Electrokinetic and dielectric response of a concentrated salt-free colloid: Different approaches to counterion finite-size effects.

In the present work, a general model is developed for the electrokinetics and dielectric response of a concentrated salt-free colloid that takes into account the finite size of the counterions released by the particles to the solution. The effects associated with the counterion finite size have been addressed using a hard-sphere model approach elaborated by Carnahan and Starling [N. F. Carnahan and K. E. Starling, Equation of state for nonattracting rigid spheres, J. Chem. Phys. 51, 635 (1969)0021-960610.1063/1.1672048]. A more simple description of the finite size of the counterions based on that by Bikerman has also been considered for comparison. The studies carried out in this work include predictions on the effect of the finite counterion size on the equilibrium properties of the colloid and its electrokinetic and dielectric response when it is subjected to constant or alternating electric fields. The results show how important the counterion finite-size effects are for most of the electrokinetic and dielectric properties of highly charged and concentrated colloids, mainly for the static and dynamic electrophoretic mobilities. Furthermore, new insights are provided on the counterion condensation effect when counterions are allowed to have finite size. Focus is placed on the changes undergone by their concentration in the condensation layer for low-salt and highly charged colloids.

Electrokinetic detection of the salt-free condition in colloids. Application to polystyrene latexes.

Because of their singular phenomenology, the so-called salt-free colloids constitute a special family of dispersed systems. Their main characteristic is that the dispersion medium ideally contains only the solvent and the ions compensating exactly the surface charge of the particles. These ions (often called released counterions) come into the solution when the surface groups responsible for the particles charge get ionized. An increasing effort is nowadays dedicated to rigorously compare theoretical model predictions for ideal salt-free suspensions, where only the released counterions are supposed to be present in solution, with appropriately devised experiments dealing with colloids as close as possible to the ideal salt-free ones. Of course, if the supporting solution is aqueous, the presence of atmospheric contamination and any other charged species different from the released counterions in the solution must be avoided. Because this is not an easy task, the presence of dissolved atmospheric CO2 and of H+ and OH- from water dissociation cannot be fully discarded in aqueous salt-free solutions (often denominated realistic in such case). Ultimately, at some point, the role of the released counterions will be comparable or even larger in highly charged concentrated colloids than that of added salts. These topics are covered in the present contribution. The model results are compared with experimental data on the dynamic mobility and dielectric dispersion of polystyrene spheres of various charges and sizes. As a rule, it is found that the model correctly predicts the significance of alpha and Maxwell-Wagner-O'Konski relaxations. Positions and amplitudes of such relaxations are well predicted, although it is necessary to assume that the released counterions are potassium or sodium instead of protons, otherwise the frequency spectra of experimental mobility and permittivity differ very significantly from those theoretically calculated. The proposed electrokinetic evaluation is an ideal tool for detecting in situ the possible contamination (or incomplete ion exchange of the latexes). A satisfactory agreement is found when potassium counterions are assumed to be in solution, mostly if one considers that the comparison is carried out without using any adjustable parameters.

Cytokines and growth factors in a biologic product obtained from patients' urine as immune-modulators to treat autoimmune and allergic diseases.

At "Instituto de Alergias y Autoinmunidad Dr. Maximiliano Ruiz Castañeda, A.C." in Mexico City, a non-traditional health care center focused on the treatment of autoimmune and allergic diseases using personalized medicine, an alternative treatment referred to as an "immune-modulator" has been developed. In this study, we will refer to this treatment substance as the "immune-modulator." In brief, a urine sample is collected from the patient and processed to obtain the peptide fraction, which is conditioned and then administered sublingually to the patient. Sample processing involves multiple steps aimed at the removal of toxic compounds and enrichment for cytokines, growth factors, and other immune peptides that may contribute to the function of the immune-modulator. This treatment has been administered for many years, and patients testify that it is useful and reliable. Despite the benefits of this treatment, the molecular mechanisms underlying its effects have not been thoroughly investigated. Therefore, this study aims to identify immunoregulatory peptides, such as cytokines and growth factors, in the immune-modulator. Urine and immune-modulator concentrations of cytokines and growth factors were assessed using a Luminex assay. Twenty-one cytokines and growth factors were identified in immune-modulator samples. MCP-1 was identified in 100% of the samples; MIP-1ß, IL-8, RANTES, INF-γ, and IP-10 were identified in approximately 65-70% of samples; IL5, IL-1B, and IL-17 in 50-60%; eotaxin, VEGF, IL-6, and FGF in about 40%; MIP-1α, IL-9, GM-CSF, G-CSF, IL-12, and IL-15 in about 20-30%; and IL-13 and PDGF-bb were identified in <6% of samples. Additionally, patients exhibited significant changes in IL-1ß, IFN-γ, and MCP-1 concentrations after treatment with the immune-modulator, whereas healthy individuals showed no significant change in response to the treatment. The immune-modulator is an alternative treatment based on the administration of cytokines and growth factors obtained from the urine of patients. In this study, its composition was characterized. The isolated products could be responsible for the effects of the immune-modulator. Further trials are required to evaluate the effective delivery of these molecules by the administration route described.

Multiionic effects on the capacitance of porous electrodes.

The rapid and reversible ionic electrosorption in the electrical double layers (EDLs) of moderately charged micropores in contact with a solution is the main concept underlying capacitive energy and desalination devices. For the usual operating conditions, the ion concentration is large enough for the confinement of ions to play an important role in their distribution in the EDL. On the other hand, although most laboratory experiments have been carried out with simple salt solutions, realistic applications require a proper analysis of the effect of the different ionic species existing in natural waters. Here we focus on the role of multiionic solutions on the double layer structure. For this purpose, a model is presented in which the EDL overlap and the existence of a Stern layer are considered. It is also taken into account that the ions can be tightly packed by using the Carnahan-Starling model. This model is applied to analyze the structure of the EDL with multiionic solutions containing divalent ions. The predictions of this model are found to largely differ from those of the better known Bikerman equation, and are more realistic. It is demonstrated that the presence of tiny amounts of divalent ions in the bulk is enough to dominate the EDL behavior, and hence, its capacitance, energy storage, and desalination properties.

Dynamic electrophoretic mobility and electric permittivity of concentrated suspensions of plate-like gibbsite particles.

In this paper we present experimental results on the electrokinetic behavior of planar gibbsite particles in concentrated suspensions. The dc electrophoretic mobility measurements are in this case of little significance, as they are scarcely informative. In the present investigation, we show that the dielectric dispersion and dynamic electrophoresis can in contrast provide such information. The complicating factors are of course the non-spherical shape and the finite particle concentration, as no complete theory of these phenomena exists for such systems. We propose to use first of all a model of dynamic electrophoresis of spheroids in which the effect of volume fraction is considered by means of an approximate theory previously obtained for spheres, based on the evaluation of electrical and hydrodynamic interactions between particles. In addition, the role of volume fraction on the high frequency inertial relaxation is also ascertained and used to obtain a volume fraction-independent radius of the gibbsite spheroids. A similar approach is used for the evaluation of dielectric dispersion data. Both the dynamic mobility and dielectric constant dependencies on frequency were obtained for gibbsite suspensions of different volume fractions in 0.5mMKCl. The theoretical treatments elaborated were applied to these data, and a coherent picture of the geometrical and electrical characteristics of the particles was obtained.

The functional PTPN22 C1858T polymorphism confers risk for rheumatoid arthritis in patients from Central Mexico.

Rheumatoid arthritis (RA) is a complex genetic disease. Human leukocyte antigen (HLA) and non-HLA genes are reportedly associated with an increased risk of RA. The protein tyrosine phosphatase non-receptor 22 gene (PTPN22), which encodes the lymphoid tyrosine phosphatase (LYP) protein, is one of the best examples of a non-HLA gene associated with a risk for RA in several populations. The functional PTPN22 C1858T (R620W) non-synonymous polymorphism is widely associated with an increased risk for RA in Europeans and non-Europeans. The aim of this study was to determine if the PTPN22 C1858T polymorphism confers susceptibility to RA in a sample of patients from Mexico. This study included 364 RA patients and 387 non-related controls from Central Mexico. Genotyping of the PTPN22 C1858T (rs2476601) polymorphism was performed using allelic discrimination assays with TaqMan probes. The functional PTPN22 C1858T polymorphism was associated with an increased risk for RA in our study population. The CC vs CT genotype in RA patients versus healthy controls had an odds ratio (OR) of 4.17 (95 % CI 1.79-9.74, p = 0.00036), while T allele had an OR of 4.06 (95 % CI 1.75-9.41, p = 0.00043). PTPN22 is a genetic risk factor for developing RA in the Mexican population.

MHC2TA and FCRL3 genes are not associated with rheumatoid arthritis in Mexican patients.

Rheumatoid arthritis (RA) is a multifactorial disease. A combination of genetic and environmental risk factors contributes to its etiology. Several genes have been reported to be associated with susceptibility to the development of RA. The MHC2TA and FCRL3 genes have been associated previously with RA in Swedish and Japanese populations, respectively. In two recent reports, we show an association between FCRL3 and juvenile rheumatoid arthritis (JRA), and MHC2TA and acute coronary syndrome (ACS) in Mexican population. We assessed the association between three single nucleotide polymorphisms (SNPs) of the MHC2TA (-168G/A; rs3087456, and +16G/C; rs4774) and FCRL3 (-169T/C; rs7528684) genes and rheumatoid arthritis in Mexican population through a genotyping method using allelic discrimination assays with TaqMan probes. Our case-control study included 249 patients with RA and 314 controls. We found no evidence of an association between the MHC2TA -168G/A and +1614G/C or FCRL3 -169T/C polymorphisms and RA in this Mexican population. In this cohort of Mexican patients with RA, we observed no association between the MHC2TA or FCRL3 genes and this autoimmune disease.

Multi-ionic effects on energy production based on double layer expansion by salinity exchange.

It has been recently shown that the free energy change upon salinity mixing in river mouths can be harvested taking advantage of the fact that the capacitance of charged solid/liquid interfaces (electrical double layers, EDLs) depends strongly on the ionic composition of the liquid medium. This has led to a new generation of techniques called Capmix technologies, one of them (CDLE or capacitive energy extraction based on DL expansion) based precisely on such dependence. Despite the solution composition playing a crucial role on the whole process, most of the research carried out so far has mainly focused on pure sodium chloride solutions. However, the effect of other species usually present in river and seawaters should be considered both theoretically and experimentally in order to succeed in optimizing a future device. In this paper, we analyse solutions of a more realistic composition from two points of view. Firstly, we find both experimentally and theoretically that the presence of ions other than sodium and chloride, even at low concentrations, may lead to a lower energy extraction in the process. Secondly, we experimentally consider the possible effects of other materials usually dispersed in natural water (mineral particles, microbes, shells, pollutants) by checking their accumulation in the carbon films used, after being exposed for a long period to natural sea water during CDLE cycles.

Modification of the surface of activated carbon electrodes for capacitive mixing energy extraction from salinity differences.

The "capacitive mixing" (CAPMIX) is one of the techniques aimed at the extraction of energy from the salinity difference between sea and rivers. It is based on the rise of the voltage between two electrodes, taking place when the salt concentration of the solution in which they are dipped is changed. We study the rise of the potential of activated carbon electrodes in NaCl solutions, as a function of their charging state. We evaluate the effect of the modification of the materials obtained by adsorption of charged molecules. We observe a displacement of the potential at which the potential rise vanishes, as predicted by the electric double layer theories. Moreover, we observe a saturation of the potential rise at high charging states, to a value that is nearly independent of the analyzed material. This saturation represents the most relevant element that determines the performances of the CAPMIX cell under study; we attribute it to a kinetic effect.

Polyelectrolyte-coated carbons used in the generation of blue energy from salinity differences.

In this work we present a method for the production of clean, renewable electrical energy from the exchange of solutions with different salinities. Activated carbon films are coated with negatively or positively charged polyelectrolytes using well-established adsorption methods. When two oppositely charged coated films are placed in contact with an ionic solution, the potential difference between them will be equal to the difference between their Donnan potentials, and hence, energy can be extracted by building an electrochemical cell with such electrodes. A model is elaborated on the operation of the cell, based on the electrokinetic theory of soft particles. All the features of the model are experimentally reproduced, although a small quantitative difference concerning the maximum open-circuit voltage is found, suggesting that the coating is the key point to improve the efficiency. In the experimental conditions used, we obtain a power of 12.1 mW m(-2). Overall, the method proves to be a fruitful and simple approach to salinity-gradient energy production.

La influencia de factores individuales, relacionados con el trabajo, socioeconómicos y de organización del sistema sanitario sobre la duración de la incapacidad temporal / The influence of individual, work-related, socioeconomic, and the health system organization factors on the duration of sick-leave

Objetivo: Estudiar la frecuencia de aparición de Eventos Adversos (EA) atribuibles a la atención sanitaria en el hospital Severo Ochoa de Leganés y analizar el tipo de EA detectado. Material y método: Se realizó un estudio descriptivo de carácter retrospectivo en pacientes dados de alta durante 2004 en dicho hospital, que constó de dos fases. En la primera fase o de screening se identificaron los casos con riesgo de aparición de un EA. En la segunda fase o de confirmación se realizó la revisión de los casos cribados para confirmar o descartar la existencia del EA. Se consideró EA tanto los Efectos Adversos como los incidentes. Los casos confirmados se analizaron tipificando sus consecuencias y valorando si eran prevenibles o no. Resultados: Se seleccionaron 240 historias clínicas, de las cuales 90 (38%) pasaron a la segunda fase de análisis del estudio. De estas 90 historias, en 47 (52%) se había producido al menos un EA. En 34 pacientes se estimó que se había producido al menos un EA y en 13 un incidente. Del total de EA detectados, el 56% se consideraron prevenibles y el 87% se produjeron durante la hospitalización. El 50% de los EA se consideraron moderados, el 36% leves y el 14% graves. La consecuencia más frecuente de los EA detectados fue haber provocado una «lesión sin secuela con prolongación de la estancia». Conclusión: La tasa de pacientes con EA fue de un 14,2%, y la tasa de pacientes con incidentes de un 5,4%. El estudio ha permitido conocer las áreas prioritarias en las cuales centrar esfuerzos para detectar y prevenir los EA (AU)

Objective: To estimate the frequency of occurrence of Adverse Events (AE) that may be attributed to health care iin Hospital Severo Ochoa de Leganés, an investigation was performed by a descriptive, retrospective study using a random sample of patients released during the year 2004. Material and method: This study is carried out by reviewing clinical records. Results: Out of 240 patients included initially in the study, 90 (38%) were taken for the second stage of the study. At least one AE was considered to have occurred in 47 (52%) of them. At least one AE occurred in 34 of them, and in 13 just an incident occurred. From the total of AE detected, 56% were considered that could be prevented, 87% happened while staying in the hospital. The 50% of the AE were considered mediums, the 36% minor and the 14% serious and the most frequent consequence detected was an «injury with no consequence with an extension of the stay in the hospital». Conclusions: The rate of patients with AE was 14,2% and the rate of patients with an incident was 5.4%. Additionally, this study has contributed to identify the main areas where the efforts should be dedicated for the detection and prevention of AE (AU)

Predictions of the maximum energy extracted from salinity exchange inside porous electrodes.

Capacitive energy extraction based on double layer expansion (CDLE) is the name of a new method devised for extracting energy from the exchange of fresh and salty water in porous electrodes. It is based on the change of the capacitance of electrical double layers (EDLs) at the electrode/solution interface when the concentration of the bulk electrolyte solution is modified. The use of porous electrodes provides huge amounts of surface area, but given the typically small pore size, the curvature of the interface and EDL overlap should affect the final result. This is the first aspect dealt with in this contribution: we envisage the electrode as a swarm of spherical particles, and from the knowledge of their EDL structure, we evaluate the stored charge, the differential capacitance and the extracted energy per CDLE cycle. In all cases, different pore radii and particle sizes and possible EDL overlap are taken into account. The second aspect is the consideration of finite ion size instead of the usual point-like ion model: given the size of the pores and the relatively high potentials that can be applied to the electrode, excluded volume effects can have a significant role. We find an extremely strong effect: the double layer capacitance is maximum for a certain value of the surface potential. This is a consequence of the limited ionic concentration at the particle-solution interface imposed by the finite size of ions, and leads to the presence of two potential ranges: for low electric potentials the capacitance increases with the ionic strength, while for large potentials we find the opposite trend. The consequences of these facts on the possibility of net energy extraction from porous electrodes, upon changing the solution in contact with them, are evaluated.

Electric permittivity of concentrated suspensions of elongated goethite particles.

This paper describes an investigation on the electric permittivity of concentrated suspensions of non-spherical particles, specifically prolate spheroids. It is first discussed how the determination of the frequency (omega) dependence of the electric permittivity (a phenomenon traditionally known as LFDD or low-frequency dielectric dispersion) can provide ample information on the properties of the dispersed material (shape, size, state of aggregation, conductivity) and of its interface with the (typically aqueous) medium. The basic quantities are the strength and frequency dependence of the dipole moment induced by the applied field, and its dimensionless counterpart, the dipole coefficient, C(*)(omega). It is explicitly shown how the (complex) relative permittivity of the suspension, epsilon(r)(*)(omega), can be calculated from it. Two theoretical models on the polarizability of spheroidal colloidal particles will be used as theoretical starting point; one of them (Model I) explicitly considers two relaxations of the permittivity, each associated to one of the particle axes. The other (Model II) is a semi-analytical theory that yields an LFDD practically independent of the axial ratio of the particles. Both models are aimed to be used if the suspensions are dilute (low volume fraction of solids, phi), and here they are generalized to concentrated systems by means of a previously published approximate evaluation of the permittivity of concentrated suspensions. Experiments are performed in the 1 kHz-1 MHz frequency range on suspensions of elongated goethite particles; the effects of ionic strength, pH, and volume fraction are investigated, and the two models are fitted to the data. In reality, taking into account that the particles are non-uniformly charged (a fact that contributes to their instability), two zeta potentials (roughly representing the lateral surface and the tip of the spheroid) are used as parameters. The results indicate that, when experimental conditions are optimal (high ionic strength and low zeta potential), the suspensions do indeed display two relaxations, that we ascribe to the long axis (and to flocs likely present in suspension) and to the short one. The permittivity increases with ionic strength, a result found with other systems, and compatible with a zeta potential that, on the average, decreases with ionic strength, an equally well known result, consequence of electric double layer compression. Another reasonable finding is the increase of estimated average dimensions and the decrease of electrokinetic potentials when the pH is close to the isoelectric point of goethite (around pH 9). The increase in volume fraction, finally, produces an overall increase in the permittivity, and the approximate model used for the evaluation of volume fraction variations can describe properly these effects, with basically constant zeta potentials and dimensions.

Permanent Genetic Resources added to Molecular Ecology Resources Database 1 August 2009-30 September 2009.

This article documents the addition of 238 microsatellite marker loci and 72 pairs of Single Nucleotide Polymorphism (SNP) sequencing primers to the Molecular Ecology Resources Database. Loci were developed for the following species: Adelges tsugae, Artemisia tridentata, Astroides calycularis, Azorella selago, Botryllus schlosseri, Botrylloides violaceus, Cardiocrinum cordatum var. glehnii, Campylopterus curvipennis, Colocasia esculenta, Cynomys ludovicianus, Cynomys leucurus, Cynomys gunnisoni, Epinephelus coioides, Eunicella singularis, Gammarus pulex, Homoeosoma nebulella, Hyla squirella, Lateolabrax japonicus, Mastomys erythroleucus, Pararge aegeria, Pardosa sierra, Phoenicopterus ruber ruber and Silene latifolia. These loci were cross-tested on the following species: Adelges abietis, Adelges cooleyi, Adelges piceae, Pineus pini, Pineus strobi, Tubastrea micrantha, three other Tubastrea species, Botrylloides fuscus, Botrylloides simodensis, Campylopterus hemileucurus, Campylopterus rufus, Campylopterus largipennis, Campylopterus villaviscensio, Phaethornis longuemareus, Florisuga mellivora, Lampornis amethystinus, Amazilia cyanocephala, Archilochus colubris, Epinephelus lanceolatus, Epinephelus fuscoguttatus, Symbiodinium temperate-A clade, Gammarus fossarum, Gammarus roeselii, Dikerogammarus villosus and Limnomysis benedeni. This article also documents the addition of 72 sequencing primer pairs and 52 allele specific primers for Neophocaena phocaenoides.

Role of surface conductivity in the dynamic mobility of concentrated suspensions.

In this article, a cell model is used for the evaluation of the alternating current (ac) mobility (dynamic mobility) of spherical particles in suspensions of arbitrary volume fractions of solids. The main subject is the consideration of the role of the electrical conductivity (SLC or K(sigmai)) of the stagnant layer (SL) on the mobility. It is assumed that the total surface conductivity (K(sigma)), resulting from both K(sigmai) and the diffuse layer conductivity (K(sigmad)), is constant in the cases considered and that it is the K(sigmai)-K(sigmad) balance that determines the SL effects. We first explore the effect of K(sigmai) on the frequency dependence of the dynamic mobility. It is found that the mobility decreases on average, for any frequency, when K(sigmai) increases. This is a consequence of stagnancy: ions in the SL, although contributing to the surface conductivity, do not drag liquid with them when they migrate and do not contribute to electro-osmotic flow or, equivalently, to electrophoresis. Three relaxations are observed in the mobility-frequency spectrum: inertial (the particle and liquid motions are hindered), Maxwell-Wagner-O'Konski (ions in the double layer cannot follow the field oscillations and can move only over a distance much smaller that the diffuse layer thickness), and the so-called alpha or concentration polarization process (the ions can rearrange around the particle, but they cannot form the electrolyte concentration field that appears at low frequency). Whereas the first two relaxations are little affected by K(sigmai), the alpha process undergoes significant changes. Thus, the mobility increases with frequency around the alpha relaxation region if K(sigmai) is negligible, but it decreases with frequency in the same interval if K(sigmai) is finite. With the aim of explaining this behavior, we calculate the capillary osmosis velocity field that is the fluid flow provoked by the concentration gradient around the particle. The calculations presented demonstrate that the velocity is reduced (for each frequency and position) when the SLC is raised. It is proposed that such a decrease adds to that due to the changes in the induced dipole moment of the particle, also favoring a decrease in the mobility. These tendencies are also present when the volume fraction of solids, phi, is modified, although higher phi values somewhat hide the effect of K(sigmai), as in fact observed with all features of electrokinetics associated with the phenomenon of concentration polarization.

Field-induced clearing in sphere-sphere and rod-sphere binary mixtures of charged colloidal particles.

Binary mixtures of larger and smaller colloids having charges of equal sign display unusual response to low-frequency electric fields. We show here that the previously reported negative torque acting on rodlike particles when in presence of a sea of smaller particles is accompanied by a field-induced clearing of the suspension. Measurements of transmitted intensity performed on mixtures of large (dilute) and small (semidilute) spherical particles indicate that such a clearing effect is universal and due to an anisotropic E2 -dependent redistribution of the small spheres around the large ones. We interpret this behavior as resulting from O(E2) electro-osmotic flows whose magnitude is greatly enhanced by the presence of the small particles.

Dynamic mobility of rodlike goethite particles.

In this work we consider how the spheroidal shape of colloidal particles and their concentration in suspension influence their electrokinetic properties in alternating (ac) electric fields, in particular, their electrophoretic mobility, traditionally known as dynamic mobility in the case of ac fields. Elaboration of a formula for the mobility is based on two previous models related to the electrokinetic response of spheroids in dilute suspensions, completed by means of an approximate formula to account for the finite concentration of particles. At the end, semianalytical formulas have been obtained in the form of the classical Helmholtz-Smoluchowski equation for the mobility with three frequency-dependent factors, each dealing with inertia relaxation, electric double layer polarization and volume fraction effects. The two resulting expressions differ basically in their consideration of double layer polarization processes, as one considers only Maxwell-Wagner-O'Konski polarization (related to the mismatch between the conductivities of the particles plus their double layers and the liquid medium), and the other also includes the concentration polarization effect. Since in the frequency range typically used in dynamic mobility measurements the latter polarization has already relaxed, both models are capable of accounting for the dynamic mobility data experimentally obtained on elongated goethite particles in the 1-18 MHz frequency range. Results are presented concerning the effects of volume fraction, ionic strength, and pH, and they indicate that the models are good descriptions of the electrokinetics of these systems, and that dynamic mobility is very sensitive not only to the zeta potential of the particles, but also to their concentration, shape, and average size, and to the stability of the suspensions. The effects of ionic strength and pH on the dynamic mobility are very well captured by both models, and a consistent description of the dimensions and zeta potentials of the particles is reached. Increasing the volume fraction of the suspensions produces mobility variations that are only partially described by the theoretical calculations due to the likely flocculation of the particles, mainly associated with the fact that goethite particles are not homogeneously charged, with attraction between positive and negative patches being possible.