No Arabic abstract
In this work, we present a mathematical model to describe the adsorption-diffusion process on fractal porous materials. This model is based on the fractal continuum approach and considers the scale-invariant properties of the surface and volume of adsorbent particles, which are well-represented by their fractal dimensions. The method of lines was used to solve the nonlinear fractal model, and the numerical predictions were compared with experimental data to determine the fractal dimensions through an optimization algorithm. The intraparticle mass flux and the mean square displacement dynamics as a function of fractal dimensions were analyzed. The results suggest that they can be potentially used to characterize the intraparticle mass transport processes. The fractal model demonstrated to be able to predict adsorption-diffusion experiments and jointly can be used to estimate fractal parameters of porous adsorbents.
The fractal properties of the total potential energy V as a function of time t are studied for a number of systems, including realistic models of proteins (PPT, BPTI and myoglobin). The fractal dimension of V(t), characterized by the exponent gamma, is almost independent of temperature and increases with time, more slowly the larger the protein. Perhaps the most striking observation of this study is the apparent universality of the fractal dimension, which depends only weakly on the type of molecular system. We explain this behavior by assuming that fractality is caused by a self-generated dynamical noise, a consequence of intermode coupling due to anharmonicity. Global topological features of the potential energy landscape are found to have little effect on the observed fractal behavior.
We developed and experimentally verified an analytical model to describe diffusion of oligonucleotides from stable hydrogel beads. The synthesized alginate beads are Fe3+-cross-linked as well as polyelectrolyte-doped for uniformity and stability at physiological pH. Data on diffusion of oligonucleotides from inside the beads provide physical insights into the volume nature of the immobilization of a fraction of oligonucleotides due to polyelectrolyte cross-linking, i.e., the absence of the surface-layer barrier in this case. Furthermore, our results suggest a new simple approach to measuring the diffusion coefficient of the mobile oligonucleotide molecules inside hydrogel. The considered alginate beads provide a model for a well-defined component in drug release systems and for the oligonucleotide-release transduction steps in drug-delivering and biocomputing applications. This is illustrated by destabilizing the beads with citrate that induces full oligonucleotide release with non-diffusional kinetics.
Understanding the behavior of biomolecules such as proteins requires understanding the critical influence of the surrounding fluid (solvent) environment--water with mobile salt ions such as sodium. Unfortunately, for many studies, fully atomistic simulations of biomolecules, surrounded by thousands of water molecules and ions are too computationally slow. Continuum solvent models based on macroscopic dielectric theory (e.g. the Poisson equation) are popular alternatives, but their simplicity fails to capture well-known phenomena of functional significance. For example, standard theories predict that electrostatic response is symmetric with respect to the sign of an atomic charge, even though response is in fact strongly asymmetric if the charge is near the biomolecule surface. In this work, we present an asymmetric continuum theory that captures the essential physical mechanism--the finite size of solvent atoms--using a nonlinear boundary condition (NLBC) at the dielectric interface between the biomolecule and solvent. Numerical calculations using boundary-integral methods demonstrate that the new NLBC model reproduces a wide range of results computed by more realistic, and expensive, all-atom molecular-dynamics (MD) simulations in explicit water. We discuss model extensions such as modeling dilute-electrolyte solvents with Debye-Huckel theory (the linearized Poisson-Boltzmann equation) and opportunities for the electromagnetics community to contribute to research in this important area of molecular nanoscience and engineering.
We investigate the dynamics of an electron coupled to dispersionless optical phonons in the Holstein model, at high temperatures. The dynamics is conventionally believed to be diffusive, as the electron is repeatedly scattered by optical phonons. In a semiclassical approximation, however, the motion is not diffusive. In one dimension, the electron moves in a constant direction and does not turn around. In two dimensions, the electron follows and then continues to retrace a fractal trajectory. Aspects of these nonstandard dynamics are retained in more accurate calculations, including a fully quantum calculation of the electron and phonon dynamics.
Polymeric nanoparticles (NPs) have a great application potential in science and technology. Their functionality strongly depends on their size. We present a theory for the size of NPs formed by precipitation of polymers into a bad solvent in the presence of a stabilizing surfactant. The analytical theory is based upon diffusion-limited coalescence kinetics of the polymers. Two relevant time scales, a mixing and a coalescence time, are identified and their ratio is shown to determine the final NP diameter. The size is found to scale in a universal manner and is predominantly sensitive to the mixing time and the polymer concentration if the surfactant concentration is sufficiently high. The model predictions are in good agreement with experimental data. Hence the theory provides a solid framework for tailoring nanoparticles with a priori determined size.