Fig. 7: Structure and dynamics of supramolecular block copolymers.
From: Living supramolecular polymerization of fluorinated cyclohexanes
a Equilibrated MD snapshots of M3-M5 copolymers models where the M3 (in orange) and M5 monomers (violet) are arranged in blocks (top), into segregated M3 and M5 intertwining columns (middle), or randomly mixed in the fiber (bottom). The arrangements of the fluorinated cyclohexane centers are shown below the MD fibers’ snapshots. The energies of the different M3-M5 mixing schemes relative to completely segregated M3 and M5 homopolymers (∆E) are reported beside each equilibrated copolymer model. b Length of the Blocks (in green), Columns (red) and Random (violet) copolymer models as a function of MD simulation time. c Structure of the Blocks fiber colored based on the clusters (molecular motifs) identified by the SOAP-PAMM analysis: fluorinated cyclohexane and amide groups in blue and red, the alkyl side chains of the monomers in gray, green and cyan66,67. d PCAs of the SOAP vectors for M3 and M5 homopolymers, and for Blocks, Columns and Random copolymers (left-to-right). e Unsupervised PAMM clustering of the PCA data (d): different colored clusters indicate different local structural/dynamic motifs in the fibers. The closer and more interconnected are the colors (e.g., gray, cyan, green surface sites), the more dynamic is the interconnection between them (e.g., indicative of a dynamic surface). Separated clusters identify static, ordered, and persistent domains in the fiber (e.g., red and blue clusters, indicative of a relatively static fiber backbone). f Schematic representation of the dynamic transitions between the clusters estimated from the MD: the higher are the transition probabilities (numbers associated to the transition arrows), the more dynamic is the exchange between the clusters. No arrows indicate no exchange. The results show that these fibers have an intrinsic dynamic diversity: with a dynamic surface, and a static and ordered backbone.
