Poisson-Boltzmann equation model

More sophisticated approaches to describe double layer interactions have been developed more recently. Using cell models, the full Poisson-Boltzmann equation can be solved for ordered stmctures. The approach by Alexander et al shows how the effective colloidal particle charge saturates when the bare particle charge is increased [4o]. Using integral equation methods, the behaviour of the primitive model has been studied, in which all the interactions between the colloidal macro-ions and the small ions are addressed (see, for instance, [44, 45]). 

How can Equation (11.79) be solved Before computers were available only simple ihapes could be considered. For example, proteins were modelled as spheres or ellipses Tanford-Kirkwood theory) DNA as a uniformly charged cylinder and membranes as planes (Gouy-Chapman theory). With computers, numerical approaches can be used to solve the Poisson-Boltzmann equation. A variety of numerical methods can be employed, including finite element and boundary element methods, but we will restrict our discussion to the finite difference method first introduced for proteins by Warwicker and Watson [Warwicker and Watson 1982]. Several groups have implemented this method here we concentrate on the work of Honig s group, whose DelPhi program has been widely used. 

The continuum treatment of electrostatics can also model salt effects by generalizing the Poisson equation (12) to the Poisson-Boltzmann equation. The finite difference approach to solving Eq. (12) extends naturally to treating the Poisson-Boltzmann equation [21], and the boundary element method can be extended as well [19]. 

Oosawa (1971) developed a simple mathematical model, using an approximate treatment, to describe the distribution of counterions. We shall use it here as it offers a clear qualitative description of the phenomenon, uncluttered by heavy mathematics associated with the Poisson-Boltzmann equation. Oosawa assumed that there were two phases, one occupied by the polyions, and the other external to them. He also assumed that each contained a uniform distribution of counterions. This is an approximation to the situation where distribution is governed by the Poisson distribution (Atkins, 1978). If the proportion of site-bound ions is negligible, the distribution of counterions between these phases is then given by the Boltzmann distribution, which relates the population ratio of two groups of atoms or ions to the energy difference between them. Thus, for monovalent counterions... 

The EDL charge distribution can be modeled by a Poisson-Boltzmann equation (see, e.g., [46]). In many practical cases values for the layer thickness between 1 and 100 nm are obtained [47]. 

The electrostatic methods just discussed suitable for nonelectrolytic solvent. However, both the GB and Poisson approaches may be extended to salt solutions, the former by introducing a Debye-Huckel parameter67 and the latter by generalizing the Poisson equation to the Poisson-Boltzmann equation.68 The Debye-Huckel modification of the GB model is valid to much higher salt concentrations than the original Debye-Huckel theory because the model includes the finite size of the solute molecules. 

Interactions between cationic micelles and uni- and divalent anions have been treated quantitatively by solving the Poisson-Boltzmann equation in spherical symmetry and considering both Coulombic and specific attractive forces. Predicted rate-surfactant profiles are similar to those based on the ion-exchange and mass-action models (Section 3), but fit the data better for reactions in solutions containing divalent anions (Bunton, C. A. and Moffatt, J. R. (1985) J. Phys. Chem. 1985, 89, 4166 1986,90, 538). 

The presence of the diffuse layer determines the shape of the capacitance-potential curves. For a majority of systems, models describing the double-layer structure are oversimplified because of taking into account only the charge of ions and neglecting their specific nature. Recently, these problems have been analyzed using new theories such as the modified Poisson-Boltzmann equation, later developed by Lamper-ski. The double-layer capacitanties calculated from these equations are... 

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 next step is to determine the electrical charge and potential distribution in this diffuse region. This is done by using relevant electrostatic and statistical mechanical theories. For a charged planar surface, this problem was solved by Gouy (in 1910) and Chapman (in 1913) by solving the Poisson-Boltzmann equation, the so called Gouy-Chapman (G-C) model. 

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 geometry. It is clear that the geometry of the system is much simplified in the slab model. Another possibility is to model the protein as a sphere and the stationary phase as a planar surface. For such systems, numerical solutions of the Poisson-Boltzmann equations are required [33]. However, by using the Equation 15.67 in combination with a Derjaguin approximation, it is possible to find an approximate expression for the interaction energy at the point where it has a minimum. The following expression is obtained [31] ... 

Rahaman and Hatton [152] developed a thermodynamic model for the prediction of the sizes of the protein filled and unfilled RMs as a function of system parameters such as ionic strength, protein charge, and size, Wq and protein concentration for both phase transfer and injection techniques. The important assumptions considered include (i) reverse micellar population is bidisperse, (ii) charge distribution is uniform, (iii) electrostatic interactions within a micelle and between a protein and micellar interface are represented by nonlinear Poisson-Boltzmann equation, (iv) the equilibrium micellar radii are assumed to be those that minimize the system free energy, and (v) water transferred between the two phases is too small to change chemical potential. 

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 ... 

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. 

An alternative theoretical approach is the application of the Poisson-Boltzmann equation on the so-called cell model, assuming a parallel and equally spaced packing of rod-like polyions [62, 63]. This allows one to calculate at finite concentration according to ... 

A number of methodologies have been developed and generalized in recent years to quantitatively describe the ion atmosphere around nucleic acids [11, 12, 17, 28, 29]. These include models based on Poisson-Boltzmann equation [11, 12], counterion condensation [17], and simulation methods, such as Monte Carlo, molecular dynamics, and Brownian dynamics [28, 29]. 

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