Cooperativity is a defining feature of supramolecular polymerization, dictating how non-
covalent interactions propagate across assembling monomers to yield highly ordered 
architectures. Yet, the molecular determinants of cooperative behavior and its dependence on 
the surrounding environment remain incompletely understood. In the first part of this 
seminar, I will show how both coarse-grained (CG) and all-atom (AA) models—ranging 
from minimalistic representations to chemically realistic polymers—can be combined with 
enhanced sampling techniques, in particular the On-the-fly Probability Enhanced Sampling 
(OPES) method, to quantitatively characterize the thermodynamics of supramolecular 
polymerization. The results highlight how the formation of hierarchical structures 
characterized by multiple binding modes, such as that of Ureidopyrimidinone-based fibers, 
can be a key determinant of cooperativity, depending on the relative strength of the binding 
modes.  
In the second part of the seminar I will focus on the impact of additional species--such as 
ions, competitors, or fuels--on supramolecular polymerization. Specifically I will discuss how 
non-homogeneous environments, typical of realistic conditions, influence the organization 
and dynamics of supramolecular polymer networks. Using CG minimalistic models, I 
investigate how ionic gradients affect supramolecular assemblies, giving rise to 
polymerization dynamics not observed in homogeneous ionic environment. 
Together, these studies provide general indications on how the self-assembly landscape of 
supramolecular polymeric systems can be shaped, relevant for the design of responsive and 
out-of-equilibrium materials.