Dynamics and Structure of Biopolyelectrolytes Characterized by Dielectric Spectroscopy

Structural properties of Na-DNA and Na-HA aqueous solutions can be quantified using dielectric spectroscopy in the frequency range 100 Hz–100 MHz. Two relaxation modes are typically detected that can be attributed to diffusive motion of polyion counterions. The overall study as a function of polyion length, concentration and added salt concentration demonstrates that the motion of polyion counterions detected at MHz frequencies probes collective properties, whereas the motion at kHz range probes single-chain properties of polyelectrolytes. Fundamental length scales found to characterize the polyelectrolyte structure differ for the dilute and semidilute regime and also depend on the strength of electrostatic interactions and the flexibility. Characteristic length scales detected in the dielectric spectroscopy measurements compare well with the fundamental length scales predicted by theory and comply with those extracted from small-angle X-ray scattering.     

High-frequency dielectric and conductometric properties of poly-l-lysine aqueous solutions at the crossover between semidilute and entangled regime

The dielectric and conductometric properties of poly-l-lysine aqueous solutions have been investigated in the frequency range from 1 MHz to 1.8 GHz, where micro-Brownian dynamics and internal motion of side-chain polar groups result in a well-defined relaxation process, intermediate between that caused by counterion polarization (characteristic of the polyelectrolyte nature of the polyion investigated) and that associated with the orientational polarization of the aqueous phase. The polymer concentration has been varied in a wide interval in order to investigate the influence of different chain conformations on the dielectric parameters as a consequence of the different concentration regimes occurring in these systems. With the help of polymer scaling theories, scaling relations for the dielectric strength and the relaxation time are presented, predicting, as the polymer concentration is increased, a transition from semidilute-unentangled to semidilute-entangled regimes. We compare these predictions with the experimental findings over the whole concentration range investigated, with a qualitative agreement. Deviations from the scaling behavior related to a crossover regime between unentangled and entangled regions are briefly discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3123–3130, 1999     

Radiofrequency dielectric loss relaxation in polyion-induced liposome aggregates

In this note, we present a set of dielectric loss relaxation measurements of aqueous charged liposome suspensions during the whole aggregation process induced by oppositely charged adsorbing polyions. The system experiences two concomitant effects known as "reentrant condensation" and "charge inversion," resulting in the formation of liposome aggregates whose average size reaches a maximum in the vicinity of the electroneutrality condition, accompanied to a progressive reduction of their overall electrical charge. Far from the neutrality, from both sides, polyion-coated liposomes exist with a charge of opposite sign. The dielectric loss relaxation in these complex aggregating systems has never been measured so far and we report here, for the first time, the dielectric loss behavior of liposomes built up by a cationic lipid and stuck together by poly(acrylate), which is a flexible oppositely charged polyion. The data are analyzed in the framework of standard electrokinetic model theory. The evolution of the aggregation process as a function of the polyion content is mainly characterized by a counterion polarization effect, governed by the surface charge density of the aggregates and hence by the zeta-potential.     

Entropy and enthalpy of polyelectrolyte complexation: Langevin dynamics simulations

We report a systematic study by Langevin dynamics simulation on the energetics of complexation between two oppositely charged polyelectrolytes of same charge density in dilute solutions of a good solvent with counterions and salt ions explicitly included. The enthalpy of polyelectrolyte complexation is quantified by comparisons of the Coulomb energy before and after complexation. The entropy of polyelectrolyte complexation is determined directly from simulations and compared with that from a mean-field lattice model explicitly accounting for counterion adsorption. At weak Coulomb interaction strengths, e.g., in solvents of high dielectric constant or with weakly charged polyelectrolytes, complexation is driven by a negative enthalpy due to electrostatic attraction between two oppositely charged chains, with counterion release entropy playing only a subsidiary role. In the strong interaction regime, complexation is driven by a large counterion release entropy and opposed by a positive enthalpy change. The addition of salt reduces the enthalpy of polyelectrolyte complexation by screening electrostatic interaction at all Coulomb interaction strengths. The counterion release entropy also decreases in the presence of salt, but the reduction only becomes significant at higher Coulomb interaction strengths. More significantly, in the range of Coulomb interaction strengths appropriate for highly charged polymers in aqueous solutions, complexation enthalpy depends weakly on salt concentration and counterion release entropy exhibits a large variation as a function of salt concentration. Our study quantitatively establishes that polyelectrolyte complexation in highly charged Coulomb systems is of entropic origin.     

聚吡咯微粒掺入的聚苯乙烯膜在电解质溶液中的介电弛豫谱及其解析

在40 Hz～11 MHz频率范围测量了聚苯乙烯膜以及混入聚吡咯粒子的聚苯乙烯膜和电解质溶液构成的体系的介电谱, 发现了特异的弛豫现象: 纯的和掺入导电性聚吡咯后的聚苯乙烯膜分别显示出单一弛豫和双弛豫的不同模式的介电谱. 在Maxwell-Wagner界面极化概念基础上解释了该弛豫机制: 高、低频弛豫分别由膜-液界面极化和膜相本身的不均一性引起的. 将体系进行了模型化, 并利用Hanai理论方法对谱进行了解析, 获得了内部电性质的诸多参数. 对不同聚吡咯掺入量的膜/溶液体系的介电测量和解析结果表明, 电解质溶液的种类、浓度以及膜中混入聚吡咯的量都影响着膜相的介电响应. 这些结论为利用加入导电粒子改善绝缘高分子聚合物的电性质的研究以及制备既具有导电功能又使基体的力学性能得到提高的高分子复合物提供了重要的线索.     

聚电解质溶液热力学性质的研究

本文采用柱形胞腔模型以及Vink的近似方法, 求解聚电解质溶液的Poisson-Boltzmann方程, 得到不同条件下聚离子周围静电势的分布。进而得到了不同条件下聚离子、反离子和同电荷离子的活度系数及溶剂的渗透系数。所得结果与实验值能较好地吻合。     

Magnetic relaxation dispersion of lithium ion in solutions of DNA

The magnetic field dependence of the nuclear spin-lattice relaxation rate constant defines the magnetic relaxation dispersion (MRD) and provides a direct characterization of the molecular dynamics that cause fluctuations in the magnetic couplings in the system and may also indicate the dimensional constraints on the motion. The counterion cloud surrounding a linear polyelectrolyte ion, such as DNA in solution, provides an interesting opportunity for ion confinement that helps in understanding the thermodynamics and the dynamics of the interactions between the polyion and other solutes. The MRD profiles of lithium ion and tetramethylammonium ion were recorded in dilute aqueous solutions of native calf thymus DNA, which provides a long, charged rod that reorients slowly. The 7Li ion relaxes through the nuclear electric quadrupole coupling and the proton-lithium dipole-dipole coupling; the protons of the tetramethylammonium ion relax by dipole-dipole coupling. MRD profiles of the 7Li+ ion are dominated by transient interactions with the DNA that yield a linear dependence of the spin-lattice relaxation rate constant on the logarithm of the Larmor frequency. This magnetic field dependence is consistent with diffusive ion motions that modulate two spatial coordinates that characterize the relaxation couplings in the vicinity of the polyion. Motions around the rod and fluctuations in the ion distance from the rod are consistent with these constraints for lithium. The magnetic field dependence of the tetramethylammonium ion proton relaxation rate constant is weak, but also approximately a linear function of the logarithm of the Larmor frequency, which implies that the field dependence is caused in part by local order in the DNA solution.     

The Dipole Moment and Molecular Mobility of Cholesteryl-Containing Monomers in Solution: Association and Gel Formation

The permittivity, molecular dipole moment, and dielectric relaxation parameters (relaxation time and activation energy) of cholesteryl esters of alkyl-, methacryloyl-ω-oxy-, and aminocarboxylic acids were studied in dilute solutions in toluene. The influence of the chemical structure of molecules on these characteristics was considered. The presence of NH groups and cholesteryl radicals (responsible for H-bonding and specific dispersion interactions) and an increase in the length of methylene chains in molecules substantially influenced dipole moments and dipole polarization relaxation times and contributed to the development of structuring processes (association and gel formation) in solutions of these compounds.     

Wide-frequency-range dielectric response of polystyrene latex dispersions

In this work we analyze the dielectric properties of dilute colloidal suspensions of nonconducting spherical particles with a thin electrical double layer from experimental data obtained by performing impedance spectroscopy experiments over a broad frequency range, from 20 Hz to 1 GHz. The electrode polarization correction was made by fitting a circuit model in the complex impedance plane (impedance spectrum) using a constant phase angle (CPA) element to fit the electrode polarization in series with the sample impedance. This simple procedure is found to be effective in eliminating the electrode contribution. The dielectric response shows two different dispersions, the alpha relaxation (counterion relaxation) that occurs at low kilohertz frequencies, and the delta relaxation (Maxwell-Wagner effect) found in the MHz range. These are reasonably well fitted over a broad frequency range by the theoretical expressions given by a simplified standard model (not including anomalous conduction) and a generalized model (including anomalous conduction) for the low-frequency dispersion, plus Maxwell-Wagner-O'Konski theory for the delta relaxation in the mid-frequency range. An analysis was also made of the need to include, for these latices, the effects of ion mobility in the Stern layer in order for the values of the zeta-potential obtained from electrophoretic and dielectric data to be compatible with each other.     

Studies of polymer solvation by dielectric relaxation spectroscopy I: polyvinyl pyrrolidone in propylene carbonate,dimethyl sulfoxide and tetramethyl urea

The dielectric relaxation behavior of the title solutions of PVP 40000 is measured in the frequency domain (50 MHz to 36 GHz) at 20 °C. The polymer content of the solutions (up to 0.25 mole fraction of monomer units) is such that it does not yet contribute significantly to dielectric loss. The solvent relaxation shows in all cases a bulk and a slowed down contribution, both characterized by concentration-independent relaxation times. The slow contribution is ascribed to the solvate. Solvation numbers for dilute solutions roughly range between 2 and 4 per PVP repeat unit.     

Counterion release from adsorbed highly charged polyelectrolyte: an electrooptical study

The adsorption of sodium poly(4-styrene sulfonate) on oppositely charged beta-FeOOH particles is studied by electrooptics. The focus of this paper is on the release of condensed counterions from adsorbed polyelectrolyte upon surface charge overcompensation. The fraction of condensed Na+ counterions on the adsorbed polyion surface is estimated according to the theory of Sens and Joanny and it is compared with the fraction of condensed counterions on nonadsorbed polyelectrolyte. The relaxation frequency of the electrooptical effect from the polymer-coated particle is found to depend on the polyelectrolyte molecular weight. This is attributed to polarization of the layer from condensed counterions on the polyion surface, being responsible for creation of the effect from particles covered with highly charged polyelectrolyte. The number of the adsorbed chains is calculated also assuming counterion condensation on the adsorbed polyelectrolyte and semiquantative agreement is found with the result obtained from the condensed counterion polarizability of the polymer-coated particle. Our findings are in line with theoretical predictions that the fraction of condensed counterions remains unchanged due to the adsorption of highly charged polyelectrolyte onto weakly charged substrate.     

Effective charges of polyelectrolytes in a salt-free solution based on counterion chemical potential

The phenomenon of counterion condensation around a flexible polyelectrolyte chain with N monomers is investigated by Monte Carlo simulations in terms of the degree of ionization alpha, which is proportional to the effective charge. It is operationally defined as the ratio of observed to intrinsic counterion concentration, alpha = co/ci. The observed counterion concentration in the dilute polyelectrolyte solution is equivalent to an electrolyte solution of concentration co with the same counterion chemical potential. It can be determined directly by thermodynamic experiments such as ion-selective electrode. With the polyelectrolyte fixed at the center of the spherical Wigner-Seitz cell, the polymer conformation, counterion distribution, and chemical potential can be obtained. Our simulation shows that the degree of ionization rises as the polymer concentration decreases. This behavior is opposite to that calculated from the infinitely long charged rod model, which is often used to study counterion condensation. Moreover, we find that, for a specified line charge density, alpha decreases with an increment in chain length and chain flexibility. In fact, the degree of ionization is found to decline with increasing polymer fractal dimension, which can be tuned by varying bending modulus and solvent quality. Those results can be qualitatively explained by a simple model of two-phase approximation.     

The effect of external orienting electric field on dielectric relaxation of segmented polyesters in dilute solution

A comparative study of dipole polarization relaxation in the absence and in the presence of an external orienting electric field was performed for linear segmented polyesters with alternating rigid (oxyfumaroylbis-4-oxybenzoates) and flexible (methylene-CH₂-, ethylene oxide-CH₂CH₂-O-, and dimethylsiloxane-Si(CH₃)₂-O-Si(CH₃)₂-) fragments in dilute solutions. Polyesters that do not display mesomorphic properties in the bulk show several regions of dielectric absorption with relaxation character. These regions are associated with the motions via the local mobility mechanisms of different polar fragments of the macromolecule. In solutions of polyesters that possess LC properties in the bulk, large-scale dipole polarization relaxation with long relaxation times and high activation energies was revealed along with local dielectric relaxation transitions. This process is associated with the cooperative motion of mesogenic fragments in their associates. In an external orienting electric field, the intensity of dielectric absorption usually increases for all types of dielectric transition; relaxation times and activation energies experience changes only for large-scale processes.     

Mechanical and dielectric studies of carrageenan sols and gels

The temperature dependence of the dynamic shear modulus, strain optical coefficient, DC conductivity, and complex dielectric spectrum of κ- and ι-carrageenan aqueous solutions with K, Ca, Cs, and Na were measured in order to clarify the formation process of the cross-linking region and the gel network structure. From the correlation analysis between the shear modulus and the strain optical coefficient, we found that the stress inducing unit orientation increases with decreasing temperature, which strongly suggests that the branching number in a cross-linking region increases with decreasing temperature, which depends on counterion species. In terms of the correlation parameters, an increasing scheme of the branching number depends on counterion species. Just below the coil-helix transition temperature, dielectric relaxation arises, with relaxation time ∼100μs and relaxation strength ∼10³. Dielectric relaxation can be assigned to the counterion fluctuation in the parallel direction to the helical axis. The fluctuation distance of the counterion estimated from the relaxation time increases sharply in the initial stage of gelation and gradually reaches a constant value. We concluded that the longitudinal length of the aggregated region increases sharply at the initial state of gelation while the number of helical molecules bundled in a cross-linking region increases successively with decreasing temperature.     

Polyion-induced liposomal vesicle aggregation: a radiowave dielectric relaxation study

The radiowave dielectric properties of aqueous heterogeneous systems during the complexation of charged polyions and oppositely charged liposomal particles have been measured in a wide frequency range, between 100 Hz and 2 GHz. The formation of a polyion-liposome complex driven by the correlated polyion adsorption at the particle surface implies two concomitant effects referred to as reentrant condensation and charge inversion. Both of them are governed by electrostatic interactions and there is now strong evidence, based on experiments and simulations, that counterion release is the driving force of the aggregation process. From this point of view, dielectric technique may offer a suitable tool in the investigation of the structural properties of these aggregates. In spite of the fact that interaction of polyions with oppositely charged surfaces was extensively experimentally investigated, there are no papers concerning the dielectric properties during the polyion-induced aggregation. To get an insight into this important topic, the authors present here an extensive set of radiowave dielectric measurements of liposomal vesicle aqueous suspensions where the liposome aggregation was induced by an oppositely charged polyion. The aggregation was followed from the beginning, when most of the isolated liposomes predominate, up to the formation of polyion-coated liposomes of inverted charge, crossing the isoelectric condition, where large, almost neutral, aggregates appear. The authors describe the observed dielectric dispersions as due to counterion polarization in the adjacency of the liposome and liposome aggregate surface, primarily governed by the zeta potential, according to the standard electrokinetic model.     

Transport,and thermodynamic investigations on sodium polystyrenesulfonate in ethylene glycol–water media

Polyion–counterion interactions in sodium polystyrenesulfonate dissolved in (ethylene glycol + water) mixed solvent media have been investigated conductometrically with special reference to their variations as functions of polyelectrolyte concentration, relative permittivity and temperature. Manning counterion condensation theory for polyelectrolyte solutions failed to describe the present experimental results. The data have, therefore, been analyzed using a new model for semidilute polyelectrolyte conductivity which takes into account the scaling arguments proposed by Dobrynin et al. The fractions of uncondensed counterions were found to depend on the polyelectrolyte concentration varying from 0.27 to 0.37, within the concentration range investigated here, indicating a strong interaction between counterions and polyion. A considerable fraction of the counterions is shown to migrate in the same direction as the polyions. The results further demonstrate that the monomer units experience more frictional resistance in solutions as the ethylene glycol content of the mixture increases or as the temperature decreases.     

Dielectric relaxation behavior of colloidal suspensions of palladium nanoparticle chains dispersed in PVP/EG solution

Dielectric measurements were carried out on colloidal suspensions of palladium nanoparticle chains dispersed in poly(vinyl pyrrolidone)/ethylene glycol (PVP/EG) solution with different particle volume fractions, and dielectric relaxation with relaxation time distribution and small relaxation amplitude was observed in the frequency range from 10(5) to 10(7) Hz. By means of the method based on logarithmic derivative of the dielectric constant and a numerical Kramers-Kronig transform method, two dielectric relaxations were confirmed and dielectric parameters were determined from the dielectric spectra. The dielectric parameters showed a strong dependence on the volume fraction of palladium nanoparticle chain. Through analyzing limiting conductivity at low frequency, the authors found the conductance percolation phenomenon of the suspensions, and the threshold volume fraction is about 0.18. It was concluded from analyzing the dielectric parameters that the high frequency dielectric relaxation results from interfacial polarization and the low frequency dielectric relaxation is a consequence of counterion polarization. They also found that the dispersion state of the palladium nanoparticle chain in PVP/EG solution is dependent on the particle volume fraction, and this may shed some light on a better application of this kind of materials.     

Pinch-off dynamics and extensional relaxation times of intrinsically semi-dilute polymer solutions characterized by dripping-onto-substrate rheometry

Stream-wise velocity-gradients associated with extensional flows arise in thinning liquid necks spontaneously formed during jetting, printing, coating, spraying, atomization, and microfluidic-based drop formation. In this contribution, we employ Dripping-onto-Substrate (DoS) rheometry protocols to measure the extensional rheology response of intrinsically semi-dilute polymer solutions by visualizing and analyzing capillary-driven thinning of a columnar neck formed between a nozzle and a sessile drop. We show that extensional viscosity that quantifies the resistance to stream-wise velocity gradients is orders of magnitude higher than the shear viscosity. Although shear flows only weakly perturb the chain dimensions, extensional flows can strongly stretch and orient the chains, thus influencing both intra- and inter-chain interactions. We find that the extensional relaxation times for intrinsically semi-dilute PEO solutions in a good solvent for five different molecular weights increase linearly with concentration, exhibiting a stronger concentration dependence than observed for dilute solutions, or anticipated by blob models, developed for relaxation of weakly perturbed chains in a good solvent. The observed distinction between the concentration-dependent relaxation dynamics of intrinsically dilute and semi-dilute solutions arises due the complex influence of stretching, conformational anisotropy, and polymer concentration on excluded volume and hydrodynamic interactions of flexible, highly extensible polymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1692–1704     

Analysis of dielectric relaxations of w/o emulsions in the light of theories of interfacial polarization

An attempt is made to apply dielectric theories of interfacial polarization to observations of dielectric relaxations for W/O emulsions. Approximate formulas for disperse systems in a W/O type were derived from the two theories: one proposed by Maxwell and Wagner for dilute disperse systems of spherical particles, and the other developed by Hanai for concentrated disperse systems. Dielectric measurements were carried out on concentrated W/O emulsions prepared from kerosene and distilled water or KCl aqueous solutions by minimal use of emulsifiers. Marked dielectric relaxations were observed with the emulsions, the dielectric parameters having been determined to characterize the relaxation data. Phase parameters such as relative permittivity, electric conductivity and volume fraction of the disperse phase were evaluated from the dielectric parameters by use of the approximate formulas of the respective theories. The phase parameters evaluated and the frequency dependence of complex permittivity of the W/O emulsions deduced from the theory for concentrated disperse systems are in excellent agreement with the observed data in comparison to that for dilute disperse systems. It is concluded that the dielectric relaxations due to the interfacial polarization of disperse systems of spheres are explained satisfactorily by the theory for concentrated disperse systems.     

Continuum Model for Electronic Polarization Based on a Novel Dielectric Response Function

A generalized response function based on the use of dielectric spectra for dielectric relaxation process is derived. We apply the general response function to the special case in order to examine how special dielectric relaxation functions developed by other authors for solvent relaxation can be derived based on our formulations. Three typical solvents, water, methanol, and acetonitrile are used to investigate the electronic polarization processes of polar solvents. The solvent electronic polarization process is shown after a linear variation with the external electric field imposed on the solvent. The results show a conclusion that the electronic polarization of the solvents will accompany the electronic transition synchronously, without time lag.