  We present a new simulation scheme which allows an efficient sampling of
reconfigurable supramolecular structures made of polymeric constructs
functionalized by reactive binding sites. The algorithm is based on the
configurational bias scheme of Siepmann and Frenkel and is powered by the
possibility of changing the topology of the supramolecular network by a
non-local Monte Carlo algorithm. Such plan is accomplished by a multi-scale
modelling that merges coarse-grained simulations, describing the typical
polymer conformations, with experimental results accounting for free energy
terms involved in the reactions of the active sites. We test the new algorithm
for a system of DNA coated colloids for which we compute the hybridisation free
energy cost associated to the binding of tethered single stranded DNAs
terminated by short sequences of complementary nucleotides. In order to
demonstrate the versatility of our method, we also consider polymers
functionalized by receptors that bind a surface decorated by ligands. In
particular we compute the density of states of adsorbed polymers as a function
of the number of ligand-receptor complexes formed. Such a quantity can be used
to study the conformational properties of adsorbed polymers useful when
engineering adsorption with tailored properties. We successfully compare the
results with the predictions of a mean field theory. We believe that the
proposed method will be a useful tool to investigate supramolecular structures
resulting from direct interactions between functionalized polymers for which
efficient numerical methodologies of investigation are still lacking.
