Surface characterization of clay particles via dielectric spectroscopy

Dedicated to Professor Emil Chibowski on the occasion of his 65th birthday.This work deals with the high frequency dielectric relaxation of clay (sodium montmorillonite, or NaMt) suspensions. By high frequency it is meant that the permittivity will be determined in the region where the Maxwell-Wagner-O’Konski relaxation takes place, roughly, the MHz frequency range. The applicability of dielectric determinations for the characterization of the electrical properties of these complex systems is demonstrated. In fact, standard electrophoresis measurements only allow to detect that the charge of the particles becomes slightly more negative upon increasing pH. Much more information is obtained from the high frequency electric permittivity for different concentrations of solids and pHs. From the characteristic frequencies of the relaxation it is possible to detect separate processes for parallel and perpendicular orientations of the clay platelets, modelled as oblate spheroids with a high aspect ratio. In addition, using a suitable model the surface conductivity of the clay particles can be estimated. Our data indicate that this quantity is minimum around pH 7, which is admitted as representative of the isoelectric point of the edges of the clay platelets. Data are also obtained on the amplitude (value of the relative permittivity at low frequency minus that at high frequency) of the relaxation, and it is found that it depends linearly on the volume fraction of solids, and that it is minimum at pH 5. These results are considered to be a manifestation of the fact that particle interactions do not affect the electric conduction inside the electric double layer, while the special behaviour at pH 5 is related to the existence of aggregates at pH 5, which increase the effective size of the particles and provoke a reduction of their effective conductivity.Financial support for this work by MEC (Spain) (Projects FIS2005-06860-C02-01, 02) and Junta de Andalucia (Spain) (Project FQM410) is gratefully acknowledged

Electro-orientation of Ag nanowires in viscoelastic fluids

In this work we study the electro-orientation (through electric birefringence experiments) of silver nanowires in polymer solutions eventually capable of forming gel networks. Information on the structure of the polymer solution is obtained by evaluating the electro-orientation of the nanowires. It is found that in presence of poly(ethylene oxide), Kerr’s law (birefringence proportional to the square of the field) is fulfilled, and the randomization process after switching off the external field is purely diffusive, controlled by the viscosity of the Newtonian polymer solution. In the case of (gelating) sodium alginate solutions, measuring at larger distances from the bottom (where the source of cross-linking Ca2+ ions is deposited) means a smaller degree of cross-linking, and a less stiff gel. In fact, it is found that after a certain time the birefringence signal gets frozen at the bottom, indicating that a gel network is formed which hinders particle orientation. The viscosity deduced up to that point agrees well with rheological determinations, with increasing deviations found at longer times due to the inhomogeneous gel formation. This process has an interesting consequence on birefringence response: Kerr’s law fails to be fulfilled, appearing a ”yield” applied electric field, larger the longer the time after preparation

Electro-optics of confined systems

Supplementary material related to this article can be found online at https://doi.org/10.1016 /j.jcis.2023.11.180Confinement in microenvironments occurs in many natural systems and technological applications. However, little is known about the behaviour of the immersed nanoparticles. In this work we show that their diffusion, electro-orientation and electric field induced polarization can be determined through electric birefringence experiments. We analyze aqueous dispersions of silver nanowires and clay particles confined inside microdroplets. We have observed that confinement reduces the amount of particles that can be oriented by the external electric field. However, the polarizability of the oriented particles is not affected by the presence of the oil/water boundary, and it is the same as in unbounded media, which agrees with the fact that the electric polarization and related phenomena are short-ranged.Grant No. PID2021-127427NB-I00 funded by MCIN/AEI/10.13039/501100011033ERDF A way of making EuropeGrant No. TED2021-131855B-I00 funded by MCIN/AEI/10. 13039/501100011033European Union Next Generation EU/PRTRGrant No. A-FQM-492-UGR20 funded by Junta de Andalucía, Spai

Stacking of capacitive cells for electrical energy production by salinity exchange

Publisher's link: http://www.sciencedirect.com/science/article/pii/S0378775316303676?np=yHa estado embargado durante 1 año, hasta julio 2017In this paper we explore methods for stacking individual cells in order to increase the amount of energy that can be extracted from salinity gradient cycles (capmix methods). Each of the cells consists of a pair of parallel electrodes made of activated carbon particles, either bare or coated by a layer of polyelectrolyte. In these methods, energy is produced based on the modifications in the electrical double layer (EDL) structure in the pores of the carbon particles upon exchange of the salinity of the surrounding medium. In the case of the bare carbon particles, the electrodes are externally charged in presence of high-salt concentration, and discharged after exchanging the solution for a dilute one (sea- vs. river-water cycles). In a first stacking approach, we simply connect the electrodes side-by-side and only the outermost ones can be connected to the external source. Using a stack where potential and current between cells can be measured, it is shown that only the external electrodes seem to work, and it is suggested that this is a consequence of internal short-circuit currents between oppositely charged electrodes of different cells through the electrolyte. In contrast, the side-by-side configuration is operational if coated electrodes are used.MICINN, Spain (Project FIS2013-47666-C3-1R)RYC-2014-16901 (MINECO)FEDER Funds E

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

This is an unedited version of this article. The publisher's edited version cab reached in this URL: http://www.sciencedirect.com/science/article/pii/S0021979714006274#The reference for this article is: Marino et al., Journal of Colloid and Interface Science 436(2014) 146-153.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.Departamento de Física Aplicad

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

This is the unedited version of this manuscript. The publisher's edited version can be reached at this URL: http://pubs.rsc.org/en/content/articlelanding/2014/cp/c4cp03527e#!divAbstractIn 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 by 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 opencircuit voltage is found, suggesting that the coating is the key point to improve the efficiency. In the used experimental conditions, we obtain a power of 12.1 mW/m2. Overall, the method proves to be a fruitful and simple approach to salinity-gradient energy production. Obtaining energy from salinity differences asDepartamento de Física AplicadaThe research leading to these results received funding from the European Union 7th Framework Programme (FP7/2007-2013) under agreement No. 256868. Further financial sup- ports from Junta de Andalucía, project PE2012-FQM694, and Ministerio de Economía y Competitividad (Spain), project FIS2013-47666-C3-1-R

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

The edited version of the manuscript can be obtained at: Delgado et al., J. Colloid Interface Science (2014); DOI http://dx.doi.org/10.1016/j.jcis.2014.08.009It 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 sea waters 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.Universidad de Granada. Departamento de Física AplicadaThe research leading to these results received funding from the European Union 7th Framework Programme (FP7/2007-2013) under agreement No. 256868. Financial support from Junta de Andalucia (Project PE2012-FQM 694) and MINECO (Project FIS2013-4766-C3-1-R) is also acknowledged. One of us, M.M.F., is grateful to the University of Granada for her FPU grant

Immigrant IBD Patients in Spain Are Younger, Have More Extraintestinal Manifestations and Use More Biologics Than Native Patients

BackgroundPrevious studies comparing immigrant ethnic groups and native patients with IBD have yielded clinical and phenotypic differences. To date, no study has focused on the immigrant IBD population in Spain. MethodsProspective, observational, multicenter study comparing cohorts of IBD patients from ENEIDA-registry who were born outside Spain with a cohort of native patients. ResultsWe included 13,524 patients (1,864 immigrant and 11,660 native). The immigrants were younger (45 +/- 12 vs. 54 +/- 16 years, p < 0.001), had been diagnosed younger (31 +/- 12 vs. 36 +/- 15 years, p < 0.001), and had a shorter disease duration (14 +/- 7 vs. 18 +/- 8 years, p < 0.001) than native patients. Family history of IBD (9 vs. 14%, p < 0.001) and smoking (30 vs. 40%, p < 0.001) were more frequent among native patients. The most prevalent ethnic groups among immigrants were Caucasian (41.5%), followed by Latin American (30.8%), Arab (18.3%), and Asian (6.7%). Extraintestinal manifestations, mainly musculoskeletal affections, were more frequent in immigrants (19 vs. 11%, p < 0.001). Use of biologics, mainly anti-TNF, was greater in immigrants (36 vs. 29%, p < 0.001). The risk of having extraintestinal manifestations [OR: 2.23 (1.92-2.58, p < 0.001)] and using biologics [OR: 1.13 (1.0-1.26, p = 0.042)] was independently associated with immigrant status in the multivariate analyses. ConclusionsCompared with native-born patients, first-generation-immigrant IBD patients in Spain were younger at disease onset and showed an increased risk of having extraintestinal manifestations and using biologics. Our study suggests a featured phenotype of immigrant IBD patients in Spain, and constitutes a new landmark in the epidemiological characterization of immigrant IBD populations in Southern Europe

Mutational Landscape of CEBPA in Mexican Pediatric Acute Myeloid Leukemia Patients: Prognostic Implications

BackgroundIn Mexico, the incidence of acute myeloid leukemia (AML) has increased in the last few years. Mortality is higher than in developed countries, even though the same chemotherapy protocols are used. CCAAT Enhancer Binding Protein Alpha (CEBPA) mutations are recurrent in AML, influence prognosis, and help to define treatment strategies. CEBPA mutational profiles and their clinical implications have not been evaluated in Mexican pediatric AML patients.Aim of the StudyTo identify the mutational landscape of the CEBPA gene in pediatric patients with de novo AML and assess its influence on clinical features and overall survival (OS).Materials and MethodsDNA was extracted from bone marrow aspirates at diagnosis. Targeted massive parallel sequencing of CEBPA was performed in 80 patients.ResultsCEBPA was mutated in 12.5% (10/80) of patients. Frameshifts at the N-terminal region were the most common mutations 57.14% (8/14). CEBPA biallelic (CEBPABI) mutations were identified in five patients. M2 subtype was the most common in CEBPA positive patients (CEBPAPOS) (p = 0.009); 50% of the CEBPAPOS patients had a WBC count &gt; 100,000 at diagnosis (p = 0.004). OS &gt; 1 year was significantly better in CEBPA negative (CEBPANEG) patients (p = 0.0001). CEBPAPOS patients (either bi- or monoallelic) had a significantly lower OS (p = 0.002). Concurrent mutations in FLT3, CSF3R, and WT1 genes were found in CEBPAPOS individuals. Their contribution to poor OS cannot be ruled out.ConclusionCEBPA mutational profiles in Mexican pediatric AML patients and their clinical implications were evaluated for the first time. The frequency of CEBPAPOS was in the range reported for pediatric AML (4.5–15%). CEBPA mutations showed a negative impact on OS as opposed to the results of other studies

IKZF1plus is a frequent biomarker of adverse prognosis in Mexican pediatric patients with B-acute lymphoblastic leukemia

BackgroundRecurrent genetic alterations contributing to leukemogenesis have been identified in pediatric B-cell Acute Lymphoblastic Leukemia (B-ALL), and some are useful for refining classification, prognosis, and treatment selection. IKZF1plus is a complex biomarker associated with a poor prognosis. It is characterized by IKZF1 deletion coexisting with PAX5, CDKN2A/2B, or PAR1 region deletions. The mutational spectrum and clinical impact of these alterations have scarcely been explored in Mexican pediatric patients with B-ALL. Here, we report the frequency of the IKZF1plus profile and the mutational spectrum of IKZF1, PAX5, CDKN2A/2B, and ERG genes and evaluate their impact on overall survival (OS) in a group of patients with B-ALL.MethodsA total of 206 pediatric patients with de novo B-ALL were included. DNA was obtained from bone marrow samples at diagnosis before treatment initiation. A custom-designed next-generation sequencing panel was used for mutational analysis. Kaplan-Meier analysis was used for OS estimation.ResultsWe identified the IKZF1plus profile in 21.8% of patients, which was higher than that previously reported in other studies. A significantly older age (p=0.04), a trend toward high-risk stratification (p=0.06), and a decrease in 5-year Overall Survival (OS) (p=0.009) were observed, although heterogeneous treatment protocols in our cohort would have impacted OS. A mutation frequency higher than that reported was found for IKZF1 (35.9%) and CDKN2A/2B (35.9%) but lower for PAX5 (26.6%). IKZF1MUT group was older at diagnosis (p=0.0002), and most of them were classified as high-risk (73.8%, p=0.02), while patients with CDKN2A/2BMUT had a higher leukocyte count (p=0.01) and a tendency toward a higher percentage of blasts (98.6%, &gt;50% blasts, p=0.05) than the non-mutated patients. A decrease in OS was found in IKZF1MUT and CDKN2A/2BMUT patients, but the significance was lost after IKZF1plus was removed.DiscussionOur findings demonstrated that Mexican patients with B-ALL have a higher prevalence of genetic markers associated with poor outcomes. Incorporating genomic methodologies into the diagnostic process, a significant unmet need in low- and mid-income countries, will allow a comprehensive identification of relevant alterations, improving disease classification, treatment selection, and the general outcome