"Swiss-cheese" polyelectrolyte gels as media with extremely inhomogeneous distribution of charged species.
"Swiss-cheese" polyelectrolyte gels (i.e., gels containing a regular set of closed spherical pores) are considered as a suitable system for modeling of a medium with extremely inhomogeneous distribution of charged species. It is shown that the inhomogeneous distribution of ions in Swiss-cheese polyelectrolyte gels can be reached simply by immersion of the gels in an aqueous solution of charged species (e.g., low-molecular 1-1 salt or multivalent ions and macroions charged likely to the gel chains). If a polymer gel is kept in such a solution for a long time, the concentration of ions within relatively big voids becomes equal to that in external solution. On the other hand, due to the Donnan effect the ion's concentration in polymer matrix is always lower than that in external solution. As a result the multivalent ions distribute between water voids and polymer matrix. The extent of this distribution is characterized by partition coefficient kD (determined as ratio kD = n(s)(void)/n(s)(mat) of the concentrations n(s)(void) and n(s)(mat) of ions in water voids and in polymer matrix, correspondingly). It is shown that the partition coefficient kD can be larger than 10 for low-molecular salt, reaches 10(3) for bivalent ions, and is higher than 10(6) for tetravalent ions. In the case of polymer macroions the partition coefficient kD tends to infinity. Our calculations show that the lower limit of characteristic scales of heterogeneity (determined by water voids size starting from which the condition of total electroneutrality is fulfilled and effect of partition is the most pronounced) can be equal to tens of nanometers.
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow 119991, Russia. vvvas@ineos.ac.ru
Valentina V
VV
Vasilevskaya
Artem A
AA
Aerov
Alexei R
AR
Khokhlov