Linearized Poisson-Boltzmann equation, solution

If there are ions in the solution, they will try to change their location according to the electrostatic potential in the system. Their distribution can be described according to Boltzmarm. Including these effects and applying some mathematics leads to the final linearized Poisson-Boltzmann equation (Eq. (43)). 

Derive and solve the appropriate linear Poisson-Boltzmann equation for the interface between two immiscible solutions. 

A more detailed view of the dynamies of a ehromatin chain was achieved in a recent Brownian dynamics simulation by Beard and Schlick [65]. Like in previous work, the DNA is treated as a segmented elastic chain however, the nueleosomes are modeled as flat cylinders with the DNA attached to the cylinder surface at the positions known from the crystallographic structure of the nucleosome. Moreover, the electrostatic interactions are treated in a very detailed manner the charge distribution on the nucleosome core particle is obtained from a solution to the non-linear Poisson-Boltzmann equation in the surrounding solvent, and the total electrostatic energy is computed through the Debye-Hiickel approximation over all charges on the nucleosome and the linker DNA. 

The Poisson-Boltzmann equation. The slab model is based on a solution of the linearized Poisson-Boltzmann equation that is valid only for low electrostatic surface potentials. As... 

The above equation is known as the linearized Poisson-Boltzmann equation since the assumption of low potentials made in reaching this result from Equation (29) has allowed us make the right-hand side of the equation linear in p. This assumption is also made in the Debye-Hiickel theory and prompts us to call this model the Debye-Hiickel approximation. Equation (33) has an explicit solution. Since potential is the quantity of special interest in Equation (33), let us evaluate the potential at 25°C for a monovalent ion that satisfies the condition e p = kBT ... 

The solution of the linearized Poisson-Boltzmann equation around cylinders also requires numerical methods, although when cylindrical symmetry and the Debye-Hiickel approximation are assumed the equation can be solved. The solution, however, requires advanced mathematical techniques and we will not discuss it here. It is nevertheless useful to note the form of the solution. The potential for symmetrical electrolytes has been given by Dube (1943) and is written in terms of the charge density a as... 

A new theory of electrolyte solutions is described. This theory is based on a Debye-Hiickel model and modified to allow for the mutual polarization of ions. From a general solution of the linearized Poisson-Boltzmann equation, an expression is derived for the activity coefficient of a central polarized ion in an ionic atmosphere of non-spherical symmetry that reduces to the Debye-Hiickel limiting laws at infinite dilution. A method for the simultaneous charging of an ion and its ionic cloud is developed to allow for ionic polarization. Comparison of the calculated activity coefficients with experimental values shows that the characteristic shapes of the log y vs. concentration curves are well represented by the theory up to moderately high concentrations. Some consequences in relation to the structure of electrolyte solutions are discussed. 

Table I. Constants of Integration for the General Solution of the Linearized Poisson—Boltzmann Equation...

At high electrolyte concentrations, the linear approximation fails and Eqs. (31a), (31b), (32a), (32b) and (33) are no longer valid. A simple solution, even approximate, of the non-linear Poisson-Boltzmann equation is more difficult to obtain however, the general behavior of the system can be understood from the following semi-quantitative analysis. 

The mean field potential for this system, a solution of the linear Poisson-Boltzmann equation, Eq. (32), will appropriately have the same periodic structure as the surface boundary condition. Thus, we expect that if/ will have the Fourier series,... 

We denote the stress tensor inside the curly brackets in Eq. (13) asT. Equation (13) shows that the solution for the potential and its gradient at the particle surface are all that are required to calculate the force on a particle via the linearized Poisson-Boltzmann equation. 

This simple and appealing result shows that, for H 1 /k, the sphere-wall interaction depends linearly on the charge densities of each surface, and decays exponentially with the separation distance. The result does not depend on whether the surfaces are considered to be constant charge density or constant potential, because the potentials of an isolated wall and sphere were used in its derivation. Phillips [13] has compared Eq. (24) with a numerical solution of the linear Poisson-Boltzmann equation, and shows that it errs by less than about 10% for xh>3 when 0.5 [Pg.257]

FIG. 3 Comparison of the linear Derjaguin approximation with a numerical solution of the linear Poisson-Boltzmann equation for (a) constant potential and (b) constant charge density boundary conditions. (From Ref. 13.)... 

In Secs. II.A and II.B above, we examined some common, approximate solutions to the linear Poisson-Boltzmann equation, and commented on the level of their agreement with exact solutions of that same equation. However, these approximations are no more accurate than the exact solutions, and the accuracy of the latter can only be ascertained by comparison with solutions to the complete, nonlinear Poisson-Boltzmann equation. From the... 

A hierarchy of approximations now exists for calculating interactions between a charged particle and a charged, planar interface in electrolyte solutions. At moderate surface potentials less than approximately 2(kT/e the linear Poisson-Boltzmann equation provides a good approximation in many circumstances, provided the solution is a 1 1 electrolyte at low to moderate ionic strength. The relative simplicity of the linear equation makes it particularly useful for examining problems that are complicated in other ways, such as interactions involving many particles, interactions with deformable interfaces, and interactions where the detailed structure and properties of the particle (or macromolecule) play an important role. 

Electrostatic. Virtually all colloids in solution acquire a surface charge and hence an electrical double layer. When particles interact in a concentrated region their double layers overlap resulting in a repulsive force which opposes further approach. Any theory of filtration of colloids needs to take into account the multi-particle nature of such interactions. This is best achieved by using a Wigner-Seitz cell approach combined with a numerical solution of the non-linear Poisson-Boltzmann equation, which allows calculation of a configurational force that implicitly includes the multi-body effects of a concentrated dispersion or filter cake. 

Electrostatic. In many practical situations, both membrane and solute have net negative charges. Hence, as the solute approaches a pore in the membrane it experiences an electrostatic repulsion. A quantitative theoretical description of this interaction requires solution of the non-linear Poisson-Boltzmann equation for the interacting solute and membrane followed by calculation of the resulting force by integrating the electric stress tensor on the solute surface. Due to the complexity of the geometry... 

W.R. Bowen and A.O. Sharif, Adaptive finite element solution of the non-linear Poisson-Boltzmann equation—a charged spherical particle at various distances from a charged cylindrical pore in a charged planar surface, J. Colloid Interface Sci. 187 (1997)... 

Consider first a prolate spheroid with a constant uniform surface potential ij/f, in an electrolyte solution (Fig. 1.17a). The potential j/ is assumed to be low enough to obey the linearized Poisson-Boltzmann equation (1.9). We choose the z-axis as the axis of symmetry and the center of the prolate as the origin. Let a and b be the major and minor axes of the prolate, respectively. The equation for the surface of the prolate is then given by... 

We also assume that the relative permittivity in membranes 1 and 2 tale the same value as that of the electrolyte solution. Suppose that membrane 1 is placed in the region —00 h (Fig. 13.2). The linearized Poisson-Boltzmann equations in the respective regions are... 

This chapter deals with a method for obtaining the exact solution to the linearized Poisson-Boltzmann equation on the basis of Schwartz s method [1] without recourse to Derjaguin s approximation [2]. Then we apply this method to derive series expansion representations for the double-layer interaction between spheres [3-13] and those between two parallel cylinders [14, 15]. 

We start with the simplest problem of the plate-plate interaction. Consider two parallel plates 1 and 2 in an electrolyte solution, having constant surface potentials i/ oi and J/o2, separated at a distance H between their surfaces (Fig. 14.1). We take an x-axis perpendicular to the plates with its origin 0 at the surface of one plate so that the region 0solution phase. We derive the potential distribution for the region between the plates (0linearized Poisson-Boltzmann equation in the one-dimensional case is... 

Consider two parallel planar ion-penetrable membranes 1 and 2, which may not be identical, at separation h in a symmetrical electrolyte solution of valence z and bulk concentration n (Fig. 16.1). We take an x-axis perpendicular to the membranes with its origin at the surface of membrane 1. The electric potential i/ (x) at position X between the membranes (relative to the bulk solution phase, where is set equal to zero) is assumed to be small so that the linearized Poisson-Boltzmann equation can be employed. Membranes 1 and 2, respectively, consist of N and M layers. All the layers are perpendicular to the x-axis. Let the thickness and the density of membrane-fixed charges of the ith layer of membrane j (7=1, 2) be and The linearized Poisson-Boltzmann equation for the /th layer... 

The three-dimensional, second-order, nonlinear, elliptic partial differential equation may be simplified in the limit of weak electrolyte solutions, where the hyperbolic sine of is well approximated by 4). This yields the linearized Poisson—Boltzmann equation... 

No experimental results are available for the nucleic acids, with or without methyl substitution, to test the theories, but we can compare the results for thymine to three theoretical estimates based on the linearized Poisson-Boltzmann equation. The AM1-SM2 and PM3-SM3 values are —16.5 and -20.1 kcal/mol, respectively. Using charges and force field parameters from the AMBER,347 CHARMM, and OPLS molecular mechanics force fields and a solute dielectric constant of 1, Mohan et al.i calculated solvation energies of -19.1, -10.4, and -8.4 kcal/mol. The wide variation is disconcerting. In light of such wide variations with off-the-shelf parameters, the SMx approach based on parameters specifically adjusted to solvation energies appears to be more reliable. 

This series arises naturally, when expressing the Coulomb potential of a charge separated by a distance s from the origin in terms of spherical coordinates. The positive powers result when r < s, while for r > s the potential is described by the negative powers. Similarly the solutions of the linearized Poisson-Boltzmann equation are generated by the analogous expansion of the shielded Coulomb potential exp[fix]/r of a non-centered point charge. Now the expansion for r > s involves the modified spherical Bessel-functions fo (x), while lor r < s the functions are the same as for the unshielded Coulomb potential,... 

Glendinning, A.B. Russel, W.B. The electrostatic repulsion between charged spheres from exact solutions to the linearized Poisson-Boltzmann equation. J. Colloid Interface Sci. 1983, 93, 95-111 Carnie, S.L. Chan, D.Y.C. Interaction free energy between identical spherical colloidal... 

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