| Autor: |
Salamatova TO; St. Petersburg National Research University of Information Technologies, Mechanics and Optics, 197101 St. Petersburg, Russia., Laktionov MY; St. Petersburg National Research University of Information Technologies, Mechanics and Optics, 197101 St. Petersburg, Russia., Zhulina EB; Institute of Macromolecular Compounds of the Russian Academy of Sciences, 199004 St. Petersburg, Russia., Borisov OV; St. Petersburg National Research University of Information Technologies, Mechanics and Optics, 197101 St. Petersburg, Russia.; Institute of Macromolecular Compounds of the Russian Academy of Sciences, 199004 St. Petersburg, Russia.; CNRS, Université de Pau et des Pays de l'Adour UMR 5254, Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux, 64053 Pau, France. |
| Abstrakt: |
The self-consistent field Poisson-Boltzmann framework is applied to analyze equilibrium partitioning of ampholytic nanoparticles (NPs) between buffer solution and polyelectrolyte (PE) polyanionic brush. We demonstrate that depending on pH and salt concentration in the buffer solution, interactions between ionizable (acidic and basic) groups on the NP surface and electrostatic field created by PE brush may either lead to the spontaneous uptake of NPs or create an electrostatic potential barrier, preventing the penetration of NPs inside PE brush. The capability of PE brush to absorb or repel NPs is determined by the shape of the insertion free energy that is calculated as a function of NP distance from the grafting surface. It is demonstrated that, at a pH value below or slightly above the isoelectric point (IEP), the electrostatic free energy of the particle is negative inside the brush and absorption is thermodynamically favorable. In the latter case, the insertion free energy exhibits a local maximum (potential barrier) at the entrance to the brush. An increase in pH leads to the shallowing of the free energy minimum inside the brush and a concomitant increase in the free energy maximum, which may result in kinetic hindering of NP uptake. Upon further increase in pH the insertion free energy becomes positive, making NP absorption thermodynamically unfavorable. An increase in salt concentration diminishes the depth of the free energy minimum inside the brush and eventually leads to its disappearance. Hence, in accordance with existing experimental data our theory predicts that an increase in salt concentration suppresses absorption of NPs (protein globules) by PE brush in the vicinity of IEP. The interplay between electrostatic driving force for NP absorption and osmotic repelling force (proportional to NP volume) indicates that for large NPs with relatively small number of ionizable groups osmotic repulsion overcomes electrostatic attraction preventing thereby absorption of NPs by PE brush. |
