Electrostatic interactions Poisson—Boltzmann equation

Tanford, C., Kirkwood, J. G. Theory of protein titration curves. I. General equations for impenetrable spheres. J. Am. Chem. Soc. 79 (1957) 5333-5339. 6. Garrett, A. J. M., Poladian, L. Refined derivation, exact solutions, and singular limits of the Poisson-Boltzmann equation. Ann. Phys. 188 (1988) 386-435. Sharp, K. A., Honig, B. Electrostatic interactions in macromolecules. Theory and applications. Ann. Rev. Biophys. Chem. 19 (1990) 301-332. 

In addition to the nearest-neighbor interaction, each ion experiences the electrostatic potential generated by the other ions. In the literature this has generally been equated with the macroscopic potential 0 calculated from the Poisson-Boltzmann equation. This corresponds to a mean-field approximation (vide infra), in which correlations between the ions are neglected. This approximation should be the better the low the concentrations of the ions. 

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. 

Recent advances in computational power have made it possible to use efficient approximations of the Poisson-Boltzmann equation also to estimate the electrostatic component of protein-ligand interactions [56]. 

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 purpose of the present chapter is to introduce some of the basic concepts essential for understanding electrostatic and electrical double-layer pheneomena that are important in problems such as the protein/ion-exchange surface pictured above. The scope of the chapter is of course considerably limited, and we restrict it to concepts such as the nature of surface charges in simple systems, the structure of the resulting electrical double layer, the derivation of the Poisson-Boltzmann equation for electrostatic potential distribution in the double layer and some of its approximate solutions, and the electrostatic interaction forces for simple geometric situations. Nonetheless, these concepts lay the foundation on which the edifice needed for more complicated problems is built. 

Unlike the other examples in this section, the equation governing the electrostatics here [i.e., Eq. (53)] is not the linearized Poisson-Boltzmann equation. However, considering interactions outside of thin double layers does have the effect of linearizing the problem. In Eq. (54), n is the fluid viscosity, K is the conductivity, is the zeta potential of the z th surface, and is a bipolar coordinate that is constant on the sphere and wall surfaces. It is this last condition (54), derived by Bike and Prieve [36] as a requirement to satisfy charge conservation, that couples the fluid mechanics with the electrostatics. 

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... 

A thorough discussion of the basic theory describing electrostatic interactions can be found in [7] the pertinent points are discussed below. Electrostatic forces arise from the osmotic pressure difference between two charged surfaces as a result of the local increase in the ionic distribution around each charged surface. For a single electrified interface, the local ion distribution is coupled to the potential distribution near that surface and can be described using the Poisson-Boltzmann equation. The solution of this equation shows that for low surface potentials the potential follows an exponential function with distance from the interface, D, given by... 

The electrostatic interaction between two flat surfaces is an extension of the single electrified interface where the ion distributions overlap at close separations. The two-surface case can also be described according to the Poisson-Boltzmann equation where the ion distributions for each charged interface are coupled. A complete solution to... 

In complementary computational studies, Gunner et al. have explored the role of long-range electrostatic interaction on electron transfer processes in the Rhodo-bacter sphaeroides reaction center [38]. The interaction domains were identified by mapping electrostatic potentials, calculated from the Poisson-Boltzmann equation, on to calculated encounter surfaces for each of the components of the reaction center. From qualitative correlation of electron transfer processes with these low-resolution potential maps, it is apparent that long-range interactions profoundly affect the reduction potential of the cofactors in the reaction center. 

Electrostatic interactions in solutions containing charged particles and ions can be described using the Poisson-Boltzmann equation. A charged surface attracts counterions into a double layer of thickness defined by the Debye length, which depends on counterion concentration and solvent dielectric constant. From simplified theories, expressions can be derived for the attractive interaction potential between charged spheres. 

A crucial parameter-free test of the theory is provided by its application to micelle formation from ionic surfactants in dilute solution [47]. There, if we accept that the Poisson-Boltzmann equation provides a sufficiently reasonable description of electrostatic interactions, the surface free energy of an aggregate of radius R and aggregation number N can be calculated horn the electrostatic free energy analytically. The whole surface free energy can be decomposed into two terms, one electrostatic, and another due to short-range molecular interactions that, from dimensional considerations, must be proportional to area per surfactant molecule, i.e. 

Linse, P, Gunnarson, G., and Jonsson, B. Electrostatic interactions in micellar solutions -a comparison between Monte-Carlo simulations and solutions of the Poisson-Boltzmann equation. Journal of Physical Chemistry, 1982, 86, No. 3, p. 413-421. 

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