Computer Simulation of the Dielectric Properties of Liquid Water

Abstract

Monte Carlo simulations of water in the NVT ensemble using three models (SPC, TIP4P and TIPS2) are reported. The internal energy, dielectric constant, and the site-site radial distribution functions of liquid water (temperature 300 K and mass density 1 gm cc^?1) were calculated and compared with experiment. It was found that of the three intermolecular potential models, SPC gives the best dielectric constant. Since SPC also yields acceptable results for the energy and structure, it is judged to be the best among the three models studied.     

Modification of the erythrocyte membrane dielectric constant by alcohols

Summary Aliphatic alcohols are found to stimulate the transmembrane fluxes of a hydrophobic cation (tetraphenylarsonium, TPA) and anion (AN-12) 5–20 times in red blood cells. The results are analyzed using the Born-Parsegian equation (Parsegian, A., 1969,Nature (London) 221:844–846), together with the Clausius-Mossotti equation to calculate membrane dielectric energy barriers. Using established literature values of membrane thickness, native membrane dielectric constant, TPA ionic radius, and alcohol properties (partition coefficient, molar volume, dielectric constant), the TPA permeability data is predicted remarkably well by theory. If the radius of AN-12 is taken as 1.9 Å, its permeability in the presence of butanol is also described by our analysis. Further, the theory quantitatively accounts for the data of Gutknecht and Tosteson (Gutknecht, J., Tosteson, D.C., 1970,J. Gen. Physiol. 55:359–374) covering alcohol-induced conductivity changes of 3 orders of magnitude in artificial bilayers. Other explanations including perturbations of membrane fluidity, surface charge, membrane thickness, and dipole potential are discussed. However, the large magnitude of the stimulation, the more pronounced effect on smaller ions, and the acceleration of both anions and cations suggest membrane dielectric constant change as the primary basis of alcohol effects.     

Citric Acid Fermentation

Abstract

Dielectrophoresis is the motion of particles caused by electrical polarization effects in inhomogeneous (nonuniform) electric fields. Unlike electrophoresis, the particles do not require a net electrical charge for motion to occur and AC rather than DC fields are employed to exploit the dielectric properties of the particles. Factors controlling the effective dielectric properties of cells and microorganisms include electrical double layers associated with surface charges, the conductivity and permittivity of their membranes and any cell walls, and their morphologies and structural architectures. In recent years, several laboratories have developed separation and manipulation techniques for cells and microorganisms based on dielectrophoresis, using both static and traveling AC fields. In this article, the basic physical factors influencing the dielectrophoretic behavior of particles are outlined, and ways in which these can be employed to achieve selective separation of cells and microorganisms are described.     

The Application of the Reaction-Field Method to the Calculation of Dielectric Constants

Abstract

The behaviour of the popular TIP3P water model has been investigated using both molecular dynamics and Monte Carlo simulation procedures. Long-range electrostatic interactions were included through a reaction-field treatment, and the nonbonded interactions were either truncated at the cutoff distance, or smoothly scaled to zero using a switching function. The thermodynamic observables, and in particular the dipole-dipole correlation functions, are found to differ between the two simulation techniques if a rigid nonbonded cutoff is applied. However, use of a switching function gives exact agreement between the simulation methodologies. This difference is ascribed to the effect of energy pumping in the molecular dynamics simulations, and suggests that dielectric constants calculated using this simulation method with the fluctuation procedure in conjunction with a reaction field should be reappraised. Thus the Monte Carlo simulation procedure offers a number of intrinsic advantages over molecular dynamics for the calculation of dielectric constants with a reaction field. The most precise value for the dielectric constant of TIP3P is calculated to be 102 ± 3 at 298 K.     

Dielectric behavior of DNA in water–organic co-solvent mixtures

The radiowave dielectric dispersions of DNA in different water–organic co-solvent mixtures have been measured in the frequency range from 100 kHz to 100 MHz, where the polarization mechanism is generally attributed to the confinement of counterions within some specific lengths, either along tangential or perpendicular to the polyion chain. The dielectric dispersions have been analyzed on the basis of two partially different dielectric models, a continuum counterion fluctuation model proposed by Mandel and a discrete charged site model, proposed by Minakata. The influence of the quality of the solvent on the dielectric parameters has been investigated in water–methanol and water–glycerol mixtures at different composition, by varying the permittivity ?_m and the viscosity η of the solvent phase. The analysis of the dielectric spectra in solvents where electrostatic and hydrodynamic interactions vary with the solvent composition suggests that both the two models are able, in principle, to account for the observed high-frequency dielectric behavior. However, while some certain assumptions are necessary about the polyion structure within the Mandel model, no structural prerequisite is needed within the Minakata model, where the polarization mechanism invoked considers a radial counterion exchange with the outer medium, which is largely independent of the local polyion conformation.     

Low Frequency Impedimetric Cell Counting: Analytical Modeling and Measurements

BackgroundBiological constituents have unique dielectric properties by virtue of which these can be analyzed both quantitatively and qualitatively by employing bio-dielectric measurement techniques and electrical impedance spectroscopy exhibits immense potential in this context.MethodsIn this study, an analytical impedimetric model has been developed to describe bio-dielectric behavior of the lymphocyte suspensions with different cell counts. Emphasis has been given to incorporate the effect of dielectric anisotropy which is apparent between the cell and nuclear membranes and measured in the low frequency range. The relatively low frequency range is chosen to probe the strong dependence of complex membrane behavior provided by the cells. Such dielectric anisotropy originates from the flow dynamics of ions through the hydrophobic interior of polar lipid-bilayer membrane. Successive models have been developed and compared with the relevant experimental data for formulating the system capacitance in a most generalized approach.ResultsThe capacitance values have been observed to decrease with both the increase of measuring frequency and cell count, however, its impedance decreases with frequency and increases with cell count. Such nature is attributed to the localization of polar response in the membrane-base solution interfaces.ConclusionThe work demonstrates a rapid and deterministic approach to estimate lymphocyte count which will augment the existing prediction techniques for relevant physiological disorders.     

Molecular Dynamics Simulations of the Unfolding of the Starch Binding Domain from Aspergillus niger Glucoamylase

Abstract

The 600 ps molecular dynamics simulations to investigate the unfolding of the starch binding domain from Aspergillus niger glucoamylase were conducted in vacuum as well as in an external field with the dielectric constant of 80 with temperature jump technique. Electrostatic interactions play an important role in determining the stability of the β-strands in this domain. The starch binding site 1 is less stable than site 2 since it is more exposed to the surface. The disulfide bond between C509 and C604 is unstable since these two residues are located near the flexible linker domain and in the mobile loop region between β-strands 6 and 7, respectively. The melting temperature, at which the total residual β-strand content is 50% that of the solution structure, is about 544K for the simulations with dielectric constant of 80, leading to the estimated unfolding timescale of 0.48 ms in vitro. In addition, the unfolding of the starch binding domain is proposed to initiate from the interior region by the lost of the integrity of the secondary structure.     

Effect of dielectric constant of medium on protonation equilibria of ethylenediamine

Abstract

The effect of dielectric constant of medium on protonation equilibria has been studied by determining protonation constants of ethylenediamine pH metrically in various concentrations (0–60%v/v) of acetoni-trile– and ethylene glycol–water mixtures, at an ionic strength of 0.16mol L^?1 and at 303.0 K. MINIQUAD75 computer program has been used for the calculation of protonation constants. Linear and non-linear variations of step-wise protonation constants with reciprocal of dielectric constant of the solvent mixtures have been attributed to the dominance of the electrostatic and non-electrostatic forces, respectively. The trend is explained on the basis of solute–solute and solute–solvent interactions, solvation, proton transfer processes and dielectric constants of the media.     

The Boundary Condition in the Gibbs Ensemble Simulation of a Stockmayer Fluid under an Applied Field

Abstract

We calculate the vapour-liquid coexistence properties of the Stockmayer fluid with reduced permanent dipole μ? = 2.0 under an applied electrostatic field E ₀? = 1.0 for various boundary conditions by the Gibbs ensemble simulation. In contrast to the system under no field, the phase behaviour of the Stockmayer fluid under the applied field calculated in simulation strongly depends on the dielectric constant of the surroundings used in the Hamiltonian. We propose that the value of the dielectric constant of the surroundings for the vapour and the liquid phase used in the simulation should be adjusted to that of the system in the corresponding phase, in order to best represent the thermodynamics of the bulk system under applied field.     

Complex Dielectric Properties of Sulfate-Reducing Bacteria Suspensions

Sulfate-reducing bacteria (SRB) can potentially enhance the remediation of heavy metals in the subsurface. Previous geophysical research has demonstrated the sensitivity of electrical measurements to SRB-mediated mineral transformation in porous media. However, the inherent dielectric properties of SRB and their direct contribution to the electrical properties of porous media are poorly understood. We studied the complex dielectric properties of SRB (Desulfovibrio vulgaris) suspensions at different concentrations and at different growth stages using a two-electrode dielectric spectroscopy measurement over the frequency range of 20 Hz to 1 MHz. Our results show higher dielectric responses (relative dielectric permittivity, real and imaginary conductivity) occurred with higher bacteria concentration at frequencies <10 kHz. Additionally, permittivity and conductivity both decreased as cells aged from mid-log phase to late stationary phase. Our results suggest that dielectric spectroscopy measurements can be used to noninvasively monitor biomass and various growth stages of SRB. Our work advances the interpretation of electrical signals associated with SRB observed in the subsurface.     

Power law dispersion in animal horn

The dielectric response of sheep horn has been measured in the frequency range from 10^–3–10⁵ Hz and over temperatures in the range 304–500 K. The dynamic behaviour of the conductance and capacitance in sheep horn has been observed to follow fractional power law dependences on frequency. It is shown that the over all dielectric response of these dead cells correspond to a dispersive imperfect bulk in series with a dispersive barrier region. It is further shown that the increase in temperature influences the reponse by eliminating the room temperature dc conductance and affecting the magnitude of the dispersion in capacitance. The magnitudes of activation energies are found as 0.33±0.02 eV for conductance, 0.40±0.02 eV for relaxation and 0.33±0.02 eV for the frequency shift.     

An electrostatic model for the dielectric effects,the adsorption of multivalent ions,and the bending of B-DNA

We have studied electrostatic properties of DNA with a discrete charge model consisting of a cylindrical dielectric core with a radius of 8 Å and a dielectric constant D_i = 4, surrounded by two helical strings of phosphate point charges at 10 Å from the axis, immersed in an aqueous medium with dielectric constant D_w = 78.54. Eliminating the dielectric core makes potentials in the phosphate surface less negative by about 0.5 kT/e. Salt effects are evaluated for the model without a dielectric core, using the shielded Coulomb potential. Smearing the phosphate charges increases their potential by about 2.5 kT/e, due mostly to the self-potential of the smeared charge. Potentials in the center of the minor and major grooves vary less than 0.02 kT/e along their helical path. The potential in the center of the minor groove is from 1.0 to 1.7 kT/e, more negative than in the center of the major groove, depending on dielectric core and salt concentration. So multivalent cations and also larger cationic ligands, such as some antibiotics, are likely to adsorb in the minor groove, in agreement with earlier computations by A. and B. Pullman. Dielectric effects on the surface potential and the local potential variations are found to be relatively small. Bending of DNA is studied by placing a multivalent cation, M^Z+, in the center of the minor or major groove, curving DNA around it for a certain length, and calculating the free energy difference between the bent and the straight configuration. Boltzmann averaged bending angles, 〈β〉, are found to be maximal in 0.03M monovalent salt, for a length of about 50 or 25 Å of curved DNA when an M^Z+ ion is adsorbed in the minor or the major groove, respectively. When the dielectric constant of water is used throughout the calculation, we find maximal bends of 〈β〉 = 11° for M²⁺ and 〈β〉 = 16° for M³⁺ in the minor groove, 〈β〉 = 13° for M³⁺ in the major groove. The absence of bends in DNA adsorbed to mica in the presence of Mg salts supports the role of Mg²⁺ in “ion bridging” between DNA and mica. The treatment of the effective dielectric constant between two points outside a dielectric cylinder in water is appended. © 1998 John Wiley & Sons, Inc. Biopoly 46: 503–516, 1998     

Optical and electrical properties of thin monoolein lipid bilayers

Summary Monoolein lipid bilayers were formed using a monolayer transfer technique and from dispersions of monoolein in squalene, triolein, 1-chlorodecane and 1-bromodecane. Measurements of optical reflectance and electrical capacitance were used to determine the thickness and dielectric constant of the bilayers. The thickness of the hydrocarbon region of the five bilayer systems ranged from 2.5 to 3.0 nm. Two of the bilayer systems (made from 1-chlorodecane and 1-bromodecane solvents) had a high dielectric constant (2.8 to 2.9) whereas the other bilayer systems had dielectric constants close to that of pure hydrocarbons (2.2). The charge-pulse technique was used to study the transport kinetics of three lipophilic ions and two ion carrier complexes in the bilayers. For the low dielectric constant bilayers, the transport of the lipophilic ions tetraphenylborate, tetraphenylarsonium and dipicrylamine was governed mainly by the thickness of the hydrocarbon region of the bilayer whereas the transport of the ion-carrier complexes proline valinomycin-K⁺ and valinomycin-Rb⁺ was nearly independent of thickness. This is consistent with previous studies on thicker monoolein bilayers. The transport of lipophilic anions across bilayers with a high dielectric constant was 20 to 50 times greater than expected on the basis of thickness alone. This agrees qualitatively with predictions based on Born charging energy calculations. High dielectric constant bilayers were three times more permeable to the proline valinomycin-K⁺ complex than were low dielectric constant bilayers but were just as permeable as low dielectric constant bilayers to the valinomycin-Rb⁺ complex.     

Dielectric and electric properties of synthetic melanin: the effect of europium ions

Detailed studies on dielectric and electric properties of synthetic pirocatechol and indolederived melanin, pure and doped with Eu³⁺, have been performed, D.C. and a.c. electrical conductivity as well as dielectric permittivity and loss angle tg have been investigated. Activation energy of d.c. conductivity for the investigated temperature range (0°C3+ doped to the samples do not influence the values of activation energy, but the addition of Eu³⁺ ions decreases the conductivity values. On the basis of depolarization current curves the energy of trap level referred to Eu³⁺ has been calculated. It equals 0.58 eV for pirocatechol and 0.60 eV for indolemelanin.     

On the Implementation of Friedman Boundary Conditions in Liquid Water Simulations

Abstract

We have applied the image approximation to the reaction field as suggested by H.L. Friedman [Mol. Phys., 29, 1533 (1975)] by investigating appropriate cavity sizes and system parameters for use in molecular simulations. The energy of and the structure around a central simple point charge (SPC) water molecule in a dielectric cavity was found to be in good agreement with the properties of a liquid sample. To confine the water molecules within the cavity, we introduced a short-range repulsion between a real charge and its image as the Lennard-Jones repulsive potential between oxygen atoms of the SPC potential. For a system of 65 water molecules a cavity radius of 10.45 Å is appropriate; this radius is altered to 12.00 Å for a cavity surrounding 113 molecules. The effect of the boundary is restricted to the outer-most water layer which is in contact with the dielectric continuum.     

Dielectric studies on water in solutions of purified lecithin vesicles

The complex permittivity of sonicated aqueous solutions of purified dimyristoylphosphatidylcholine has been measured as a function of frequency between 3 kHz and 40 GHz. The dielectric spectrum of the samples shows two dispersion/absorption regions, one centered at about 80 MHz the other at about 20.GHz (30°C). Otherwise than in previous studies no additional dispersion/absorption process has been found at frequencies below 10 MHz.The complex dielectric spectrum of the samples is discussed with respect to the dynamical state of solvent water in solutions of single-bilayer vesicles. The main relaxation time of the solvent water, τ₁ ((2πτ₁)^?1 ≈ 20 GHz), is smaller than that of pure water, τ_W, at the same temperature. This effect results from the action of internal depolarizing fields which obviously overcompensate and enhancement of τ₁ due to specific solute/solvent interactions (hydration) as had been previously found with micellar solutions of lysolecithins.It cannot be excluded, that some solvent water shows unusual dynamical behaviour. If there exists a substantial amount of such motionally perturbed water, however, it must be characterized by a relaxation time close to that of the phosphorylcholine zwitterions, τ₂ ((2πτ₂)^?1 ≈ 80 MHz).     

Molecular shape and dipole moment of alamethicin-like synthetic peptides

The peptides Boc-(l-Ala-Aib-l-Ala-Aib-l-Ala)_n-OMe, with n=2 (P10) and n=4 (P20), have been synthesized as purely hydrophobic models of the antibiotic alamethicin, which is known to be a voltage-dependent pore former in membranes and is apparently -helical in lipophilic media. These peptides were investigated in 1-octanol, a solvent which resembles the membrane environment. From dielectric dispersion studies quantitative information on the molecular shape and dipole moments could be derived. Further independent data concerning conformation and extent of aggregation of the peptides were obtained by circular dichroism and ultracentrifuge measurements. The results suggest that the peptides assume the form of elongated particles having a significant amount of ordered secondary structure and carrying a dipole parallel to the long axis. Apparently the monomeric peptide molecules undergo, to some extent, a head-to-tail aggregation which is slightly enhanced at lower temperatures. Based on the high-frequency parts of the dielectric dispersion curves the lengths, diameters, and dipole moments of the monomer particles have been determined as 22.5 Å, 10 Å, 36 D (P10) and 28.5 Å, 12 Å, 64 D (P20).     

Dielectric properties of muscle and liver from 500 MHz–40 GHz

Dielectric properties are the most important parameters determining energy deposition when biological tissues are exposed to radio frequency and microwave fields. Energy absorption is determined by the specific absorption rate (SAR). SAR distributions can be computed accurately only if the complex relative permittivity of the target tissue is known to a sufficiently high accuracy, and currently there is a lack of data on the dielectric properties of biological tissues at high frequencies. In this study, tissue dielectric properties are measured using an open-ended coaxial probe technique from 500 MHz up to 40 GHz. We present dielectric data for ex vivo bovine and porcine muscle and liver tissues at 37 °C. One-pole Cole–Cole model is used to fit the measured data as a function of frequency and the dispersion parameters are presented. This data is supported by an accurate study on reference liquids such as methanol and ethanediol.     

Quantitative assessment of dielectric parameters for membrane lipid bi‐layers from RF permittivity measurements

In this article, we propose and validate theoretical and experimental methods to quantitatively assess the Debye dielectric model of membrane lipid bi‐layers. This consists of two steps: permittivity measurements of biological solutions (liposomes), and estimation of the model parameters by inverse application of the Effective Medium Theory. The measurements are conducted in the frequency domain between 100 MHz and 2 GHz using a modified coaxial connector, at the temperatures of 27 and 30 °C. Estimations have been performed using a three‐layered model based on the Maxwell–Wagner formulation. Debye parameters (mean value ± standard error) found from fitting experimental data are: ε_s = 11.69 ± 0.09, ε_∞ = 4.00 ± 0.07, f_relax = 179.85 ± 6.20 MHz and ε_s = (1.1 ± 0.1) × 10^?7 S/m. This model can be used in microdosimetric studies aiming to precisely determine the E‐field distribution in a biological target down to the single cell level. In this context the use of an accurate membrane dielectric model, valid through a wide frequency range, is particularly appropriate. Bioelectromagnetics 30:286–298, 2009. © 2009 Wiley‐Liss, Inc.     

The dielectric method of investigating bound water in biological material: An appraisal of the technique

Three independent dielectric methods for the measurement of water of hydration (bound water) in a biological material are described and discussed comparatively. For well-defined aqueous solutions of biological molecules, hydration can be obtained from direct observations made on the δ dispersion or from measurement of the dielectric values of the β dispersion. For whole tissue, however, neither of these two methods is applicable, and to deduce the hydration, it is necessary to use the third technique in which the volume of the hydrated biological particle is obtained by measuring the effect of it on the known dielectric properties of pure water. The hydration can then be calculated by deducting the volume of the anhydrous particle from the experimentally determined volume of the hydrated particle. Owing to possible systemmatic errors the uncertainty in the absolute hydration value associated with this technique is rather larger than that obtained with the other two dielectric methods. For studying the differences between hydration in similar tissues, however, this objection disappears.