The uptake and sorption of charged molecules by responsive polymer membranes and hydrogels in aqueous solutions is of key importance for the development of soft functional materials. Here we investigate the partitioning of simple monoatomic (Na$^+$, K$^+$, Cs$^+$, Cl$^-$, I$^-$) and one molecular ion (4-nitrophenolate; NP$^-$) within a dense, electroneutral poly($N$-isopropylacrylamide) membrane using explicit-water molecular dynamics simulations. Inside the predominantly hydrophobic environment water distributes in a network of polydisperse water nanoclusters. The average cluster size determines the mean electrostatic self-energy of the simple ions, which preferably reside deeply inside them; we therefore find substantially larger partition ratios $Ksimeq>$10$^{-1}$ than expected from a simple Born picture using a uniform dielectric constant. Despite their irregular shapes we observe that the water clusters possess a universal negative electrostatic potential with respect to their surrounding, as is known for aqueous liquid-vapor interfaces. This potential, which we find concealed in cases of symmetric monoatomic salts, can dramatically impact the transfer free energies of larger charged molecules because of their weak hydration and increased affinity to interfaces. Consequently, and in stark contrast to the simple ions, the molecular ion NP$^-$ can have a partition ratio much larger than unity, $Ksimeq>$10-30 (depending on the cation type) or even $10^3$ in excess of monovalent salt, which explains recent observations of enhanced reaction kinetics of NP$^-$ reduction catalyzed within dense polymer networks. These results also suggest that ionizing a molecule can even enhance the partitioning in a collapsed, rather hydrophobic gel, which strongly challenges the traditional simplistic reasoning.
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