Model-based studies on helix–coil transition and folding cooperativity of synthetic polypeptides have contributed to the understanding of protein folding and stability and to the development of polypeptide-based functional materials. Polypeptide-containing macromolecules with complex architectures, however, remain a challenge in the model-based analysis. Herein, a modified Schellman–Zimm–Bragg model has been utilized to quantitatively analyze the folding cooperativity of polypeptide-containing macromolecules. While the helix–coil transition of homopolypeptides (e.g., poly(ε-benzyloxycarbonyl-l-lysine) (PZLL)) can be described by the classic model, the folding of grafted polypeptide chains in the comb macromolecules (e.g., polynorbornene-g-poly(ε-benzyloxycarbonyl-l-lysine) (PN-g-PZLL)) cannot be accurately predicted by the existing theories, due to the side-chain interactions between grafted polypeptides in the comb macromolecules. Incorporating nonlocal interaction explicability into the statistical mechanics treatment is found to be instructive to account for the possible “tertiary” interactions of polypeptides in the macromolecules with complex architectures.

Supramolecular polymerization or assembly of proteins or large macromolecular units by a homogeneous nucleation mechanism can be quite slow and require specific solution conditions. In nature, protein assembly is often regulated by molecules that modulate the electrostatic interactions of the protein subunits for various association strengths. The key to this regulation is the coupling of the assembly process with a reversible or irreversible chemical reaction that occurs within the constituent subunits. However, realizing this complex process by the rational design of synthetic molecules or macromolecules remains a challenge. Herein, we use a synthetic polypeptide-grafted comb macromolecule to demonstrate how the in situ modulation of interactions between the charged macromolecules affects their resulting supramolecular structures. The kinetics of structural formation was studied and can be described by a generalized model of nucleated polymerization containing secondary pathways. Basic thermodynamic analysis indicated the delicate role of the electrostatic interactions between the charged subunits in the reaction-induced assembly process. This approach may be applicable for assembling a variety of ionic soft matters that are amenable to chemical reactions in situ.

Polycatalytic enzyme complexes made by immobilization of industrial enzymes on polymer- or nanoparticle-based scaffolds are technologically attractive due to their recyclability and their improved substrate binding and catalytic activities. Herein, we report the synthesis of polycatalytic complexes by the immobilization of nonprocessive cellulases on the surface of colloidal polymers with a magnetic nanoparticle core and the study of their binding and catalytic activities. These polycatalytic cellulase complexes have increased binding affinity for the substrate. But due to their larger size, these complexes were unable to access to the internal surfaces of cellulose and have significantly lower binding capacity when compared to those of the corresponding free enzymes. Analysis of released soluble sugars indicated that the formation of complexes may promote the prospect of having consistent, multiple attacks on cellulose substrate. Once bound to the substrate, polycatalytic complexes tend to remain on the surface with very limited mobility due to their strong, multivalent binding to cellulose. Hence, the overall performance of polycatalytic complexes is limited by its substrate accessibility as well as mobility on the substrate surface.

•A general approach to obtain composite chitosan nanofibers is proposed.•The method is based on mechanistic understanding of chain entanglements in solution.•The composite fibers provide a useful platform to support a variety of catalysts.•“Post-modification” of the fibers further improves the stability of supported catalysts.Using electrospinning technique to prepare chitosan (CS) nanofibers from an inexpensive solvent such as acetic acid has been a challenge, due to the lack of sufficient entanglements in these semi-rigid polyelectrolytes. Incorporating polymers such as poly(methacrylic acid) (PMAA) into the solution lowers the entanglement concentration of the polymers, and make all three morphology regimes (polymer droplets, beaded nanofibers and nanofibers with uniform thickness) accessible to electrospinning method. Uniform composite nanofibers are found at concentrations well above the entanglement concentration. The thickness and morphology of nanofibers can be regulated by addition of small amount of organic solvents such as dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The composite nanofibers are subsequently crosslinked at an elevated temperature to improve their thermal and solvent stability. The mechanical properties of the crosslinked CS/PMAA fibers can be modulated by varying the amount and molecular weight of PMAA incorporated in the blend. The composite fiber materials provide a useful platform to support a variety of catalysts. As a demonstration, palladium catalyst has been immobilized on the crosslinked CS/PMAA nanofibers to carry out Mizoroki–Heck cross-coupling reactions of aromatic halides and acrylates. We found remarkable catalytic efficiency and stability in these materials. We also demonstrate that, by the “post-modification” of the nanofibers with ligands that chelate metal catalysts, a variety of metal catalysts can be incorporated into the fiber platform, with further improved stability and activity.