Macroion solutions in the cell model studied by field theory and Monte Carlo simulations

Aqueous solutions of charged spherical macroions with variable dielectric permittivity and their associated counterions are examined within the cell model using a field theory and Monte Carlo simulations. The field theory is based on separation of fields into short- and long-wavelength terms, which are subjected to different statistical-mechanical treatments. The simulations were performed by using a new, accurate, and fast algorithm for numerical evaluation of the electrostatic polarization interaction. The field theory provides counterion distributions outside a macroion in good agreement with the simulation results over the full range from weak to strong electrostatic coupling. A low-dielectric macroion leads to a displacement of the counterions away from the macroion

Bulk simulation of polar liquids in spherical symmetry.

Molecular simulations of strongly coupled dipolar systems of varying size have been carried out, using particles confined inside a dielectric cavity and an image charge approach to treat the dielectric response from the surroundings. A simple method using penalty functions was employed to create an isotropic and homogeneous distribution of particles inside the cavity. The dielectric response of the molecular system was found to increase as the number of particles N was increased. Nevertheless, a significant surface effect remained even for the largest systems (N=10,000), manifesting itself through a decrease in the dielectric constant of the system as the confining surface was approached. The surface effect was significantly reduced by using a negative dielectric constant of the surrounding dielectric medium, although accomplishing a full dielectric solvation of the molecular system was not possible

Neutron reflectometry to investigate the delivery of lipids and DNA to interfaces (Review)

The application of scattering methods in the study of biological and biomedical problems is a field of research that is currently experiencing fast growth. In particular, neutron reflectometry (NR) is a technique that is becoming progressively more widespread, as indicated by the current commissioning of several new reflectometers worldwide. NR is valuable for the characterization of biomolecules at interfaces due to its capability to provide quantitative structural and compositional information on relevant molecular length scales. Recent years have seen an increasing number of applications of NR to problems related to drug and gene delivery. We start our review by summarizing the experimental methodology of the technique with reference to the description of biological liquid interfaces. Various methods for the interpretation of data are then discussed, including a new approach based on the lattice mean-field theory to help characterize stimulus-responsive surfaces relevant to drug delivery function. Recent progress in the subject area is reviewed in terms of NR studies relevant to the delivery of lipids and DNA to surfaces. Lastly, we discuss two case studies to exemplify practical features of NR that are exploited in combination with complementary techniques. The first case concerns the interactions of lipid-based cubic phase nanoparticles with model membranes (a drug delivery application), and the second case concerns DNA compaction at surfaces and in the bulk solution (a gene delivery application). (C) 2008 American Vacuum Society. [DOI: 10.1116/1.2976448

Nondielectric long-range solvation of polar liquids in cubic symmetry

Long-range solvation properties of strongly coupled dipolar systems simulated using the Ewald and reaction field methods are assessed by using electric fluctuation formulas for a dielectric medium. Some components of the fluctuating electric multipole moments are suppressed, whereas other components are favored as the boundary of the simulation box is approached. An analysis of electrostatic interactions in a periodic cubic system suggests that these structural effects are due to the periodicity embedded in the Ewald method. Furthermore, the results obtained using the reaction field method are very similar to those obtained using the Ewald method, an effect which we attribute to the use of toroidal boundary conditions in the former case. Thus, the long-range solvation properties of polar liquids simulated using either of the two methods are nondielectric in their character. (C) 2009 American Institute of Physics. [doi:10.1063/1.3250941

Structural Anisotropy in Polar Fluids Subjected to Periodic Boundary Conditions

A heuristic model based on dielectric continuum theory for the long-range solvation free energy of a dipolar system possessing periodic boundary conditions (PBCs) is presented. The predictions of the model are compared to simulation results for Stockmayer fluids simulated using three different cell geometries. The boundary effects induced by the PBCs are shown to lead to anisotropies in the apparent dielectric constant and the long-range solvation free energy of as much as 50%. However, the sum of all of the anisotropic energy contributions yields a value that is very close to the isotropic one derived from dielectric continuum theory, leading to a total system energy close to the dielectric value. It is finally shown that the leading-order contribution to the energetic and structural anisotropy is significantly smaller in the noncubic simulation cell geometries compared to when using a cubic simulation cell