This work deals with molecular dynamics simulations of
human telomeric
i-motif DNA interacting with functionalized single-walled carbon nanotubes.
We study two kinds of i-motifs differing by the protonation state
of cytosines, i.e., unprotonated ones representative to neutral pH
and with half of the cytosines protonated and representative to acidic
conditions. These i-motifs interact with two kinds of carbon nanotubes
differing mainly in chirality (diameter), i.e., (10, 0) and (20, 0).
Additionally, these nanotubes were on-tip functionalized by amino
groups or by guanine- containing residues. We found that protonated
i-motif adsorbs strongly, although not specifically, on the nanotube
surfaces with its 3’ and 5’ ends directed toward the
surface and that adsorption does not affect the i-motif shape and
hydrogen bonds existing between C:C+ pairs. The functional
groups on the nanotube tips have minimal effect either on position
of i-motif or on its binding strength. Unprotonated i-motif, in turn,
deteriorates significantly during interaction with the nanotubes and
its binding strength is rather high as well. We found that (10, 0)
nanotubes destroy the i-motif shape faster than (20, 0). Moreover
the i-motif either tries to wrap the nanotube or migrates to its tip
and becomes immobilized due to interaction with guanine residue localized
on the nanotube tip and attempts to incorporate its 3’ end
into the nanotube interior. No hydrogen bonds exist within the unprotonated
i-motif prior to and after adsorption on the nanotube. Thus, carbon
nanotubes do not improve the stability of unprotonated i-motif due
to simple adsorption or just physical interactions. We hypothesize
that the stabilizing effect of carbon nanotubes reported in the literature
is due to proton transfer from the functional group in the nanotube
to cytosines and subsequent formation of C:C+ pairs.