Valence-Selective Electrophoretic Transport in Neutral Carbon Nanotubes

Abstract

Understanding how confinement alters the transport of charged molecules is central to the advancement of separation, energy, and sensing technologies. Polyamines are small, linear molecules with ionizable groups, making them an ideal model for investigating charge transport in confinement beyond monatomic ions. Using all-atom molecular dynamics (MD) simulations, we investigate how molecular length, net charge, and charge placement affect the electrophoretic transport of polyamines through single-walled carbon nanotubes (CNTs). We find that nanometer-scale confinement reverses the mobility ordering observed in free solution -- in a CNT of radius 0.68 nm, spermine (q = +4) travels more slowly than ethylamine (q = +1), contrasting with the expected scaling of mobility with valence in bulk. Further, we find that mobility decreases faster than the inverse of valence, though molecular size and length vary alongside this trend. Comparisons of doubly protonated spermidine microspecies reveal the additional influence of charge placement at fixed net valence. Upon moving one proton of dicationic spermidine from the central to a terminal nitrogen, the mobility is increased by 42%. We analyze hydration structure and solute-solvent association, identifying local-solvation differences between protonation topologies that accompany these distinct transport responses under confinement. These results suggest that neutral CNTs could support valence-selective nanofluidic transport, with additional sensitivity to molecular structure and protonation topology.