In order to understand how live matter functions one needs to understand the interaction between polyelectrolytes. We discover a general dependence of polyelectrolyte conductivity valid in at least nine decades of polyelectrolyte concentration spanning dilute and semidilute pure water solutions. Furthermore, we showed that current state of the art theories can not explain polyelectrolyte conductivity and suggest the path in transport theories which needs to be taken in order to explain polyelectrolyte conductivity.
Dissolved ions can alter the local permittivity of water, nevertheless most theories and simulations ignore this fact. We present a novel algorithm for treating spatial and temporal variations in the permittivity and use it to measure the equivalent conductivity of a salt-free polyelectrolyte solution. Our new approach quantitatively reproduces experimental results unlike simulations with a constant permittivity that even qualitatively fail to describe the data. We can relate this success to a change in the ion distribution close to the polymer due to the built-up of a permittivity gradient.
Amorphous polymers are known as thermal insulators, increasing their thermal conductivities have not been guided by fully understood physics. In this work, we use molecular dynamics simulations to study the thermal transport mechanism of solid polyelectrolytes, poly(acrylic acid) (PAA) and its ionized forms. The thermal conductivity of PAA increases monotonically with the ionization strength. Although stronger ionization induces larger Coulombic interactions, the Coulombic interaction does not directly contribute to the thermal conductivity enhancement. Instead, it enhances thermal transport t…
We address the long standing problem of the dependence of the electrostatic persistence length $l_e$ of a flexible polyelectrolyte (PE) on the screening length $r_s$ of the solution within the linear Debye-Huckel theory. The standard Odijk, Skolnick and Fixman (OSF) theory suggests $l_e \propto r_s^2$, while some variational theories and computer simulations suggest $l_e \propto r_s$. In this paper, we use Monte-Carlo simulations to study the conformation of a simple polyelectrolyte. Using four times longer PEs than in previous simulations and refined methods for the treatment of the simulatio…
We demonstrate in this paper the influence of solvent quality on the structure of the semi-dilute solution of a hydrophobic polyelectrolyte, partially sulfonated Poly-Styrene Sulfonate. Two solvents are used: (i) one mixture of water and an organic solvent: THF, which is also slightly polar; (ii) DMSO, a polar organic solvent. In case (i), it is shown by SAXS study that the structure - namely the scattering from all chains, characterised by a maximum ("polyelectrolyte peak"), of the aqueous hydrophobic polyelectrolyte solutions (PSS) depends on the solvent quality through the added amount of o…
The role of electrostatics on the interfacial properties of polyelectrolyte microgels has been discussed controversially in the literature. It is not yet clear if, or how, Coulomb interactions affect their behavior under interfacial confinement. In this work, we combine compression isotherms, atomic force microscopy imaging, and computer simulations to further investigate the behavior of pH-responsive microgels at oil-water interfaces. At low compression, charged microgels can be compressed more than uncharged microgels. The in-plane effective area of charged microgels is found to be smaller i…
Synchrotron-X-ray and surface tension studies of a strong polyelectrolyte (PE) in the semi-dilute regime (~ 0.1M monomer-charges) with varying surfactant concentrations show that minute surfactant concentrations induce the formation of a PE-surfactant complex at the gas/solution interface. X-ray reflectivity and grazing angle X-ray diffraction (GIXD) provide detailed information of the top most layer, where it is found that the surfactant forms a two-dimensional liquid-like monolayer, with a noticeable disruption of the structure of water at the interface. With the addition of salt (NaCl) colu…
In this communication we illustrate the occurrence of a recently reported new phenomenon of surface-charge amplification, SCA, (originally dubbed overcharging, OC), [Jimenez-Angeles F. and Lozada-Cassou M., J. Phys. Chem. B, 2004, 108, 7286] by means of molecular dynamics simulation of aqueous electrolytes solutions involving multivalent cations in contact with charged graphene walls and the presence of short-chain lithium polystyrene sulfonates where the solvent water is described explicitly with a realistic molecular model. We show that the occurrence of SCA in these systems, in contrast to …
The form factor of partially sulfonated polystyrene PSSNa (degree of sulfonation f =1, 0.72, 0.64 and 0.36), at polymer concentration 0.17M and 0.34M, without or with added salt (0 M, 0.34M, & 0.68M), is measured by Small Angle Neutron Scattering using the Zero Average Contrast method. The total scattering function is also measured, allowing extracting the distinct interchain function and an apparent structure factor. The main result is the behavior of the form factor which shows contributions of spherical entities as well as extended chain parts. This is striking for 0.64, while for f = 0.36 …
The low-frequency limit of the electrical conductivity (d.c. conductivity) of differently flexible polyions in aqueous solutions has been measured over an extended polyion concentration range, covering both the dilute and semidilute (entangled and unentangled) regime, up to the concentrated regime. The data have been analyzed taking into account the different flexibility of the polymer chains according to the scaling theory of polyion solutions, in the case of flexible polyions, and according to the Manning model, in the case of rigid polyions. In both cases, the fraction f of free counterions…
The structure of spherical micelles of the diblock poly(styrene-block-acrylic acid) [PS-b-PA] copolymer in water was investigated up to concentrations where the polyelectrolyte coronal layers have to shrink and/or interpenetrate in order to accommodate the micelles in the increasingly crowded volume. We obtained the partial structure factors pertaining to the core and corona density correlations with small angle neutron scattering (SANS) and contrast matching in the water. The counterion structure factor was obtained with small angle X-ray scattering (SAXS) with a synchrotron radiation source.…
In order to better understand the collapse of polyions in poor solvent conditions the effective charge and the solvent quality of the hypothetically uncharged polymer backbone need to be known. In the present work this is achieved by utilizing poly-2-vinylpyridine quaternized to 4.3% with ethylbromide. Conductivity and light scattering measurements were utilized to study the polyion collapse in isorefractive solvent/non-solvent mixtures consisting of 1-propanol and 2-pentanone, respectively, at nearly constant dielectric constant. The solvent quality of the uncharged polyion could be quantifie…
For a tailored functionalization of cellulose based papers, the interaction between paper fibers and functional additives have to be understood. Planar cellulose surfaces present a suitable model system for studying the binding of additives. In this work, polyelectrolyte multilayers (PEMs) as model surfaces are prepared by alternating dip coating of the negatively charged cellulose derivate carboxymethyl cellulose and a polycation, either PDADMAC or chitosan. The varied parameters of the PEM formation are the polyelectrolyte concentrations and pH (pH=2-6). Both PEM systems exhibit an exponenti…
Polyelectrolyte multilayers (PEM) in combination with good electrolyte solvents, e.g., ionic liquids (ILs) are potential candidates for the new generation of electrochemical separators. Swelling PEM with aqueous IL solutions is one way to incorporate IL in PEM. In addition to quantifying the IL uptake in PEM, physical characterization of the swollen PEM is essential for their potential applications and to uncover the underlying molecular process of the swelling. In this article, thickness and viscoelasticity of PEI(PSS/PADMAC)4PSS and PEI(PSS/PAH)4PSS multilayers were determined upon uptake of…
The analysis of the low-frequency conductivity spectra of the clay-water mixtures is presented. The conductivity spectra for samples at different water content values are shown to collapse to a single master curve when appropriately rescaled. The frequency dependence of the conductivity is shown to follow the power-law with the exponent n=0,67 before reaching the frequency-independent part. It is argued that the observed conductivity dispersion is a consequence of the anomalously diffusing ions in the clay-water system. The fractional Langevin equation is then used to describe the stochastic d…
Theoretical calculations of the conductivity of sodium nitrate in water are presented and compared with experimental measurements. The method of direct correlation force in the framework of the interionic theory is used for the calculation of transport properties in connection with the associative mean spherical approximation (AMSA). The effective interactions between ions in solutions are derived with the help of Monte Carlo and Molecular Dynamics calculations on the Born-Oppenheimer level. This work is based on earlier theoretical and experimental studies of the structure of concentrated aqu…
We report a new anomaly of water, a minimum in the thermal conductivity in the supercooled region. Our findings are consistent with the presence of a liquid-liquid phase transition in water
We have used coarse-grained simulation methods to investigate the effect of stretching-induced structure orientation on the proton conductivity of Nafion-like polyelectrolyte membranes. Recent experimental data on the morphology of ionomers describe Nafion as an aggregation of polymeric backbone chains forming elongated objects embedded in a continuous ionic medium. Uniaxial stretching of a recast Nafion film causes a preferential orientation of these objects in the direction of stretching. Our simulations of humid Nafion show that this has a strong effect on the proton conductivity, which is …
Motivated by recent experiments we have studied the optical conductivity of DNA in its natural environment containing water molecules and counter ions. Our density functional theory calculations (using SIESTA) for four base pair B-DNA with order 250 surrounding water molecules suggest a thermally activated doping of the DNA by water states which generically leads to an electronic contribution to low-frequency absorption. The main contributions to the doping result from water near DNA ends, breaks, or nicks and are thus potentially associated with temporal or structural defects in the DNA.
We have studied the ionic conductivity and the dipolar reorientational dynamics of aqueous solutions of a prototypical deep eutectic solvent (DES), ethaline, by using dielectric spectroscopy on a broad range of frequency (MHz-Hz) and for temperatures ranging from 128 to 283 K. The fraction of water in the DES was varied systematically to cover different regimes, starting from pure DES and its water-in-DES mixtures to the diluted electrolyte solutions. Depending on these parameters, different physical states were examined, including low viscosity liquid, supercooled viscous liquid, amorphous so…
Nanofluids are suspensions of nanoparticles in a base heat-transfer liquid. They have been widely investigated to boost heat transfer since they were proposed in the 1990's. We present a statistical correlation analysis of experimentally measured thermal conductivity of water-based nanofluids available in the literature. The influences of particle concentration, particle size, temperature and surfactants are investigated. For specific materials (alumina, titania, copper oxide, copper, silica and silicon carbide), separate analyses are performed. The conductivity increases with the concentratio…
The intriguing relationship between entropy and diffusion is a subject of much current interest. However, the experimentally observed unusual non-monotonic dependence of limiting ionic conductivity on inverse ion size is neither described by the Adam-Gibbs entropy crisis theory nor by the Rosenfeld entropy scaling. This failure is obvious because throughout the size variation the bulk entropy of the solvent remains the same, or undergoes infinitesimal change. We show that it is the entropy experienced by the tagged ion that needs to be calculated. This entropy can be quantified, at least partl…
Using dielectric spectroscopy and differential scanning calorimetry, we have performed a detailed investigation of the influence of water uptake on the translational and reorientational glassy dynamics in the typical ionic liquid 1-Butyl-3-methyl-imidazolium chloride. From a careful analysis of the measured dielectric permittivity and conductivity spectra, we find a significant acceleration of cation reorientation and a marked increase of the ionic conductivity for higher water contents. The latter effect mainly arises due to a strong impact of water content on the glass temperature, which for…
A soliton model for proton conductivity in Langmuir films is presented. The model contains three real scalar fields describing the hydrogen involved in the conduction, the hydrophilic head of the Langmuir film, and the water. Soliton solutions that describe proton motion along the hydrogen bonds are found. Under compression of the film, the distance between the minima of the proton potential and the strength of the hydrogen bonds between the film molecule and the water are changed. Such changes increase the probability of soliton creation. The model presented allows proton conductivity data in…
The dielectric spectrum of liquid water, $10^{4} - 10^{11}$ Hz, is interpreted in terms of diffusion of charges, formed as a result of self-ionization of H$_{2}$O molecules. This approach explains the Debye relaxation and the dc conductivity as two manifestations of this diffusion. The Debye relaxation is due to the charge diffusion with a fast recombination rate, $1/τ_{2}$, while the dc conductivity is a manifestation of the diffusion with a much slower recombination rate, $1/τ_{1}$. Applying a simple model based on Brownian-like diffusion, we find $τ_{2} \simeq 10^{-11}$ s and $τ_{1} \simeq …
The microstructure and electrical conductivity of suspensions of multi-walled carbon nanotubes (MWCNTs) in binary liquid mixtures water-1-Cyclohexyl-2-pyrrolidone (CHP) were studied in the heating and cooling cycles. The concentration of MWCNTs was varied in the interval between 0-1 wt.% and the content of water in a binary mixture X = [water]/([CHP]+[water]) was varied within 0-1.0. The experimental data have shown that dispersing quality of MWCNTs in a mixture of good (CHP) and bad (water) solvents may be finely regulated by adjustment of composition of the CHP+ water mixtures. The aggregati…
