number density lead to an abrupt population inversion in the confined fluid and an entropy driven prewetting transition at the outside wall of the pore. These phenomena are a function of the pore size, the non-additivity parameter, the bulk number density, and particles relative number fraction. We discuss our results in relation to the phase separation in the bulk.Comment: 7 pages, 8 Figure