Molecular dynamics simulation of the behaviour of water in nano-confined ionic liquid-water mixtures.

This work describes the behaviour of water molecules in 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid under nanoconfinement, between graphene sheets. By means of molecular dynamics simulations, the adsorption of water molecules at the graphene surface is studied. A depletion of water molecules in the vicinity of the neutral and negatively charged graphene surfaces, and their adsorption at the positively charged surface are observed in line with the preferential hydration of the ionic liquid anions. The findings are appropriately described using a two-level statistical model. The confinement effect on the structure and dynamics of the mixtures is thoroughly analyzed using the density and the potential of mean force profiles, as well as by the vibrational densities of the states of water molecules near the graphene surface. The orientation of water molecules and the water-induced structural transitions in the layer closest to the graphene surface are also discussed.

Structural and electronic properties of zigzag InP nanoribbons with Stone-Wales type defects.

By means of density-functional-theoretic calculations, we investigate the structural and electronic properties of a hexagonal InP sheet and of hydrogen-passivated zigzag InP nanoribbons (ZInPNRs) with Stone-Wales (SW)-type defects. Our results show that the influence of this kind of defect is not limited to the defected region but it leads to the formation of ripples that extend across the systems, in keeping with the results obtained recently for graphene and silicene sheets. The presence of SW defects in ZInPNRs causes an appreciable broadening of the band gap and transforms the indirect-bandgap perfect ZInPNR into a direct-bandgap semiconductor. An external transverse electric field, regardless of its direction, reduces the gap in both the perfect and defective ZInPNRs.

Electrical conductivity of seven binary systems containing 1-ethyl-3-methyl imidazolium alkyl sulfate ionic liquids with water or ethanol at four temperatures.

We present experimental measurements of specific electrical (or ionic) conductivity of seven binary systems of 1-ethyl-3-methyl imidazolium alkyl sulfate (EMIM-C(n)S) with water or ethanol. Electrical conductivity was measured at 298.15 K in all ranges of concentrations and selected mixtures also at 288.15, 308.15, and 318.15 K. The alkyl chains of the anions used are ethyl (EMIM-ES), butyl (EMIM-BS), hexyl (EMIM-HS), and, only for mixtures with ethanol, octyl (EMIM-OS). Let us note that the four ionic liquids (ILs) measured are miscible in water and ethanol at those temperatures and atmospheric pressure in all ranges of concentrations, but EMIM-OS jellifies for a given range of concentration with water. We compare the measured data in terms of the alkyl chain length and solvent nature. Data are compared with previously scarce results for these same systems and also for other aqueous and ethanol mixtures with ILs. In addition, we verify that our data fit the universal theoretical expression with no fitting parameters given by the pseudolattice-based Bahe-Varela model, except for IL concentrated mixtures. To fit well all ranges of concentrations, we add to the original equation two phenomenological terms with one fitting parameter each. Finally, we calculate the molar conductivity and fit it successfully with an expression derived from Onsager theory.

Effect of temperature and cationic chain length on the physical properties of ammonium nitrate-based protic ionic liquids.

We report a systematic study of the effect of the cationic chain length and degree of hydrogen bonding on several equilibrium and transport properties of the first members of the alkylammonium nitrate protic ionic liquids (PILs) family (ethylammonium, propylammonium, and butylammonium nitrate) in the temperature range between 10 and 40 °C. These properties were observed by means of several experimental techniques, including density, surface tension, refractometry, viscosimetry, and conductimetry. The dilatation coefficients and compressibilities, as well as the Rao coefficients, were calculated, and an increase of these magnitudes with alkyl chain length was detected. Moreover, the surface entropies and enthalpies of the studied PILs were analyzed, and the temperature dependence of the surface tension was observed to be describable by means of a harmonic oscillator model with surface energies and critical temperatures that are increasing functions of the cationic chain length. Moreover, the refractive indexes were measured and the thermo-optic coefficient and Abbe numbers were calculated, and the contribution of the electrostrictive part seemed to dominate the temperature dependence of the electric polarization. The electric conductivity and the viscosity were measured and the influence of the degree of hydrogen bonding in the supercooled liquid region analyzed. Hysteresis loops were detected in freezing-melting cycles and the effect of the length of the alkyl chain of the cation on the size of the loop analyzed, showing that longer chains lead to a narrowing of the supercooled region. The temperature dependence of the conductivity was studied in the Vogel-Fulcher-Tamman (VFT) framework and the fragility indices, the effective activation energies, and the Vogel temperatures obtained. A high-temperature Arrhenius analysis was also performed, and the activation energies of conductivity and viscosity were calculated, showing that these transport processes are governed by two distinct mechanisms. The exponents of the fractional Walden rule for the different compounds were obtained. Finally, the ionicities and fragilities of the studied PILs were analyzed, proving that all the studied PILs are subionic and fragile liquids, with propylammonium nitrate showing the lowest fragility and the greater ionicity of all the studied compounds.

Molecular dynamics simulations of the structural and thermodynamic properties of imidazolium-based ionic liquid mixtures.

In this work, extensive molecular dynamics simulations of mixtures of alcohols of several chain lengths (methanol and ethanol) with the ionic liquids (ILs) composed of the cation 1-hexyl-3-methylimidazolium and several anions of different hydrophobicity degrees (Cl(-), BF(4)(-), PF(6)(-)) are reported. We analyze the influence of the nature of the anion, the length of the molecular chain of the alcohol, and the alcohol concentration on the thermodynamic and structural properties of the mixtures. Densities, excess molar volumes, total and partial radial distribution functions, coordination numbers, and hydrogen bond degrees are reported and analyzed for mixtures of the ILs with methanol and ethanol. The aggregation process is shown to be highly dependent on the nature of the anion and the size of the alcohol, since alcohol molecules tend to interact predominantly with the anionic part of the IL, especially in mixtures of the halogenated IL with methanol. Particularly, our results suggest that the formation of an apolar network similar to that previously reported in mixtures of ILs with water does not take place in mixtures with alcohol when the chloride anion is present, the alcohol molecules being instead homogeneously distributed in the polar network of IL. Moreover, the alcohol clusters formed in mixtures of [HMIM][PF(6)] with alcohol were found to have a smaller size than in mixtures with water. Additionally, we provide a semiquantitative analysis of the dependence of the hydrogen bonding degree of the mixtures on the alcohol concentration.

Demanda y atención a la población pediátrica por médicos no pediatras en un punto de atención continuada / Demand at an urban urgent care center where 24-hour pediatric care by non-pediatricians is available

Objective: Overcrowding is a significant problem for pediatric emergency departments of hospitals. Some of the patients brought to such services could receive care outside the hospital. Our objective was to determine demand forL. M. Trejo Varela et al.302 Emergencias 2011; 23: 299-302 pediatric care at an urban urgent care center that ensured 24-hour coverage; care was provided by non-pediatricians who received training in pediatric urgent care. Methods: Retrospective, descriptive, observational study of patients under the age of 14 years treated at an urban urgent care center in 1 year. We analyzed sociodemographic data, reasons for consulting, diagnoses, treatments, and referral or not to a hospital. Results: A total of 2711 requests for pediatric urgent care were managed at this center. The most frequent reasons for seeking care were fever (30.3%), respiratory symptoms without breathing difficulty (29.5%), skin lesions (11%), and blunt trauma or cuts (10%). The main diagnoses were upper respiratory tract infection (21.5%), sore throat or tonsillitis(14.4%), fever syndrome (13.8%), and cuts and blunt trauma (10%). The most commonly prescribed treatments were antipyretics, analgesics (paracetamol and/or ibuprofen), and/or written or verbal recommendations (57%), and antibiotics (24.2%). The patient was referred to a hospital in 5.7% of the cases, most often for treatment of blunt trauma or cuts (35.7%).Conclusions: Fever and respiratory symptoms in the absence of respiratory difficulty were the reasons for seeking care for most pediatric patients. Most cases could be managed on the basis of physical examination and history taking. This type of urgent care center is a promising approach to reducing hospital emergency department overcrowding (AU)

Objetivo: Un problema importante de los servicios de urgencias de pediatría hospitalarios es la saturación de los mismos por la afluencia de pacientes que podrían recibir atención extrahospitalaria. Por ello, se estudió la demanda y la asistencia pediátricas en un punto de atención continuada (PAC) urbano por parte de médicos no pediatras que han recibido formación en atención pediátrica urgente. Métodos: Estudio retrospectivo, descriptivo y observacional de los pacientes menores de 14 años atendidos en un PAC urbano durante 1 año. Se analizan datos sociodemográficos, motivos de consulta, diagnósticos, tratamientos y derivación o no a un hospital. Resultados: Se realizaron 2.771 atenciones pediátricas en el PAC. Los motivos de consulta más frecuentes fueron fiebre (30,3%), síntomas respiratorios sin dificultad respiratoria(29,5%), lesiones cutáneas (11%) y traumatismos y heridas (10%). Los diagnósticos principales fueron infección de vías respiratorias altas (21,5%), faringo-amigdalitis(14,4%), síndrome febril (13,8%) y heridas y traumatismos (10%). Los tratamientos más habituales fueron antitérmicos, analgésicos (paracetamol y/o ibuprofeno) y/o recomendaciones verbales o escritas (57%) y antibióticos (24,2%). El 5,7% de pacientes se trasladó al hospital, principalmente por traumatismos y heridas (35,7%).Conclusiones: La mayoría de las consultas pediátricas están motivadas por fiebre y síntomas respiratorios sin dificultad respiratoria. En la mayoría de los casos una correcta valoración clínica y exploración son suficientes para el manejo de estos niños. En consecuencia, la posibilidad de acceder a este tipo de servicio puede resultar útil para disminuirla masificación de las urgencias hospitalarias (AU)

Surfactant self-assembly nanostructures in protic ionic liquids.

The existence and properties of mesoscopic self-assembly structures formed by surfactants in protic ionic liquid solutions are reported. Micellar aggregates of n-alkyltrimethylammonium (n = 10, 12, 14, 16) chlorides and bromides and of n-alkylpyridinium (n = 12, 16) chlorides in ethylammonium nitrate and propylammonium nitrate were observed by means of several experimental techniques, including surface tension, transmission electron micrography, dynamic light scattering, and potentiometry using surfactant-selective electrodes. The effect of the alkyl chain length of both solute and solvent molecules on the critical micelle concentration is discussed, and a Stauff-Klevens law is seen to apply to surfactant solutions in both protic ionic liquids. The counterion role is also a matter of study in the case of alkyltrimethylammonium-based surfactants, and the presently reported evidence suggests that the place of the surfactant counterion in the Hoffmeister's series could determine its effect on micellization in IL solution. The size distribution of the aggregates is also analyzed together with the Gibbs free energies of micellization and the minimum surface area per monomer in all of the studied cases. All of the hereby reported evidence suggests that the negative entropic contribution arising from the release of the solvent layer upon micellization is also the driving force of conventional surfactant self-association in protic ionic liquids.

Pseudolattice theory of the surface tension of ionic liquid-water mixtures.

A theoretical model for ionic liquids (ILs) based on a pseudoreticular structural model for the bulk mixture is reported. The original Bahe-Varela pseudolattice theory of concentrated ionic solutions is modified and the short-range interactions modeled by a Lennard-Jones potential. In this framework, the surface tension of the pure IL is calculated and the correct dependence of this magnitude on the density of the liquid, as provided by the parachor, is recovered. The anions in the mixture are assumed to form a continuum structureless neutralizing background, and that the organic cations and water molecules are placed in the nodes of the pseudolattice. The surface pressure of IL-water mixtures is calculated using a localized model for the adsorption of particles in the surface of the mixture and a mean-field Bragg-Williams approximation for the chemical potential of the adsorbed particles in the pseudolattice. The theoretical predictions are tested with experimental data of several ionic liquid aqueous mixtures.

Nonequilibrium nanothermodynamics.

Entropy production for a system outside the thermodynamic limit is formulated using Hill's nanothermodynamics, in which a macroscopic ensemble of such systems is considered. The external influence of the environment on the average nanosystem is connected to irreversible work with an explicit formula based on the Jarzynski equality. The entropy production retains its usual form as a sum of products of fluxes and forces and Onsager's symmetry principle is proven to hold for the average nanosystem, if it is assumed to be valid for the macroscopic ensemble, by two methods. The first one provides expressions that relate the coefficients of the two systems. The second gives a general condition for a system under an external force to preserve Onsager's symmetry.

Sphere to rod transitions in homologous alkylpyridinium salts: a Stauff-Klevens-type equation for the second critical micelle concentration.

In the present paper, we analyze the dependence of the second critical micelle concentration (second cmc) of ionic amphiphiles on the number of atoms in the hydrocarbon molecular chain, n(c). A molecular thermodynamic model for the interaction energy between the end caps of rodlike micelles, g(N), is introduced and the linear dependence of this object on n(c) analyzed, thus leading to a Stauff-Klevens-like behavior of the second cmc. The predictions agree with previously reported data for n-alkyldimethylbenzylammonium chloride (C(n)BACl) for n-alkylpyridinium chloride (C(n)PyCl) and n-alkyltrymethylammonium bromide (C(n)TABr) at 35 degrees C. These conclusions are reinforced by the conductivity, density, and ultrasound velocity measurements of the second cmc of several C(n)PyCl (n=12, 14, 16) and n-alkylpyridinium bromides (C(n)PyBr, n=12, 14, 15, 16) presented in this paper.

Electrical conductivity of aqueous solutions of aluminum salts.

We present experimental measurements of the specific electrical conductivity (sigma) in aqueous solutions of aluminum salts at different temperatures, covering all salt concentrations from saturation to infinite dilution. The salts employed were AlCl(3), AlBr(3), AlI(3), and Al(NO(3))(3), which present a 1:3 relationship between the electrical charges of anion and cation. In addition, we have measured the density in all ranges of concentrations of the four aqueous electrolyte solutions at 298.15 K. The measured densities show an almost linear behavior with concentration, and we have fitted it to a second order polynomial with very high degree of approximation. The measurement of the specific conductivity at constant temperature reveals the existence of maxima in the conductivity vs concentration curves at molar concentrations around 1.5M for the three halide solutions studied, and at approximately 2M for the nitrate. We present a theoretical foundation for the existence of these maxima, based on the classical Debye-Hu ckel-Onsager hydrodynamic mean-field framework for electrical transport and its high concentration extensions, and also a brief consideration of ionic frictional coefficients using mode-coupling theory. We also found that the calculated values of the equivalent conductance vary in an approximately linear way with the square root of the concentration at concentrations as high as those where the maximum of sigma appears. Finally, and for completeness, we have measured the temperature dependence of the electrical conductivity at selected concentrations from 283 to 353 K, and performed a fit to an exponential equation of the Vogel-Fulcher-Tamman type. The values of the calculated temperatures of null mobility of the four salts are reported.

Adsorption of an amphiphilic penicillin onto human serum albumin: characterisation of the complex.

The complex formed by the interaction of the amphiphilic penicillin drug nafcillin and human serum albumin (HSA) in water at 25 degrees C has been characterised using a range of physicochemical techniques. Measurements of the solution conductivity and the electrophoretic mobility of the complexes have shown an ionic adsorption of the drug on the protein surface leading to a surface saturation at a nafcillin concentration of 0.012 mmol kg(-1) and subsequent formation of drug micelles in solutions of higher nafcillin concentration. Measurements of the size of the complex and the thickness of the adsorbed layer by static and dynamic light scattering have shown a gradual change in hydrodynamic radius of the complex with increasing drug concentration typical of a saturation rather than a denaturation process, the magnitude of the change being insufficient to account for any appreciable extension or unfolding of the HSA molecule. The interaction potential between the HSA/nafcillin complexes, and the stability of the complexes were determined from the dependence of diffusion coefficients on protein concentration by application of the DLVO colloidal stability theory. The results indicate decreasing stability of the colloidal dispersion of the drug/protein complexes with an increase in the concentration of added drug.

TNFalpha induces NFkappaB/p50 in association with the growth and morphogenesis of normal and transformed rat mammary epithelial cells.

In contrast to the cytotoxic or cytostatic effect of TNFalpha on many breast cancer cell lines, TNFalpha stimulates growth and morphogenesis of normal rat mammary epithelial cells (MEC). The present studies were carried out to determine whether there are intrinsic differences between normal and malignant MEC which may explain the differing responsiveness to TNFalpha. Freshly isolated rat MEC organoids from normal mammary gland or 1-methyl-1-nitrosourea-induced mammary tumors were treated with TNFalpha for 21 days. Unexpectedly, TNFalpha stimulated growth and morphogenesis of both normal and transformed MEC in primary culture, although in transformed cells its effects were delayed and the majority of the colonies were histologically abnormal, with multiple cell layers and no lumen. Since NFkappaB is a key mediator of TNFalpha action and has been implicated in carcinogenesis, the expression of the p50, p52, p65, and c-rel NFkappaB proteins in normal and transformed MEC was determined. Expression of p52 was significantly reduced in tumor cells, and p50 was absent, although its putative precursor, p105 was abundant. There were no changes in the levels of p65 or c-rel. TNFalpha induced a pronounced and sustained increase of a p50 homodimeric NFkappaB/DNA complex in both normal and transformed MEC. However, in transformed MEC, NFkappaB binding was initially undetectable but then increased in response to TNFalpha. Thus, NFkappaB expression and DNA binding activity are altered during mammary carcinogenesis. In addition, the significant increase in NFkappaB/p50 DNA-binding was temporally coincident with TNFalpha-induced growth and morphogenesis, suggesting that it may play a significant role in both normal development and carcinogenesis.

Selective changes in EGF receptor expression and function during the proliferation, differentiation and apoptosis of mammary epithelial cells.

Epidermal growth factor (EGF) is a multifunctional regulator of mammary epithelial cells (MEC) that transduces its signals through the EGF receptor (EGFR). To clarify the role of the EGFR in the mammary gland, EGFR expression, localization and function were examined during different developmental stages in rats. Immunoblot analysis demonstrated high levels of EGFR during puberty, pregnancy and involution as well as at sexual maturity, and low levels throughout lactation. An immunohistochemical assay was used to show that EGFR was distinctly expressed in a variety of cell types throughout mammary glands from virgin rats and rats during pregnancy and involution, and was down-regulated in all cell types throughout lactation. To examine the relationship between EGFR expression and function, primary MEC were cultured under conditions that induced physiologically relevant growth, morphogenesis and lactogenesis. Cultured MEC expressed an in vivo-like profile of EGFR. EGFR was high in immature MEC, down-regulated in functionally differentiated MEC, and then up-regulated in terminally differentiated and apoptotic MEC. An inhibitor of the tyrosine kinase domain of EGFR was used to demonstrate that EGFR signaling was required for growth and differentiation of immature MEC, and for survival of terminally differentiated MEC, but not for maintaining functional differentiation.

The epidermal growth factor receptor is not required for tumor necrosis factor-alpha action in normal mammary epithelial cells.

Our laboratory has shown that tumor necrosis factor-alpha (TNF alpha) can regulate normal mammary epithelial cell (MEC) growth, morphogenesis, and, under certain circumstances, functional differentiation in a manner similar to epidermal growth factor (EGF). As TNF alpha has been shown to up-regulate EGF receptor (EGFR) expression and function in other systems, the present studies were undertaken to determine whether TNF alpha action in MEC was indirect through stimulation of the EGFR. An inhibitor of EGFR tyrosine kinase activity, PD158780, failed to block proliferation induced by 40 ng/ml TNF alpha and only partially inhibited growth in response to 2 ng/ml TNF alpha. PD158780 was also unable to suppress the extensive morphological development induced by either TNF alpha concentration. In contrast, the effects of TNF alpha and PD158780 on functional differentiation (i.e. casein accumulation) were time dependent. When measured on day 7 after 48 h of treatment, casein accumulation was unaffected by either concentration of TNF alpha or by PD158780. When assessed on day 21 after 16 days of treatment, however, casein levels were decreased by 40 ng/ml TNF alpha and increased by PD158780. Significantly, this PD158780-induced increase in casein was not observed in MEC that had been treated with both PD158780 and TNF alpha. These results thus suggest that EGFR tyrosine kinase activity is not necessary for TNF alpha action in normal MEC.

Tumor necrosis factor-alpha: a multifunctional regulator of mammary gland development.

To determine whether tumor necrosis factor-alpha (TNF alpha) plays a physiological role in normal mammary gland development, TNF alpha and TNF receptor expression were measured in epithelial cells (MEC) isolated from mammary glands of virgin, pregnant, lactating, and postlactational (day 7 of involution) rats. TNF alpha messenger RNA (mRNA) increased significantly during pregnancy, then decreased during lactation and involution. The 26-kDa transmembrane form of TNF alpha protein, undetectable in MEC from virgin rats, increased throughout pregnancy and lactation, and disappeared during involution. In contrast, p55 TNF receptor (TNFR) mRNA levels peaked in early lactation and declined thereafter, whereas p75 TNFR mRNA levels rose steadily through lactation. Using agonistic antibodies specific to either TNFR, the individual roles of each TNFR were investigated in MEC in primary culture. The p55 TNFR was found to be the sole mediator of TNF alpha-induced proliferation. Intriguingly, the two receptors were found to have opposing effects on functional differentiation (casein accumulation), with inhibition occurring through the p55 receptor and stimulation through the p75 receptor. Taken together, these results suggest that TNF alpha plays a role in the growth and development of the mammary gland. In addition, both TNF receptors are important for TNF alpha function and may mediate different effects.